CN102776785B - Water-collecting polymer filament imitating spider silk structure and preparation method thereof - Google Patents
Water-collecting polymer filament imitating spider silk structure and preparation method thereof Download PDFInfo
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Abstract
The invention relates to water-collecting polymer filament imitating the spider silk structure and a preparation method thereof. The preparation method comprises the following steps of: immersing common artificial silks into polymer solution mixed by a good solvent and a poor solvent containing polymer, then horizontally pulling out the artificial silks from the polymer solution along the axial direction of the artificial silks, and further enabling the polymer solution to wrap the surfaces of the artificial silks to form a liquid film; then due to Rayleigh instability, causing that the liquid film of the polymer solution on the surfaces of the artificial silks evolutes (break) into a string of liquid drops hung on the artificial silks; by adjusting the humidity and the temperature of the environment, drying the polymer liquid drops hung on the artificial silks so as to form spindle knots with periodic arrangement and a spindle-shaped structure on the surfaces of the artificial silks; and enabling the spindle knots which are in alignment along the axial direction of the artificial silks to form a coarse structure on the surfaces of the artificial silks, and further obtaining the water collecting polymer silks with the similar spider-silk structure by biomimetic synthesis.
Description
Technical field
The present invention relates to biomimetic water catchment fiber and preparation method thereof, particularly the method for catchment polymer filament and large-scale continuous this polymer filament of preparation thereof of imitative spider silk structure.
Background technology
Water resources shortage not only has a strong impact on sustainable development and the National Ecological Security of national economy, and the mankind's existence has been formed to very large threat.According to the data of United Nations Environment Programme, the area of global arid area accounts for 41% of the land gross area.Er China, the area of arid area has also reached 2.5 * 106km
2, account for 1/4 of area.And along with the caused unusual weather conditions of global warming, the problem of water resources shortage also grows in intensity at some places.In addition, some coastal areas also, because face the situation of freshwater resources scarcity, are had to expend a large amount of energy and are carried out desalinization.Yet meanwhile, people but notice, even a large amount of moisture is also contained in the area of extreme lack of water in fog.Therefore,, if can make full use of the moisture in fog, it is condensed under certain condition and just collects to be expected to solve to a great extent the problem of water resources shortage.
People's discovery in to natural observation and exploration, the biology that occurring in nature has can obtain the ability of surviving in the environment of extreme lack of water through long-term evolutionary process.Bionic preparation low energy consumption, high efficiency, the eco-friendly novel material that catchments are expected to become the new way that solves water resources shortage problem.Traditional material that catchments is generally hydrophilic fabric or the good metal of thermal conductive property.For example, Peru government is exploitation fog resource, and Gai state borders on Pacific foggy area in the west and set up fog gathering station.Fog collector is made with nylon wire, under nylon wire support, with a large iron pan, collects the water being obtained by fog, and every square metre of nylon wire can be collected 20 to 50 liters of fogs average every day.Spain scientist has also invented a kind of artificial tree of being made by polyurethane, and this polyester foam water absorbing properties is very strong, very large again with the contact area of mist, dispels the heat very fast, thereby can condense a large amount of moisture.It is not unique, but has its counterpart, and the many residents that live in foggy climatological region of China have also started from fog, to collect fresh water with the similar tradition material that catchments.
But the efficiency of above-mentioned these catchment methods is not very high, and the cost that catchments having is but very high, cannot meet the needs of the people of water-deficient area to water, uses in a large number in addition the plastics of the difficult degradations such as polypropylene can work the mischief to environment again.
Summary of the invention
One of object of the present invention is that to overcome the water collection efficiency of existing catchment method not high, cannot meet the demand of vast water-deficient area people to water, and it is high also to exist the cost that catchments, to the disagreeableness defect of environment, research based on phenomenon that occurring in nature natural spider silk is catchmented, imitate the periodicity spindle junction structure of spider silk, the polymer filament of catchmenting that a kind of water collection efficiency is high, with low cost, prepare simple imitative spider silk structure is provided.
The catchment large-scale continuous preparation method of polymer filament of the imitative spider silk structure that another object of the present invention is to provide object one.
The present invention is that the phenomenon of being decorated by sparkling and crystal-clear water droplet from the spider silk of occurring in nature is inspired, by the observation to spider silk microstructure, utilize polymer solution to apply the polymer liquid film that artificial silk forms parcel artificial silk, afterwards polymer liquid film develop (break) become spindle knot, bionic preparation has obtained having the polymer filament of catchmenting (as shown in Figure 2) of imitative spider silk structure of spindle junction structure of the periodic arrangement of similar spider silk thus.
The surface of the polymer filament of catchmenting of imitative spider silk structure of the present invention has the spindle junction structure of periodic arrangement of the axial direction along the polymer filament orientation of similar spider silk, and the spindle junction structure of this periodic arrangement makes the surface of described polymer filament obtain coarse structure.The polymer filament of catchmenting of imitative spider silk structure of the present invention is by ordinary artificial silk being immersed in the polymer solution that the good solvent that contains polymer and poor solvent mix, then described artificial silk axial direction level along artificial silk from described polymer solution is pulled out to (can utilize the rotation of motor to draw at the uniform velocity stably described artificial silk), and then the surface that makes described artificial silk is taken a certain amount of polymer solution out of, the surperficial liquid film that also forms of the artificial silk described in the polymer solution of taking out of is wrapped in; Due to Rayleigh unstability (Rayleigh instability), cause becoming a string drop to be suspended on described artificial silk in the liquid film evolution (break) of the lip-deep polymer solution of described artificial silk subsequently; By regulating environmental humidity and temperature, make to be suspended on these polymer droplet dryings on described artificial silk, thereby the structure that has formed periodic arrangement on the surface of described artificial silk is fusiform spindle knot, and these knots of spindle along the axial direction orientations of described artificial silk, surface structure at described artificial silk goes out coarse structure, and then bionic preparation has obtained the polymer filament of similar spider silk structure.
The polymer filament of catchmenting (as shown in Figure 2) of imitative spider silk structure of the present invention, to be coated with one layer of polymeric film at artificial silk, and upper along the axial direction orientation of described artificial silk is fusiform spindle knot by the described polymer film structure that (break) go out a string periodic arrangement that develops, this spindle junction structure goes out coarse structure at the surface structure of described artificial silk, forms the polymer filament of catchmenting with similar spider silk structure.
The diameter of described artificial silk is 10 μ m～1000 μ m, and preferably diameter is 10 μ m～40 μ m.
Described artificial silk is selected from a kind of in nylon fiber, polypropylene fiber, spandex fibre, carbon fiber, glass fibre and wire.
Described wire can be selected from a kind of in copper wire, iron wire and nickel wire etc.
Described polymer is selected from least one in the group that polymethyl methacrylate (PMMA), polystyrene (PS), Kynoar (PVDF), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), Merlon (PC) and polyvinylpyrrolidone (PVP) etc. form.
In described polymer, also include and be selected from one or more in ultra-violet stabilizer, ultra-violet absorber, ozone stabilizing agent and antioxidant.
Described ultra-violet stabilizer is two (2,2,6,6-tetramethyl-piperidyl) sebacates (commodity be called light stabilizer 770), and its content in the polymer solution catchmenting during polymer filament of the imitative spider silk structure described in preparation is 0.8wt%.
Described ultra-violet absorber is Octocrylene, and its addition of catchmenting during polymer filament in the described imitative spider silk structure of preparation is less than 0.3% of polymer solution weight.
Described ozone stabilizing agent is phenol triazine, and its addition of catchmenting during polymer filament in the described imitative spider silk structure of preparation is less than 0.1% of polymer solution weight.
Described antioxidant is 2,6-di-tert-butyl-4-methy phenol (trade name UltranoxTM226), and its addition of catchmenting during polymer filament in the described imitative spider silk structure of preparation is less than 1.3% of polymer solution weight.
The preparation method of the polymer filament of catchmenting of imitative spider silk structure of the present invention comprises the following steps:
(1) ordinary artificial silk is immersed in the polymer solution that the good solvent that contains polymer and poor solvent mix, wherein, the quality percentage composition of the polymer in polymer solution is 3%～15% (preferred mass percentage composition is 7%～11%), the quality percentage composition of poor solvent is 0.5%～3% (preferred mass percentage composition is 1%～1.5%), and surplus is good solvent;
(2) step (1) is immersed in described artificial silk in polymer solution along the axial direction of artificial silk at the uniform velocity stably from polymer solution level pull out, obtain by the described artificial silk that liquid film wrapped up of described polymer solution;
(3) it is 10～40 ℃ (preferably temperature is 25～30 ℃) that the described artificial silk that liquid film wrapped up by described polymer solution step (2) being obtained horizontally suspends in temperature, in relative humidity is 30～80% environment of (preferably relative humidity is 40～70%), be dried, obtain the polymer filament of catchmenting (as shown in Figure 2) of imitative spider silk structure of the present invention; It is artificial silk be coated with one layer of polymeric film, and upper along the axial direction orientation of described artificial silk is fusiform spindle knot by the described polymer film structure that (break) go out a string periodic arrangement that develops, this spindle junction structure goes out coarse structure at the surface structure of described artificial silk, forms the polymer filament of catchmenting with similar spider silk structure.
Described by artificial silk along the axial direction of artificial silk at the uniform velocity stably from polymer solution level pull out, that one end of described artificial silk is connected with motor, then regulate the rotary speed of described motor, utilize the rotation of motor to draw at the uniform velocity stably described artificial silk (as shown in Figure 1).
The described artificial silk speed that level is pulled out from polymer solution is 1～14mm/s; Favor speed is 5～9mm/s.
The diameter of described artificial silk is 10 μ m～1000 μ m, and preferably diameter is 10 μ m～40 μ m.
Described artificial silk is selected from a kind of in nylon fiber, polypropylene fiber, spandex fibre, carbon fiber, glass fibre and wire.
Described wire can be selected from a kind of in copper wire, iron wire and nickel wire etc.
Described polymer is selected from least one in the group that polymethyl methacrylate (PMMA), polystyrene (PS), Kynoar (PVDF), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), Merlon (PC) and polyvinylpyrrolidone (PVP) etc. form.
In described polymer solution, also include and be selected from one or more in ultra-violet stabilizer, ultra-violet absorber, ozone stabilizing agent and antioxidant.
Described ultra-violet stabilizer is two (2,2,6,6-tetramethyl-piperidyl) sebacates (commodity be called light stabilizer 770), and its content in the polymer solution catchmenting during polymer filament of the imitative spider silk structure described in preparation is 0.8wt%.
Described ultra-violet absorber is Octocrylene, and its addition of catchmenting during polymer filament in the described imitative spider silk structure of preparation is less than 0.3% of polymer solution weight.
Described ozone stabilizing agent is phenol triazine, and its addition of catchmenting during polymer filament in the described imitative spider silk structure of preparation is less than 0.1% of polymer solution weight.
Described antioxidant is 2,6-di-tert-butyl-4-methy phenol (trade name UltranoxTM226), and its addition of catchmenting during polymer filament in the described imitative spider silk structure of preparation is less than 1.3% of polymer solution weight.
Described good solvent is selected from DMF (DMF), DMA (DMAc), oxolane (THF), chloroform (CHCl
3), at least one in the group that forms of toluene and dimethylbenzene.
Described poor solvent is selected from least one in the group that ethanol, water, acetone, methyl alcohol, isopropyl alcohol and espeleton form.
The polymer filament of catchmenting of imitative spider silk structure of the present invention can be used for collecting fog, and has higher fog collection efficiency.The structure that this function comes from the periodic arrangement of similar natural spider silk is fusiform spindle knot.From single spindle, tie, owing to being enclosed with the diameter of spindle knot position of the artificial silk of polymer, be greater than the diameter that there is no spindle knot position, the drop Laplce suffered in spindle knot position who causes condensing in polymer filament presses and do not have the suffered Laplce in spindle knot position to press imbalance, and the Laplce's pressure reduction that occurs a sensing spindle knot position, this Laplce's pressure differential condenses in does not have the droplet of spindle knot position to move to spindle knot position, on the other hand, due to catchmenting during polymer filament in the imitative spider silk structure of preparation, in polymer solution, there is the existence of poor solvent, make to be enclosed with in ordinary artificial silk's the process of one layer of polymeric film at desiccated surface, spontaneous formation is greater than along the roughness of the spindle knot position of artificial silk axial direction orientation the roughness that there is no spindle knot position, this coarse structure is different from formed surface can gradient cause again condensing in the drop on the artificial silk that is enclosed with polymer, spindle knot position with do not have the wettability of spindle knot position to occur difference, the spindle knot that hydrophilic polymer forms makes spindle knot position be greater than and there is no the compatibility of spindle knot position to water the compatibility of water, finally cause drop can under gradient, to spindle knot position, move on unbalanced surface.Under the acting in conjunction of surface laplacian pressure reduction and surface energy gradient, the polymer filament of catchmenting of imitative spider silk structure of the present invention can be caught airborne droplet rapidly, and utilize fusellal fabric and surface orientation structure, position by caught drop directed transport to the spindle knot in polymer filament that catchments of described imitative spider silk structure, as shown by the arrows in Figure 3; The surface of newly exposing can start again the fog transmitting procedure of next round, collects, thereby realized fog rapidly, continuously as shown in circle in Fig. 3.
Compared with prior art, the effect having is also in the present invention:
(1) polymer filament of catchmenting of imitative spider silk structure of the present invention is with low cost, has good outdoor stability, and service life is long, and water collection efficiency is high and collecting water from runoff is large.
(2) the continuable large-scale of the polymer filament of catchmenting of imitative spider silk structure of the present invention is prepared.
(3) application operating of the polymer filament of catchmenting of imitative spider silk structure of the present invention is simple, therefore can be applied to arid foggy areas such as desert, island, ocean ship and foggy mountain area as offshore area and the fog in coastal area short of rain and collect, in order to collect fresh water.
(4) in the polymer by the polymer filament of catchmenting in preparation imitative spider silk structure of the present invention, add ultra-violet stabilizer, ultra-violet absorber, ozone stabilizing agent, antioxidant etc., make the polymer filament of catchmenting of imitative spider silk structure of the present invention be difficult for degraded, more durable, can extend service life.
Accompanying drawing explanation
Fig. 1. a kind of large-scale continuous method schematic diagram being prepared of the polymer filament of catchmenting of imitative spider silk structure of the present invention.
Fig. 2. the polymer filament of catchmenting of imitative spider silk structure of the present invention.
Fig. 3. the polymer filament of catchmenting of the typical imitative spider silk structure preparing in the embodiment of the present invention 1 is placed in the process of the catchmenting schematic diagram that fog occurs.
The specific embodiment
Below in conjunction with embodiment, further the present invention will be described, but in cited embodiment, concrete material used and consumption and other process conditions should not be regarded as limitation of the present invention.The sign of the ability of catchmenting of the polymer filament of catchmenting of the imitative spider silk structure in embodiment is to carry out on the Dataphysics OCA40 video contact angle measurement producing in Germany; The YADU ultrasonic humidifier (35W) that fog atmosphere is produced by Beijing provides; Polymer P MMA, PS, PVDF, PVAc, PVA, PC, PVP are purchased from A Faaisha (Tianjin) Chemical Co., Ltd.; Good solvent DMF, DMAc, THF, CHCl
3, toluene, dimethylbenzene, and poor solvent ethanol, acetone, methyl alcohol, isopropyl alcohol, espeleton are all purchased from Beijing chemical reagents corporation.The artificial silk of using in embodiment is purchased from nine divisions of China in remote antiquity, Nantong chemical fibre Co., Ltd.
Embodiment 1. has the preparation of the fiber that catchments of the imitative spider silk structure of PMMA spindle knot
(1) preparation contains ultra-violet stabilizer two (2,2,6,6-tetramethyl-piperidyl) DMF of PMMA that the mass fraction of sebacate is 3% and the mixed solution of water, wherein ultra-violet stabilizer two (2,2,6,6-tetramethyl-piperidyl) mass fraction of sebacate in the DMF of PMMA and the mixed solution of water is 0.8wt%, and the mass fraction of water in the DMF of PMMA and the mixed solution of water is 0.5wt%, and surplus is DMF;
(2) by diameter, be the artificial nylon fiber of 10 μ m be submerged into that step (1) obtains completely contain ultra-violet stabilizer two (2, 2, 6, 6-tetramethyl-piperidyl) in the mass fraction of sebacate is 3% the DMF of PMMA and the mixed solution of water, the rotary speed of the motor that adjusting nylon fiber one end connects, make nylon fiber with the speed of 1mm/s along the axial direction of nylon fiber at the uniform velocity stably from above-mentioned mixed solution level pull out (as shown in Figure 1), obtain by containing ultra-violet stabilizer two (2, 2, 6, 6-tetramethyl-piperidyl) nylon fiber that the liquid film of the DMF of the PMMA of sebacate and the mixed solution of water wraps up,
(3) what step (2) is obtained is contained ultra-violet stabilizer two (2,2,6,6-tetramethyl-piperidyl) it is 10 ℃ that the nylon fiber that the liquid film of the DMF of the PMMA of sebacate and the mixed solution of water wraps up horizontally suspends in temperature, relative humidity is dry in 30% environment, obtains having the PMMA fiber that catchments of the imitative spider silk structure of PMMA spindle knot.
The PMMA fiber that catchments of the imitative spider silk structure with PMMA spindle knot of gained is as main silk by artificial nylon fiber, it is coated with one deck PMMA film, and upper along the axial direction orientation of described artificial nylon fiber is that fusiform spindle is tied by the described PMMA film structure that a string periodic arrangement that develops, as shown in Figure 2; And the existence due to poor solvent water, in dry run, the spontaneous formation of this spindle junction structure is along the axial direction orientation of nylon fiber, at the surface structure of described artificial nylon fiber, goes out coarse structure, forms the PMMA fiber that catchments with similar spider silk structure.The PMMA fiber that catchments of this PMMA of having spindle knot can be collected moisture continuously, rapidly from fog, as shown in Figure 3.
The PMMA fiber that catchments gained to the imitative spider silk structure of PMMA spindle knot is placed in the fog atmosphere of the YADU ultrasonic humidifier simulation of producing in Beijing, the Dataphysics OCA40 video contact angle measurement that utilizes Germany to produce, to the catchment sign of ability of the PMMA fiber that catchments of the imitative spider silk structure with PMMA spindle knot of gained.In the situation that fog flow velocity is about 75cm/s, the collecting water from runoff of every meter of individual thread be 2.5 to 7 milliliters per hour.
Embodiment 2. has the preparation of the fiber that catchments of the imitative spider silk structure of PS spindle knot
(1) preparation contains antioxidant 2, the mass fraction of 6-di-tert-butyl-4-methy phenol is 15% the DMAc of PS and the mixed solution of ethanol, wherein antioxidant 2, the addition of 6-di-tert-butyl-4-methy phenol is 1.2% of the DMAc of PS and the mixed solution weight of ethanol, the mass fraction of ethanol in the DMAc of PS and the mixed solution of ethanol is 3wt%, and surplus is DMAc;
(2) by diameter, be the artificial polypropylene fiber of 1000 μ m be submerged into that step (1) obtains completely contain antioxidant 2, the mass fraction of 6-di-tert-butyl-4-methy phenol is in 15% the DMAc of PS and the mixed solution of ethanol, the rotary speed of the motor that adjusting polypropylene fiber one end connects, make polypropylene fiber with the speed of 14mm/s along the axial direction of polypropylene fiber at the uniform velocity stably from above-mentioned mixed solution level pull out (as shown in Figure 1), obtain by containing antioxidant 2, the polypropylene fiber that the liquid film of the DMAc of the PS of 6-di-tert-butyl-4-methy phenol and the mixed solution of ethanol wraps up,
(3) what step (2) is obtained is contained antioxidant 2, it is 40 ℃ that the polypropylene fiber that the liquid film of the DMAc of the PS of 6-di-tert-butyl-4-methy phenol and the mixed solution of ethanol wraps up horizontally suspends in temperature, relative humidity is dry in 80% environment, obtains having the PS fiber that catchments of the imitative spider silk structure of PS spindle knot.
The PS fiber that catchments of the imitative spider silk structure with PS spindle knot of gained is as main silk by artificial polypropylene fiber, it is coated with one deck PS film, and upper along the axial direction orientation of described artificial polypropylene fiber is that fusiform spindle is tied by the described PS film structure that a string periodic arrangement that develops, as shown in Figure 2; And the existence due to poor solvent ethanol, in dry run, the spontaneous formation of this spindle junction structure is along the axial direction orientation of polypropylene fiber, at the surface structure of described artificial polypropylene fiber, goes out coarse structure, forms the PS fiber that catchments with similar spider silk structure.The PS fiber that catchments of this PS of having spindle knot can be collected moisture continuously, rapidly from fog.
The PS fiber that catchments gained to the imitative spider silk structure of PS spindle knot is placed in the fog atmosphere of the YADU ultrasonic humidifier simulation of producing in Beijing, the Dataphysics OCA 40 video contact angle measurements that utilize Germany to produce, to the catchment sign of ability of the PS fiber that catchments of the imitative spider silk structure with PS spindle knot of gained.In the situation that fog flow velocity is about 75cm/s, the collecting water from runoff of every meter of individual thread be 2 to 8 milliliters per hour.
Embodiment 3. has the preparation of the fiber that catchments of the imitative spider silk structure of PVDF spindle knot
(1) preparation contains antioxidant 2, 6-di-tert-butyl-4-methy phenol, ultra-violet absorber 2-cyano group-3, the THF of PVDF and the mixed solution of acetone that the mass fraction of 3-diphenylacrylate 2-Octyl Nitrite is 9%, wherein antioxidant 2, the addition of 6-di-tert-butyl-4-methy phenol is 0.8% of the THF of PVDF and the mixed solution weight of acetone, ultra-violet absorber 2-cyano group-3, the addition of 3-diphenylacrylate 2-Octyl Nitrite is 0.2% of the THF of PVDF and the mixed solution weight of acetone, the mass fraction of acetone in the THF of PVDF and the mixed solution of acetone is 1.5wt%, surplus is THF,
(2) by diameter, be the artificial spandex fibre of 200 μ m be submerged into that step (1) obtains completely contain antioxidant 2, 6-di-tert-butyl-4-methy phenol, ultra-violet absorber 2-cyano group-3, in the THF of PVDF and the mixed solution of acetone that the mass fraction of 3-diphenylacrylate 2-Octyl Nitrite is 9%, the rotary speed of the motor that adjusting spandex fibre one end connects, make spandex fibre with the speed of 9mm/s along the axial direction of spandex fibre at the uniform velocity stably from above-mentioned mixed solution level pull out (as shown in Figure 1), obtain by containing antioxidant 2, 6-di-tert-butyl-4-methy phenol, ultra-violet absorber 2-cyano group-3, the spandex fibre that the THF of PVDF of 3-diphenylacrylate 2-Octyl Nitrite and the liquid film of the mixed solution of acetone wrap up,
(3) what step (2) is obtained is contained antioxidant 2,6-di-tert-butyl-4-methy phenol, ultra-violet absorber 2-cyano group-3, it is 20 ℃ that the spandex fibre that the THF of PVDF of 3-diphenylacrylate 2-Octyl Nitrite and the liquid film of the mixed solution of acetone wrap up horizontally suspends in temperature, relative humidity is dry in 50% environment, obtains having the PVDF fiber that catchments of the imitative spider silk structure of PVDF spindle knot.
The PVDF fiber that catchments of the imitative spider silk structure with PVDF spindle knot of gained is as main silk by artificial spandex fibre, it is coated with one deck pvdf membrane, and upper along the axial direction orientation of described artificial spandex fibre by the described pvdf membrane structure that a string periodic arrangement that develops, be that fusiform spindle is tied; And the existence due to poor solvent acetone, in dry run, the spontaneous formation of this spindle junction structure is along the axial direction orientation of spandex fibre, at the surface structure of described artificial spandex fibre, goes out coarse structure, forms the PVDF fiber that catchments with similar spider silk structure.The PVDF fiber that catchments of this PVDF of having spindle knot can be collected moisture continuously, rapidly from fog.
The PVDF fiber that catchments gained to the imitative spider silk structure of PVDF spindle knot is placed in the fog atmosphere of the YADU ultrasonic humidifier simulation of producing in Beijing, the Dataphysics OCA 40 video contact angle measurements that utilize Germany to produce, to the catchment sign of ability of the PVDF fiber that catchments of the imitative spider silk structure with PVDF spindle knot of gained.In the situation that fog flow velocity is about 75cm/s, the collecting water from runoff of every meter of individual thread be 1.3 to 11.7 milliliters per hour.
Embodiment 4. has the preparation of the fiber that catchments of the imitative spider silk structure of PVAc spindle knot
(1) CHCl of the PVAc that preparation mass fraction is 10%
3with the mixed solution of methyl alcohol, wherein methyl alcohol is at the CHCl of PVAc
3with the mass fraction in the mixed solution of methyl alcohol be 2.0wt%, surplus is CHCl
3;
(2) by diameter, be the CHCl that artificial carbon's fiber of 100 μ m is submerged into the PVAc that mass fraction that step (1) obtains is 10% completely
3in the mixed solution of methyl alcohol, the rotary speed of the motor that adjusting carbon fiber one end connects, make carbon fiber with the speed of 5mm/s along the axial direction of carbon fiber at the uniform velocity stably from above-mentioned mixed solution level pull out (as shown in Figure 1), obtain the CHCl by PVAc
3the carbon fiber wrapping up with the liquid film of the mixed solution of methyl alcohol;
(3) CHCl by PVAc step (2) being obtained
3it is 40 ℃ that the carbon fiber wrapping up with the liquid film of the mixed solution of methyl alcohol horizontally suspends in temperature, dry in the environment that relative humidity is 60%, obtains having the PVAc fiber that catchments of the imitative spider silk structure of PVAc spindle knot.
The PVAc fiber that catchments of the imitative spider silk structure with PVAc spindle knot of gained is as main silk by artificial carbon's fiber, it is coated with one deck PVAc film, and upper along the axial direction orientation of described artificial carbon's fiber by the described PVAc film structure that a string periodic arrangement that develops, be that fusiform spindle is tied; And the existence due to poor solvent methyl alcohol, in dry run, the spontaneous formation of this spindle junction structure is along the axial direction orientation of carbon fiber, at the surface structure of described artificial carbon's fiber, goes out coarse structure, forms the PVAc fiber that catchments with similar spider silk structure.The PVAc fiber that catchments of this PVAc of having spindle knot can be collected moisture continuously, rapidly from fog.
The PVAc fiber that catchments gained to the imitative spider silk structure of PVAc spindle knot is placed in the fog atmosphere of the YADU ultrasonic humidifier simulation of producing in Beijing, the Dataphysics OCA 40 video contact angle measurements that utilize Germany to produce, to the catchment sign of ability of the PVAc fiber that catchments of the imitative spider silk structure with PVAc spindle knot of gained.In the situation that fog flow velocity is about 75cm/s, the collecting water from runoff of every meter of individual thread be 4.9 to 15.3 milliliters per hour.
Embodiment 5. has the preparation of the fiber that catchments of the imitative spider silk structure of PVA spindle knot
(1) preparation mass fraction is 11% the toluene of PVA and the mixed solution of isopropyl alcohol, wherein the mass fraction of isopropyl alcohol in the toluene of PVA and the mixed solution of isopropyl alcohol is 2.5wt%, surplus is toluene;
(2) by diameter, be that the man-made vitreous fibres of 500 μ m is submerged in the toluene of PVA and the mixed solution of isopropyl alcohol that mass fraction that step (1) obtains is 11% completely, the rotary speed of the motor that adjusting glass fibre one end connects, make glass fibre with the speed of 12mm/s along the axial direction of glass fibre at the uniform velocity stably from above-mentioned mixed solution level pull out (as shown in Figure 1), obtain the glass fibre that the liquid film by the toluene of PVA and the mixed solution of isopropyl alcohol wraps up;
(3) it is 25 ℃ that the glass fibre that the liquid film by the toluene of PVA and the mixed solution of isopropyl alcohol step (2) being obtained wraps up horizontally suspends in temperature, relative humidity is dry in 50% environment, obtains having the PVA fiber that catchments of the imitative spider silk structure of PVA spindle knot.
The PVA fiber that catchments of the imitative spider silk structure with PVA spindle knot of gained by man-made vitreous fibres as main silk, it is coated with one deck PVA film, and upper along the axial direction orientation of described man-made vitreous fibres by the described PVA film structure that a string periodic arrangement that develops, be that fusiform spindle is tied; And the existence due to poor solvent isopropyl alcohol, in dry run, the spontaneous formation of this spindle junction structure is along the axial direction orientation of glass fibre, at the surface structure of described man-made vitreous fibres, goes out coarse structure, forms the PVA fiber that catchments with similar spider silk structure.The PVA fiber that catchments of this PVA of having spindle knot can be collected moisture continuously, rapidly from fog.
The PVA fiber that catchments gained to the imitative spider silk structure of PVA spindle knot is placed in the fog atmosphere of the YADU ultrasonic humidifier simulation of producing in Beijing, the Dataphysics OCA 40 video contact angle measurements that utilize Germany to produce, to the catchment sign of ability of the PVA fiber that catchments of the imitative spider silk structure with PVA spindle knot of gained.In the situation that fog flow velocity is about 75cm/s, the collecting water from runoff of every meter of individual thread be 1.7 to 9.4 milliliters per hour.
Embodiment 6. has the preparation of the fiber that catchments of the imitative spider silk structure of PC spindle knot
(1) preparation mass fraction is 13% the dimethylbenzene of PC and the mixed solution of espeleton, wherein the mass fraction of espeleton in the dimethylbenzene of PC and the mixed solution of espeleton is 3wt%, surplus is dimethylbenzene;
(2) by diameter, be that the metal copper wire of 300 μ m is submerged in the dimethylbenzene of PC and the mixed solution of espeleton that mass fraction that step (1) obtains is 13% completely, the rotary speed of the motor that adjusting metal copper wire one end connects, make metal copper wire with the speed of 7mm/s along the axial direction of metal copper wire at the uniform velocity stably from above-mentioned mixed solution level pull out (as shown in Figure 1), obtain the metal copper wire that the liquid film by the dimethylbenzene of PC and the mixed solution of espeleton wraps up;
(3) it is 30 ℃ that the metal copper wire that the liquid film by the dimethylbenzene of PC and the mixed solution of espeleton step (2) being obtained wraps up horizontally suspends in temperature, relative humidity is dry in 40% environment, obtains having the PC fiber that catchments of the imitative spider silk structure of PC spindle knot.
The PC fiber that catchments of the imitative spider silk structure with PC spindle knot of gained is as main silk by metal copper wire, it is coated with one deck PC film, and upper along the axial direction orientation of described metal copper wire by the described PC film structure that a string periodic arrangement that develops, be that fusiform spindle is tied; And the existence due to poor solvent espeleton, in dry run, the spontaneous formation of this spindle junction structure is along the axial direction orientation of metal copper wire, at the surface structure of described metal copper wire, goes out coarse structure, forms the PC fiber that catchments with similar spider silk structure.The PC fiber that catchments of this PC of having spindle knot can be collected moisture continuously, rapidly from fog.
The PC fiber that catchments gained to the imitative spider silk structure of PC spindle knot is placed in the fog atmosphere of the YADU ultrasonic humidifier simulation of producing in Beijing, the Dataphysics OCA 40 video contact angle measurements that utilize Germany to produce, to the catchment sign of ability of the PC fiber that catchments of the imitative spider silk structure with PC spindle knot of gained.In the situation that fog flow velocity is about 75cm/s, the collecting water from runoff of every meter of individual thread be 1.5 to 12.3 milliliters per hour.
Claims (9)
1. a preparation method for the polymer filament of catchmenting of imitative spider silk structure, is characterized in that, the method comprises the following steps:
(1) artificial silk is immersed in the polymer solution that the good solvent that contains polymer and poor solvent mix, wherein, the quality percentage composition of the polymer in polymer solution is 3%～15%, and the quality percentage composition of poor solvent is 0.5%～3%, and surplus is good solvent;
(2) step (1) is immersed in described artificial silk in polymer solution along the axial direction of artificial silk at the uniform velocity stably from polymer solution level pull out, obtain by the described artificial silk that liquid film wrapped up of described polymer solution;
(3) it is 10～40 ℃ that the described artificial silk that liquid film wrapped up by described polymer solution step (2) being obtained horizontally suspends in temperature, relative humidity is to be dried in 30～80% environment, obtain being coated with one layer of polymeric film at artificial silk, and upper along the axial direction orientation of described artificial silk is that fusiform spindle is tied by the described polymer film structure that a string periodic arrangement that develops, this spindle junction structure goes out coarse structure at the surface structure of described artificial silk, forms the polymer filament of catchmenting with spider silk structure;
Described good solvent is selected from least one in the group that DMF, DMA, oxolane, chloroform, toluene and dimethylbenzene forms;
Described poor solvent is selected from least one in the group that ethanol, water, acetone, methyl alcohol, isopropyl alcohol and espeleton form.
2. preparation method according to claim 1, is characterized in that: the quality percentage composition of the polymer in described polymer solution is 7%～11%, and the quality percentage composition of poor solvent is 1%～1.5%, and surplus is good solvent.
3. preparation method according to claim 1, it is characterized in that: described by artificial silk along the axial direction of artificial silk at the uniform velocity stably from polymer solution level pull out, that one end of described artificial silk is connected with motor, then regulate the rotary speed of described motor, utilize the rotation of motor to draw at the uniform velocity stably described artificial silk.
4. according to the preparation method described in claim 1 or 3, it is characterized in that: the described artificial silk speed that level is pulled out from polymer solution is 1～14mm/s.
5. preparation method according to claim 1, is characterized in that: the diameter of described artificial silk is 10 μ m～1000 μ m.
6. preparation method according to claim 1 or 5, is characterized in that: described artificial silk is selected from a kind of in nylon fiber, polypropylene fiber, spandex fibre, carbon fiber, glass fibre and wire.
7. preparation method according to claim 1, is characterized in that: described polymer is selected from least one in the group that polymethyl methacrylate, polystyrene, Kynoar, polyvinyl acetate, polyvinyl alcohol, Merlon and polyvinylpyrrolidone form.
8. according to the preparation method described in claim 1 or 7, it is characterized in that: in described polymer, include and be selected from one or more in ultra-violet stabilizer, ultra-violet absorber, ozone stabilizing agent and antioxidant.
9. preparation method according to claim 8, it is characterized in that: described ultra-violet stabilizer is two (2,2,6,6-tetramethyl-piperidyl) sebacate, its content in the polymer solution catchmenting during polymer filament of the described imitative spider silk structure of preparation is 0.8wt%;
Described ultra-violet absorber is Octocrylene, and its addition of catchmenting during polymer filament in the described imitative spider silk structure of preparation is less than 0.3% of polymer solution weight;
Described ozone stabilizing agent is phenol triazine, and its addition of catchmenting during polymer filament in the described imitative spider silk structure of preparation is less than 0.1% of polymer solution weight;
Described antioxidant is 2,6-di-tert-butyl-4-methy phenol, and its addition of catchmenting during polymer filament in the described imitative spider silk structure of preparation is less than 1.3% of polymer solution weight.
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