CN1880592A - Bionic water-collecting composite electrospun film and its preparation method and use - Google Patents
Bionic water-collecting composite electrospun film and its preparation method and use Download PDFInfo
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- CN1880592A CN1880592A CN 200510011943 CN200510011943A CN1880592A CN 1880592 A CN1880592 A CN 1880592A CN 200510011943 CN200510011943 CN 200510011943 CN 200510011943 A CN200510011943 A CN 200510011943A CN 1880592 A CN1880592 A CN 1880592A
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Abstract
The invention relates to a bionic water collect composite film, which comprises a base with many round micro hydrophilic polymer projections on its above hydrophobic polymer film; said hydrophobic polymer is the polystyrene that doped with 20-30wt% silica dioxide whose average diameter is 2-100nm; the hydrophilic polymer is the polymer of amido, hydroxyl or carboxyl doped with 10-70wt% titania whose average diameter 1-100micrometer; the hydrophobic polymer film comprises one or several of ultraviolet stabilizer, ultraviolet absorber, ozone stabilizer, and antioxidant. The inventive film can collect fog drop or disperse dense fog. The invention has high water collecting efficiency, long service life, and better hydrophilic/ hydrophobic property.
Description
Technical field
The present invention relates to a kind of bionic water-collecting composite electrospun film, and its production and use.
Background technology
Thick fog is a kind of meteorological disaster, and it is not only made troubles to people trip, sometimes even can cause life and property loss, therefore, is carrying out the research of low-cost arrtificial fog dissipation abroad always.On the other hand, along with the swift and violent increase of global warming and population, the problem of lack of water becomes more and more outstanding.For example in China, because the diversity of geographical and weather makes a lot of areas of China all be in exsiccosis for a long time, this has greatly restricted the development of local economic development, particularly west area.Recently, new technical system---" fog engineering " just quietly risen in some countries and regions, the world.The method of " catching the mist water intaking " can reduce and eliminate the harm that thick fog brings on the one hand, can collect the small water droplet in the humid air on the other hand and obtain spendable fresh water, thereby become the important channel that many countries and regions, particularly Gan Han mountain area, desert area and island, seagoing vessel etc. solve the fresh water deficiencies.
The method of existing " catching the mist water intaking " is to adopt the metal of rapid heat dissipation, as aluminium, makes the cylinder of any surface finish, is erected in the foggy air, just at the very fast water that is condensed into of the mist of its surface attachment, constantly down trickling generates fresh water continuously.On desert area and general land, evening high humidity; And in island and ocean (on the naval vessel), the humidity in daytime and evening is all very big.In this class area, all can suit measures to local conditions to utilize this principle from mist, to fetch water.
In the Qiong Gong fruit village that is located in to the north of the Chile Santiago of Atacama Desert, daytime temperature is very high, and rainwater rareness, annual precipitation only have 400 millimeters, and production and living water use are very nervous.But be a foggy district, and humidity is very big herein.People adopt BP (UK Patent Application No.0109814.4) disclosed method, installed huge fog conversion equipment on the hillside---the huge net of plastic optical fibre that mesh is superfine, can catch the mist liter more than 10,000 of fetching water every night, thereby solve local lack of water resident's water difficulty.
And in the foggy mountain area in China Mount Lushan, people adopt the water droplet by the pine needle surface aggregation such as the straightforward procedure collection of placing wooden barrel under pine tree.
United States Patent (USP) 4,536, a kind of hygroscopicity coating that is made by the mixture of colloid acrylic resin and cataloid is disclosed in 420, this coating surface has the hydrophobic groove of cracking, and the hydrophilic region area is less than hydrophobic region, and fog drips and can form water at hydrophilic region earlier and sprawl layer, will form water droplet once more after the accumulation, and pool big drop, and in hydrophobic groove, flow, collect and obtain spendable fresh water.
But above-mentioned these method water collection efficiencies are not very high, and the cost that has is but very high, can't satisfy the needs of vast water-deficient area to water; In addition owing to a large amount of use the plastics of difficult degradation such as polypropylene and influence environment.
Summary of the invention
The water collection efficiency that the objective of the invention is to overcome prior art is not high, can't satisfy the needs of vast water-deficient area to water, and the defective of cost height, not environmental protection provides a kind of membrane structure with hydrophilic region and hydrophobic region, can collect small water droplet in the air efficiently and make it to become available fresh water, and bionic water-collecting composite electrospun film that can demist.
Another object of the present invention is to provide the preparation method of above-mentioned bionic water-collecting composite electrospun film.
A further object of the present invention is to provide the purposes of above-mentioned bionic water-collecting composite electrospun film in the collection fog drips or dispels the thick fog.
The objective of the invention is to realize by the following technical solutions:
Bionic water-collecting composite electrospun film provided by the invention, be that crust collection fog and the cobweb of intending the ground beetle insect from the desert can be hung the inspiration that obtains the phenomenon of dewdrops, as shown in Figure 1, the surface of this composite electrospun film has the composite construction of hydrophilic region and hydrophobic region, it comprises a substrate, hydrophobic polymer electrospun film on it reaches the circular projection at the many small hydrophilic polymers in hydrophobic polymer electrospun film surface; The thickness of described hydrophobic polymer electrospun film is less than 0.5mm; The diameter of described projection is 0.1～1.5mm, highly is 0.2～1mm, and the distance between the projection central point is 2～7mm.
Described base material is conductive aluminum foil or tinfoil paper.
Described hydrophobic polymer is the polystyrene of doping silicon dioxide; The average grain diameter of described silica is 2～100nm, preferred 5～50nm; Its doping is 20～30wt%.
Described hydrophilic polymer is the titania-doped polymer that contains amide groups, hydroxyl or carboxyl, comprises the copolymer of polyvinyl alcohol, polyvinylpyrrolidone and acrylic or methacrylic acid, the preferably polyethylene pyrrolidones; The average grain diameter of described titanium dioxide is 1～100 μ m, preferred 5～50 μ m; Its doping is 10～70wt%, preferred 20～50wt%, more preferred 30～40wt%.
The preferred diameter of described projection is 0.2～0.7mm, and preferred heights is 0.3～0.5mm, and the distance between the preferred projection central point is 3～6mm.
Can also comprise in the hydrophobic polymer film of bionic water-collecting composite electrospun film of the present invention and be selected from ultra-violet stabilizer, ultra-violet absorber, ozone stabilizing agent, the antioxidant one or more.
Described ultra-violet stabilizer is two (2,2,6, the 6-tetramethyl-piperidyl) sebacates (commodity are called light stabilizer 770), and addition is the 1wt% of described hydrophobic polymer;
Described ultra-violet absorber is a 2-cyano group-3,3-diphenylacrylate 2-Octyl Nitrite, and addition is less than the 0.5wt% of described hydrophobic polymer;
Described ozone stabilizing agent is the phenol triazine, and addition is the 0.3wt% less than described hydrophobic polymer;
Described antioxidant is 2,6-di-tert-butyl-4-methy phenol (trade name Ultranox
TM226), addition is 0.5～1wt% of described hydrophobic polymer.
The invention provides a kind of method for preparing above-mentioned bionic water-collecting composite electrospun film, as shown in Figure 1, electrospinning one deck hydrophobic polymer nano wire film on metal substrate at first; The equally distributed hydrophilic polymer microballoon of electrospinning one deck again on it specifically comprises following step:
1) preparation hydrophobic polymer solution:
Polystyrene and silica are under agitation slowly joined in dimethyl-formamide, and fully after the swelling, constant temperature stirs and dissolved fully to polystyrene in 2 hours, and the doping of silica is 20～30wt%; With solution left standstill 12 hours, bubble collapse in solution made hydrophobic polymer solution then;
The average grain diameter of described silica is 2～100nm, preferred 5～50nm;
2) preparation hydrophilic polymer solution:
Hydrophilic polymer and titanium dioxide are under agitation slowly joined in the secondary water deionized water, fully after the swelling, be warming up to 80 ℃, constant temperature stirs and dissolved fully to hydrophilic polymer in 2 hours, the doping of titanium dioxide is 10～70wt%, continues under the room temperature to stir 2 hours; With solution left standstill 12 hours, bubble collapse in solution made hydrophilic polymer solution then.
Described hydrophilic polymer is the polymer that contains amide groups, hydroxyl or carboxyl, comprises the copolymer of polyvinyl alcohol, polyvinylpyrrolidone and acrylic or methacrylic acid, the preferably polyethylene pyrrolidones;
The average grain diameter of described titanium dioxide is 1～100 μ m, preferred 5～50 μ m; Preferred 20～the 50wt% of its doping, more preferred 30～40wt%;
3) electrospinning hydrophobic film:
The hydrophobic polymer solution that step 1) is made is packed in the device for storing liquid of existing device for spinning, and electrospinning operating distance (needle point is to the distance between the receiving device) is 10cm; Open high voltage source, regulate spinning voltage to 10～28kV, polymer electrospinning solution sprays from injection apparatus, and obtains the hydrophobic polymer electrospun film of thickness less than 0.5mm on receiving system---the polystyrene of the silica that mixed;
Described existing electric spinning equipment comprises high-voltage DC power supply, device for storing liquid, injection apparatus and receiving system four parts; The output voltage of employed high-voltage DC power supply is 0～30kV, and device for storing liquid is vertically placed, and injection apparatus adopts single injector head to spray, and receiving system (base material) is conductive aluminum foil or tinfoil paper;
4) electrospinning laminated film:
With step 2) in the hydrophilic polymer solution that makes on the electric spinning equipment of step 3) and spray, be 0.1～1.5mm, highly be that distance between 0.2～1mm, the central point is the circular projection of the small hydrophilic polymer of 2～7mm obtaining diameter on the polystyrene film that step 3) makes; Vacuum drying is all volatilized solvent, promptly obtains bionic water-collecting composite electrospun film of the present invention.
The preferred diameter of described projection is 0.2～0.7mm, and preferred heights is 0.3～0.5mm, and the distance between the preferred projection central point is 3～6mm.
The preparation method of above-mentioned bionic water-collecting composite electrospun film provided by the invention also is included in the hydrophobic polymer thin layer to add and is selected from ultra-violet stabilizer, ultra-violet absorber, ozone stabilizing agent, the antioxidant one or more.
Described ultra-violet stabilizer is two (2,2,6, the 6-tetramethyl-piperidyl) sebacates (commodity are called light stabilizer 770), and addition is the 1wt% of described hydrophobic polymer;
Described ultra-violet absorber is a 2-cyano group-3,3-diphenylacrylate 2-Octyl Nitrite, and addition is less than the 0.5wt% of described hydrophobic polymer;
Described ozone stabilizing agent is the phenol triazine, and addition is the 0.3wt% less than described hydrophobic polymer
Described antioxidant is 2,6-di-tert-butyl-4-methy phenol (trade name Ultranox
TM226), addition is 0.5～1wt% of described hydrophobic polymer.
Above-mentioned bionic water-collecting composite electrospun film provided by the invention can be used for collecting fog and drips or dispel the thick fog.It has and efficiently catchments or the function of dispersing fog, can increase the gathering of airborne water droplet on the composite electrospun film surface, reduces airborne moisture simultaneously, thereby improves the visibility of air.Under air themperature that is fit to and humidity, airborne moisture is attracted by the hydrophilic region on this composite electrospun film surface and rapid drawout, sprawling gathering in a large number and forming bigger water droplet at hydrophobic surface along with aqueous vapor.When electrospun film tilts or vertically installs, in the catch basin of these big water droplet rolling film plates and compile and be spendable fresh water.
The invention provides and a kind ofly use above-mentioned bionic water-collecting composite electrospun film to collect the device that fog drips or dispels the thick fog, as shown in Figure 2, comprise: 2 elevating levers 1 that drive by small machine, gutter channel 6 by four levels links to each other therebetween, one end of gutter channel is connected in aqueduct 2, in the steel ladle 3 below aqueduct 2 inserts; Spacing is 1 meter between the gutter channel 6, vertical therebetween installation bionic water-collecting composite electrospun film 7 provided by the invention; Elevating lever 1 is fixing by static line 4 and spud pile 5.
Described gutter channel is the groove that plastics or metal are made.
Described aqueduct is the pipe of plastic production.
The height of described elevating lever is 7～10 meters, and spacing is 10～15 meters.
When dense fog occurred, elevating lever drove gutter channel, bionic water-collecting composite electrospun film and aqueduct simultaneously and stretches out automatically thereupon by electronic rise; The fresh water that bionic water-collecting composite electrospun film is collected flow in the gutter channel, and enters in the steel ladle through aqueduct; After dense fog dispersed, the electronic elevating lever of falling, gutter channel, bionic water-collecting composite electrospun film and aqueduct entered thereupon falling in the storage box, to avoid material aging.
The device that uses above-mentioned bionic water-collecting composite electrospun film to collect fog to drip or dispel the thick fog (abbreviation catchment installing rack) can in-line be installed in island (seashore), high mountain etc. and facings the wind on the external wall of place, gentle slope and foggy district building to collect fresh water; also can two row or number row lay; many foggy and the problem of water consumption of water-deficient area helps these regional ecological protections and improves local resident's living standard to solve China.In the thick fog prone areas, also it can be installed in the place, isolation strip on speedway both sides or the place, vacant lot around the aerodrome, and suitably improve the length of elevating lever, can play the effect that dispels the thick fog and improve air visibility, thereby significantly reduce the economic loss that thick fog brings.
Composite membrane of biomimetic water catchment provided by the invention, be that crust collection fog and the cobweb of intending the ground beetle insect from the desert can be hung the inspiration that obtains the phenomenon of dewdrops, as shown in Figure 1, the surface of this composite electrospun film has the composite construction of hydrophilic region and hydrophobic region, and the area of hydrophilic region is less than the area of hydrophobic region, compared with prior art, the invention has the advantages that:
1, hydrophilic region has increased hydrophilic area by the projection of rule, especially the formed projection of hydrophilic polymer of using inorganic oxide particles to mix, its surface has the more projection or the micropore of microcosmic again, more increased the area of hydrophilic region, increase the collision probability and the spreading rate of air water droplet, made the efficient of catchmenting be improved.
2, hydrophilic polymer used in the present invention has good outdoor stability;
3, inorganic oxide particles used in the present invention has low cost, hydrophily is good, the characteristic good with the compatibility of polymer;
4, by adding ultra-violet stabilizer, ultra-violet absorber, ozone stabilizing agent, antioxidant etc., make bionic water-collecting composite electrospun film provided by the invention be difficult for degraded, more durable, can prolong service life; Polymer is owing to present the nanofiber state, and very thin, environment polluted substantially compliance with environmental protection requirements.
5, this bionic water-collecting composite electrospun film originally has good hydrophobic/hydrophilic nmature, in room temperature the water droplet of 3 μ m is measured, the static contact angle of its hydrophilic region (static contact angle) is less than 30 °, even can be as small as 10 °, and the static contact angle of hydrophobic region surpasses 80 °, even can be above 110 °;
6, bionic water-collecting composite electrospun film of the present invention provides the collecting water from runoff under the different humidity, durability and economy.Therefore should be used in the desert, strand, island, ocean ship and foggy mountain area etc., collecting airborne water droplet becomes spendable fresh water, and the thick fog around the airport, speedway, beacon etc. disperses and eliminates.Because the method for this collection fresh water is energy free consumption, so its cost is far below Cost of seawater desalination.
Description of drawings
Fig. 1 is the preparation method's of a composite membrane of biomimetic water catchment provided by the invention schematic diagram;
Fig. 2 is to use composite membrane of biomimetic water catchment of the present invention to collect the schematic representation of apparatus that fog drips or dispels the thick fog; Wherein, 1. elevating lever highly is 7 meters, and two distance between tie rods are 10 meters; 2. aqueduct, 3. steel ladle, 4. static line, 5. spud pile, 6. gutter channel, composite membrane of biomimetic water catchment 7. provided by the invention.
The specific embodiment
In following examples, further specify advantage of the present invention and other details, but concrete material of quoting among the embodiment and consumption and other condition and details should not be regarded as the present invention has been carried out inappropriate restriction.Unless otherwise indicated, all temperature among the embodiment all in degree centigrade, all umbers and percentage number average are by weight.
The gained thin-film material is carried out the Static Water contact angle experiments, use water droplet 2 μ L, produce on the dataphisicsOCA-20 video contact angle measurement in Germany and carry out.
Embodiment 1
1) preparation hydrophobic polymer solution:
With the polystyrene of 10 weight portions and the average grain diameter of 2 weight portions is that 100nm silica under agitation slowly joins in the dimethyl-formamide of 90 weight portions, and fully after the swelling, constant temperature stirs and dissolved fully to polystyrene in 2 hours; With solution left standstill 12 hours, bubble collapse in solution made hydrophobic polymer solution then;
2) preparation hydrophilic polymer solution:
With the average grain diameter of the polyvinyl alcohol of 15 weight portions and 3 weight portions is that the titanium dioxide granule of 100 μ m under agitation slowly joins in the secondary water deionized water of 85 weight portions, fully after the swelling, be warming up to 80 ℃, constant temperature stirs and to dissolve fully to polyvinyl alcohol in 2 hours, continues under the room temperature to stir 2 hours; With solution left standstill 12 hours, bubble collapse in solution made hydrophilic polymer solution then.
3) electrospinning hydrophobic film:
The hydrophobic polymer solution that step 1) is made is packed in the device for storing liquid of existing device for spinning, and electrospinning operating distance (needle point is to the distance between the receiving device) is 10cm; Open high voltage source, regulate spinning voltage to 10～28kV, polymer electrospinning solution sprays from injection apparatus, and obtains the hydrophobic polymer electrospun film that thickness is 0.3mm---the polystyrene of the silica that mixed on receiving system;
Described existing electric spinning equipment comprises high-voltage DC power supply, device for storing liquid, injection apparatus and receiving system four parts; The output voltage of employed high-voltage DC power supply is 0～30kV, and device for storing liquid is vertically placed, and injection apparatus adopts single injector head to spray, and receiving system (base material) is a conductive aluminum foil;
4) electrospinning laminated film:
With step 2) in the hydrophilic polymer solution that makes on the electric spinning equipment of step 3) and spray, be 1.5mm, highly be that distance between 1mm, the central point is the circular projection of the small hydrophilic polymer of 7mm obtaining diameter on the polystyrene film that step 3) makes; Vacuum drying is all volatilized solvent, promptly obtains bionic water-collecting composite electrospun film of the present invention.
This thin-film material is carried out the Static Water contact angle experiments, in room temperature the water droplet of 3 μ m is measured, the static contact angle of its hydrophilic region is less than 15 °, and the static contact angle of hydrophobic region is greater than 110 °.
Embodiment 2
1) preparation hydrophobic polymer solution:
With the polystyrene of 10 weight portions and the average grain diameter of 3 weight portions is that 2nm silica under agitation slowly joins in the dimethyl-formamide of 90 weight portions, and fully after the swelling, constant temperature stirs and dissolved fully to polystyrene in 2 hours; With solution left standstill 12 hours, bubble collapse in solution made hydrophobic polymer solution then;
2) preparation hydrophilic polymer solution:
With the average grain diameter of the polyvinyl alcohol of 15 weight portions and 7.5 weight portions is that the titanium dioxide granule of 1 μ m under agitation slowly joins in the secondary water deionized water of 85 weight portions, fully after the swelling, be warming up to 80 ℃, constant temperature stirs and to dissolve fully to polyvinyl alcohol in 2 hours, continues under the room temperature to stir 2 hours; With solution left standstill 12 hours, bubble collapse in solution made hydrophilic polymer solution then.
3) electrospinning hydrophobic film:
The hydrophobic polymer solution that step 1) is made is packed in the device for storing liquid of existing device for spinning, and electrospinning operating distance (needle point is to the distance between the receiving device) is 10cm; Open high voltage source, regulate spinning voltage to 10～28kV, polymer electrospinning solution sprays from injection apparatus, and obtains the hydrophobic polymer electrospun film that thickness is 0.4mm---the polystyrene of the silica that mixed on receiving system;
Described existing electric spinning equipment comprises high-voltage DC power supply, device for storing liquid, injection apparatus and receiving system four parts; The output voltage of employed high-voltage DC power supply is 0～30kV, and device for storing liquid is vertically placed, and injection apparatus adopts single injector head to spray, and receiving system (base material) is conduction tinfoil paper;
4) electrospinning laminated film:
With step 2) in the hydrophilic polymer solution that makes on the electric spinning equipment of step 3) and spray, be 0.1mm, highly be that distance between 0.2mm, the central point is the circular projection of the small hydrophilic polymer of 2mm obtaining diameter on the polystyrene film that step 3) makes; Vacuum drying is all volatilized solvent, promptly obtains bionic water-collecting composite electrospun film of the present invention.
This thin-film material is carried out the Static Water contact angle experiments, in room temperature the water droplet of 3 μ m is measured, the static contact angle of its hydrophilic region is less than 15 °, and the static contact angle of hydrophobic region is greater than 110 °.
Embodiment 3
1) preparation hydrophobic polymer solution:
With the polystyrene of 10 weight portions, the average grain diameter of 2.5 weight portions is 50nm silica and 0.05 weight portion ultra-violet absorber 2-cyano group-3,3-diphenylacrylate 2-Octyl Nitrite under agitation slowly joins in the dimethyl-formamide of 90 weight portions, fully after the swelling, constant temperature stirs and dissolved fully to polystyrene in 2 hours; With solution left standstill 12 hours, bubble collapse in solution made hydrophobic polymer solution then;
2) preparation hydrophilic polymer solution:
With the average grain diameter of the polyvinyl alcohol of 15 weight portions and 1.5 weight portions is that the titanium dioxide granule of 50 μ m under agitation slowly joins in the secondary water deionized water of 85 weight portions, fully after the swelling, be warming up to 80 ℃, constant temperature stirs and to dissolve fully to polyvinyl alcohol in 2 hours, continues under the room temperature to stir 2 hours; With solution left standstill 12 hours, bubble collapse in solution made hydrophilic polymer solution then.
3) electrospinning hydrophobic film:
The hydrophobic polymer solution that step 1) is made is packed in the device for storing liquid of existing device for spinning, and electrospinning operating distance (needle point is to the distance between the receiving device) is 10cm; Open high voltage source, regulate spinning voltage to 10～28kV, polymer electrospinning solution sprays from injection apparatus, and obtains the hydrophobic polymer electrospun film that thickness is 0.5mm---the polystyrene of the silica that mixed on receiving system;
Described existing electric spinning equipment comprises high-voltage DC power supply, device for storing liquid, injection apparatus and receiving system four parts; The output voltage of employed high-voltage DC power supply is 0～30kV, and device for storing liquid is vertically placed, and injection apparatus adopts single injector head to spray, and receiving system (base material) is a conductive aluminum foil;
4) electrospinning laminated film:
With step 2) in the hydrophilic polymer solution that makes on the electric spinning equipment of step 3) and spray, be 0.7mm, highly be that distance between 0.5mm, the central point is the circular projection of the small hydrophilic polymer of 6mm obtaining diameter on the polystyrene film that step 3) makes; Vacuum drying is all volatilized solvent, promptly obtains bionic water-collecting composite electrospun film of the present invention.
This thin-film material is carried out the Static Water contact angle experiments, in room temperature the water droplet of 3 μ m is measured, the static contact angle of its hydrophilic region is less than 15 °, and the static contact angle of hydrophobic region is greater than 110 °.
Embodiment 4
1) preparation hydrophobic polymer solution:
With the polystyrene of 10 weight portions and the average grain diameter of 2 weight portions is that 5nm silica under agitation slowly joins in the dimethyl-formamide of 90 weight portions, and fully after the swelling, constant temperature stirs and dissolved fully to polystyrene in 2 hours; With solution left standstill 12 hours, bubble collapse in solution made hydrophobic polymer solution then;
2) preparation hydrophilic polymer solution:
With the polyvinyl alcohol of 15 weight portions, the average grain diameter of 4.5 weight portions is the titanium dioxide granule of 5 μ m, 0.015 weight portion ultra-violet stabilizer two (2,2,6, the 6-tetramethyl-piperidyl) antioxidant 2 of sebacate (commodity are called light stabilizer 770), 0.03 weight portion ozone stabilizing agent phenol triazine and 0.15 weight portion, 6-di-tert-butyl-4-methy phenol (trade name Ultranox
TM226) under agitation slowly join in the secondary water deionized water of 85 weight portions, fully after the swelling, be warming up to 80 ℃, constant temperature stirs and dissolved fully to polyvinyl alcohol in 2 hours, continues under the room temperature to stir 2 hours; With solution left standstill 12 hours, bubble collapse in solution made hydrophilic polymer solution then.
3) electrospinning hydrophobic film:
The hydrophobic polymer solution that step 1) is made is packed in the device for storing liquid of existing device for spinning, and electrospinning operating distance (needle point is to the distance between the receiving device) is 10cm; Open high voltage source, regulate spinning voltage to 10～28kV, polymer electrospinning solution sprays from injection apparatus, and obtains the hydrophobic polymer electrospun film that thickness is 0.2mm---the polystyrene of the silica that mixed on receiving system;
Described existing electric spinning equipment comprises high-voltage DC power supply, device for storing liquid, injection apparatus and receiving system four parts; The output voltage of employed high-voltage DC power supply is 0～30kV, and device for storing liquid is vertically placed, and injection apparatus adopts single injector head to spray, and receiving system (base material) is a conductive aluminum foil;
4) electrospinning laminated film:
With step 2) in the hydrophilic polymer solution that makes on the electric spinning equipment of step 3) and spray, be 0.2mm, highly be that distance between 0.3mm, the central point is the circular projection of the small hydrophilic polymer of 3mm obtaining diameter on the polystyrene film that step 3) makes; Vacuum drying is all volatilized solvent, promptly obtains bionic water-collecting composite electrospun film of the present invention.
This thin-film material is carried out the Static Water contact angle experiments, in room temperature the water droplet of 3 μ m is measured, the static contact angle of its hydrophilic region is less than 15 °, and the static contact angle of hydrophobic region is greater than 110 °.
Embodiment 5
The bionic water-collecting composite electrospun film of use embodiment 1 preparation provided by the invention is collected the device that fog drips or dispels the thick fog, and as shown in Figure 2, comprising: 2 elevating levers 1 that drive by small machine, and the height of elevating lever is 10 meters, spacing is 12 meters.The stream of plastic tank 6 of four levels has been installed between two bars, and its width is 15cm, and the spacing of gutter channel is 1 meter.One end of gutter channel is connected in plastics aqueduct 2, and its internal diameter is Φ 20mm.Φ 100 * 80m below aqueduct 2 inserts
3In the steel ladle 3; Between the gutter channel 6 vertical install embodiment 1 preparation bionic water-collecting composite electrospun film 7; Elevating lever 1 is fixing by static line 4 and spud pile 5.Elevating lever is 100 watts Motor Drive lifting by power, drives the lifting thereupon of gutter channel, water collection sheet and aqueduct simultaneously.
When dense fog occurred, elevating lever drove gutter channel, bionic water-collecting composite electrospun film and aqueduct simultaneously and stretches out automatically thereupon by electronic rise; The fresh water that bionic water-collecting composite electrospun film is collected flow in the gutter channel, and enters in the steel ladle through aqueduct; After dense fog dispersed, the electronic elevating lever of falling, gutter channel, bionic water-collecting composite electrospun film and aqueduct entered thereupon falling in the storage box, to avoid material aging.
15 ℃, relative humidity 90% time, an area is 0.5m
2Water-collecting composite electrospun film rise fresh water at the diel 30-50 that can catchment, have than higher water collection efficiency.
Claims (10)
1, a kind of bionic water-collecting composite electrospun film, it comprises a substrate, the hydrophobic polymer electrospun film on it reaches the circular projection at the many small hydrophilic polymers in hydrophobic polymer electrospun film surface; The thickness of described hydrophobic polymer electrospun film is less than 0.5mm; The diameter of described projection is 0.1～1.5mm, highly is 0.2～1mm, and the distance between the projection central point is 2～7mm.
2, bionic water-collecting composite electrospun film as claimed in claim 1 is characterized in that: described hydrophobic polymer is the polystyrene of 2～100nm silica for the 20～30wt% that mixes, average grain diameter.
3, bionic water-collecting composite electrospun film as claimed in claim 1 is characterized in that: described hydrophilic polymer is the polymer that contains amide groups, hydroxyl or carboxyl of 1～100 μ m titanium dioxide for the 10～70wt% that mixes, average grain diameter.
4, as claim 1 or 3 described bionic water-collecting composite electrospun films, it is characterized in that: described hydrophilic polymer is the copolymer of polyvinyl alcohol, polyvinylpyrrolidone and acrylic or methacrylic acid.
5, bionic water-collecting composite electrospun film as claimed in claim 1 is characterized in that: also comprise in the described hydrophobic polymer film being selected from ultra-violet stabilizer, ultra-violet absorber, ozone stabilizing agent, the antioxidant one or more.
6, a kind of method for preparing the described bionic water-collecting composite electrospun film of claim 1 comprises following step:
1) preparation hydrophobic polymer solution:
With polystyrene and average grain diameter is that 2～100nm silica under agitation slowly joins in dimethyl-formamide, and fully after the swelling, constant temperature stirs and dissolved fully to polystyrene in 2 hours, and the doping of silica is 20～30wt%; With solution left standstill 12 hours, bubble collapse in solution made hydrophobic polymer solution then;
2) preparation hydrophilic polymer solution:
With hydrophilic polymer and average grain diameter is that 1～100 μ m titanium dioxide under agitation slowly joins in the secondary water deionized water, fully after the swelling, be warming up to 80 ℃, constant temperature stirs and to dissolve fully to hydrophilic polymer in 2 hours, the doping of titanium dioxide is 10～70wt%, continues under the room temperature to stir 2 hours; With solution left standstill 12 hours, bubble collapse in solution made hydrophilic polymer solution then;
Described hydrophilic polymer is the polymer that contains amide groups, hydroxyl or carboxyl, comprises the copolymer of polyvinyl alcohol, polyvinylpyrrolidone and acrylic or methacrylic acid;
3) electrospinning hydrophobic film:
The hydrophobic polymer solution that step 1) is made is packed in the device for storing liquid of existing device for spinning, and the electrospinning operating distance is 10cm; Open high voltage source, regulate spinning voltage to 10～28kV, polymer electrospinning solution sprays from injection apparatus, and obtains the hydrophobic polymer electrospun film of thickness less than 0.5mm on receiving system;
4) electrospinning laminated film:
With step 2) in the hydrophilic polymer solution that makes on the electric spinning equipment of step 3) and spray, be 0.1～1.5mm, highly be that distance between 0.2～1mm, the central point is the circular projection of the small hydrophilic polymer of 2～7mm obtaining diameter on the polystyrene film that step 3) makes; Vacuum drying is all volatilized solvent, obtains bionic water-collecting composite electrospun film of the present invention.
7, preparation method as claimed in claim 6 also is included in the hydrophobic polymer thin layer to add and is selected from ultra-violet stabilizer, ultra-violet absorber, ozone stabilizing agent, the antioxidant one or more.
8, the purposes of the described bionic water-collecting composite electrospun film of claim 1 in the collection fog drips or dispels the thick fog.
9, a kind of described bionic water-collecting composite electrospun film of claim 1 that uses is collected the device that fog drips or dispels the thick fog, comprise: 2 elevating levers (1) that drive by small machine, gutter channel (6) by four levels links to each other therebetween, one end of gutter channel is connected in aqueduct (2), in the steel ladle (3) below aqueduct (2) inserts; Spacing is 1 meter between the gutter channel (6), the vertical therebetween bionic water-collecting composite electrospun film provided by the invention (7) of installing; Elevating lever (1) is fixing by static line (4) and spud pile (5).
10, device as claimed in claim 9 is characterized in that: described gutter channel is the groove that plastics or metal are made; Described aqueduct is the pipe of plastic production.
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| CNB2005100119435A CN100445479C (en) | 2005-06-16 | 2005-06-16 | Bionic water-collecting composite electrospun film and its preparation method and use |
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