CN101456016A - Preparation method of polymer hydrophobic surface - Google Patents
Preparation method of polymer hydrophobic surface Download PDFInfo
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- CN101456016A CN101456016A CN 200810205055 CN200810205055A CN101456016A CN 101456016 A CN101456016 A CN 101456016A CN 200810205055 CN200810205055 CN 200810205055 CN 200810205055 A CN200810205055 A CN 200810205055A CN 101456016 A CN101456016 A CN 101456016A
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Abstract
The invention provides a method for preparing a polymer hydrophobic surface and belongs to the technical field of polymer chemical material. The method comprises: preparing a polymer desperation and hydrophobic silica desperation; uniformly mixing the polymer desperation and the hydrophobic silica desperation for preparing a hydrophobic coating; spraying the hydrophobic coating onto a completely cleaned base surface uniformly with a spray gun; and finally, subjecting the sprayed base surface to heat treatment and cooling the base surface to obtain the polymer hydrophobic surface. The surface of a coating processed by the method is obvious in super-hydrophobic performance, uniform in luster and stable in performance, free from damage caused by scrubbing to the super-hydrophobic performance, simple in preparation process, low in preparation process implementation cost and applicable surfaces made from various materials without damaging the original materials by corrosive materials.
Description
Technical field
That the present invention relates to is the preparation method of technical field of polymer in a kind of chemical materials, specifically is a kind of preparation method of polymer hydrophobic surface.
Background technology
Wetability is one of critical nature of the surface of solids, weighs at the contact angle of the surface of solids with liquid usually.Generally the contact angle of water is called super hydrophobic surface greater than the surface of solids that 150 ° and water droplet are easy to tumble, have wide practical use in a lot of fields such as automatically cleaning material, microfluid and harmless liquid transmission.People have had been found that the representative instance of super-hydrophobic lotus leaf surface at occurring in nature, and recognize that the size of its contact angle depends primarily on surface free energy and two factors of micro-geometry.Therefore two class methods of preparation super hydrophobic surface have been developed, i.e. the special surface texture of preparation on low-energy surface; Perhaps has the material of modifying low-surface-energy on the surface of micron and nanometer composite structure.
Find through literature search prior art, the article " Prepared by Sol Gel Method biomimetic super hydrophobic film " that Feng Zhou etc. delivered on " chemical journal " (2006 64 8 phases of volume), this article has prepared the film with super-hydrophobicity by sol-gel process and self assembly, the balance static contact angle of water droplet on this film is 155 °, and tumbling the angle is 5 ° (water droplets of 3 μ L).Its weak point is a complex steps, needs repeatedly assembling, simultaneously assembling material and substrate is had the coupling requirement.
Also find in the retrieval, Zhigang Guo etc. are at " J.Am.Chem.Soc. " (" JACS ") (2005,127,15670) article of delivering on " Stable Biomimetic Super-HydrophobicEngineering Materials ", the preparation method of super-hydrophobic aluminium and aluminium alloy is proposed in this article, concrete grammar is to adopt sodium hydroxide solution etching aluminium and aluminium alloy earlier, after modifying through the dimethyl silicone polymer of Perfluorononane and ethenyl blocking respectively, obtain super-hydrophobicity, method is simple for this, its weak point is to need just can carry out hydrophobic treatment behind the pending surface of first etching, and this technology is undeclared how at glass simultaneously, prepare hydrophobic surface on the materials such as silicon.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of preparation method of polymer hydrophobic surface is provided, the present invention has caking property for pottery, glass, metal, plastics, needn't use corrosive substance to destroy original basal plane and can prepare surface with hydrophobic property, method step of the present invention is simple, is easy to popularize.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
1. prepared polymer dispersion liquid and hydrophobic silica dispersion liquid;
Described polymer dispersion liquid is to be that the mode of concentration by ultrasonic dispersion of 20g/L～100g/L is dispersed or dissolved in the organic solvent with the mass percent with polyphenylene sulfide micro mist, polystyrene, polymethyl methacrylate or PETG;
Described hydrophobic silica dispersion liquid is to be that the mode of concentration by ultrasonic dispersion of 67g/L～100g/L is scattered in the organic solvent with the mass percent with the silicon dioxide drainage micro mist of dimethyl silicone polymer modified and surfactant;
Described organic solvent is meant absolute ethyl alcohol, isobutanol, toluene, chloroform, N, dinethylformamide, N, a kind of in N-dimethylacetylamide, the oxolane or the anhydrous or moisture mixed solvent that it combines.
Described surfactant is polyoxyethylene groups ether, PVP, neopelex, odium stearate, alkyl trimethyl ammonium bromide.
2. be after the ratio of 1:2～1:1 mixes, to make hydrophobic coating with polymer dispersion liquid and hydrophobic silica dispersion liquid with the volume ratio;
3. adopt spray gun hydrophobic coating evenly to be sprayed on the basal plane that cleans up;
Described basal plane is meant the surface of pottery, glass, metal or plastic sheet.
Described even spraying is meant that through the hydrophobic coating thickness on the basal plane after the spraying be 3.2 μ m～4.2 μ m.
4. will heat-treat through the basal plane of spraying at last, the hydrophobic surface contact angle that obtains after cooling is greater than 150 °, and roll angle is less than 10 °.
Described heat treatment is meant in oven dry under 60 ℃～80 ℃ the environment and is incubated 1.5 hours again under 160 ℃～300 ℃ environment after 0.5 hour; Perhaps directly under 60 ℃～80 ℃ environment, dried 6～8 hours.
The coating surface of gained has significant ultra-hydrophobicity after the present invention handles, and the surface color homogeneous that obtains, stable performance, do not have destroyed through cleaning ultra-hydrophobicity, preparation technology is simple and implementation cost is lower, can be applicable to the surface of various materials, and needn't use corrosive substance to destroy original material.
Description of drawings
Fig. 1 is a water droplet contact angle photo among the embodiment 1;
Fig. 2 tumbles the angle photo for water droplet among the embodiment 1;
Fig. 3 is the electron scanning micrograph of the hydrophobic surface among the embodiment 1.
The specific embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is that prerequisite is implemented with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
(1) take by weighing 6g polyphenylene sulfide micro mist, the ultrasonic volume ratio that is scattered in is a water: among the mixed solvent 80mL of absolute ethyl alcohol: isobutanol=2:5:1, make polymer dispersion liquid;
(2) take by weighing the silicon dioxide drainage micro mist of 8g dimethyl silicone polymer modified, the ultrasonic volume ratio that is scattered in is a water: among the mixed solvent 120mL of absolute ethyl alcohol: isobutanol=2:5:1, add 0.5g surfactant Nonyl pheno base ether again, ultrasonic processing made it to be uniformly dispersed in 5 minutes, made the hydrophobic silica dispersion liquid;
(3) polymer dispersion liquid 80mL and hydrophobic silica dispersion liquid 120mL are mixed, ultrasonic again processing made it to be uniformly dispersed in 5 minutes, made hydrophobic coating;
(4) adopt spray gun that the pressure of hydrophobic coating with 0.2MPa is sprayed onto on the ceramic tile of cleaning in advance and drying, then ceramic tile is incubated 1.5 hours at 300 ℃ 80 ℃ of oven dry half an hour again, promptly obtain having the ceramic tile of super-hydrophobic coat after the cooling, the hydrophobic coating thickness on the ceramic tile is 3.2 μ m.
As shown in Figure 1, be the water droplet enlarged photograph on the hydrophobic surface that obtains among the embodiment 1, this water droplet is 166 ° at the contact angle of ceramic tile surface as seen from the figure.
As shown in Figure 2, be the water droplet enlarged photograph on the hydrophobic surface that obtains among the embodiment 1, as seen from the figure, the tumble angle of this water droplet on hydrophobic surface is 5 °.
As shown in Figure 3, electron scanning micrograph for the hydrophobic surface that obtains among the embodiment 1, as can be seen from the figure, form coarse surface by the fine silica powder particle agglomeration, particle grain size is not of uniform size, Nano grade particle and micron level particle exist simultaneously, and are woven into a mesh structure.
Embodiment 2
(1) take by weighing 6g polyphenylene sulfide micro mist, ultrasonic being scattered among the mixed solvent 60mL that volume ratio is absolute ethyl alcohol: isobutanol=1:1 made polymer dispersion liquid;
(2) take by weighing the silicon dioxide drainage micro mist of 6g dimethyl silicone polymer modified, ultrasonic being scattered among the mixed solvent 60mL that volume ratio is absolute ethyl alcohol: isobutanol=1:1, add 0.5g surfactant odium stearate again, ultrasonic processing made it to be uniformly dispersed in 5 minutes, made the hydrophobic silica dispersion liquid;
(3) polymer dispersion liquid 60mL and hydrophobic silica dispersion liquid 60mL are mixed, ultrasonic again processing made it to be uniformly dispersed in 5 minutes, made hydrophobic coating;
(4) with spray gun the pressure of hydrophobic coating with 0.2MPa is sprayed onto on the steel disc of cleaning in advance and drying, then steel disc is incubated 1.5 hours at 200 ℃ 60 ℃ of oven dry half an hour again, promptly obtain having the steel disc of super-hydrophobic coat after the cooling, the hydrophobic coating thickness on the steel disc is 4.0 μ m.The contact angle that present embodiment prepares the hydrophobic surface of gained is 160 °, and tumbling the angle is 5 °.
Embodiment 3
(1) take by weighing 6g polyphenylene sulfide micro mist, ultrasonic being scattered in the 60mL absolute ethyl alcohol made polymer dispersion liquid;
(2) take by weighing the silicon dioxide drainage micro mist of 8g dimethyl silicone polymer modified, ultrasonic being scattered in the 120mL absolute ethyl alcohol, add 0.5g surfactant softex kw again, ultrasonic processing made it to be uniformly dispersed in 5 minutes, made the hydrophobic silica dispersion liquid;
(3) polymer dispersion liquid 60mL and hydrophobic silica dispersion liquid 120mL are mixed, ultrasonic again processing made it to be uniformly dispersed in 5 minutes, made hydrophobic coating;
(4) with spray gun the pressure of hydrophobic coating with 0.2MPa is sprayed onto on the plastic plate of cleaning in advance and drying, then plastic plate is incubated 1.5 hours at 160 ℃ 80 ℃ of oven dry half an hour again, promptly obtain having the plastic plate of super-hydrophobic coat after the cooling, the hydrophobic coating thickness on the plastic plate is 3.8 μ m.The contact angle that present embodiment prepares the hydrophobic surface of gained is 155 °, and tumbling the angle is 5 °.
Embodiment 4
(1) take by weighing the 0.6g granules of polystyrene, ultrasonic dissolution is made polymer dispersion liquid in 30mL toluene.
(2) take by weighing the silicon dioxide drainage micro mist of 3g dimethyl silicone polymer modified, ultrasonic being scattered in the 30mL toluene, add 0.5g surfactant PVP again, ultrasonic processing made it to be uniformly dispersed in 5 minutes, made the hydrophobic silica dispersion liquid;
(3) polymer dispersion liquid 30mL and hydrophobic silica dispersion liquid 30mL are mixed, ultrasonic again processing made it to be uniformly dispersed in 5 minutes, made hydrophobic coating;
(4) with spray gun the pressure of hydrophobic coating with 0.2MPa is sprayed onto on the sheet glass of cleaning in advance and drying, then sheet glass was dried 8 hours at 60 ℃, promptly obtain having the sheet glass of super-hydrophobic coat after the cooling, the hydrophobic coating thickness on the sheet glass is 3.5 μ m.The contact angle that present embodiment prepares the hydrophobic surface of gained is 152 °, and roll angle is 6 °.
Embodiment 5
(1) take by weighing the 0.4g poly methyl methacrylate particle, ultrasonic dissolution is made polymer dispersion liquid in the 20mL chloroform;
(2) take by weighing the silicon dioxide drainage micro mist of 4g dimethyl silicone polymer modified, ultrasonic being scattered in the 40mL chloroform, add 0.5g surfactant Nonyl pheno base ether again, ultrasonic processing made it to be uniformly dispersed in 5 minutes, made the hydrophobic silica dispersion liquid;
(3) polymer dispersion liquid 20mL and hydrophobic silica dispersion liquid 40mL are mixed, ultrasonic again processing made it to be uniformly dispersed in 5 minutes, made hydrophobic coating;
(4) with spray gun the pressure of hydrophobic coating with 0.2MPa is sprayed onto on the sheet glass of cleaning in advance and drying, then sheet glass was dried 6 hours at 60 ℃, promptly obtain having the sheet glass of super-hydrophobic coat after the cooling, the hydrophobic coating thickness on the sheet glass is 4.2 μ m.The contact angle that present embodiment prepares the hydrophobic surface of gained is 158 °, and roll angle is 5 °.
Embodiment 6
(1) take by weighing 0.5g PETG particle, ultrasonic dissolution is made polymer dispersion liquid in the 30mL chloroform;
(2) take by weighing the silicon dioxide drainage micro mist of 4g dimethyl silicone polymer modified, ultrasonic being scattered in the 30mL chloroform, add 0.5g surfactant Nonyl pheno base ether again, ultrasonic processing made it to be uniformly dispersed in 5 minutes, made the hydrophobic silica dispersion liquid;
(3) polymer dispersion liquid 30mL and hydrophobic silica dispersion liquid 30mL are mixed, ultrasonic again processing made it to be uniformly dispersed in 5 minutes, made hydrophobic coating;
(4) with spray gun the pressure of hydrophobic coating with 0.2MPa is sprayed onto on the ceramic tile of cleaning in advance and drying, then ceramic tile was dried 8 hours at 60 ℃, promptly obtain having the ceramic tile of super-hydrophobic coat after the cooling, the hydrophobic coating thickness on the ceramic tile is 4.0 μ m.The contact angle that present embodiment prepares the hydrophobic surface of gained is 157 °, and roll angle is 5 °.
Claims (8)
1, a kind of preparation method of polymer hydrophobic surface is characterized in that may further comprise the steps:
1. prepared polymer dispersion liquid and hydrophobic silica dispersion liquid: polyphenylene sulfide micro mist, polystyrene, polymethyl methacrylate or the PETG mode by ultrasonic dispersion is dispersed or dissolved in the organic solvent; To be scattered in the organic solvent through the silicon dioxide drainage micro mist of dimethyl silicone polymer modified and surfactant mode simultaneously by ultrasonic dispersion;
2. the ratio that with polymer dispersion liquid and hydrophobic silica dispersion liquid with the volume ratio is 1:2～1:1 mixes, and makes hydrophobic coating;
3. adopt spray gun evenly to be sprayed into hydrophobic coating on the basal plane;
4. at last basal plane is heat-treated, obtain hydrophobic surface after cooling.
2, the preparation method of polymer hydrophobic surface according to claim 1, it is characterized in that the mass percent concentration of described polyphenylene sulfide micro mist, polystyrene, polymethyl methacrylate or PETG dispersion liquid is 20g/L～100g/L.
3, the preparation method of polymer hydrophobic surface according to claim 1 is characterized in that, the mass percent concentration of described hydrophobic silica dispersion liquid is 67g/L～100g/L.
4, the preparation method of polymer hydrophobic surface according to claim 1, it is characterized in that, described organic solvent is meant absolute ethyl alcohol, isobutanol, toluene, chloroform, N, dinethylformamide, N, a kind of in N-dimethylacetylamide, the oxolane or the anhydrous or moisture mixed solvent that it combines.
5, the preparation method of polymer hydrophobic surface according to claim 1 is characterized in that, described surfactant is polyoxyethylene groups ether, PVP, neopelex, odium stearate or alkyl trimethyl ammonium bromide.
6, the preparation method of polymer hydrophobic surface according to claim 1 is characterized in that, described basal plane is meant the surface of pottery, glass, metal or plastic sheet.
7, the preparation method of polymer hydrophobic surface according to claim 1 is characterized in that, described even spraying is meant that through the hydrophobic coating thickness on the basal plane after the spraying be 3.2～4.2 μ m.
8, the preparation method of polymer hydrophobic surface according to claim 1 is characterized in that, described heat treatment is meant in oven dry under 60 ℃～80 ℃ the environment and is incubated 1.5 hours again under 160 ℃～300 ℃ environment after 0.5 hour; Perhaps directly under 60 ℃～80 ℃ environment, dried 6～8 hours.
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