CN101838496A - 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 PDF

Info

Publication number
CN101838496A
CN101838496A CN 201010145642 CN201010145642A CN101838496A CN 101838496 A CN101838496 A CN 101838496A CN 201010145642 CN201010145642 CN 201010145642 CN 201010145642 A CN201010145642 A CN 201010145642A CN 101838496 A CN101838496 A CN 101838496A
Authority
CN
China
Prior art keywords
hydrophobic
super
oxide nano
particles
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 201010145642
Other languages
Chinese (zh)
Other versions
CN101838496B (en
Inventor
陈苏
王丽芳
杨胜洋
陈莉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JIANGSU FENGMANG COMPOSITE MATERIAL S&T GROUP CO Ltd
Original Assignee
Nanjing Tech University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Tech University filed Critical Nanjing Tech University
Priority to CN 201010145642 priority Critical patent/CN101838496B/en
Publication of CN101838496A publication Critical patent/CN101838496A/en
Application granted granted Critical
Publication of CN101838496B publication Critical patent/CN101838496B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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

A kind of super hydrophobic polyurethane/oxide nano-particles hybrid coating material and preparation method thereof
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 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 research of transparent hydrophobic coating at present 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 (ThinSolid Films.2005 such as H.M.Shang, (472): be raw material then 37-43) with TEOS, MPS, MTES, 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 Zui Da contact angle reaches nearly 165 °.
(Thin Solid Films.1997 such as plasma method such as Hozumi, 303:222~225) after employing chemical vapor deposition (CVD) method makes the surface of deposited film obtain certain roughness, as source of the gas, make transparent super-hydrophobicity film with the silane that contains perfluoroalkyl through Cement Composite Treated by Plasma.(Applied Surface Science.2008, (254): 5299-5303) then utilize magnetron sputtering technique that boron nitride pellicle is deposited to silicon substrate surface, pass through CF then 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 technology is loaded down with trivial details, and need modify raw material costliness and condition harshness with chemical deposition by the long-chain perfluor silane with low surface energy behind 400 ℃ of high temperature sinterings; And patent CN200810218808.1 with the silicon dioxide colloid electrophoretic deposition to conductive glass, transmittance height, but can not prepare on a large scale.
Above-mentioned coating process complicated process of preparation, the cost costliness, and need harsh electrochemical conditions and technology, and perhaps carrying out finishing with comparatively expensive silicon fluoride, 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 scale preparation and the method on the transparent hydrophobic surface of application.
Summary of the invention
Purpose of the present invention has proposed a kind of super hydrophobic polyurethane/oxide nano-particles 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-particles 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 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 back and solvent in baking oven, ultra-sonic dispersion evenly back adds reactor, heats up, and adds silane coupling agent subsequently, the temperature rising reflux that stirs reaction; At last with product through absolute ethanol washing and centrifugation, get the modified oxide nanoparticle through vacuum-drying, place moisture eliminator standby;
The preparation of B. 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 toluene, dimethylbenzene, N, one or more in dinethylformamide, hexanaphthene, the methylene dichloride; Solvent load is 10-50 a 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 a 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.
The solvent that is made among the preferred steps B in the super-hydrophobic oxide nano-particles solution is toluene, dimethylbenzene, N, one or more in dinethylformamide, hexanaphthene, the methylene dichloride; Contain 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 one or more; The solvent that dissolving contains the hydrophobic chain chemical substance is tetrahydrofuran (THF), N, dinethylformamide, 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), N, dinethylformamide, 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 acetone, methylethylketone, pimelinketone, vinyl acetic monomer, methylene dichloride, tetrahydrofuran (THF), N, in dinethylformamide, the dioxane one or more; Be preferably tetrahydrofuran (THF) or N, dinethylformamide.
The present invention also provides the method for above-mentioned super hydrophobic polyurethane/oxide nano-particles 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 and urethane mass ratio by modification are 1: the mixed of 1-8, afterreaction stirs, by concentrating, promptly make the transparent hydrophobic surface coating agent to remove unnecessary solvent;
(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, promptly make modified polyurethane/oxide nano-particles coating with transparent hydrophobic performance.
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 that as spraying method processing area is limited by processed geometrical shape greatly and not; Spin-coating and drip method are applicable to the plane that relative area is less; 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 for use 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, promptly make urethane/modified oxide nanoparticle coating with transparent hydrophobic performance, the bake out temperature of preferred coatings is 40-65 ℃, the water contact angle of gained material 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 bigger surface contact angle (greater than 150 °) and less roll angle, realizes self-cleaning function thereby the globule can freely roll and take away surface dirt in the above;
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 that possessing hydrophobic property, also have hardness height, wear-resisting, characteristics such as heat insulating ability good, specific inductivity is low, chemical stability is good, good development prospect is arranged in fields such as microelectronic device, the device of optical film, transmitters.
5. the transparent hydrophobic coating of the inventive method preparation; can be used for occasions such as windshield glass such as automobile, aircraft, spacecraft, building curtain wall; can be used as dustproof, the antifog supercoat of solid surface such as glass simultaneously, the waterproof insulating layer that also can be used as in microelectronic device, the transmitter etc. uses.
Description of drawings
Fig. 1 is the 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 a 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 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 (
Figure GSA00000083182300051
Germany) drop pattern analyser records.
Visible light transmissivity is recorded by Perkin Elmer Lambda20 type ultraviolet-visible instrument.
Provide specific embodiments of the invention below, but the present invention not merely is defined in these embodiment, these embodiment do not constitute 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 6.4g γ-glycidyl ether oxygen propyl trimethoxy silicane by the hydrolysis of 20g toluene, 30 minutes dropping time, continue to stir after 30 minutes, be warming up to 110 ℃ and refluxed 10 hours, 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 standby.
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 50g N, in the dinethylformamide, 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 following 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 supersonic cleanser KQ-200KDE under 100W power, promptly 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. on body material, prepare transparent hydrophobic coating
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 with 150g toluene after dry 2 hours to being uniformly dispersed; Be warming up to 70 ℃, drip 15g γ-glycidyl ether oxygen propyl trimethoxy silicane by the hydrolysis of 20g toluene, 30 minutes dropping time, continue to stir after 30 minutes, be warming up to 110 ℃ and refluxed 5 hours, 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 standby.
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 following 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 supersonic cleanser KQ-200KDE ultrasonic 50min under 100W power promptly to make the transparent hydrophobic surface coating agent, wherein polyurethane solution is that 1.6g urethane magnetic agitation is dissolved in 20g N, join in the dinethylformamide.
4. on body material, prepare transparent hydrophobic coating
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 after dry 2 hours with 90g N, dinethylformamide places the there-necked flask of 250ml ultrasonic to being uniformly dispersed; Be warming up to 90 ℃, drip 6.4g γ-glycidyl ether oxygen propyl trimethoxy silicane by the hydrolysis of 20g toluene, 30 minutes dropping time, continue to stir after 30 minutes, be warming up to 120 ℃ and refluxed 10 hours, 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 standby.
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 8g N, in the mixed solvent of dinethylformamide 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 ℃ dry down, 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 promptly 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 50g N, join in the dinethylformamide.
4. on body material, prepare transparent hydrophobic coating
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 after dry 2 hours with 90g N, dinethylformamide places the there-necked flask of 250ml ultrasonic to being uniformly dispersed; Be warming up to 90 ℃, drip 6.4g γ-glycidyl ether oxygen propyl trimethoxy silicane by the hydrolysis of 20g toluene, 30 minutes dropping time, continue to stir after 30 minutes, be warming up to 120 ℃ and refluxed 10 hours, 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 standby.
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 ℃ dry down, 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 promptly 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 50g N, join in the dinethylformamide.
4. on body material, prepare transparent hydrophobic coating
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 6.4g γ-An Bingjisanyiyangjiguiwan by the hydrolysis of 20g toluene, 30 minutes dropping time, continue to stir after 30 minutes, be warming up to 110 ℃ and refluxed 10 hours, 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 standby.
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 100g N, in the dinethylformamide, 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 pottery and go up in 25 ℃ of following seasoninies, must have the modified Nano aluminium sesquioxide film of ultra-hydrophobicity, 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 supersonic cleanser KQ-200KDE promptly 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. on body material, prepare transparent hydrophobic coating
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 with 150g toluene after dry 2 hours to being uniformly dispersed; Be warming up to 70 ℃, drip 15g (3-epoxypropyl propoxy-) Trimethoxy silane by the hydrolysis of 20g toluene, 30 minutes dropping time, continue to stir after 30 minutes, be warming up to 110 ℃ and refluxed 5 hours, 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 standby.
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 8g N, in the dinethylformamide, 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 following 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 supersonic cleanser KQ-200KDE ultrasonic 50min under 100W power promptly makes the transparent hydrophobic surface coating agent, wherein polyurethane solution is that 3g urethane magnetic agitation is dissolved in 20g N, join in the dinethylformamide.
4. on body material, prepare transparent hydrophobic coating
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 (10)

1. super hydrophobic polyurethane/oxide nano-particles hybrid coating material, the surface water contact angle that it is characterized in that the super hydrophobic surface hybrid material is 140 °-168 °, roll angle is 1-20 °; Its feed composition is 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 back and solvent in baking oven, ultra-sonic dispersion evenly back adds reactor, heats up, and adds silane coupling agent subsequently, the temperature rising reflux that stirs reaction; At last with product through absolute ethanol washing and centrifugation, get the modified oxide nanoparticle through vacuum-drying, place moisture eliminator standby;
The preparation of B. 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%.
2. coated material according to claim 1 is characterized in that 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; The described solvent of steps A is toluene, dimethylbenzene, N, one or more in dinethylformamide, hexanaphthene, the methylene dichloride; Solvent load is 10-50 a 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 a times of oxide nano-particles weight.
3. coated material according to claim 1 is characterized in that being warming up to 60-100 ℃ in the steps A behind the ultra-sonic dispersion; Add silane coupling agent, be warming up to 100-140 ℃ of back flow reaction 6-12 hour.
4. coated material according to claim 1, the solvent that it is characterized in that being made among the step B in the super-hydrophobic oxide nano-particles solution is toluene, dimethylbenzene, N, one or more in dinethylformamide, hexanaphthene, the methylene dichloride; Contain 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 one or more; The solvent that dissolving contains the hydrophobic chain chemical substance is tetrahydrofuran (THF), N, dinethylformamide, diethylformamide, trichloromethane, methylene dichloride, normal hexane, hexanaphthene, alkyl cyclohexane or tetracol phenixin.
5. coated material according to claim 1, the quality solid content that it is characterized in that described polyurethane solution is 1-15%; Solvent is acetone, methylethylketone, pimelinketone, vinyl acetic monomer, methylene dichloride, tetrahydrofuran (THF), N, one or more in dinethylformamide, the dioxane.
6. one kind prepares the method for super hydrophobic polyurethane/oxide nano-particles hybrid coating material according to claim 1, 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 and urethane mass ratio by modification are 1: the mixed of 1-8, afterreaction stirs, by concentrating, promptly make the transparent hydrophobic surface coating agent to remove unnecessary solvent;
(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, promptly make modified polyurethane/oxide nano-particles coating with transparent hydrophobic performance.
7. according to the described method of claim 6, it is characterized in that described base material is metal, inorganic or organic densification or porous material.
8. according to the described method of claim 7, it is characterized in that described base material is for being aluminium foil, glass, silicon, pottery, semi-conductor or macromolecular material.
9. method according to claim 6, its feature coating method are that spraying method, spin coating method, crystal pulling method or dropping liquid are annotated embrane method.
10. method according to claim 6 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 ℃.
CN 201010145642 2010-04-09 2010-04-09 Super-hydrophobic polyurethane/ oxide nano particle hybrid coating material and preparation method thereof Active CN101838496B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201010145642 CN101838496B (en) 2010-04-09 2010-04-09 Super-hydrophobic polyurethane/ oxide nano particle hybrid coating material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201010145642 CN101838496B (en) 2010-04-09 2010-04-09 Super-hydrophobic polyurethane/ oxide nano particle hybrid coating material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN101838496A true CN101838496A (en) 2010-09-22
CN101838496B CN101838496B (en) 2013-02-06

Family

ID=42742179

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201010145642 Active CN101838496B (en) 2010-04-09 2010-04-09 Super-hydrophobic polyurethane/ oxide nano particle hybrid coating material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN101838496B (en)

Cited By (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102358807A (en) * 2011-07-30 2012-02-22 吉林大学 Hydrophobic nano composite automobile finish and preparation method thereof
CN102653628A (en) * 2012-04-24 2012-09-05 东莞上海大学纳米技术研究院 Preparation method and application of nano sol modified waterborne polyurethane emulsion
CN103342953A (en) * 2013-06-19 2013-10-09 北京大学 Aircraft coating and preparation method thereof, and method for forming aircraft coating
CN103449736A (en) * 2012-05-28 2013-12-18 中国科学院兰州化学物理研究所 Preparation method of self-repair super-hydrophobic polyurethane coating
CN103555184A (en) * 2013-10-23 2014-02-05 三棵树涂料股份有限公司 Super-amphiphobic nano composite finish varnish, and preparation method thereof
CN103614063A (en) * 2013-12-02 2014-03-05 苏州市姑苏新型建材有限公司 Transparent waterborne waterproof coating for building and preparation method thereof
CN103642378A (en) * 2013-11-14 2014-03-19 重庆大学 Antiseptic super-hydrophobic paint for electric power system fittings and preparation method
CN104017489A (en) * 2014-05-29 2014-09-03 中国石油大学(华东) Nano-TiO2 modified acrylic polyurethane finish paint and preparation method thereof
CN104046217A (en) * 2013-03-12 2014-09-17 无锡市顺业科技有限公司 Preparation method of high strength superhydrophobic coating
CN104117396A (en) * 2013-04-26 2014-10-29 中国科学院化学研究所 Super-hydrophobic pipette gun head and preparation method thereof
CN104210197A (en) * 2014-09-25 2014-12-17 海安浩驰科技有限公司 Super-hydrophobic film and preparation method and application thereof
CN104387889A (en) * 2014-11-19 2015-03-04 广西大学 Preparation method of silicon-dioxide particle acrylonitrile silicone copolymerized resin coating
CN104449357A (en) * 2014-11-26 2015-03-25 浙江大学 Transparent super-hydrophobic coating material and method for preparing transparent super-hydrophobic coating by transparent super-hydrophobic coating material
CN104649711A (en) * 2013-11-18 2015-05-27 纳米及先进材料研发院有限公司 Hydrophobic coating composition and method of imparting hydrophobicity onto a surface
CN104822777A (en) * 2012-09-28 2015-08-05 Ut-巴特勒有限责任公司 Durable superhydrophobic coatings
CN104987520A (en) * 2015-07-09 2015-10-21 北京航空航天大学 Super-hydrophobic nanometer transparent coating and preparation method thereof
CN105102558A (en) * 2013-01-30 2015-11-25 伊利诺斯工具制品有限公司 Super hydrophobic coating
CN105399979A (en) * 2015-12-22 2016-03-16 上海仪耐新材料科技有限公司 Oleophylic hydrophobic cellulose sponge and preparation method thereof
CN105462453A (en) * 2015-12-02 2016-04-06 铜陵市肆得科技有限责任公司 Polyester fluorocarbon resin mixed powder coating added with white bamboo charcoal
CN106118422A (en) * 2016-07-28 2016-11-16 中国林业科学研究院林产化学工业研究所 Nano-meter SiO_22compound polysiloxane-modified aqueous terpenyl EP/PU super-hydrophobic automatic cleaning polymer and preparation method thereof
CN106189706A (en) * 2016-08-09 2016-12-07 河南大学 A kind of super-hydrophobic resin-coated preparation method
CN106433437A (en) * 2016-09-14 2017-02-22 陕西科技大学 Spray method for preparing super-hydrophobic and super-oleophilic copper net
WO2017092674A1 (en) * 2015-11-30 2017-06-08 Dazzeon Technology Co., Ltd. Electrical device capable of water-resisting, vapor resistant and electrically conducting in moisture-containing environment and method for making the same
CN107141992A (en) * 2017-05-23 2017-09-08 天津天盈新型建材有限公司 A kind of super-hydrophobic transparent coating liquid and preparation method thereof
CN107163808A (en) * 2017-05-11 2017-09-15 冯智勇 A kind of super-hydrophobic polyurethane protective paint coating
CN107227555A (en) * 2017-07-21 2017-10-03 江苏科来材料科技有限公司 A kind of nano modification melt-blown non-woven cloth material and its manufacture method
CN108047916A (en) * 2017-12-28 2018-05-18 浙江工业大学 A kind of aqueous polyurethane super hydrophobic coating and preparation method thereof
CN108373609A (en) * 2016-11-18 2018-08-07 北京易净星科技有限公司 It is used to prepare the coating and its preparation and application of transparent hydrophobic coating
CN108587396A (en) * 2018-04-27 2018-09-28 上海大学 A kind of nano paint and preparation method thereof and a kind of nano coating high-strength steel
CN108753132A (en) * 2018-04-28 2018-11-06 南京林业大学 A kind of preparation method of the super-hydrophobic suppression ice coating of Novel road
US10150875B2 (en) 2012-09-28 2018-12-11 Ut-Battelle, Llc Superhydrophobic powder coatings
CN109107619A (en) * 2017-06-23 2019-01-01 南京理工大学 Digital microcurrent-controlled chip of compound medium layer and preparation method thereof
CN109207042A (en) * 2018-08-27 2019-01-15 武汉理工大学 A kind of preparation method of the super-hydrophobic long-lived coating of the depollution of environment
CN109679428A (en) * 2018-12-27 2019-04-26 安徽伊法拉电力科技有限公司 A kind of preparation method of the self-cleaning hydrophobic coating of insulator anti-corrosion
CN109734325A (en) * 2019-02-20 2019-05-10 邹玉 A kind of preparation method of super-hydrophobic antifog glass
CN109957346A (en) * 2019-03-26 2019-07-02 东莞奥得时精密电子有限公司 Antifog laminating film and its material and technique
CN110615998A (en) * 2019-09-06 2019-12-27 上海大学 Wear-resistant super-hydrophobic coating composition
CN111154389A (en) * 2018-11-07 2020-05-15 现代自动车株式会社 Polyurethane-silicon dioxide composite material coating composition, polyurethane-silicon dioxide composite film and preparation method thereof
CN111304922A (en) * 2020-04-07 2020-06-19 浙江理工大学 Preparation method and product of super-hydrophobic polylactic acid non-woven material
CN111303743A (en) * 2020-03-05 2020-06-19 江苏理工学院 Waterproof and mildewproof circuit board and preparation method thereof
CN111842090A (en) * 2020-07-06 2020-10-30 南昌航空大学 Preparation method of polyurethane nano zinc oxide super-hydrophobic coating
CN112011199A (en) * 2020-09-01 2020-12-01 深圳市三曜科技有限公司 Special super-hydrophobic coating for air cooler and preparation method thereof
CN112424142A (en) * 2018-07-17 2021-02-26 赢创运营有限公司 Particulate mixed oxide material and thermal insulation composition based thereon
CN112778905A (en) * 2019-11-07 2021-05-11 香港城市大学深圳研究院 Self-repairing super-hydrophobic coating and preparation method thereof
CN113533139A (en) * 2021-06-28 2021-10-22 福建农林大学 Long-time stable polymer surface modification method
CN113933917A (en) * 2021-11-22 2022-01-14 广西五行材料科技有限公司 Nano material for dewatering and anti-fogging of glasses
CN114874407A (en) * 2022-05-31 2022-08-09 东北石油大学 Super-hydrophobic-super-oleophylic sponge and preparation method thereof
CN115445895A (en) * 2022-09-22 2022-12-09 上海大学 Super-hydrophobic material based on bionic micro-nano structure and preparation method and application thereof
CN115895322A (en) * 2022-09-21 2023-04-04 浙江悦茂科技发展有限公司 Anti-fouling coating and anti-fouling self-cleaning drainage pipeline system
CN116769396A (en) * 2023-05-10 2023-09-19 中国华能集团清洁能源技术研究院有限公司 Super-hydrophobic wind power blade surface protective coating and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101117713A (en) * 2007-07-30 2008-02-06 北京航空航天大学 Method for preparing super-hydrophobic modified SiO2-polyurethane composite coating by using immersion-self-assembly
CN101270260A (en) * 2008-01-28 2008-09-24 南京工业大学 Ultra-hydrophobic surface coating material and preparation method thereof
CN101575478A (en) * 2008-05-05 2009-11-11 中国科学院宁波材料技术与工程研究所 Method for preparing epoxy resin super-hydrophobic coat
US20100068457A1 (en) * 2007-04-13 2010-03-18 Anke Soellner Biocidal/hydrophobic inner coating of condenser pipes (of industrial turbines and subsidiary cooling cycles)

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100068457A1 (en) * 2007-04-13 2010-03-18 Anke Soellner Biocidal/hydrophobic inner coating of condenser pipes (of industrial turbines and subsidiary cooling cycles)
CN101117713A (en) * 2007-07-30 2008-02-06 北京航空航天大学 Method for preparing super-hydrophobic modified SiO2-polyurethane composite coating by using immersion-self-assembly
CN101270260A (en) * 2008-01-28 2008-09-24 南京工业大学 Ultra-hydrophobic surface coating material and preparation method thereof
CN101575478A (en) * 2008-05-05 2009-11-11 中国科学院宁波材料技术与工程研究所 Method for preparing epoxy resin super-hydrophobic coat

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《聚氨酯工业》 20080628 刘丹等 聚氨酯/二氧化硅复合材料研究进展 第5-9页 1-10 第23卷, 第3期 *

Cited By (71)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102358807A (en) * 2011-07-30 2012-02-22 吉林大学 Hydrophobic nano composite automobile finish and preparation method thereof
CN102653628A (en) * 2012-04-24 2012-09-05 东莞上海大学纳米技术研究院 Preparation method and application of nano sol modified waterborne polyurethane emulsion
CN102653628B (en) * 2012-04-24 2014-03-05 东莞上海大学纳米技术研究院 Preparation method and application of nano sol modified waterborne polyurethane emulsion
CN103449736A (en) * 2012-05-28 2013-12-18 中国科学院兰州化学物理研究所 Preparation method of self-repair super-hydrophobic polyurethane coating
CN103449736B (en) * 2012-05-28 2015-11-18 中国科学院兰州化学物理研究所 The preparation method of self-repairing super hydrophobic polyurethane coating
CN104822777A (en) * 2012-09-28 2015-08-05 Ut-巴特勒有限责任公司 Durable superhydrophobic coatings
US10150875B2 (en) 2012-09-28 2018-12-11 Ut-Battelle, Llc Superhydrophobic powder coatings
US9828521B2 (en) 2012-09-28 2017-11-28 Ut-Battelle, Llc Durable superhydrophobic coatings
CN105102558A (en) * 2013-01-30 2015-11-25 伊利诺斯工具制品有限公司 Super hydrophobic coating
CN104046217A (en) * 2013-03-12 2014-09-17 无锡市顺业科技有限公司 Preparation method of high strength superhydrophobic coating
CN104117396B (en) * 2013-04-26 2016-08-10 中国科学院化学研究所 Liquid-transfering gun rifle head with super-hydrophobicity and preparation method thereof
CN104117396A (en) * 2013-04-26 2014-10-29 中国科学院化学研究所 Super-hydrophobic pipette gun head and preparation method thereof
CN103342953A (en) * 2013-06-19 2013-10-09 北京大学 Aircraft coating and preparation method thereof, and method for forming aircraft coating
CN103342953B (en) * 2013-06-19 2016-05-04 北京大学 The method of coating for aircraft coating, its preparation method and formation aviation
CN103555184B (en) * 2013-10-23 2016-04-20 三棵树涂料股份有限公司 Super two thin nano combined finishing varnish and preparation method thereof
CN103555184A (en) * 2013-10-23 2014-02-05 三棵树涂料股份有限公司 Super-amphiphobic nano composite finish varnish, and preparation method thereof
CN103642378A (en) * 2013-11-14 2014-03-19 重庆大学 Antiseptic super-hydrophobic paint for electric power system fittings and preparation method
CN103642378B (en) * 2013-11-14 2016-03-30 重庆大学 Power system gold utensil rot-resistant super hydrophobic coating and preparation method thereof
CN104649711A (en) * 2013-11-18 2015-05-27 纳米及先进材料研发院有限公司 Hydrophobic coating composition and method of imparting hydrophobicity onto a surface
CN104649711B (en) * 2013-11-18 2016-08-17 纳米及先进材料研发院有限公司 Hydrophobic coating compositions and the method giving surface hydrophobic
CN103614063A (en) * 2013-12-02 2014-03-05 苏州市姑苏新型建材有限公司 Transparent waterborne waterproof coating for building and preparation method thereof
CN103614063B (en) * 2013-12-02 2016-01-20 苏州市姑苏新型建材有限公司 A kind of clear aqueous waterproof paint for building and preparation method thereof
CN104017489A (en) * 2014-05-29 2014-09-03 中国石油大学(华东) Nano-TiO2 modified acrylic polyurethane finish paint and preparation method thereof
CN104210197A (en) * 2014-09-25 2014-12-17 海安浩驰科技有限公司 Super-hydrophobic film and preparation method and application thereof
CN104387889A (en) * 2014-11-19 2015-03-04 广西大学 Preparation method of silicon-dioxide particle acrylonitrile silicone copolymerized resin coating
CN104449357B (en) * 2014-11-26 2017-01-04 浙江大学 A kind of transparent hydrophobic coating material and the method preparing transparent hydrophobic coating thereof
CN104449357A (en) * 2014-11-26 2015-03-25 浙江大学 Transparent super-hydrophobic coating material and method for preparing transparent super-hydrophobic coating by transparent super-hydrophobic coating material
CN104987520A (en) * 2015-07-09 2015-10-21 北京航空航天大学 Super-hydrophobic nanometer transparent coating and preparation method thereof
CN104987520B (en) * 2015-07-09 2018-04-17 北京航空航天大学 A kind of super-hydrophobic nano clear coat and preparation method thereof
WO2017092674A1 (en) * 2015-11-30 2017-06-08 Dazzeon Technology Co., Ltd. Electrical device capable of water-resisting, vapor resistant and electrically conducting in moisture-containing environment and method for making the same
US10717881B2 (en) 2015-11-30 2020-07-21 Dazzeon Technology Co., LTD Electrical device capable of water-resisting, vapor resistant and electrically conducting in moisture-containing environment and method for making the same
CN105462453A (en) * 2015-12-02 2016-04-06 铜陵市肆得科技有限责任公司 Polyester fluorocarbon resin mixed powder coating added with white bamboo charcoal
CN105399979A (en) * 2015-12-22 2016-03-16 上海仪耐新材料科技有限公司 Oleophylic hydrophobic cellulose sponge and preparation method thereof
CN106118422A (en) * 2016-07-28 2016-11-16 中国林业科学研究院林产化学工业研究所 Nano-meter SiO_22compound polysiloxane-modified aqueous terpenyl EP/PU super-hydrophobic automatic cleaning polymer and preparation method thereof
CN106118422B (en) * 2016-07-28 2018-07-06 中国林业科学研究院林产化学工业研究所 Nano-meter SiO_22Compound polysiloxane-modified aqueous terpenyl EP/PU super-hydrophobic automatic cleaning polymer and preparation method thereof
CN106189706A (en) * 2016-08-09 2016-12-07 河南大学 A kind of super-hydrophobic resin-coated preparation method
CN106433437A (en) * 2016-09-14 2017-02-22 陕西科技大学 Spray method for preparing super-hydrophobic and super-oleophilic copper net
CN108373609B (en) * 2016-11-18 2020-02-07 北京易净星科技有限公司 Coating for preparing transparent super-hydrophobic coating and preparation and use methods thereof
CN108373609A (en) * 2016-11-18 2018-08-07 北京易净星科技有限公司 It is used to prepare the coating and its preparation and application of transparent hydrophobic coating
CN107163808A (en) * 2017-05-11 2017-09-15 冯智勇 A kind of super-hydrophobic polyurethane protective paint coating
CN107141992B (en) * 2017-05-23 2019-07-02 天津天盈新型建材有限公司 A kind of super-hydrophobic transparent coating liquid and preparation method thereof
CN107141992A (en) * 2017-05-23 2017-09-08 天津天盈新型建材有限公司 A kind of super-hydrophobic transparent coating liquid and preparation method thereof
CN109107619A (en) * 2017-06-23 2019-01-01 南京理工大学 Digital microcurrent-controlled chip of compound medium layer and preparation method thereof
CN107227555A (en) * 2017-07-21 2017-10-03 江苏科来材料科技有限公司 A kind of nano modification melt-blown non-woven cloth material and its manufacture method
CN108047916A (en) * 2017-12-28 2018-05-18 浙江工业大学 A kind of aqueous polyurethane super hydrophobic coating and preparation method thereof
CN108587396A (en) * 2018-04-27 2018-09-28 上海大学 A kind of nano paint and preparation method thereof and a kind of nano coating high-strength steel
CN108753132A (en) * 2018-04-28 2018-11-06 南京林业大学 A kind of preparation method of the super-hydrophobic suppression ice coating of Novel road
CN112424142A (en) * 2018-07-17 2021-02-26 赢创运营有限公司 Particulate mixed oxide material and thermal insulation composition based thereon
CN109207042A (en) * 2018-08-27 2019-01-15 武汉理工大学 A kind of preparation method of the super-hydrophobic long-lived coating of the depollution of environment
CN109207042B (en) * 2018-08-27 2020-01-31 武汉理工大学 preparation method of environment-purifying super-hydrophobic durable coating
CN111154389A (en) * 2018-11-07 2020-05-15 现代自动车株式会社 Polyurethane-silicon dioxide composite material coating composition, polyurethane-silicon dioxide composite film and preparation method thereof
US11873419B2 (en) 2018-11-07 2024-01-16 Hyundai Motor Company Polyurethane-silica composite-based coating composition, polyurethane-silica composite film, and method of preparing the same
US11299640B2 (en) 2018-11-07 2022-04-12 Hyundai Motor Company Polyurethane-silica composite-based coating composition, polyurethane-silica composite film, and method of preparing the same
CN109679428A (en) * 2018-12-27 2019-04-26 安徽伊法拉电力科技有限公司 A kind of preparation method of the self-cleaning hydrophobic coating of insulator anti-corrosion
CN109734325A (en) * 2019-02-20 2019-05-10 邹玉 A kind of preparation method of super-hydrophobic antifog glass
CN109957346A (en) * 2019-03-26 2019-07-02 东莞奥得时精密电子有限公司 Antifog laminating film and its material and technique
CN109957346B (en) * 2019-03-26 2021-06-18 东莞奥得时精密电子有限公司 Antifogging adhesive film and its material and technology
CN110615998A (en) * 2019-09-06 2019-12-27 上海大学 Wear-resistant super-hydrophobic coating composition
CN112778905A (en) * 2019-11-07 2021-05-11 香港城市大学深圳研究院 Self-repairing super-hydrophobic coating and preparation method thereof
CN111303743A (en) * 2020-03-05 2020-06-19 江苏理工学院 Waterproof and mildewproof circuit board and preparation method thereof
CN111304922B (en) * 2020-04-07 2022-10-04 浙江理工大学 Preparation method and product of super-hydrophobic polylactic acid non-woven material
CN111304922A (en) * 2020-04-07 2020-06-19 浙江理工大学 Preparation method and product of super-hydrophobic polylactic acid non-woven material
CN111842090A (en) * 2020-07-06 2020-10-30 南昌航空大学 Preparation method of polyurethane nano zinc oxide super-hydrophobic coating
CN112011199A (en) * 2020-09-01 2020-12-01 深圳市三曜科技有限公司 Special super-hydrophobic coating for air cooler and preparation method thereof
CN112011199B (en) * 2020-09-01 2022-02-22 深圳市三曜科技有限公司 Special super-hydrophobic coating for air cooler and preparation method thereof
CN113533139A (en) * 2021-06-28 2021-10-22 福建农林大学 Long-time stable polymer surface modification method
CN113933917A (en) * 2021-11-22 2022-01-14 广西五行材料科技有限公司 Nano material for dewatering and anti-fogging of glasses
CN114874407A (en) * 2022-05-31 2022-08-09 东北石油大学 Super-hydrophobic-super-oleophylic sponge and preparation method thereof
CN115895322A (en) * 2022-09-21 2023-04-04 浙江悦茂科技发展有限公司 Anti-fouling coating and anti-fouling self-cleaning drainage pipeline system
CN115445895A (en) * 2022-09-22 2022-12-09 上海大学 Super-hydrophobic material based on bionic micro-nano structure and preparation method and application thereof
CN116769396A (en) * 2023-05-10 2023-09-19 中国华能集团清洁能源技术研究院有限公司 Super-hydrophobic wind power blade surface protective coating and preparation method thereof

Also Published As

Publication number Publication date
CN101838496B (en) 2013-02-06

Similar Documents

Publication Publication Date Title
CN101838496B (en) Super-hydrophobic polyurethane/ oxide nano particle hybrid coating material and preparation method thereof
Ramezani et al. Preparation of silane-functionalized silica films via two-step dip coating sol–gel and evaluation of their superhydrophobic properties
Purcar et al. Antireflective coating based on TiO2 nanoparticles modified with coupling agents via acid-catalyzed sol-gel method
Mahadik et al. Thermally stable and transparent superhydrophobic sol–gel coatings by spray method
Purcar et al. Fabrication of hydrophobic and antireflective coatings based on hybrid silica films by sol–gel process
Lin et al. Highly transparent superhydrophobic organic–inorganic nanocoating from the aggregation of silica nanoparticles
Liu et al. One-step hydrothermal creation of hierarchical microstructures toward superhydrophilic and superhydrophobic surfaces
Liu et al. Fabrication of superhydrophobic wood surfaces via a solution-immersion process
Xu et al. Fabrication of highly transparent superhydrophobic coatings from hollow silica nanoparticles
Ke et al. Fabrication of mechanically robust superhydrophobic surfaces based on silica micro-nanoparticles and polydimethylsiloxane
Tao et al. Sol-gel based antireflective coatings with superhydrophobicity and exceptionally low refractive indices built from trimethylsilanized hollow silica nanoparticles
Bu et al. Fabrication of TiO2 porous thin films using peg templates and chemistry of the process
Wang et al. Fabrication of transparent superhydrophobic silica-based film on a glass substrate
CN106800885A (en) A kind of large-scale preparation method of transparent hydrophobic/super-amphiphobic coating
CN104910656B (en) A kind of method that super-hydrophobic silica powder and super-hydrophobic coat are prepared with compound silicon source
CN107629492B (en) The preparation method and its gained coating of a kind of super hydrophobic coating and the application for preparing high transparency super-hydrophobic coat
Moriguchi et al. Preparation of TiO2 ultrathin film by newly developed two-dimensional sol-gel process
Hu et al. Constructing non-fluorinated porous superhydrophobic SiO2-based films with robust mechanical properties
CN106752255A (en) A kind of material surface protection super-hydrophobic coat spray and its preparation and application
CN103408762A (en) Crosslinkable fluorosilicone resin, painting and super-amphiphobic coating prepared by same
Janowicz et al. Fluorine-free transparent superhydrophobic nanocomposite coatings from mesoporous silica
Wang et al. Influences of VTMS/SiO2 ratios on the contact angle and morphology of modified super-hydrophobic silicon dioxide material by vinyl trimethoxy silane
CN104789124A (en) A preparing method of a stable superamphiphobic surface
CN102849962A (en) Preparation method of SiO2 super-hydrophobic film and super-hydrophobic material
CN101805434A (en) Super hydrophobic silicon-fluorine polymer/nanometer silica hybridization nanometer material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20190314

Address after: 212200 Huangshantao Farm, Yangzhong City, Zhenjiang City, Jiangsu Province

Patentee after: Jiangsu Fengmang Composite Material S&T Group Co., Ltd.

Address before: 210009 No. 200, Zhongshan North Road, Jiangsu, Nanjing

Patentee before: Nanjing University of Technology

TR01 Transfer of patent right