CN105111875A - Self-cleaning nano protective liquid used for glass and preparation method - Google Patents
Self-cleaning nano protective liquid used for glass and preparation method Download PDFInfo
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- CN105111875A CN105111875A CN201510480895.8A CN201510480895A CN105111875A CN 105111875 A CN105111875 A CN 105111875A CN 201510480895 A CN201510480895 A CN 201510480895A CN 105111875 A CN105111875 A CN 105111875A
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- 239000007788 liquid Substances 0.000 title claims abstract description 73
- 239000011521 glass Substances 0.000 title claims abstract description 57
- 238000004140 cleaning Methods 0.000 title claims abstract description 44
- 230000001681 protective effect Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 240000002853 Nelumbo nucifera Species 0.000 claims abstract description 8
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims abstract description 8
- 235000006510 Nelumbo pentapetala Nutrition 0.000 claims abstract description 8
- 238000009501 film coating Methods 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 70
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 65
- 239000000178 monomer Substances 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 229920005989 resin Polymers 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 40
- 235000012239 silicon dioxide Nutrition 0.000 claims description 36
- 239000000377 silicon dioxide Substances 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- 239000003999 initiator Substances 0.000 claims description 30
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- 239000002253 acid Substances 0.000 claims description 25
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- 239000006185 dispersion Substances 0.000 claims description 12
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 12
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- 239000002245 particle Substances 0.000 claims description 11
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- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
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- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 239000007888 film coating Substances 0.000 claims description 4
- 238000009775 high-speed stirring Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000002075 main ingredient Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 67
- 238000000576 coating method Methods 0.000 abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 48
- 230000003373 anti-fouling effect Effects 0.000 abstract description 8
- 239000010409 thin film Substances 0.000 abstract description 7
- 239000000428 dust Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 238000011109 contamination Methods 0.000 abstract 1
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- 238000000034 method Methods 0.000 description 32
- 229960001866 silicon dioxide Drugs 0.000 description 28
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000007766 curtain coating Methods 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 229920006222 acrylic ester polymer Polymers 0.000 description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
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- 150000003254 radicals Chemical class 0.000 description 1
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Abstract
The present invention relates to a self-cleaning nano protective liquid used for glass and a preparation method. According to the self-cleaning nano protective liquid used for glass, a thin film coating formed by the nano protective liquid is provided with a similar structure of a lotus leaf surface in nature, wherein the structure is a nano-micro composite layer structure, and the coating is a colorless transparent thin film coating, with a thickness of 400-1000nm. The coating provided by the present invention has superior properties of water-proofing, oil-proofing, anti-fouling, anti-fogging, moisture-proofing, and the like. A contact angle of the coating and water is 140-155 DEG (a droplet volume is measured as 4 mu L), a roll angle of a water droplet on a coating surface is less than 5 DEG (a droplet volume is measured as 4 mu L). The water droplet existed on the the coating surface is freely rollably, meanwhile contaminations of dust and the like are removed, and thereby achieving the superior properties of anti-fogging, anti-fouling and the like.
Description
(1) technical field
The invention belongs to coating processing technique field, particularly a kind of super-hydrophobic automatic cleaning nano protecting liquid for glass and preparation method thereof.
(2) background technology
Glass is the important materials of the modern life and decoration, keeps cleaning glass transparent mainly through manual cleaning.The glass curtain wall that Highrise buildings adopts, the dirty pollutent such as air, rainwater can make it in eclipse, and transmittance declines, and adopts Conventional cleaning method, and cleaning costly, and exists potential safety hazard; Windshield and rear vision mirror can form moisture film in the rainy day, and may result in an automobile accident generation; Winter, temperature was very low, and vehicle glass can produce frost, and conventional manual mode or heating are set out on a journey after being cleared up by frost again, very inconvenient; In life, mirror and glasses also usually tie mist, bring inconvenience to our life.
Self-cleaning glass refers to that simple glass is through special processing, and surface produces unique physics-chem characteristic, makes glass without the need to just can be reached the glass of cleaning effect by manual cleaning.Two large classes can be divided into: super hydrophilic automatically cleaning and super-hydrophobic automatic cleaning from principle.At ultra-hydrophilic surface, water droplet sprawls rapidly formation moisture film, in anti-reflection, antifog, have good effect; The static contact angle of super hydrophobic surface and water is greater than 150 °, and roll angle is less than 10 °, can produce as drop free rolling phenomenon on lotus leaf surface, utilizes drop its own face tension force to adhere to and takes away the dirts such as matrix surface dust, thus keep material surface cleaning.Super-hydrophobicity has broad application prospects, and except preventing pollution thing, frost, also can be used for suppressing surface oxidation, burn into reduce conduction of current etc.
Start from the fifties in last century to the research of super-hydrophobic coating in the world, fundamental research and applied research have obtained obvious achievement all.In hydrophobic field, using at present and have wax class, organosilicon and organic fluorine series more widely, realizing hydrophobic effect mainly through reducing surface tension.Paraffin class material as hydrophobic surface, have good water-repellancy, but oil preventing performance is general, can not be effectively antifouling; Lacquer tree fat and silicone resin are used for furniture, car detailing industry by CN101967283, have good water resistance, but its weather resistance and ventilation property unsatisfactory.The electronegativity of fluorine atom is large, and radius is little, and the bond energy of carbon-fluorine bond is large, and surface tension can be made significantly to reduce, and shows excellent hydrophobic oleophobic performance, and C-F key shields by fluorine atom simultaneously, and protection carbon atom and carbochain, show high heat-resistant stability and chemical stability.CN200510095423.7 discloses ultra-fine fibre enhancing fluorine-containing coat and possesses the advantages such as super-hydrophobic and oleophobic, but preparation method is more loaded down with trivial details, is difficult to construct at large-area engineering surface.Acrylic polymer has good film-forming property, and network structure is more loose, introduces fluorine-containing groups, can have good hydrophobic oleophobic performance, and its film-forming process is simple at its side chain.The raising main manifestations of hydrophobic oleophobic performance is that the contact angle of coating and water increases, but this raising is limited, and the research such as Zisman, W.A. shows that the most multipotency of plane surface contact angle is increased to about 120 °, the effect of the soil resistant that cannot reach; The people such as Barthlott observe lotus leaf surface wax crystalline form looks, have found the surface roughness of nano-micrometre level projection, and guess that this structure is the reason of lotus leaf surface super-hydrophobicity; The people such as state's inland river thunder are found by surface biomimetic modeling effort: the hydrophobic portion faces of animals and plants, the micro-nano projection of ubiquity.This structure not only reduces the contact area between solid, liquid two-phase, and makes the reaction force attenuation on pollutent moon surface.Be easy to take away the pollutents such as surface dirt when drop rolls.
The open resin being contained non-reacted nanoparticle and fluoropolymer by UV photocuring of US Patent No. 6068911, prepare shaggy super-hydrophobic coat, easy volatile solvent can by low surface energy fluorine polymer belt to surface, but need UV light to be used for solidified coating, preparation technology bothers, and is very restricted during use, patent CN101029137A discloses a kind of fluorine-containing POSS acrylate block copolymer resin and synthetic method thereof, adopt atom transfer radical polymerization method (ATRP) synthesis, after film forming, the contact angle of coating and water is 85 ~ 120 °, and process is more loaded down with trivial details, limited efficiency, CN103012700A and CN102775567A adopts reversible addion-fragmentation chain transfer free radical polymerisation process (RAFT) to construct low surface energy, preparation technology's more complicated, and hydrophobic effect is remarkable not, a kind of preparation method of thermoplastic fluorine-containing acrylic ester resin disclosed in patent CN101619116, but it passes through fluorinated acrylate monomer, methyl methacrylate monomer and other function monomers carry out solution copolymerization reaction, the weather resistance of film and stain resistant performance improve, but wherein fluorinated acrylate monomer parts by weight are 15 ~ 25 parts, large usage quantity, the cost of fluoropolymer is higher, CN1322775A, the method preparing fluoroacrylic resin coating is all proposed in the patents such as CN102617783A, there is the large problem of fluorochemical monomer consumption equally in these methods.
The present invention uses acrylic ester monomer to be polymerized, and fluorochemical monomer introduced by side chain, improves waterproof and oilproof performance, carries out surface treatment and make silicon dioxide granule itself have rough surface structure, improve surface property further to silicon-dioxide.Preparation and film-forming process simply, use a small amount of fluorochemical monomer, and coating just possesses excellent hydrophobic oleophobic performance, and contact angle can reach 140 °-155 °, and roll angle is less than 10 °; For glasswork, have certain anti-reflection effect, transmittance can reach more than 92.0%.Can be used for the aspect such as antifouling antifog of building glass, vehicle glass and life glass.
(3) summary of the invention
The present invention, in order to make up the deficiencies in the prior art, provides the self-cleaning nona protective liquid for glass and preparation method, and this protective liquid making method is simple, easy to operate.Prepared nano protecting liquid is mainly used in the antifouling, antifog, moistureproof of glass surface, and what form coating has nano-micrometre multi-stage surface structure, excellent hydrophobic oleophobic performance,
wellheat-resistant stability and chemical-resistant stability, to glass, there is certain anti-reflection effect.
The present invention is achieved through the following technical solutions:
A kind of self-cleaning nona protective liquid for glass, its special character is: this nano protecting liquid form film coating there is the lotus leaf surface analog structure with occurring in nature, for nano-micrometre compound hierarchical structure, be colorless and transparent film coating, thickness is 400-1000nm.
Nano protecting liquid of the present invention is colourless (or faint yellow) transparent liquid, to form super-hydrophobic automatic cleaning coating be Clear coating, be mainly used in glass surface hydrophobic oleophobic, antifouling antifog, have certain anti-reflection effect, described protective liquid is the hydrophobic copolymer and hydrophilic nano SiO prepared by fluorinated acrylate and acrylic ester monomer copolymerization
2particle organic-inorganic two kinds of components are composited, and its surface topography has the nano-micrometre compound hierarchical structure similar with occurring in nature lotus leaf surface.The SiO of described nano-micrometre compound hierarchical structure to be particle diameter be 20 ~ 100nm
2even particulate dispersion in coatingsurface, and is the SiO of 20 ~ 100nm by particle diameter
2the near-spherical projection combination structure of 1 ~ 10 μm that cluster of grains is polymerized to forms.
For obtaining target nano protecting liquid, the present invention is that fluorin modified crylic acid ester resin is prepared from the Nano particles of silicon dioxide compound processed, prepared by solution polymerization mode, by once feeding in raw material or constant pressure dropping two kinds of modes, with fluorin modified crylic acid ester weight resin for benchmark, silicon dioxide granule addition is 0.3-0.8 part.Concrete steps are:
Add in fluorin modified crylic acid resin by the Nano particles of silicon dioxide processed, high-speed stirring forms uniform dispersion, obtained self-cleaning nona protective liquid;
Maybe the Nano particles of silicon dioxide processed is mixed with the same polymerization single polymerization monomer preparing fluorin modified crylic acid ester resin and carry out polyreaction after adding and form Homogeneous phase mixing liquid, obtained self-cleaning nona protective liquid.
Be specially again: the present invention is the radical polymerization by acrylic ester monomer, and the fluorinated acrylate monomer of polymerization can occur to prepare fluorin modified crylic acid ester resin in later stage introducing, then carry out blending dispersion with treated silicon dioxide granule.Concrete scheme is as follows:
Add organic solvent 80-200 part and initiator 0.5-1.2 part in advance in a reservoir, drip acrylic ester monomer 79-105 part, carry out Raolical polymerizable under nitrogen protection, the later stage adds fluorinated acrylate monomer 3-10 part, carry out insulation reaction, obtain fluorin modified crylic acid ester resin; Add in resin by treated Nano particles of silicon dioxide, high-speed stirring obtains nano protecting liquid, in this process, can add vinylbenzene 0-30 part vinyl as modified monomer.
Above-mentioned acrylic ester monomer is (methyl) methyl acrylate, butyl acrylate, one or more in (methyl) vinylformic acid.
Above-mentioned fluorinated acrylate monomer is one or more in Hexafluorobutyl mathacrylate, vinylformic acid hexafluoro butyl ester or perfluorooctylethyl group methacrylic ester.
Above-mentioned organic solvent is toluene or dimethylbenzene.
Above-mentioned initiator is the one in dibenzoyl peroxide or Diisopropyl azodicarboxylate.
Above-mentioned Nano particles of silicon dioxide particle diameter is 25-100nm, carries out etching processing prepare shaggy silicon dioxide granule R-SiO through sodium borohydride aqueous solution
2, have and natural raspberry fruit similar structures, through silane coupling agent KH560 process, better multipolymer consistency can also be made it have on this basis, make blending dispersion evenly, more stable.
In above-mentioned preparation method, its concrete steps are as follows:
(1) add organic solvent 8-20 part in reaction vessel, initiator 0.05-0.12 part, set temperature is 75-85 DEG C, and logical nitrogen protection is also stirred (preferably the logical nitrogen gas stirring time is 20-30 minute, and stir speed (S.S.) is 280-450r/min);
(2) methyl methacrylate 4-7 part, butyl acrylate 3-6 part, (methyl) vinylformic acid 0-0.5 part, vinylbenzene 0-3 part configuration mix monomer is got, constant pressure funnel is used to drop in reaction vessel in 1-2 hour, insulation reaction 0.5 hour under continuing nitrogen protection at 75-85 DEG C;
(3) get fluorochemical monomer 0.3-1 part, use constant pressure funnel slowly to drip, and add a certain amount of solvent and initiator, insulation reaction 2-4 hour under continuing nitrogen protection at 75-85 DEG C, is cooled to 50-60 DEG C.
(4) get Nano particles of silicon dioxide (25-100nm), carry out etching processing through sodium borohydride aqueous solution and prepare shaggy silicon dioxide granule R-SiO
2, dispersed for improving in silicon dioxide granule repolymerization thing, silane coupling agent KH560 process silicon-dioxide can be adopted in its surface grafting functional group;
(5) add in (3) gained fluorin modified crylic acid resin by Nano particles of silicon dioxide after (4) gained process, high-speed stirring forms uniform dispersion; After process, Nano particles of silicon dioxide also in (1), can carry out polyreaction after adding form Homogeneous phase mixing liquid with polymerization single polymerization monomer mixing.
Nano protecting liquid can be obtained by above step, nano protecting liquid proterties is colourless (or light yellow transparent liquid), viscosity can add solvent adjustment as required, gained nano protecting liquid is adopted dip-coating method or drips casting method and form hydrophobic coating at glass surface, realize especially by following steps:
(1) dry clean glass sheet (the Pirhana solution of newly joining: mass percent concentration is about the H of 98% will be washed
2sO
4solution and mass concentration are about the H of 30%
2o
2the mixed solution of solution, wherein, H
2sO
4solution and H
2o
2the volume ratio of solution is 7: 3), be immersed in prepared nano protecting liquid, sheet glass is slowly lifted out, prepare shaggy Clear coating in glass sheet surface; Or get proper amount of nano protective liquid and drop to glass surface, casting method is formed to be evenly distributed on glass surface and to form coating;
(2) it is heat in 40-60 DEG C of vacuum drying oven to carry out bubble removing and Procuring process half an hour that sheet glass surface with coarse coating is placed on temperature, solidify under room temperature condition subsequently, obtained colourless coating is described super-hydrophobic automatic cleaning coating.
Containing hydrophobicity fluorinated acrylate copolymer-containing resin and the coarse Nano-meter SiO_2 of hydrophilic surface in dispersion liquid in the present invention
2particle two kinds of components, a certain component be used alone wherein can not form the coarse three-dimensional arrangement needed for super-hydrophobic coat.The effect of the film-forming properties good due to acrylic ester polymer and reunion bead surface tension force, the near-spherical projection of micron-nanometer can more firmly be attached in substrate.
The invention has the advantages that: coating is raw-material chooses in preparation, the film-forming properties of selected acrylic ester polymer is good, when fluorochemicals usage quantity is lower, reaches good water and oil repellant performance.To ensure that at glass surface form the homogeneity of coating, main raw material(s) SiO
2, fluorine resin itself chemical stability, have again mildew-resistant, anticorrosion, the good characteristic that reduces surface current conduction etc. concurrently.Coating starting material are common commercial product simultaneously.Coating provided by the invention possess waterproof, grease proofing, antifouling, antifog, moistureproof, etc. premium properties.
The invention has the advantages that and just can obtain excellent hydrophobic oleophobic performance with a small amount of fluorine.
The invention has the advantages that and use sodium borohydride aqueous solution process silicon-dioxide, build nano-micrometre compound hierarchical structure further, improve coatingsurface performance further.
The invention has the advantages that the method preparing coating selects Best-Effort request or casting method, preparation method's operating procedure be simple, favorable reproducibility.
Described coating and the contact angle of water be (measuring droplet size is 4 μ L) between 140 ° ~ 155 °, and water droplet is less than 5 ° (measuring droplet size is 4 μ L) in the roll angle of described coatingsurface.The water droplet that described coatingsurface exists can Free-rolling, the pollutents such as surface dirt can be taken away simultaneously, thus reaches the premium properties such as antifog, antifouling.
(4) embodiment
Accompanying drawing 1 is the scanning electron microscope (SEM) photograph of the nano-micrometre compound hierarchical structure micron order projection a of super-hydrophobic automatic cleaning coating of the present invention;
Accompanying drawing 2 is the scanning electron microscope (SEM) photograph of the nano-micrometre compound hierarchical structure micron order projection b of super-hydrophobic automatic cleaning coating of the present invention;
Accompanying drawing 3 is the scanning electron microscope (SEM) photograph of the nano-micrometre compound hierarchical structure nano level agglomerating particles of super-hydrophobic automatic cleaning coating of the present invention;
Accompanying drawing 4-8 is that picture is tested with the contact angle of water in embodiment of the present invention 1-5 super-hydrophobic automatic cleaning coating surface, and wherein, volume is the water droplet of 4 μ L, above angular values be contact angle, below angular values be roll angle, in figure, a-e is corresponding in turn to embodiment 1-5;
Accompanying drawing 9 is that the contact angle of comparative example hydrophobic coating surface and water tests picture.
(5) embodiment
In order to the present invention being described, below embodiment the invention will be described further, but the present invention's scope required for protection be not limited to embodiment illustrate scope.
Embodiment 1
(1) use sodium borohydride aqueous solution process Nano particles of silicon dioxide, make surface have coarse structure: by 3gSiO
2nanoparticle and 2.5g polyvinylpyrrolidone (PVP) are scattered in 100mL water, and 100W ultrasonic disperse 1h, adds 6gNaBH
4strong stirring, subsequently stirring at room temperature 0.5h simultaneously, 50 DEG C are stirred 5h, Centrifugal dispersion, distilled water and ethanol purge, and stored dry is for subsequent use;
(2) in the four-hole boiling flask that thermometer, logical nitrogen, reflux condensing tube, dropping funnel are housed, add the toluene solvant of 15ml, take initiator dibenzoyl peroxide BPO0.08g, add the silicon dioxide granule 1.00g after process in (1), after being warming up to 85 DEG C, stir speed (S.S.) is 350r/min, logical nitrogen;
(3) by the monomer mixture (methyl methacrylate 4.50g, butyl acrylate 3.50g, vinylformic acid is 0.50g, and vinylbenzene is 1.50g) of certain proportioning, constant pressure funnel is used to be added drop-wise within a certain period of time in reaction flask, insulation reaction 0.5h;
(4) use constant pressure funnel to add Hexafluorobutyl mathacrylate 0.50g, and add initiator 0.02g, continue reaction 2.5h, namely obtain the SiO with certain molecular weight
2-fluorin modified crylic acid resin is prepared nano protecting liquid, is light yellow transparent liquid, can adjusts viscosity as required;
(5) (mass percent concentration is about the H of 98% sheet glass to be immersed the Pirhana solution of newly joining
2sO
4solution and mass concentration are about the H of 30%
2o
2the mixed solution of solution, wherein, H
2sO
4solution and H
2o
2the volume ratio of solution is 7: 3) in, after soaking 5 ~ 20 minutes, taking-up distilled water wash, nitrogen dries up;
(6) step (4) being obtained by reacting protective liquid is added drop-wise on the clean dried glass substrate of step (5), is formed the automatically cleaning SiO of hydrophobic yellow transparent by curtain coating at glass surface
2antifogging coating;
After stable on this hydrophobic coating of (7) 4 μ L water droplets static contact angle be 142.5 ° (as
fig. 4shown in), the roll angle of 4 μ L water droplets on this hydrophobic coating is 2.0 °, and transmittance is 93.6%.
Embodiment 2
(1) in the four-hole boiling flask that thermometer, logical nitrogen, reflux condensing tube, dropping funnel are housed, add the toluene solvant of 15ml, take initiator Diisopropyl azodicarboxylate AIBN0.08g, add the silicon dioxide granule 1.00g after step (1) process in embodiment 1, after being warming up to 80 DEG C, stir speed (S.S.) is 350r/min, logical nitrogen;
(2) by the monomer mixture (methyl methacrylate 5.00g, butyl acrylate 3.50g, vinylformic acid is 0.50g, and vinylbenzene is 1.00g) of certain proportioning, constant pressure funnel is used to be added drop-wise within a certain period of time in reaction flask, insulation reaction 0.5h;
(3) use constant pressure funnel to add Hexafluorobutyl mathacrylate 0.50g, and add initiator 0.02g, continue reaction 3h, namely obtain the SiO with certain molecular weight
2-fluorin modified crylic acid resin is prepared nano protecting liquid, is colourless transparent liquid;
(4) step (3) being obtained by reacting protective liquid is added drop-wise on the clean dried glass substrate of step (5) in embodiment 1, forms hydrophobic and transparent automatically cleaning SiO by curtain coating at glass surface
2antifogging coating;
After stable on this hydrophobic coating of (5) 4 μ L water droplets static contact angle be 144.5 ° (as
fig. 5shown in), the roll angle of 4 μ L water droplets on this hydrophobic coating is 1.5 °, and transmittance is 93.5%.
Embodiment 3
(1) in the four-hole boiling flask that thermometer, logical nitrogen, reflux condensing tube, dropping funnel are housed, add the toluene solvant of 15ml, take initiator Diisopropyl azodicarboxylate AIBN0.08g, after being warming up to 80 DEG C, stir speed (S.S.) is 280r/min, logical nitrogen;
(2) by the monomer mixture (methyl methacrylate 4.50g, butyl acrylate 3.00g, vinylformic acid is 0.40g, and vinylbenzene is 2.10g) of certain proportioning, constant pressure funnel is used to be added drop-wise within a certain period of time in reaction flask, insulation reaction 0.5h;
(3) use constant pressure funnel to add Hexafluorobutyl mathacrylate 0.60g, and add initiator 0.02g, continue reaction 3h, namely obtain the fluorin modified crylic acid resin with certain molecular weight, after being steamed by solvent by rotary evaporation, obtain solid resin;
(4) (1) gained surface irregularity SiO in Example 1
2nanoparticle 1.00g disperses acetone or toluene solvant, ultrasonic 10min, then the solid resin 1.00g that step (3) obtains to be dissolved in solvent be uniformly dispersed to be prepared nano protecting liquid;
(
5) get and clean dried glass substrate immerses step (4) be obtained by reacting in protective liquid, slowly lift, surface forms thin film, and namely self-vulcanizing forms the transparent hydrophobic coating with rough surface structure;
(
6) static contact angle is after stable on this hydrophobic coating of 4 μ L water droplets
149.8 °(as
fig. 6shown in), the roll angle of 4 μ L water droplets on this hydrophobic coating is 1.2 °, and transmittance is 93.2%.
Embodiment 4
(1) in the four-hole boiling flask that thermometer, logical nitrogen, reflux condensing tube, dropping funnel are housed, add the toluene solvant of 20ml, take initiator Diisopropyl azodicarboxylate AIBN0.10g, after being warming up to 80 DEG C, stir speed (S.S.) is 280r/min, logical nitrogen;
(2) by the monomer mixture (methyl methacrylate 5.50g, butyl acrylate 4.00g, vinylformic acid is 0.50g) of certain proportioning, constant pressure funnel is used to be added drop-wise within a certain period of time in reaction flask, insulation reaction 0.5h;
(3) use constant pressure funnel to add Hexafluorobutyl mathacrylate 0.80g, and add initiator 0.02g, continue reaction 3h, namely obtain the fluorin modified crylic acid resin with certain molecular weight, after being steamed by solvent by rotary evaporation, obtain solid resin;
(4) step (1) gained surface irregularity SiO in Example 1
2nanoparticle 1.00g disperses acetone or toluene solvant, ultrasonic 10min, then the solid resin 1.00g that step (3) obtains to be dissolved in solvent be uniformly dispersed to be prepared nano protecting liquid;
(
5) get and clean dried glass substrate immerses step (4) be obtained by reacting in protective liquid, slowly lift, surface forms thin film, and namely self-vulcanizing forms the transparent hydrophobic coating with rough surface structure;
(
6) after stable on this hydrophobic coating of 4 μ L water droplets static contact angle be 151.5 ° (as
fig. 7shown in), the roll angle of 4 μ L water droplets on this hydrophobic coating is 2.4 °, and transmittance is 92.5%.
Embodiment 5
(1) in the four-hole boiling flask that thermometer, logical nitrogen, reflux condensing tube, dropping funnel are housed, add the toluene solvant of 15ml, take initiator Diisopropyl azodicarboxylate AIBN0.08g, after being warming up to 85 DEG C, stir speed (S.S.) is 280r/min, logical nitrogen;
(2) by the monomer mixture (methyl methacrylate 5.50g, butyl acrylate 3.00g, vinylbenzene is 1.50g) of certain proportioning, constant pressure funnel is used to be added drop-wise within a certain period of time in reaction flask, insulation reaction 0.5h;
(3) constant pressure funnel is used to add Hexafluorobutyl mathacrylate 0.50g, and add initiator 0.02g, continue reaction 2.5h, namely obtain the fluorin modified crylic acid resin with certain molecular weight, after being steamed by solvent by rotary evaporation, obtain solid resin;
(4) step (1) gained surface irregularity SiO in Example 1
2nanoparticle dispersion acetone or toluene solvant, ultrasonic 10min, then the solid resin 1.00g that step (3) obtains to be dissolved in solvent be uniformly dispersed to be prepared nano protecting liquid;
(
5) get and clean dried glass substrate immerses step (4) be obtained by reacting in protective liquid, slowly lift, surface forms thin film, and namely self-vulcanizing forms the transparent hydrophobic coating with rough surface structure;
(
6) after 4 μ L water droplets are stable on this hydrophobic coating static contact angle be 149.5 ° (as
fig. 8shown in), the roll angle of 4 μ L water droplets on this hydrophobic coating is 0.5 °, and transmittance is 94.1%.
Embodiment 6
(1) use sodium borohydride aqueous solution process Nano particles of silicon dioxide, make surface have coarse structure: by 3gSiO
2nanoparticle and 2.5g polyvinylpyrrolidone (PVP) are scattered in 100mL water, and 100W ultrasonic disperse 1h, adds 6gNaBH
4strong stirring, subsequently stirring at room temperature 0.5h simultaneously, 50 DEG C are stirred 4h, Centrifugal dispersion, distilled water and ethanol purge, and stored dry is for subsequent use;
(2) in the four-hole boiling flask that thermometer, logical nitrogen, reflux condensing tube, dropping funnel are housed, add the xylene solvent of 9.3ml, take initiator Diisopropyl azodicarboxylate 0.03g, add the silicon dioxide granule 1.00g after process in (1), after being warming up to 85 DEG C, stir speed (S.S.) is 400r/min, logical nitrogen;
(3) by the monomer mixture (methyl acrylate 3g, butyl acrylate 3.50g, methacrylic acid is 4g) of certain proportioning, constant pressure funnel is used to be added drop-wise within a certain period of time in reaction flask, insulation reaction 0.7h;
(4) use constant pressure funnel to add fluorochemical monomer vinylformic acid hexafluoro butyl ester 0.30g, and add initiator 0.02g, continue reaction 2h, namely obtain the SiO with certain molecular weight
2-fluorin modified crylic acid resin is prepared nano protecting liquid, is light yellow transparent liquid, can adjusts viscosity as required;
(5) (mass percent concentration is about the H of 98% sheet glass to be immersed the Pirhana solution of newly joining
2sO
4solution and mass concentration are about the H of 30%
2o
2the mixed solution of solution, wherein, H
2sO
4solution and H
2o
2the volume ratio of solution is 7: 3) in, after soaking 5 ~ 20 minutes, taking-up distilled water wash, nitrogen dries up;
(6) step (4) being obtained by reacting protective liquid is added drop-wise on the clean dried glass substrate of step (5), is formed the automatically cleaning SiO of hydrophobic yellow transparent by curtain coating at glass surface
2antifogging coating;
After stable on this hydrophobic coating of (7) 4 μ L water droplets, static contact angle is 141.2 °, and the roll angle of 4 μ L water droplets on this hydrophobic coating is 2.0 °, performance and other embodiments similar.
Embodiment 7
(1) in the four-hole boiling flask that thermometer, logical nitrogen, reflux condensing tube, dropping funnel are housed, add the xylene solvent of 23.2ml, take initiator Diisopropyl azodicarboxylate AIBN0.08g, add the silicon dioxide granule 1.00g after step (1) process in embodiment 1, after being warming up to 80 DEG C, stir speed (S.S.) is, logical nitrogen;
(2) by the monomer mixture (methyl methacrylate 10.00g, vinylbenzene is 0.8g) of certain proportioning, constant pressure funnel is used to be added drop-wise within a certain period of time in reaction flask, insulation reaction 0.7h;
(3) use constant pressure funnel to add fluorochemical monomer perfluorooctylethyl group methacrylic ester 1.00g, and add initiator 0.04g, continue reaction 1.5h, namely obtain the SiO with certain molecular weight
2-fluorin modified crylic acid resin is prepared nano protecting liquid, is colourless transparent liquid;
(4) step (3) being obtained by reacting protective liquid is added drop-wise on the clean dried glass substrate of step (5) in embodiment 1, forms hydrophobic and transparent automatically cleaning SiO by curtain coating at glass surface
2antifogging coating;
After stable on this hydrophobic coating of (5) 4 μ L water droplets, static contact angle is 144.3 °, and the roll angle of 4 μ L water droplets on this hydrophobic coating is 2.0 °, performance and other embodiments similar.
Embodiment 8
(1) in the four-hole boiling flask that thermometer, logical nitrogen, reflux condensing tube, dropping funnel are housed, add the xylene solvent of 23.2ml, take initiator Diisopropyl azodicarboxylate AIBN0.06g, add the silicon dioxide granule 1.00g after step (1) process in embodiment 1, after being warming up to 80 DEG C, stir speed (S.S.) is 450r/min, logical nitrogen;
(2) by the monomer mixture of certain proportioning ((methyl) vinylformic acid 10.00g, vinylbenzene is 0.8g for methyl methacrylate, butyl acrylate), constant pressure funnel is used to be added drop-wise within a certain period of time in reaction flask, insulation reaction 0.7h;
(3) use constant pressure funnel to add fluorochemical monomer perfluorooctylethyl group methacrylic ester 1.00g, and add initiator 0.04g, continue reaction 1.5h, namely obtain the SiO with certain molecular weight
2-fluorin modified crylic acid resin is prepared nano protecting liquid, is colourless transparent liquid;
(4) step (3) being obtained by reacting protective liquid is added drop-wise on the clean dried glass substrate of step (5) in embodiment 1, forms hydrophobic and transparent automatically cleaning SiO by curtain coating at glass surface
2antifogging coating;
After stable on this hydrophobic coating of (5) 4 μ L water droplets, static contact angle is 144.1 °, and the roll angle of 4 μ L water droplets on this hydrophobic coating is 1.8 °, performance and other embodiments similar.
Embodiment 9
(1) in the four-hole boiling flask that thermometer, logical nitrogen, reflux condensing tube, dropping funnel are housed, add the xylene solvent of 22ml, take initiator Diisopropyl azodicarboxylate AIBN0.06g, add the silicon dioxide granule 1.00g after step (1) process in embodiment 1, after being warming up to 80 DEG C, stir speed (S.S.) is 380r/min, logical nitrogen;
(2) by the monomer mixture (butyl acrylate 9.5g, vinylbenzene is 0.8g) of certain proportioning, constant pressure funnel is used to be added drop-wise within a certain period of time in reaction flask, insulation reaction 0.6h;
(3) use constant pressure funnel to add fluorochemical monomer Hexafluorobutyl mathacrylate 0.30g, vinylformic acid hexafluoro butyl ester 0.60g, and add initiator 0.04g, continue reaction 1.2h, namely obtain the SiO with certain molecular weight
2-fluorin modified crylic acid resin is prepared nano protecting liquid, is colourless transparent liquid;
(4) step (3) being obtained by reacting protective liquid is added drop-wise on the clean dried glass substrate of step (5) in embodiment 1, forms hydrophobic and transparent automatically cleaning SiO by curtain coating at glass surface
2antifogging coating;
After stable on this hydrophobic coating of (5) 4 μ L water droplets, static contact angle is 144.2 °, and the roll angle of 4 μ L water droplets on this hydrophobic coating is 1.9 °, performance and other embodiments similar.
Embodiment 10
(1) in the four-hole boiling flask that thermometer, logical nitrogen, reflux condensing tube, dropping funnel are housed, add the xylene solvent of 20ml, take initiator Diisopropyl azodicarboxylate AIBN0.06g, add the silicon dioxide granule 1.10g after step (1) process in embodiment 1, after being warming up to 75 DEG C, stir speed (S.S.) is
450r/min, logical nitrogen;
(2) by the monomer mixture (methacrylic acid 10.00g, vinylbenzene is 0.8g) of certain proportioning, constant pressure funnel is used to be added drop-wise within a certain period of time in reaction flask, insulation reaction 0.8h;
(3) use constant pressure funnel to add fluorochemical monomer vinylformic acid hexafluoro butyl ester 0.30g, perfluorooctylethyl group methacrylic ester 0.60g, and add initiator 0.04g, continue reaction 1.4h, namely obtain the SiO with certain molecular weight
2-fluorin modified crylic acid resin is prepared nano protecting liquid, is colourless transparent liquid;
(4) step (3) being obtained by reacting protective liquid is added drop-wise on the clean dried glass substrate of step (5) in embodiment 1, forms hydrophobic and transparent automatically cleaning SiO by curtain coating at glass surface
2antifogging coating;
After stable on this hydrophobic coating of (5) 4 μ L water droplets, static contact angle is 144.3 °, and the roll angle of 4 μ L water droplets on this hydrophobic coating is 1.7 °, performance and other embodiments similar.
Embodiment 11
(1) use sodium borohydride aqueous solution process Nano particles of silicon dioxide, make surface have coarse structure: by 3gSiO
2nanoparticle and 3.0g polyvinylpyrrolidone (PVP) are scattered in 100mL water, and 100W ultrasonic disperse 0.5h, adds 6.5gNaBH
4strong stirring, subsequently stirring at room temperature 0.5h simultaneously, 55 DEG C are stirred 4h, Centrifugal dispersion, distilled water and ethanol purge, and stored dry is for subsequent use;
(2) in the four-hole boiling flask that thermometer, logical nitrogen, reflux condensing tube, dropping funnel are housed, add the xylene solvent of 20ml, take initiator dibenzoyl peroxide BPO0.08g, add the silicon dioxide granule 1.00g after process in (1), after being warming up to 90 DEG C, stir speed (S.S.) is 400r/min, logical nitrogen;
(3) by the monomer mixture (butyl acrylate 4.50g, vinylformic acid is 5.50g, and vinylbenzene is 3.00g) of certain proportioning, constant pressure funnel is used to be added drop-wise within a certain period of time in reaction flask, insulation reaction 0.5h;
(4) use constant pressure funnel to add fluorochemical monomer vinylformic acid hexafluoro butyl ester 1.00g, and add initiator 0.04g, continue reaction 1h, namely obtain the SiO with certain molecular weight
2-fluorin modified crylic acid resin is prepared nano protecting liquid, is light yellow transparent liquid, can adjusts viscosity as required;
(5) (mass percent concentration is about the H of 98% sheet glass to be immersed the Pirhana solution of newly joining
2sO
4solution and mass concentration are about the H of 30%
2o
2the mixed solution of solution, wherein, H
2sO
4solution and H
2o
2the volume ratio of solution is 7: 3) in, after soaking 5 ~ 20 minutes, taking-up distilled water wash, nitrogen dries up;
(6) step (4) being obtained by reacting protective liquid is added drop-wise on the clean dried glass substrate of step (5), is formed the automatically cleaning SiO of hydrophobic yellow transparent by curtain coating at glass surface
2antifogging coating;
After stable on this hydrophobic coating of (7) 4 μ L water droplets, static contact angle is 148.5 °, and the roll angle of 4 μ L water droplets on this hydrophobic coating is 1.5 °, performance and other embodiments similar.
Comparative example
(1) in the four-hole boiling flask that thermometer, logical nitrogen, reflux condensing tube, dropping funnel are housed, add the toluene solvant of 15ml, take initiator Diisopropyl azodicarboxylate AIBN0.08g, after being warming up to 85 DEG C, stir speed (S.S.) is 280r/min, logical nitrogen;
(2) by monomer mixture (the first methyl methacrylate 5.50g of certain proportioning, butyl acrylate 4.00g, vinylformic acid is 0.50g), constant pressure funnel is used to be added drop-wise within a certain period of time in reaction flask, insulation reaction 3.5h, obtain acrylate resin, obtain solid resin after being steamed by solvent by rotary evaporation;
(3) the solid resin 1.00g that step (2) obtains is dissolved in solvent to make to be uniformly dispersed and obtain the macromolecular solution of acrylate copolymer;
(4) get and clean dried glass substrate immerses step (3) be obtained by reacting in macromolecular solution, slowly lift, surface forms thin film, and namely self-vulcanizing forms transparent thin film coatings;
After stable on this hydrophobic coating of (5) 4 μ L water droplets static contact angle be 70.2 ° (as
fig. 9shown in), the roll angle of 4 μ L water droplets on this hydrophobic coating is 22 °, and transmittance is 92.1%.
Protective liquid of the present invention is the hydrophobic copolymer and hydrophilic nano SiO prepared by fluorinated acrylate and acrylic ester monomer copolymerization
2particle organic-inorganic two kinds of components are composited, and its surface topography has the nano-micrometre compound hierarchical structure similar with occurring in nature lotus leaf surface.The SiO of described nano-micrometre compound hierarchical structure to be particle diameter be 20 ~ 100nm
2even particulate dispersion in coatingsurface (as
fig. 1 and 2), and be the SiO of 20 ~ 100nm by particle diameter
2the near-spherical projection of cluster of grains 1 ~ 10 μm of being polymerized to (
as Fig. 3) combination structure form.
Does is scope 280 ~ 400.450?
Claims (10)
1. the self-cleaning nona protective liquid for glass, it is characterized in that: this nano protecting liquid form film coating there is the lotus leaf surface analog structure with occurring in nature, for nano-micrometre compound hierarchical structure, be colorless and transparent film coating, thickness is 400-1000nm.
2. the self-cleaning nona protective liquid for glass according to claim 1, is characterized in that: the Nano particles of silicon dioxide that main ingredient is fluorin modified crylic acid ester resin and processed.
3. the self-cleaning nona protective liquid for glass according to claim 2, is characterized in that: fluorin modified crylic acid ester resin is made primarily of the raw material of following parts by weight:
Acrylic ester monomer is 79-105 part, and fluorinated acrylate monomer is 3-10 part, and initiator is 0.5-1.2 part, and organic solvent is 80-200 part.
4. the self-cleaning nona protective liquid for glass according to claim 1, is characterized in that: also comprise 0-30 part modified monomer.
5. the self-cleaning nona protective liquid for glass according to claim 3, it is characterized in that: acrylic ester monomer is (methyl) methyl acrylate, butyl acrylate, one or more in (methyl) vinylformic acid, fluorinated acrylate monomer is Hexafluorobutyl mathacrylate, one or more in vinylformic acid hexafluoro butyl ester or perfluorooctylethyl group methacrylic ester, organic solvent is the one in toluene or dimethylbenzene, initiator is the one in dibenzoyl peroxide or Diisopropyl azodicarboxylate, the Nano particles of silicon dioxide particle size range processed is 25-100nm.
6. the self-cleaning nona protective liquid for glass according to claim 4, is characterized in that: modified monomer is vinyl.
7. a preparation method for the self-cleaning nona protective liquid for glass according to claim 2, is characterized in that: comprise the following steps: fluorin modified crylic acid ester resin and the Nano particles of silicon dioxide compound preparation processed.
8. the preparation method of the self-cleaning nona protective liquid for glass according to claim 7, it is characterized in that: comprise the following steps: the Nano particles of silicon dioxide processed is added in fluorin modified crylic acid resin, high-speed stirring forms uniform dispersion, obtained self-cleaning nona protective liquid.
9. the preparation method of the self-cleaning nona protective liquid for glass according to claim 7 or 8, it is characterized in that: comprise the following steps: the Nano particles of silicon dioxide processed mix with the same polymerization single polymerization monomer preparing fluorin modified crylic acid ester resin add after carry out polyreaction and form Homogeneous phase mixing liquid, obtained self-cleaning nona protective liquid.
10. the preparation method of the self-cleaning nona protective liquid for glass according to claim 9; it is characterized in that: the preparation process of fluorin modified crylic acid ester resin: add organic solvent and initiator in a reservoir in advance; drip acrylic ester monomer; Raolical polymerizable is carried out under nitrogen protection; later stage adds fluorinated acrylate monomer; carry out insulation reaction, obtain fluorin modified crylic acid ester resin
The preparation process of Nano particles of silicon dioxide: particle diameter is that the Nano particles of silicon dioxide of 20 ~ 100nm carries out etching processing through sodium borohydride aqueous solution and prepares shaggy silicon dioxide granule R-SiO
2.
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