CN101792553B - Preparation method of porous super hydrophobic polypropylene film - Google Patents
Preparation method of porous super hydrophobic polypropylene film Download PDFInfo
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- CN101792553B CN101792553B CN2010101202801A CN201010120280A CN101792553B CN 101792553 B CN101792553 B CN 101792553B CN 2010101202801 A CN2010101202801 A CN 2010101202801A CN 201010120280 A CN201010120280 A CN 201010120280A CN 101792553 B CN101792553 B CN 101792553B
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Abstract
The invention discloses a porous super hydrophobic polypropylene film and a preparation method thereof. The aperture distribution range on the surface of the porous super hydrophobic polypropylene film is 100 nanometers to 10 micrometers, the average aperture is 650 nanometers to 1 micrometer, a contact angle of the surface of the film with water is 150-165 degrees, and roll angles of water dropson the surface of the film are below 5 degrees. The preparation method comprises the following steps of: uniformly mixing polypropylene granules and polystyrene granules in a mixer according to a mass ratio of (1-10):1; preparing the mixed materials into a film semi-finished product consisting of polypropylene and polystyrene by adopting a tape casting method, an extruding method or a calenderingmethod; putting the film semi-finished product in chloroform or tetrahydrofuran for soaking so as to ensure that the polystyrene contained in the film semi-finished product is sufficiently dissolved;and then taking out and drying to obtain the porous super hydrophobic polypropylene film. The porous super hydrophobic polypropylene film has stable super hydrophobic property, good super hydrophobiceffect, simple preparation process, good controllability, low production cost and environmental protection.
Description
Technical field
The present invention relates to a kind of organic polymer macromolecular material and preparation method thereof, relate in particular to a kind of high molecular film material and preparation method thereof with superhydrophobic characteristic.
Background technology
As everyone knows, the wettability of solid surface is by the chemical constitution and the surfaceness decision on surface.Contact angle at the minimum surface of smooth solid of surface energy can only be brought up to 120 ° at most, (contact angle of material surface and water is greater than 150 ° and there are a large amount of super-hydrophobic surfaces in physical environment, and water droplet has less roll angle from the teeth outwards), most typical is exactly lotus leaf surface, water droplet forms the glistening spherical globule usually at lotus leaf surface, these globules can not stably rest on lotus leaf surface, under the reactive force in the gentle breeze or the external world, as long as shake lotus leaf a little, its surperficial globule just can tumble and take away the dust of lotus leaf surface, plays self-cleaning effect.Except lotus leaf, also there is a large amount of super hydrophobic surfaces in occurring in nature, as the feather of taro leaves, bird, the wing of butterfly, the leg of water skipper etc.
Because the contact area of water droplet on super hydrophobic surface be very little, and water droplet can not stably stop at super hydrophobic surface, thereby the oxidation on the super hydrophobic surface, burn into conduction of current, frost etc. can effectively be suppressed.Therefore, superhydrophobic surface material is with a wide range of applications in industrial and agricultural production and daily life, has caused extensive studies interest.In recent years, there are a lot of methods to be used to make up super hydrophobic surface, as Xu Jian etc. at " Macromolecular Rapid Communications " 2005,26, reported on the 1075-108 and utilized wet air to pour into a mould the super-hydrophobic polycarbonate surface that film forming method prepares the class patellate, its contact angle is 161.8 ± 2.2 °; Jin Meihua etc. have reported on the 1977-1981 and have utilized aluminum oxide to prepare super-hydrophobic polystyrene film for template at " Advanced Materials " 2005,17; Erbil etc. have reported on " Science " 2003,299,1377 and have utilized the method that is separated to prepare gelatinous super-hydrophobic polypropylene surface that its contact angle reaches 160 °; Except above method, also have sol-gel method, fluorinated coating method, chemical Vapor deposition process, electrochemical deposition method, polyelectrolyte alternating deposit method, anonizing, mechanical stretching method etc.Yet, existing these methods or the expensive material of use, or need special processing units or complicated technological process, be difficult to industrialization.Therefore inventing a kind of technology simple and that be easy to industrialization prepares super hydrophobic surface and is necessary.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provide a kind of superhydrophobic property stable, super-hydrophobic effective porous super hydrophobic polypropylene film, provide also that a kind of operating procedure is simple, controllability good, production cost is little and the preparation method of the porous super hydrophobic polypropylene film of environmental protection.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of porous super hydrophobic polypropylene film, it is characterized in that: the pore size distribution range on described super-hydrophobic polypropylene film surface is 100nm～10 μ m, mean pore size is 650nm～1 μ m, described super-hydrophobic polypropylene film surface is 150 °～165 ° with the contact angle of water, and the roll angle of water droplet on described super-hydrophobic polypropylene film surface is (general in 3 °～5 ° scope) below 5 °.
In the technique scheme, the pore size distribution range on described super-hydrophobic polypropylene film surface is preferably 500nm～5 μ m, and mean pore size is preferably at 700nm～800nm.
In the technique scheme, the thickness of described super-hydrophobic polypropylene film is preferably below the 1mm in known scope, but 3mm can both realize with interior thickness.
The white porous surface that the super-hydrophobic polypropylene film surface of the invention described above is made up of a large amount of micron orders, nano grade pore, the superhydrophobic property on this porous super hydrophobic polypropylene film surface is stable, in temperature range is that 0 ℃～40 ℃, relative humidity are to place 1 year in 30%～90% the environment, and superhydrophobic property does not change.
As a total technical conceive, the present invention also provides a kind of preparation method of porous super hydrophobic polypropylene film, may further comprise the steps:
(1) by (1～10): 1 mass ratio is uniform mixing in mixer with polypropylene GRANULES and granules of polystyrene;
(2) batch mixing after adopting casting method, extrusion molding or rolling process with above-mentioned uniform mixing is prepared into the film work in-process of being made up of described polypropylene and polystyrene;
(3) place trichloromethane or tetrahydrofuran (THF) to soak described film work in-process, the polystyrene that contains in these film work in-process is fully dissolved, take out oven dry then, obtain porous super hydrophobic polypropylene film.
Among the preparation method of above-mentioned porous super hydrophobic polypropylene film, the time of described immersion is preferably 1h～10h, and the temperature during immersion is controlled at 20 ℃～60 ℃.By preferred soak time and the soaking temperature polystyrene component in the dissolving films work in-process better.
Compared with prior art, the invention has the advantages that: the invention provides stable, the super-hydrophobic effective porous super hydrophobic polypropylene film of a kind of superhydrophobic property, the more important thing is, the present invention provides also that a kind of operating procedure is simple, favorable reproducibility, need not any expensive device input, also need not to carry out the preparation method of the porous super hydrophobic polypropylene film that complicated chemical handles, this method is not only simple, be easy to industrialization, and environmental protection, have broad application prospects.
Description of drawings
Fig. 1 is the porous super hydrophobic polypropylene film surface that makes in the embodiment of the invention 1 contact angle test pattern with water.
Fig. 2 is the sem photograph on the porous super hydrophobic polypropylene film surface that makes in the embodiment of the invention 1.
Fig. 3 is the porous super hydrophobic polypropylene film surface that makes in the embodiment of the invention 2 contact angle test pattern with water.
Fig. 4 is the porous super hydrophobic polypropylene film surface that makes in the embodiment of the invention 3 contact angle test pattern with water.
Fig. 5 is the porous super hydrophobic polypropylene film surface that makes in the embodiment of the invention 4 contact angle test pattern with water.
Embodiment
Embodiment 1
A kind of porous super hydrophobic polypropylene film of the present invention, the pore size distribution range on this porous super hydrophobic polypropylene film surface is 100nm～10 μ m, mean pore size is 1 μ m, this porous super hydrophobic polypropylene film surface is 158 ° ± 1.9 ° with the contact angle of water, the roll angle of water droplet on this porous super hydrophobic polypropylene film surface is 3 °, and the thickness of this porous super hydrophobic polypropylene film is 0.2mm.
The porous super hydrophobic polypropylene film of above-mentioned present embodiment is to adopt following steps to prepare: at first, take by weighing the polypropylene GRANULES of 500g and the granules of polystyrene of 100g, then polypropylene GRANULES that will weigh up and granules of polystyrene in mixer under 180 ℃ of temperature even batch mixing 30min, be the thick film work in-process of forming by polypropylene and polystyrene blends of 0.2mm under 200 ℃ of temperature, the batch mixing behind the uniform mixing being made thickness on the rolling press again, then these film work in-process are soaked 10h in trichloromethane under 50 ℃ temperature, take out the back in loft drier under 60 ℃ environment dry 1h, obtain the white porous super hydrophobic polypropylene film of present embodiment.Test this porous super hydrophobic polypropylene film wettability of the surface with OCA20 contact angle tester, test result as shown in Figure 1, the test result of Fig. 1 shows that the contact angle of this surface and water is 158 ° ± 1.9 °; Roll angle is 3 °, and (the roll angle testing method is as follows: the sample that will test is fixed on the sample table, with microsyringe 5 μ L water droplets are dropped on the sample table again, since 0 ° of sample table that tilts carefully, the pitch angle of sample table just was this surperficial water droplet roll angle when water droplet tumbled sample surfaces then).The surface topography of this porous super hydrophobic polypropylene film is observed with FEI Quanta 200 environmental scanning electron microscopes, observations as shown in Figure 2, as seen from Figure 2, the porous surface formed by a large amount of micron orders and nano grade pore of this porous super hydrophobic polypropylene film.
Embodiment 2
A kind of porous super hydrophobic polypropylene film of the present invention, the pore size distribution range on this porous super hydrophobic polypropylene film surface is 100nm～10 μ m, mean pore size is 800nm, this porous super hydrophobic polypropylene film surface is 156 ° ± 1.8 ° with the contact angle of water, the roll angle of water droplet on this porous super hydrophobic polypropylene film surface is 5 °, and the thickness of this porous super hydrophobic polypropylene film is 0.3mm.
The porous super hydrophobic polypropylene film of above-mentioned present embodiment is to adopt following steps to prepare: at first, take by weighing the polypropylene GRANULES of 8kg and the granules of polystyrene of 1kg, then polypropylene GRANULES that will weigh up and granules of polystyrene in mixer under 200 ℃ of temperature even batch mixing 60min, batch mixing behind the uniform mixing being made thickness under 200 ℃ of temperature with forcing machine again is the thick film work in-process of being made up of polypropylene and polystyrene blends of 0.3mm, then these film work in-process are soaked 8h in trichloromethane under 40 ℃ temperature, take out the back in loft drier under 80 ℃ environment dry 1h, obtain the white porous super hydrophobic polypropylene film of present embodiment.Test this porous super hydrophobic polypropylene film wettability of the surface with OCA20 contact angle tester, test result shows that the contact angle of this surface and water is 156 ° ± 1.8 ° (as shown in Figure 3); Roll angle is 5 °.
Embodiment 3
A kind of porous super hydrophobic polypropylene film of the present invention, the pore size distribution range on this porous super hydrophobic polypropylene film surface is 500nm～5 μ m, mean pore size is 1 μ m, this porous super hydrophobic polypropylene film surface is 159 ° ± 1.6 ° with the contact angle of water, the roll angle of water droplet on this porous super hydrophobic polypropylene film surface is 3 °, and the thickness of this porous super hydrophobic polypropylene film is 0.01mm.
The porous super hydrophobic polypropylene film of above-mentioned present embodiment is to adopt following steps to prepare: at first, take by weighing the polypropylene GRANULES of 1.5kg and the granules of polystyrene of 200g, then polypropylene GRANULES that will weigh up and granules of polystyrene in mixer under 210 ℃ of temperature even batch mixing 60min, batch mixing behind the uniform mixing being made thickness under 200 ℃ of temperature with casting method again is the thick film work in-process of being made up of polypropylene and polystyrene blends of 0.01mm, then these film work in-process are soaked 5h in trichloromethane under 50 ℃ temperature, take out the back in loft drier under 100 ℃ environment dry 1h, obtain the white porous super hydrophobic polypropylene film of present embodiment.Test this porous super hydrophobic polypropylene film wettability of the surface with OCA20 contact angle tester, test result shows that the contact angle of this surface and water is 159 ° ± 1.6 ° (as shown in Figure 4); Roll angle is 3 °.
Embodiment 4
A kind of porous super hydrophobic polypropylene film of the present invention, the pore size distribution range on this porous super hydrophobic polypropylene film surface is 500nm～5 μ m, mean pore size is 800nm, this porous super hydrophobic polypropylene film surface is 155 °+1.9 ° with the contact angle of water, the roll angle of water droplet on this porous super hydrophobic polypropylene film surface is 5 °, and the thickness of this porous super hydrophobic polypropylene film is 0.01mm.
The porous super hydrophobic polypropylene film of above-mentioned present embodiment is to adopt following steps to prepare: at first, take by weighing the polypropylene GRANULES of 1.5kg and the granules of polystyrene of 200g, then polypropylene GRANULES that will weigh up and granules of polystyrene in mixer under 210 ℃ of temperature even batch mixing 60min, batch mixing behind the uniform mixing being made thickness under 200 ℃ of temperature with casting method again is the thick film work in-process of being made up of polypropylene and polystyrene blends of 0.01mm, then these film work in-process are soaked 8h in tetrahydrofuran (THF) under 50 ℃ temperature, take out the back in loft drier under 100 ℃ environment dry 1h, obtain the white porous super hydrophobic polypropylene film of present embodiment.Test this porous super hydrophobic polypropylene film wettability of the surface with OCA20 contact angle tester, test result shows that the contact angle of this surface and water is 155 ° ± 1.9 ° (as shown in Figure 5); Roll angle is 5 °.
Claims (2)
1. the preparation method of a porous super hydrophobic polypropylene film may further comprise the steps:
(1) by (1～10): 1 mass ratio is uniform mixing in mixer with polypropylene GRANULES and granules of polystyrene;
(2) batch mixing after adopting casting method, extrusion molding or rolling process with above-mentioned uniform mixing is prepared into the film work in-process of being made up of described polypropylene and polystyrene;
(3) place trichloromethane or tetrahydrofuran (THF) to soak described film work in-process, the polystyrene that contains in these film work in-process is fully dissolved, take out oven dry then, obtain porous super hydrophobic polypropylene film;
The pore size distribution range on described super-hydrophobic polypropylene film surface is 100nm～10 μ m, mean pore size is 650nm～1 μ m, described super-hydrophobic polypropylene film surface is 150 °～165 ° with the contact angle of water, and the roll angle of water droplet on described super-hydrophobic polypropylene film surface is below 5 °.
2. the preparation method of porous super hydrophobic polypropylene film according to claim 1, it is characterized in that: the time of described immersion is 1h～10h, the temperature during immersion is controlled at 20 ℃～60 ℃.
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| CN2010101202801A CN101792553B (en) | 2010-03-09 | 2010-03-09 | Preparation method of porous super hydrophobic polypropylene film |
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| CN102838772B (en) * | 2012-09-07 | 2013-12-18 | 昌源集团有限公司 | Super-hydrophobic polypropylene film |
| CN110577687A (en) * | 2018-06-08 | 2019-12-17 | 康美包（苏州）有限公司 | lyophobic film and preparation method and application thereof |
| CN110437481B (en) * | 2019-08-12 | 2022-10-14 | 扬州大学 | Method for assembling oligomeric propylene derivative molecules into spiral chiral nano material |
| CN112403282B (en) * | 2019-08-23 | 2022-06-03 | 中国石油化工股份有限公司 | Amphiphilic polypropylene porous membrane and preparation method and application thereof |
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| JPH03261481A (en) * | 1990-03-13 | 1991-11-21 | Terumo Corp | Blood treating device having porous membrane and its production |
| CN1285649C (en) * | 2004-06-04 | 2006-11-22 | 中国科学院化学研究所 | Hydrophobic composite polymer film in micron and nanometer structure and its prepn |
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