CN101838496B - Super-hydrophobic polyurethane/ oxide nano particle hybrid coating material and preparation method thereof - Google Patents
Super-hydrophobic polyurethane/ oxide nano particle hybrid coating material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a super-hydrophobic polyurethane/ oxide nano particle hybrid coating and a preparation method thereof. The super-hydrophobic coating is prepared by oxide nano particles, silane coupling agent and polyurethane which have wide material source and are easily obtained through a self-assembly method, and has the contact angle of 140-168 degrees and the rolling angle of 1-20 degrees as well as good visible light permeability. The invention solves the problems that the currently prepared transparent super-hydrophobic coating needs extremely low surface energy perfluorinated silane modification, has high production cost and complicated technique, and can not realize large-scale production. The method has simple technique, easily obtained raw material and low cost; and the prepared super-hydrophobic coating can be taken as a dustproof and antifogging protective coating of the surface of solids such as glass and the like, and a waterproof insulating layer used in a micro-electronic device, a sensor and the like.
Description
Technical field
The invention belongs to the super-hydrophobic coat preparing technical field, in particular, relate to a kind of super hydrophobic polyurethane/oxide nano-particles hybrid coating and preparation method thereof.
Background technology
Super-hydrophobic (the surface static contact angle is greater than 150 °) coating has the performances such as waterproof, anti-pollution, anti-oxidation, automatically cleaning, thereby enjoys people to pay close attention to.And transparent hydrophobic coating, not only possess the character of super hydrophobic surface but also have good visible light permeability, be used for outdoor photoelectricity and display equipment, the self-cleaning glass of Highrise buildings, as windshield glass of automobile, aircraft etc. etc., has huge using value.
The at present research of transparent hydrophobic coating is also few, and the preparation method mainly comprises sol-gel method, phase separation method, self-assembly method and plasma method etc.
Sol-gel method such as patent CN200710070728.1 immerse transparent base material crystal pulling method in the colloidal sol that sol-gel method organic aluminium salt chelating makes and prepare transparent film; (Adv Mater.1999, (11): 1365-1368) with sublimable powder compound Al (C such as Naka jimaA
2H
7O
2)
3Join silicon sol or aluminium colloidal sol prepares Clear coating, these all need to modify with extremely low free energy perfluoroalkyl chlorosilane or perfluoroalkyl organoalkoxysilane after thermal treatment obtains certain roughness, thereby make transparent high hydrophobicity coating.And (the ThinSolid Films.2005 such as H.M.Shang, (472): be raw material with TEOS, MPS, MTES then 37-43), through silicon sol dip-coating that hydrolysis obtains under the effect of CTMS and TFCS, carrying out self-assembly after the surface of glass slide, the silica-based transparent film transparency that forms all is higher than 90%, and wherein maximum contact angle reaches nearly 165 °.
(the Thin Solid Films.1997 such as plasma method such as Hozumi, 303:222～225) after employing chemical vapour deposition (CVD) method makes the surface of deposited film obtain certain roughness, as source of the gas, make transparent superhydrophobic film through Cement Composite Treated by Plasma with the silane that contains perfluoroalkyl.(Applied Surface Science.2008, (254): 5299-5303) then utilize magnetron sputtering technique that boron nitride pellicle is deposited to silicon substrate surface, then pass through CF such as Li Guoxing
4Plasma treatment obtained the roughness of two yardsticks on the surface, obtained contact angle and be 159 ° transparent hydrophobic film.
Self-assembly method such as Javier Bravo etc. (Langmuir.2007, (23): 7293-7298) utilize the LBL self-assembly method three layers of surface of glass slide dip-coatings, at first adsorption layer is PAH/SPS, has strengthened the bonding force of polymkeric substance and nanoparticle; The middle layer is PAH/ silicon-dioxide (50+20nm), and the roughness structure of super-hydrophobic required two yardsticks is provided; Top layer is PAH/ silicon-dioxide (20nm), reduces the surface free energy of film by silane.The contact angle of this film is 160 °, and receding angle is less than 10 °, and optical transmittance is higher than 90% in the visible region.Patent CN200910066706.7 is then with electronegative oxide nano-particles and cationic polymers LBL layer assembly, although transmittance is very high, but technique is loaded down with trivial details, and need modify with chemical deposition by the long-chain perfluor silane with low surface energy behind 400 ℃ of high temperature sinterings, and raw material costliness and condition are harsh; And patent CN200810218808.1 with the silicon dioxide colloid electrophoretic deposition to conductive glass, transmittance is high, but can not prepare on a large scale.
Above-mentioned coating process complicated process of preparation, cost is expensive, and needs harsh electrochemical conditions and technique, perhaps carries out finishing with comparatively expensive silicon fluoride, and these have all limited super-hydrophobic coat in industrial widespread use.Therefore, need a kind of simple to operately, raw material is easy to get, and cost is low and can the mass-producing preparation and the method on the transparent hydrophobic surface of using.
Summary of the invention
Purpose of the present invention has proposed a kind of super-hydrophobic polyurethane/oxide nano particle hybrid coating material; another object of the present invention also provides the preparation method of above-mentioned materials, solved in the current preparation transparent hydrophobic coating need the perfluor of utmost point low surface energies hydride modified more, production cost is high, complex process, can not large-scale production problem.
The technical scheme that realizes the object of the invention is: a kind of super-hydrophobic polyurethane/oxide nano particle hybrid coating material, the surface water contact angle that it is characterized in that super-hydrophobic hybrid coating material are 140 °-168 °, and roll angle is 1-20 °; Its feed composition is the super-hydrophobic oxide nano-particles solution of modification and polyurethane solution; Wherein the mass ratio of urethane and the super-hydrophobic oxide nano-particles of modification is 1-8: 1; The super-hydrophobic oxide nano-particles solution of described modification is made by following steps:
A. oxide nano-particles pre-treatment: take by weighing oxide nano-particles dry rear and solvent in baking oven, ultra-sonic dispersion is the rear reactor that adds evenly, heats up, and adds subsequently silane coupling agent, and the temperature rising reflux that stirs reacts; At last with product through absolute ethanol washing and centrifugation, get the modified oxide nanoparticle through vacuum-drying, place moisture eliminator for subsequent use;
B. the preparation of super-hydrophobic oxide nano-particles solution: get above-mentioned modified oxide nanoparticle ultra-sonic dispersion and in solvent, be made into oxide nano-particles solution; To be dispersed in the solvent for the 0.75-2 hydrophobic chain chemical substance that contains doubly of modified oxide nanoparticle weight subsequently, under magnetic agitation, add in the oxide nano-particles solution, make super-hydrophobic oxide nano-particles mixing solutions, the quality solid content of control mixing solutions is 1-5%.
Wherein the oxide nano-particles described in the steps A is nano silicon, nano-aluminium oxide, nano titanium oxide or nano zirconium dioxide; Particle diameter 1-1000nm; Preferred nano silicon; The described solvent of steps A is one or more in toluene, dimethylbenzene, DMF, hexanaphthene, the methylene dichloride; Solvent load is 10-50 times of oxide nano-particles weight; Described silane coupling agent is one or more in γ-glycidyl ether oxygen propyl trimethoxy silicane, methyltrimethoxy silane, trimethylethoxysilane, the poly-dimethyl silyl oxygen alkane, and the coupling agent consumption is 0.5-5 times of oxide nano-particles weight.
Be warming up to 60-100 ℃ among the preferred steps A behind the ultra-sonic dispersion; Add silane coupling agent, be warming up to 100-140 ℃ of back flow reaction 6-12 hour.
Be made into solvent in the super-hydrophobic oxide nano-particles solution among the preferred steps B and be one or more in toluene, dimethylbenzene, DMF, hexanaphthene, the methylene dichloride; Contain one or more in alkyl trichlorosilane, tetrahydrochysene perfluor or the C6-C12 alkyltrialkoxysilaneand of fluorine-containing lipid acid, tetrahydrochysene perfluor C6-C12 of alkyltrialkoxysilaneand, the C6-C12 of alkyl trichlorosilane, the C8-C22 of acid amides that the hydrophobic chain chemical substance is C8-C22, C8-C22; The solvent that dissolving contains the hydrophobic chain chemical substance is tetrahydrofuran (THF), DMF, diethylformamide, trichloromethane, methylene dichloride, normal hexane, hexanaphthene, alkyl cyclohexane or tetracol phenixin; The solvent that preferred dissolution contains the hydrophobic chain chemical substance is tetrahydrofuran (THF), DMF, trichloromethane or methylene dichloride.
Urethane of the present invention is solvent borne polyurethane; The quality solid content of optimization polyurethane solution is 1-15%; Solvent is in acetone, methylethylketone, pimelinketone, vinyl acetic monomer, methylene dichloride, tetrahydrofuran (THF), DMF, the dioxane one or more; Be preferably tetrahydrofuran (THF) or DMF.
The present invention also provides the method for above-mentioned super-hydrophobic polyurethane/oxide nano particle hybrid coating material, its concrete steps are as follows: (1) preparation polyurethane solution, super-hydrophobic oxide nano-particles mixing solutions and polyurethane solution with modification, super-hydrophobic oxide nano-particles in modification is 1 with the urethane mass ratio: the ratio of 1-8 is mixed, afterreaction stirs, to remove unnecessary solvent, namely make the transparent hydrophobic surface coating agent by concentrated;
(2) coating thermal treatment: the transparent hydrophobic surface coating agent is coated in substrate material surface, in 30-80 ℃, dries to solvent and volatilize fully, namely make modified polyurethane with transparent hydrophobic performance/oxide nano-particles coating.
Described base material is metal, inorganic or organic densification or porous material.The preferred substrate material is for being aluminium foil, glass, silicon, pottery, semi-conductor or macromolecular material.
Preferred reaction conditions is ultrasonic or 60-120 ℃ of reflux; Concentrated mode is that underpressure distillation or heating vacuumize.
The selection of coating procedure can be selected according to processed body material size and geometrical shape.Wherein coating method can be spraying method, spin coating method, crystal pulling method or dropping liquid and annotates embrane method.Be applicable to processing area greatly and not limited by processed geometrical shape such as spraying method; Spin-coating and drip method are applicable to the less plane of relative area; Crystal pulling method is also little to the restriction of body material geometrical shape, can directly immerse the self-assembly chemical reaction that carries out 10-16h in the coating-forming agent.
No matter select which kind of coating method that the transparent hydrophobic surface coating agent is coated in substrate material surface, through simple thermal treatment, dry to solvent and volatilize fully, namely make urethane with transparent hydrophobic performance/modified oxide nanoparticle coating, the bake out temperature of preferred coatings is 40-65 ℃, the water contact angle on resulting materials surface is 140-168 °, is generally about 155 °, and roll angle is 1-20 °.
Beneficial effect:
1. the raw material of coating-forming agent preparation is easy to get, and cost is low, and required equipment and preparation technology are simple, and film-forming temperature is lower, and just can obtain the transparent hydrophobic surface by simple coating, and is easy to use, effect stability.
2. the transparent hydrophobic coating of the inventive method preparation has larger surface contact angle (greater than 150 °) and less roll angle, thereby the globule in the above can Free-rolling and taken away surface dirt and realize self-cleaning function;
3. the transparent hydrophobic coating of the present invention's preparation has good visible light permeability, and average visible light transmissivity is greater than 60%.
4. hydrophobicity oxide nano-particles such as silicon-dioxide are except possessing hydrophobic property, also have the characteristics such as hardness is high, wear-resisting, heat insulating ability is good, specific inductivity is low, chemical stability is good, in microelectronic device, the device of optical film, sensor field good development prospect is arranged.
5. the transparent hydrophobic coating of the inventive method preparation; can be used for the occasions such as the windshield glass such as automobile, aircraft, spacecraft, building curtain wall; can be used as simultaneously dustproof, the antifog supercoat of the solid surface such as glass, the waterproof insulating layer that also can be used as in microelectronic device, the sensor uses.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph that adopts under the transparent hydrophobic coating different amplification that the inventive method prepares.Figure a is for amplifying 600 times Electronic Speculum figure, and figure b amplifies 10000 times Electronic Speculum figure.
Fig. 2 is the amplification picture that contact angle instrument obtains.Figure c is that (the water droplet volume: 5 μ L), figure d is corresponding roll angle (water droplet volume: 9 μ L) to the contact angle of water droplet on the surface.
Fig. 3 is the digital photograph of transparent hydrophobic coating.
Fig. 4 is the scanning electron microscope (SEM) photograph of embodiment 2 prepared transparent hydrophobic coatings.Figure e is for amplifying 600 times Electronic Speculum figure, and figure f amplifies 2500 times Electronic Speculum figure.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Stereoscan photograph is recorded by the Dutch Philips-FEI product QUANTA200 of company scanning electron microscope.
The contact angle data by Drop Shape Analysis System G10/DSA100 (
Germany) drop pattern analyser records.
Visible light transmissivity is recorded by Perkin Elmer Lambda20 type ultraviolet-visible instrument.
The below provides specific embodiments of the invention, but the present invention not merely is defined in these embodiment, and these embodiment do not consist of the restriction to claim saturation range of the present invention.
Embodiment 1
1. nano silicon pre-treatment
Take by weighing 3g precipitator method nano silicon (median size 50nm, specific surface area 150m
2/ g), in 100 ℃ of baking ovens, place the there-necked flask ultra-sonic dispersion of 250ml even with 30g toluene after dry 2 hours; Be warming up to 80 ℃, drip the 6.4g γ-glycidyl ether oxygen propyl trimethoxy silicane by the hydrolysis of 20g toluene, time for adding 30 minutes continues to stir after 30 minutes, is warming up to 110 ℃ and refluxes 10 hours, and it is fully reacted; With product absolute ethanol washing 4 times and centrifugation, in 110 ℃ vacuum drying oven, get improved silica in dry 17 hours at last, place moisture eliminator for subsequent use.
2. the preparation of super-hydrophobic silica:
Get above-mentioned treated improved silica 1.5g ultra-sonic dispersion and in 75g toluene, be made into silicon dioxde solution; Subsequently with 2.25g stearylamide ultra-sonic dispersion in the 50g DMF, under magnetic stirring apparatus 80r/min rotating speed, slowly add in the silicon dioxde solution and stir 15min, make the super-hydrophobic silica mixing solutions.The super-hydrophobic silica mixing solutions dripped be applied on the sheet glass 25 ℃ of lower seasoninies, must have the modified manometer silicon dioxide film of ultra-hydrophobicity, its surface water contact angle is 150 °, and roll angle is 10 °.
3. the preparation of coating solution
The super-hydrophobic silica mixing solutions is added in the polyurethane solution, place superpower numerical control ultrasonic cleaner KQ-200KDE under 100W power, namely to make the transparent hydrophobic surface coating agent in ultrasonic 45 minutes, wherein polyurethane solution is that 6g urethane magnetic agitation is dissolved in 50gN, join in the dinethylformamide.
4. prepare transparent hydrophobic coating at body material
Urethane/silica dioxide coating agent is dripped and is applied on the sheet glass, leaves standstill oven dry and both got transparent hydrophobic coating in 55 ℃ of baking ovens.
Accompanying drawing 1 is the stereoscan photograph of coatingsurface.As shown in Figure 2, the surface water contact angle of this coating reaches 160 °, 2.1 ° of roll angles, and coating has good visible light permeability simultaneously, and average visible light transmissivity reaches 67%.Transparent hydrophobic glass pictorial diagram is placed on resulting transparent hydrophobic glass on the picture as shown in Figure 3, below picture high-visible, and water droplet is easy to tumble from the teeth outwards.
Embodiment 2
1. nano silicon pre-treatment
Take by weighing 3g precipitator method nano silicon (median size 50nm, specific surface area 150m
2/ g), in 100 ℃ of baking ovens, place the there-necked flask of 500ml ultrasonic to being uniformly dispersed with 150g toluene after dry 2 hours; Be warming up to 70 ℃, drip the 15g γ-glycidyl ether oxygen propyl trimethoxy silicane by the hydrolysis of 20g toluene, time for adding 30 minutes continues to stir after 30 minutes, is warming up to 110 ℃ and refluxes 5 hours, and it is fully reacted; With product absolute ethanol washing 4 times and centrifugation, in 110 ℃ vacuum drying oven, get improved silica in dry 17 hours at last, place moisture eliminator for subsequent use.
2. the preparation of super-hydrophobic silica:
Get above-mentioned treated improved silica 0.2g ultra-sonic dispersion and in 15g toluene, be made into silicon dioxde solution; Subsequently with 0.3g stearylamide ultra-sonic dispersion in 15gN, in the dinethylformamide, under magnetic stirring apparatus 80r/min rotating speed, add in the silicon dioxde solution and stir 30min, make the super-hydrophobic silica mixing solutions.Sheet glass is immersed in behind the super-hydrophobic silica mixing solutions self-assembling reaction 5h in 20 ℃ of lower seasoninies, must has the modified manometer silicon dioxide film of ultra-hydrophobicity, its surface water contact angle is 151 °, and roll angle is 13 °.
3. the preparation of coating solution
The super-hydrophobic silica mixing solutions is added in the polyurethane solution, place superpower numerical control ultrasonic cleaner KQ-200KDE ultrasonic 50min under 100W power namely to make the transparent hydrophobic surface coating agent, wherein polyurethane solution is that 1.6g urethane magnetic agitation is dissolved in and joins in the 20g DMF.
4. prepare transparent hydrophobic coating at body material
The sheet glass crystal pulling method is immersed in self-assembling reaction 5h in urethane/silica dioxide coating agent, in 45 ℃ of baking ovens, leaves standstill oven dry and both got transparent hydrophobic coating.
The surface water contact angle of this coating reaches 154 °, 2 ° of roll angles, and coating has good visible light permeability simultaneously, and average visible light transmissivity reaches 73%.
Embodiment 3
1. nano silicon pre-treatment
Take by weighing 3g fumed nano silicon-dioxide (median size 30nm, specific surface area 380m
2/ g), in 100 ℃ of baking ovens, place the there-necked flask of 250ml ultrasonic to being uniformly dispersed with the 90g DMF after dry 2 hours; Be warming up to 90 ℃, drip the 6.4g γ-glycidyl ether oxygen propyl trimethoxy silicane by the hydrolysis of 20g toluene, time for adding 30 minutes continues to stir after 30 minutes, is warming up to 120 ℃ and refluxes 10 hours, and it is fully reacted; With product absolute ethanol washing 5 times and centrifugation, in 110 ℃ vacuum drying oven, get improved silica in dry 17 hours at last, place moisture eliminator for subsequent use.
2. the preparation of super-hydrophobic silica:
Get above-mentioned treated improved silica 0.2g ultra-sonic dispersion and in 10g toluene, be made into silicon dioxde solution; Subsequently with 0.3g stearylamide ultra-sonic dispersion in the mixed solvent of 8g DMF and 2g toluene, under magnetic stirring apparatus 90r/min rotating speed, dropwise add in the silicon dioxde solution and stir 30min, make the super-hydrophobic silica mixing solutions.With the super-hydrophobic silica mixing solutions drip be coated on the aluminium foil in 36 ℃ lower dry, must have the modified manometer silicon dioxide film of ultra-hydrophobicity, its surface water contact angle is 151 °, roll angle is 15 °.
3. the preparation of coating solution
The super-hydrophobic silica mixing solutions dropped in the polyurethane solution namely make the transparent hydrophobic surface coating agent in 90 ℃ of stirring and refluxing, wherein polyurethane solution is that 1.2g urethane magnetic agitation is dissolved in and joins in the 50g DMF.
4. prepare transparent hydrophobic coating at body material
Urethane/silica dioxide coating agent is dripped and is applied on the aluminium foil, leaves standstill oven dry and both got transparent hydrophobic coating in 45 ℃ of baking ovens.
The surface water contact angle of this coating reaches 152 °, 2 ° of roll angles, and coating has good visible light permeability simultaneously, and average visible light transmissivity reaches 62%.Accompanying drawing 4 is the stereoscan photograph of coatingsurface.
Embodiment 4
1. nano silicon pre-treatment
Take by weighing 3g fumed nano silicon-dioxide (median size 30nm, specific surface area 380m
2/ g), in 100 ℃ of baking ovens, place the there-necked flask of 250ml ultrasonic to being uniformly dispersed with the 90g DMF after dry 2 hours; Be warming up to 90 ℃, drip the 6.4g γ-glycidyl ether oxygen propyl trimethoxy silicane by the hydrolysis of 20g toluene, time for adding 30 minutes continues to stir after 30 minutes, is warming up to 120 ℃ and refluxes 10 hours, and it is fully reacted; With product absolute ethanol washing 4 times and centrifugation, in 110 ℃ vacuum drying oven, get improved silica in dry 17 hours at last, place moisture eliminator for subsequent use.
2. the preparation of super-hydrophobic silica:
Get above-mentioned treated improved silica 0.2g ultra-sonic dispersion and in 10g toluene, be made into silicon dioxde solution; Subsequently with the fluorine-containing lipid acid ultra-sonic dispersion of 0.15g C12 in 8g N, in the mixed solvent of dinethylformamide and 2g toluene, under magnetic stirring apparatus 80r/min rotating speed, slowly add in the silicon dioxde solution and stir 30min, make the super-hydrophobic silica mixing solutions.With the super-hydrophobic silica mixing solutions be sprayed on the aluminium foil in 36 ℃ lower dry, must have the modified manometer silicon dioxide film of ultra-hydrophobicity, its surface water contact angle is 153 °, roll angle is 15 °.
3. the preparation of coating solution
The super-hydrophobic silica mixing solutions dropped in the polyurethane solution namely make the transparent hydrophobic surface coating agent in 90 ℃ of stirring and refluxing, wherein polyurethane solution is that 1.8g urethane magnetic agitation is dissolved in and joins in the 50g DMF.
4. prepare transparent hydrophobic coating at body material
Urethane/silica dioxide coating agent is sprayed on the aluminium foil, leaves standstill oven dry and both got transparent hydrophobic coating in 45 ℃ of baking ovens.
The surface water contact angle of this coating reaches 155 °, 7 ° of roll angles, and coating has good visible light permeability simultaneously, and average visible light transmissivity reaches 65%.
Embodiment 5
1. nano-aluminium oxide pre-treatment
Take by weighing 3g nano-aluminium oxide (median size 50nm), in 100 ℃ of baking ovens, place the there-necked flask ultra-sonic dispersion of 250ml even with 30g toluene after dry 2 hours; Be warming up to 80 ℃, drip the 6.4g γ-aminopropyl triethoxysilane by the hydrolysis of 20g toluene, time for adding 30 minutes continues to stir after 30 minutes, is warming up to 110 ℃ and refluxes 10 hours, and it is fully reacted; With product absolute ethanol washing 4 times and centrifugation, in 110 ℃ vacuum drying oven, get the modification aluminium sesquioxide in dry 17 hours at last, place moisture eliminator for subsequent use.
2. the preparation of super-hydrophobic aluminium sesquioxide:
Get above-mentioned treated modification aluminium sesquioxide 1g ultra-sonic dispersion and in 100g toluene, be made into aluminium sesquioxide solution; Subsequently with 1.5g stearic acid ultra-sonic dispersion in the 100g DMF, under magnetic stirring apparatus 80r/min rotating speed, slowly add in the aluminium sesquioxide solution and stir 15min, make super-hydrophobic aluminium sesquioxide mixing solutions.Vacuumize to remove behind the unnecessary solvent super-hydrophobic aluminium sesquioxide mixing solutions dripped and be coated in that pottery is upper must to have the modified Nano aluminium sesquioxide film of ultra-hydrophobicity in 25 ℃ of lower seasoninies, its surface water contact angle is 150 °, and roll angle is 6 °.
3. the preparation of coating solution
Super-hydrophobic aluminium sesquioxide mixing solutions is added in the polyurethane solution, superpower numerical control ultrasonic cleaner KQ-200KDE namely made the transparent hydrophobic surface coating agent in ultrasonic 45 minutes under 100W power, wherein polyurethane solution is that 16g urethane magnetic agitation is dissolved in 70g N, join in the dinethylformamide, coating-forming agent vacuumizes to remove unnecessary solvent.
4. prepare transparent hydrophobic coating at body material
Urethane/aluminum oxide coating agent is dripped and is applied on the polyfluortetraethylene plate, leaves standstill oven dry and both got transparent hydrophobic coating in 50 ℃ of baking ovens.
Embodiment 6
1. nano titanium oxide pre-treatment
Take by weighing 3g nano titanium oxide (median size 50nm), in 100 ℃ of baking ovens, place the there-necked flask of 500ml ultrasonic to being uniformly dispersed with 150g toluene after dry 2 hours; Be warming up to 70 ℃, drip 15g (the 3-epoxypropyl propoxy-) Trimethoxy silane by the hydrolysis of 20g toluene, time for adding 30 minutes continues to stir after 30 minutes, is warming up to 110 ℃ and refluxes 5 hours, and it is fully reacted; With product absolute ethanol washing 4 times and centrifugation, in 110 ℃ vacuum drying oven, get modifying titanium dioxide in dry 17 hours at last, place moisture eliminator for subsequent use.
2. the preparation of super dewatering titanium oxide:
Get above-mentioned treated modifying titanium dioxide 0.2g ultra-sonic dispersion and in 8g toluene, be made into titania solution; Subsequently with the fluorine-containing lipid acid ultra-sonic dispersion of 0.2g C12 in the 8g DMF, under magnetic stirring apparatus 80r/min rotating speed, add in the titania solution and stir 30min, make the super dewatering titanium oxide mixing solutions.Super dewatering titanium oxide mixing solutions crystal pulling method to be coated on the polyfluortetraethylene plate in 20 ℃ of lower seasoninies, must be had the modified nano-titanium dioxide thin film of ultra-hydrophobicity, and its surface water contact angle is 151 °, and roll angle is 13 °.
3. the preparation of coating solution
The super dewatering titanium oxide mixing solutions is added in the polyurethane solution, superpower numerical control ultrasonic cleaner KQ-200KDE ultrasonic 50min under 100W power namely makes the transparent hydrophobic surface coating agent, wherein polyurethane solution is that 3g urethane magnetic agitation is dissolved in and joins in the 20g DMF.
4. prepare transparent hydrophobic coating at body material
Urethane/coating of titanium dioxide agent is dripped and is applied on the aluminium foil, has both got transparent hydrophobic coating at 32 ℃ of freeze-day with constant temperature.
The surface water contact angle of this coating reaches 150 °, 16 ° of roll angles, and coating has good visible light permeability simultaneously, and average visible light transmissivity reaches 60%.
Claims (8)
1. super-hydrophobic polyurethane/oxide nano particle hybrid coating material, the surface water contact angle that it is characterized in that described hybrid coating material is 140 °-168 °, roll angle is 1 °-20 °; Its feed composition is the super-hydrophobic oxide nano-particles solution of modification and polyurethane solution; Wherein the mass ratio of urethane and the super-hydrophobic oxide nano-particles of modification is 1-8:1; The quality solid content of described polyurethane solution is 1-15%; The super-hydrophobic oxide nano-particles solution of described modification is made by following steps:
A. oxide nano-particles pre-treatment: take by weighing oxide nano-particles dry rear and solvent in baking oven, ultra-sonic dispersion is the rear reactor that adds evenly, be warming up to 60-100 ℃, add subsequently silane coupling agent, stirring is warming up to 100-140 ℃ of back flow reaction 6-12 hour; At last with product through absolute ethanol washing and centrifugation, get the modified oxide nanoparticle through vacuum-drying, place moisture eliminator for subsequent use; Wherein said oxide nano-particles is nano silicon, nano-aluminium oxide, nano titanium oxide or nano zirconium dioxide; Particle diameter 1-1000 nm; Described solvent be toluene, dimethylbenzene,
N, NIn-dimethyl formamide, hexanaphthene, the methylene dichloride one or more; Solvent load is 10-50 times of oxide nano-particles weight; Described silane coupling agent is one or more in γ-glycidyl ether oxygen propyl trimethoxy silicane, methyltrimethoxy silane, trimethylethoxysilane, the polydimethylsiloxane, and the coupling agent consumption is 0.5-5 times of oxide nano-particles weight;
B. the preparation of super-hydrophobic oxide nano-particles solution: get above-mentioned modified oxide nanoparticle ultra-sonic dispersion and in solvent orange 2 A, be made into oxide nano-particles solution; To be dispersed among the solvent B for the 0.75-2 hydrophobic chain chemical substance that contains doubly of modified oxide nanoparticle weight subsequently, under magnetic agitation, add in the oxide nano-particles solution, make super-hydrophobic oxide nano-particles mixing solutions, the quality solid content of control mixing solutions is 1-5%; The described hydrophobic chain chemical substance that contains is C
8-C
22Acid amides, C
8-C
22Alkyl trichlorosilane, C
8-C
22Alkyltrialkoxysilaneand or C
6-C
12Fluorine-containing lipid acid in one or more.
2. coated material according to claim 1, it is characterized in that being made among the step B solvent orange 2 A in the oxide nano-particles solution and be toluene, dimethylbenzene,
N, NIn-dimethyl formamide, hexanaphthene, the methylene dichloride one or more; The solvent B that dissolving contains the hydrophobic chain chemical substance be tetrahydrofuran (THF),
N, N-dimethyl formamide, diethylformamide, trichloromethane, methylene dichloride, normal hexane, hexanaphthene, alkyl cyclohexane or tetracol phenixin.
3. coated material according to claim 1, it is characterized in that solvent in the described polyurethane solution be acetone, methylethylketone, pimelinketone, vinyl acetic monomer, methylene dichloride, tetrahydrofuran (THF),
N, NIn-dimethyl formamide, the dioxane one or more.
4. one kind prepares the as claimed in claim 1 method of super-hydrophobic polyurethane/oxide nano particle hybrid coating material, its concrete steps are as follows: (1) preparation polyurethane solution, super-hydrophobic oxide nano-particles mixing solutions and polyurethane solution with modification, be that the ratio of 1:1-8 is mixed in the super-hydrophobic oxide nano-particles of modification and urethane mass ratio, afterreaction stirs, to remove unnecessary solvent, namely make the transparent hydrophobic surface coating agent by concentrated;
(2) coating thermal treatment: the transparent hydrophobic surface coating agent is coated in substrate material surface, in 30-80 ℃, dries to solvent and volatilize fully, namely make the super-hydrophobic polyurethane/oxide nano particle hybrid coating material with transparent hydrophobic performance.
5. described method according to claim 4 is characterized in that described base material is inorganic or organic densification or porous material.
6. described method according to claim 4 is characterized in that described base material is for being aluminium foil, glass, pottery or macromolecular material.
7. method according to claim 4, its feature coating method are that spraying method, spin coating method, crystal pulling method or dropping liquid are annotated embrane method.
8. method according to claim 4 is characterized in that reaction conditions is ultrasonic or 60-120 ℃ of reflux; Concentrated mode is that underpressure distillation or heating vacuumize; The bake out temperature of coating is 40-65 ℃.
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