CN102776785A - 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 the sustainable development and the national ecological safety of national economy, and human existence has been constituted very big threat.According to the data of United Nations Environment Programme, the area of global arid area accounts for 41% of the land gross area.And in 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, also because face the deficient situation of freshwater resources, the energy of the labor of having to carries out desalinization in the coastal area that has.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 the fog, it is condensed and just collects to be expected to solve to a great extent the problem of water resources shortage under certain condition.
People are finding to natural observation and in exploring, and the biology that occurring in nature has can obtain the ability of in the environment of extreme lack of water, surviving through the evolution of long period of time process.Bionical preparation low energy consumption, high efficiency, the eco-friendly novel material that catchments are expected to become the new way that solves the water resources shortage problem.Traditional material that catchments generally is hydrophilic fabric or the good metal of thermal conductive property.For example, Peru government borders on Pacific foggy area in the west in this state and has set up the fog gathering station for exploitation fog resource.Fog collector is processed with nylon wire, and the nylon wire support is collected the water that is obtained by fog with a big iron pan down, and every square metre of nylon wire can be collected 20 to 50 liters of fogs average every day.The Spain scientist has also invented a kind of artificial tree of being processed by polyurethane, and this polyester foam water absorbing properties is very strong, and is very big again with the contact area of mist, and it is very fast to dispel the heat, 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 begun from fog, to collect fresh water with the similar tradition material that catchments.
But the efficient of above-mentioned these catchment methods is not very high, and the cost that catchments that has is but very high, can't satisfy the needs of the people of water-deficient area to water, uses the plastics of difficult degradations such as polypropylene can work the mischief to environment again in addition in a large number.
Summary of the invention
One of the object of the invention is that to overcome the water collection efficiency of existing catchment method not high; Can't satisfy the demand of vast water-deficient area people to water; And also exist the cost height that catchments, to the disagreeableness defective of environment, based on phenomenon Study that the occurring in nature natural spider silk is catchmented; The periodicity spindle junction structure of imitation spider silk provides the polymer filament of catchmenting that a kind of water collection efficiency is high, with low cost, the spider silk structure is simply imitated in preparation.
The catchment large-scale continuous preparation method of polymer filament of the imitative spider silk structure that another object of the present invention provides purpose one.
The present invention is inspired from the phenomenon that the spider silk of occurring in nature is decorated by sparkling and crystal-clear water droplet; Through observation to the spider silk microstructure; Utilize polymer solution to apply the polymer liquid film that artificial silk forms parcel artificial silk; Afterwards the polymer liquid film develop (break) become the spindle knot, the polymer filament of catchmenting (as shown in Figure 2) of the imitative spider silk structure of the bionical thus spindle junction structure that has prepared periodic arrangement with similar spider silk.
The surface of the polymer filament of catchmenting of imitative spider silk structure of the present invention has the spindle junction structure along the periodic arrangement of the axial direction of polymer filament orientation of similar spider silk, and the spindle junction structure of this periodic arrangement makes the surface of said polymer filament obtain coarse structure.The polymer filament of catchmenting of imitative spider silk structure of the present invention is through the ordinary artificial silk being immersed in the polymer solution that the good solvent that contains polymer and poor solvent mix; Then said artificial silk axial direction level along artificial silk from said polymer solution is pulled out (said artificial silk is drawn in the rotation of motor capable of using at the uniform velocity stably); And then the surface that makes said artificial silk takes a certain amount of polymer solution out of, and the polymer solution of being taken out of is wrapped in the surface of described artificial silk and forms liquid film; Owing to Rayleigh unstability (Rayleigh instability), cause becoming a string drop to be suspended on the said artificial silk subsequently in the liquid film evolution (break) of the lip-deep polymer solution of said artificial silk; Through regulating ambient humidity and temperature; Make these polymer droplet dryings that are suspended on the described artificial silk; Thereby the structure that has formed periodic arrangement on the surface of said artificial silk is fusiform spindle knot; And these construct coarse structure along the spindle knot of the axial direction orientations of said artificial silk on the surface of described artificial silk, and then the bionical polymer filament that has prepared similar spider silk structure.
The polymer filament of catchmenting (as shown in Figure 2) of imitative spider silk structure of the present invention; Be to be coated with the one layer of polymeric film at artificial silk; And going up by the described polymer film structure that (break) go out a string periodic arrangement that develops along the axial direction of said artificial silk orientation is fusiform spindle knot; This spindle junction structure constructs coarse structure on the surface 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 preferred 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 the wire.
Described wire can be selected from a kind of in copper wire, iron wire and the nickel wire etc.
Described polymer is selected from least a in the group that polymethyl methacrylate (PMMA), polystyrene (PS), Kynoar (PVDF), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), Merlon (PC) and polyvinylpyrrolidone (PVP) etc. are formed.
Also include in the described polymer and be selected from ultra-violet stabilizer, ultra-violet absorber, ozone stabilizing agent and the anti-oxidant one or more.
Described ultra-violet stabilizer is two (2,2,6, the 6-tetramethyl-piperidyl) sebacates (commodity be called light stabilizer 770), and its content in preparing polymer solution during polymer filament of catchmenting of described imitative spider silk structure is 0.8wt%.
Described ultra-violet absorber is a 2-cyanic acid-3,3-diphenylacrylate 2-Octyl Nitrite, its in addition during polymer filament of catchmenting of the described imitative spider silk structure of preparation less than 0.3% of polymer solution weight.
Described ozone stabilizing agent is the phenol triazine, its in addition during polymer filament of catchmenting of the described imitative spider silk structure of preparation less than 0.1% of polymer solution weight.
Described anti-oxidant is 2,6-di-tert-butyl-4-methy phenol (trade name UltranoxTM226), its in addition during polymer filament of catchmenting of the described imitative spider silk structure of preparation 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 may further comprise the 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 the polymer solution is 3%～15% (the preferred mass percentage composition is 7%～11%); The quality percentage composition of poor solvent is 0.5%～3% (the preferred mass percentage composition is 1%～1.5%), and surplus is a good solvent;
(2) with step (1) be immersed in the polymer solution described artificial silk 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 ℃ (preferred temperature is 25～30 ℃) that the described artificial silk that liquid film wrapped up by described polymer solution that step (2) is obtained horizontally suspends in temperature; Carry out drying in relative humidity is 30～80% environment of (preferred relative humidity is 40～70%), 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 the one layer of polymeric film; And going up by the described polymer film structure that (break) go out a string periodic arrangement that develops along the axial direction of said artificial silk orientation is fusiform spindle knot; This spindle junction structure constructs coarse structure on the surface of described artificial silk, forms the polymer filament of catchmenting with similar spider silk structure.
Described with artificial silk along the axial direction of artificial silk at the uniform velocity stably from polymer solution level pull out; Be that a end with described artificial silk is connected with motor; Regulate the rotary speed of described motor then, utilize the rotation of motor to draw said artificial silk (as shown in Figure 1) at the uniform velocity stably.
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 preferred 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 the wire.
Described wire can be selected from a kind of in copper wire, iron wire and the nickel wire etc.
Described polymer is selected from least a in the group that polymethyl methacrylate (PMMA), polystyrene (PS), Kynoar (PVDF), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), Merlon (PC) and polyvinylpyrrolidone (PVP) etc. are formed.
Also include in the described polymer solution and be selected from ultra-violet stabilizer, ultra-violet absorber, ozone stabilizing agent and the anti-oxidant one or more.
Described ultra-violet stabilizer is two (2,2,6, the 6-tetramethyl-piperidyl) sebacates (commodity be called light stabilizer 770), and its content in preparing polymer solution during polymer filament of catchmenting of described imitative spider silk structure is 0.8wt%.
Described ultra-violet absorber is a 2-cyanic acid-3,3-diphenylacrylate 2-Octyl Nitrite, its in addition during polymer filament of catchmenting of the described imitative spider silk structure of preparation less than 0.3% of polymer solution weight.
Described ozone stabilizing agent is the phenol triazine, its in addition during polymer filament of catchmenting of the described imitative spider silk structure of preparation less than 0.1% of polymer solution weight.
Described anti-oxidant is 2,6-di-tert-butyl-4-methy phenol (trade name UltranoxTM226), its in addition during polymer filament of catchmenting of the described imitative spider silk structure of preparation less than 1.3% of polymer solution weight.
Described good solvent is selected from N, dinethylformamide (DMF), DMAC N,N (DMAc), oxolane (THF), chloroform (CHCl
3), at least a in the group formed of toluene and xylene.
Described poor solvent is selected from least a 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.Tie from single spindle; The diameter of tying the position owing to the spindle of the artificial silk that is enclosed with polymer is greater than the diameter that does not have spindle knot position; The drop Laplce pressure suffered at spindle knot position that causes condensing on the polymer filament pressed imbalance with there being the spindle knot suffered Laplce in position; And the Laplce's pressure reduction that a sensing spindle knot position occurs, this Laplce's pressure differential condense in the droplet that does not have spindle knot position and move to spindle knot position; On the other hand; Because catchmenting during polymer filament of the imitative spider silk structure of preparation; The existence of poor solvent is arranged in polymer solution; Make at desiccated surface and be enclosed with in ordinary artificial silk's the process of one layer of polymeric film; Spontaneous formation is tied the roughness at position greater than the roughness that does not have spindle knot position along the spindle of artificial silk axial direction orientation, this coarse structure is different from formed surface energy gradient and causes condensing in the drop on the artificial silk that is enclosed with polymer again, occurs difference at spindle knot position with the wettability that does not have spindle knot position; The spindle knot that hydrophilic polymer forms make spindle knot position to the compatibility of water greater than the compatibility that does not have spindle knot position to water, finally cause drop under unbalanced surface energy gradient to the position motion of spindle knot.Under the acting in conjunction of surperficial Laplce's 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 apace; And utilize fusellal fabric and surface orientation structure; With the position of the spindle knot of the drop directed transport of being caught on the polymer filament of catchmenting of said imitative spider silk structure, shown in arrow among Fig. 3; The surface of newly exposing can begin the fog transmission course of next round again, thereby has realized fog collection rapidly, continuously, shown in circle among Fig. 3.
The present invention compared with prior art, the effect that is had also is:
(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 height and collecting water from runoff are big.
(2) continuable extensiveization of the polymer filament of catchmenting of imitative spider silk structure of the present invention prepares.
(3) application operating of the polymer filament of catchmenting of imitative spider silk structure of the present invention is simple; Therefore arid foggy area such as desert, island, ocean ship and foggy mountain area and the fog in coastal area short of rain that can be applied to like the offshore area are collected, in order to collect fresh water.
(4) through in the polymer of the polymer filament of catchmenting for preparing imitative spider silk structure of the present invention, adding ultra-violet stabilizer, ultra-violet absorber, ozone stabilizing agent, anti-oxidant etc.; Make the polymer filament of catchmenting of imitative spider silk structure of the present invention be difficult for degraded; More durable, can prolong service life.
Description of drawings
Fig. 1. a kind of large-scale continuous method sketch map for preparing 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 process of the catchmenting sketch map that the polymer filament of catchmenting of the typical imitative spider silk structure for preparing in the embodiment of the invention 1 places fog to take place.
The specific embodiment
Further the present invention will be described below in conjunction with embodiment, but used concrete material and consumption and other process conditions should not be regarded as limitation of the present invention among the cited embodiment.The sign of the ability of catchmenting of the polymer filament of catchmenting of the imitative spider silk structure among the embodiment is on the Dataphysics OCA40 video contact angle measurement that Germany produces, to carry out; The YADU ultrasonic humidifier (35W) that fog atmosphere is produced by Beijing provides; Polymer P MMA, PS, PVDF, PVAc, PVA, PC, PVP are available from the chemical Co., Ltd of A Faaisha (Tianjin); Good solvent DMF, DMAc, THF, CHCl
3, toluene, xylene, and poor solvent ethanol, acetone, methyl alcohol, isopropyl alcohol, espeleton are all available from Beijing chemical reagents corporation.The artificial silk of using among the embodiment is available from the chemical fibre Co., Ltd in nine divisions of China in remote antiquity, Nantong.
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; The 6-tetramethyl-piperidyl) mass fraction of sebacate is the DMF of 3% PMMA and the mixed solution of water, and wherein ultra-violet stabilizer two (2,2; 6; The 6-tetramethyl-piperidyl) mass fraction of sebacate in the mixed solution of the DMF of PMMA and water is 0.8wt%, and the mass fraction of water in the mixed solution of the DMF of PMMA and water is 0.5wt%, and surplus is DMF;
(2) with diameter be the artificial nylon fiber of 10 μ m be submerged into fully that step (1) obtains contain ultra-violet stabilizer two (2; 2,6,6-tetramethyl-piperidyl) mass fraction of sebacate is in the mixed solution of DMF and water of 3% PMMA; The rotary speed of the motor that adjusting nylon fiber one end is connected; 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 liquid film wrapped up of the mixed solution of the DMF of the PMMA of sebacate and water;
(3) quilt that step (2) is obtained contains ultra-violet stabilizer two (2; 2; 6; The 6-tetramethyl-piperidyl) to horizontally suspend in temperature be 10 ℃ to the nylon fiber that liquid film wrapped up of the mixed solution of the DMF of the PMMA of sebacate and water, and relative humidity is dry in 30% the 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 go up by the described PMMA film structure that a string periodic arrangement that develops along the axial direction of said artificial nylon fiber orientation and to be fusiform spindle knot, as shown in Figure 2; And because the existence of poor solvent water; In dry run; The spontaneous formation of this spindle junction structure constructs coarse structure along the axial direction orientation of nylon fiber on the surface of described artificial nylon fiber, 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, apace from fog, as shown in Figure 3.
The PMMA fiber that catchments that gained is had the imitative spider silk structure of PMMA spindle knot places the fog atmosphere of the YADU ultrasonic humidifier simulation of Beijing product; The Dataphysics OCA40 video contact angle measurement that utilizes Germany to produce is to the catchment sign of ability of the PMMA fiber that catchments of the imitative spider silk structure with PMMA spindle knot of gained.At the fog flow velocity is under the situation of about 75cm/s, the collecting water from runoff of every meter 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 anti-oxidant 2; The mass fraction of 6-di-tert-butyl-4-methy phenol is the DMAc of 15% PS and the mixed solution of ethanol; Wherein anti-oxidant 2; The addition of 6-di-tert-butyl-4-methy phenol be PS DMAc and ethanol mixed solution weight 1.2%, the mass fraction of ethanol in the mixed solution of the DMAc of PS and ethanol is 3wt%, surplus is DMAc;
(2) with diameter be the artificial polypropylene fiber of 1000 μ m be submerged into fully that step (1) obtains contain anti-oxidant 2; The mass fraction of 6-di-tert-butyl-4-methy phenol is in the mixed solution of DMAc and ethanol of 15% PS; The rotary speed of the motor that adjusting polypropylene fiber one end is connected; 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 anti-oxidant 2, the polypropylene fiber that liquid film wrapped up of the DMAc of the PS of 6-di-tert-butyl-4-methy phenol and the mixed solution of ethanol;
(3) quilt that step (2) is obtained contains anti-oxidant 2; It is 40 ℃ that the polypropylene fiber that liquid film wrapped up of the DMAc of the PS of 6-di-tert-butyl-4-methy phenol and the mixed solution of ethanol horizontally suspends in temperature; Relative humidity is dry in 80% the 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 go up by the described PS film structure that a string periodic arrangement that develops along the axial direction of said artificial polypropylene fiber orientation and to be fusiform spindle knot, as shown in Figure 2; And because the existence of poor solvent ethanol; In dry run; The spontaneous formation of this spindle junction structure constructs coarse structure along the axial direction orientation of polypropylene fiber on the surface of described artificial polypropylene fiber, 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, apace from fog.
The PS fiber that catchments that gained is had the imitative spider silk structure of PS spindle knot places the fog atmosphere of the YADU ultrasonic humidifier simulation of Beijing product; The Dataphysics OCA 40 video contact angle measurements that utilize Germany to produce are to the catchment sign of ability of the PS fiber that catchments of the imitative spider silk structure with PS spindle knot of gained.At the fog flow velocity is under the situation of about 75cm/s, the collecting water from runoff of every meter 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 anti-oxidant 2; 6-di-tert-butyl-4-methy phenol, ultra-violet absorber 2-cyanic acid-3, the mass fraction of 3-diphenylacrylate 2-Octyl Nitrite are the THF of 9% PVDF and the mixed solution of acetone; Wherein anti-oxidant 2; The addition of 6-di-tert-butyl-4-methy phenol be PVDF THF and acetone mixed solution weight 0.8%, ultra-violet absorber 2-cyanic acid-3, the addition of 3-diphenylacrylate 2-Octyl Nitrite be PVDF THF and acetone mixed solution weight 0.2%; The mass fraction of acetone in the mixed solution of the THF of PVDF and acetone is 1.5wt%, and surplus is THF;
(2) with diameter be the artificial spandex fibre of 200 μ m be submerged into fully that step (1) obtains contain anti-oxidant 2; 6-di-tert-butyl-4-methy phenol, ultra-violet absorber 2-cyanic acid-3; The mass fraction of 3-diphenylacrylate 2-Octyl Nitrite is in the mixed solution of THF and acetone of 9% PVDF; The rotary speed of the motor that adjusting spandex fibre one end is connected; 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 anti-oxidant 2,6-di-tert-butyl-4-methy phenol, ultra-violet absorber 2-cyanic acid-3, the spandex fibre that liquid film wrapped up of the THF of the PVDF of 3-diphenylacrylate 2-Octyl Nitrite and the mixed solution of acetone;
(3) quilt that step (2) is obtained contains anti-oxidant 2; 6-di-tert-butyl-4-methy phenol, ultra-violet absorber 2-cyanic acid-3; It is 20 ℃ that the spandex fibre that liquid film wrapped up of the THF of the PVDF of 3-diphenylacrylate 2-Octyl Nitrite and the mixed solution of acetone horizontally suspends in temperature; Relative humidity is dry in 50% the 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 to go up by the described pvdf membrane structure that a string periodic arrangement that develops along the axial direction of said artificial spandex fibre orientation be fusiform spindle knot; And because the existence of poor solvent acetone; In dry run; The spontaneous formation of this spindle junction structure constructs coarse structure along the axial direction orientation of spandex fibre on the surface of described artificial spandex fibre, 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, apace from fog.
The PVDF fiber that catchments that gained is had the imitative spider silk structure of PVDF spindle knot places the fog atmosphere of the YADU ultrasonic humidifier simulation of Beijing product; The Dataphysics OCA 40 video contact angle measurements that utilize Germany to produce are to the catchment sign of ability of the PVDF fiber that catchments of the imitative spider silk structure with PVDF spindle knot of gained.At the fog flow velocity is under the situation of about 75cm/s, the collecting water from runoff of every meter 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) the preparation mass fraction is the CHCl of 10% PVAc
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) be that artificial carbon's fiber of 100 μ m is submerged into the CHCl that mass fraction that step (1) obtains is 10% PVAc fully with diameter
3In the mixed solution of methyl alcohol, regulate the rotary speed of the motor that carbon fiber one end connected, 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 CHCl by PVAc
3The carbon fiber that liquid film wrapped up with the mixed solution of methyl alcohol;
(3) the CHCl that step (2) is obtained by PVAc
3Horizontally suspending in temperature with the carbon fiber that liquid film wrapped up of the mixed solution of methyl alcohol is 40 ℃, and relative humidity is dry in 60% the environment, 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 to go up by the described PVAc film structure that a string periodic arrangement that develops along the axial direction of said artificial carbon's fiber orientation be fusiform spindle knot; And because the existence of poor solvent methyl alcohol; In dry run; The spontaneous formation of this spindle junction structure constructs coarse structure along the axial direction orientation of carbon fiber on the surface of described artificial carbon's fiber, 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, apace from fog.
The PVAc fiber that catchments that gained is had the imitative spider silk structure of PVAc spindle knot places the fog atmosphere of the YADU ultrasonic humidifier simulation of Beijing product; The Dataphysics OCA 40 video contact angle measurements that utilize Germany to produce are to the catchment sign of ability of the PVAc fiber that catchments of the imitative spider silk structure with PVAc spindle knot of gained.At the fog flow velocity is under the situation of about 75cm/s, the collecting water from runoff of every meter 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) the preparation mass fraction is the toluene of 11% PVA and the mixed solution of isopropyl alcohol, and wherein the mass fraction of isopropyl alcohol in the mixed solution of the toluene of PVA and isopropyl alcohol is 2.5wt%, and surplus is a toluene;
(2) be that the man-made vitreous fibres of 500 μ m is submerged in the mixed solution of toluene that mass fraction that step (1) obtains is 11% PVA and isopropyl alcohol fully with diameter; The rotary speed of the motor that adjusting glass fibre one end is connected; 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 liquid film wrapped up by the mixed solution of the toluene of PVA and isopropyl alcohol;
(3) it is 25 ℃ that the glass fibre that liquid film wrapped up by the mixed solution of the toluene of PVA and isopropyl alcohol that step (2) is obtained horizontally suspends in temperature; Relative humidity is dry in 50% the 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 to go up by the described PVA film structure that a string periodic arrangement that develops along the axial direction of said man-made vitreous fibres orientation be fusiform spindle knot; And because the existence of poor solvent isopropyl alcohol; In dry run; The spontaneous formation of this spindle junction structure constructs coarse structure along the axial direction orientation of glass fibre on the surface of described man-made vitreous fibres, 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, apace from fog.
The PVA fiber that catchments that gained is had the imitative spider silk structure of PVA spindle knot places the fog atmosphere of the YADU ultrasonic humidifier simulation of Beijing product; The Dataphysics OCA 40 video contact angle measurements that utilize Germany to produce are to the catchment sign of ability of the PVA fiber that catchments of the imitative spider silk structure with PVA spindle knot of gained.At the fog flow velocity is under the situation of about 75cm/s, the collecting water from runoff of every meter 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) the preparation mass fraction is the xylene of 13% PC and the mixed solution of espeleton, and wherein the mass fraction of espeleton in the mixed solution of the xylene of PC and espeleton is 3wt%, and surplus is an xylene;
(2) be that the metal copper wire of 300 μ m is submerged in the mixed solution of xylene that mass fraction that step (1) obtains is 13% PC and espeleton fully with diameter; The rotary speed of the motor that adjusting metal copper wire one end is connected; Make the 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 liquid film wrapped up by the mixed solution of the xylene of PC and espeleton;
(3) it is 30 ℃ that the metal copper wire that liquid film wrapped up by the mixed solution of the xylene of PC and espeleton that step (2) is obtained horizontally suspends in temperature; Relative humidity is dry in 40% the 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 the metal copper wire; It is coated with one deck PC film, and to go up by the described PC film structure that a string periodic arrangement that develops along the axial direction of said metal copper wire orientation be fusiform spindle knot; And because the existence of poor solvent espeleton; In dry run; The spontaneous formation of this spindle junction structure constructs coarse structure along the axial direction orientation of metal copper wire on the surface of described metal copper wire, 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, apace from fog.
The PC fiber that catchments that gained is had the imitative spider silk structure of PC spindle knot places the fog atmosphere of the YADU ultrasonic humidifier simulation of Beijing product; The Dataphysics OCA 40 video contact angle measurements that utilize Germany to produce are to the catchment sign of ability of the PC fiber that catchments of the imitative spider silk structure with PC spindle knot of gained.At the fog flow velocity is under the situation of about 75cm/s, the collecting water from runoff of every meter individual thread be 1.5 to 12.3 milliliters per hour.
Claims (15)
1. the polymer filament of catchmenting of an imitative spider silk structure; It is characterized in that: the polymer filament of catchmenting of described imitative spider silk structure is to be coated with the one layer of polymeric film at artificial silk; And going up by the described polymer film structure that a string periodic arrangement that develops along the axial direction of said artificial silk orientation is fusiform spindle knot; This spindle junction structure constructs coarse structure on the surface of described artificial silk, forms the polymer filament of catchmenting with spider silk structure.
2. the polymer filament of catchmenting of imitative spider silk structure according to claim 1 is characterized in that: the diameter of described artificial silk is 10 μ m～1000 μ m.
3. the polymer filament of catchmenting of imitative spider silk structure according to claim 1 and 2 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 the wire.
4. the polymer filament of catchmenting of imitative spider silk structure according to claim 1 is characterized in that: described polymer is selected from least a in the group that polymethyl methacrylate, polystyrene, Kynoar, polyvinyl acetate, polyvinyl alcohol, Merlon and polyvinylpyrrolidone form.
5. according to the polymer filament of catchmenting of claim 1 or 4 described imitative spider silk structures, it is characterized in that: include in the described polymer and be selected from ultra-violet stabilizer, ultra-violet absorber, ozone stabilizing agent and the anti-oxidant one or more.
6. the polymer filament of catchmenting of imitative spider silk structure according to claim 5; It is characterized in that: described ultra-violet stabilizer is two (2; 2; 6,6-tetramethyl-piperidyl) sebacate, its content in polymer solution during polymer filament of catchmenting of the described imitative spider silk structure of preparation is 0.8wt%;
Described ultra-violet absorber is a 2-cyanic acid-3,3-diphenylacrylate 2-Octyl Nitrite, its in addition during polymer filament of catchmenting of the described imitative spider silk structure of preparation less than 0.3% of polymer solution weight;
Described ozone stabilizing agent is the phenol triazine, its in addition during polymer filament of catchmenting of the described imitative spider silk structure of preparation less than 0.1% of polymer solution weight;
Described anti-oxidant is 2, the 6-di-tert-butyl-4-methy phenol, its in addition during polymer filament of catchmenting of the described imitative spider silk structure of preparation less than 1.3% of polymer solution weight.
7. preparation method according to the polymer filament of catchmenting of any described imitative spider silk structure of claim 1～6 is characterized in that this method may further comprise the 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 the polymer solution is 3%～15%, and the quality percentage composition of poor solvent is 0.5%～3%, and surplus is a good solvent;
(2) with step (1) be immersed in the polymer solution described artificial silk 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 that step (2) is obtained horizontally suspends in temperature; Relative humidity is to carry out drying in 30～80% the environment; Obtain being coated with the one layer of polymeric film at artificial silk; And going up by the described polymer film structure that a string periodic arrangement that develops along the axial direction of said artificial silk orientation is fusiform spindle knot; This spindle junction structure constructs coarse structure on the surface of described artificial silk, forms the polymer filament of catchmenting with spider silk structure;
Described good solvent is selected from N, at least a in the group that dinethylformamide, DMAC N,N, oxolane, chloroform, toluene and xylene are formed;
Described poor solvent is selected from least a in the group that ethanol, water, acetone, methyl alcohol, isopropyl alcohol and espeleton form.
8. preparation method according to claim 7 is characterized in that: the quality percentage composition of the polymer in the described polymer solution is 7%～11%, and the quality percentage composition of poor solvent is 1%～1.5%, and surplus is a good solvent.
9. preparation method according to claim 7; It is characterized in that: described with artificial silk along the axial direction of artificial silk at the uniform velocity stably from polymer solution level pull out; Be that a end with described artificial silk is connected with motor; Regulate the rotary speed of described motor then, utilize the rotation of motor to draw said artificial silk at the uniform velocity stably.
10. according to claim 7 or 9 described preparation methods, it is characterized in that: the described artificial silk speed that level is pulled out from polymer solution is 1～14mm/s.
11. preparation method according to claim 7 is characterized in that: the diameter of described artificial silk is 10 μ m～1000 μ m.
12. according to claim 7 or 11 described preparation methods, it 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 the wire.
13. preparation method according to claim 7 is characterized in that: described polymer is selected from least a in the group that polymethyl methacrylate, polystyrene, Kynoar, polyvinyl acetate, polyvinyl alcohol, Merlon and polyvinylpyrrolidone form.
14., it is characterized in that: include in the described polymer and be selected from ultra-violet stabilizer, ultra-violet absorber, ozone stabilizing agent and the anti-oxidant one or more according to claim 7 or 13 described preparation methods.
15. preparation method according to claim 14; It is characterized in that: described ultra-violet stabilizer is two (2,2,6; The 6-tetramethyl-piperidyl) sebacate, its content in polymer solution during polymer filament of catchmenting of the described imitative spider silk structure of preparation is 0.8wt%;
Described ultra-violet absorber is a 2-cyanic acid-3,3-diphenylacrylate 2-Octyl Nitrite, its in addition during polymer filament of catchmenting of the described imitative spider silk structure of preparation less than 0.3% of polymer solution weight;
Described ozone stabilizing agent is the phenol triazine, its in addition during polymer filament of catchmenting of the described imitative spider silk structure of preparation less than 0.1% of polymer solution weight;
Described anti-oxidant is 2, the 6-di-tert-butyl-4-methy phenol, its in addition during polymer filament of catchmenting of the described imitative spider silk structure of preparation less than 1.3% of polymer solution weight.
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