Background technology
How electrospinning for producing one of rice fiber (Nanofibers) manufacturing technology, its principle mainly is to remove to overcome the surface tension and the viscosity of Polymer Solution with the electric field driven power between positive and negative electrode, after being aided with Polymer Solution process nozzle (Spinneret) ejection, because of being with electrical and mutually exclusive, after solvent evaporates, can get superfine fiber, so also be called electrospinning silk (Electrospinning Fibers).Traditional spun fibre fineness approximate number micron of textile technology, yet the fiber of being produced with electrospinning are because of also add electrostatic force except mechanicals efforts in the forming process of macromolecule filament, so can reach the purpose of fibrous refinement.And, with the spun cloth of electrospinning method greater porosity being arranged, surface area is big, and is therefore little than conventional fabrics, thereby favored.
In No. the 6th, 616,435, United States Patent (USP) notification number, disclose a kind of technology of utilizing the electrospinning silk to finish the high score subnet, its electric spinning equipment comprises storage cylinder, wherein places more than one liquid macroimolecule material at least; Pump can pressurize and provide the liquid macroimolecule material; Spinning portion has many group packaged type nozzles, provides the liquid macroimolecule material to spinning portion by pump, and the nozzle of self-rechargeable sprays the liquid macroimolecule material and makes fine fibre; The high-voltage power device, charged through nozzle the time so as to making macromolecular material; And collecting electrode, can collect fine fibre and be combined into polymer web.This electric spinning equipment cooperates the plane conveyer belt simultaneously, can possess the young production capacity that quantizes.
At United States Patent (USP) notification number the 6th, 110, in No. 590, disclose a kind of how rice fibrous reticular structure of natural silk Nonwovens, wherein in hexafluoroisopropanol (Hexafluroisopropanol), the silk solution concentration accounts for about 0.2 to 1.5 percentage by weight (wt%), and how the fineness of rice fiber between 2 to 2000 rice (Nanometer how; Nm), mainly provide medical.
In No. the 2003/0211135th, Application No., disclose a kind of X-Y axle moving nozzle mode of utilizing, the production fineness is less than 100 microns laminated film fiber web, and its product can be used for fuel cell, medical material etc.
In brief, systematic parameter by the regulation and control electric spinning equipment, as the molecular weight of Polymer Solution, viscosity, electrical conductivity, surface tension etc., and control manipulation parameter, such as humiture of current potential, Polymer Solution flow, polar plate spacing and the operating environment of discharge electrode etc., can prepare the macromolecule filament of different fineness size.Yet said nozzle is many with reciprocating type mobile formation polymer web, but problem of uneven distribution is easily arranged.See also Fig. 1, it is the track schematic diagram of existing nozzle on carrier.Whennozzle 101 sprays the macromolecule filament with reciprocating, carrier is to advance with the direct oftravel 109 perpendicular to the nozzle moving direction, therefore formed WEB is closeer in the macromolecule filament distribution at regional M place, and the distribution of the macromolecule filament outside regional M is thinner.See also Fig. 2, it is the track schematic diagram of existing another nozzle on carrier.Whennozzle 101 sprays the macromolecule filament with reciprocating equally, carrier is to advance with the direct oftravel 109 perpendicular to the nozzle moving direction, therefore formed WEB is closeer in the macromolecule filament distribution at regional N place, and the distribution of the macromolecule filament outside regional N is thinner.
Except the above-mentioned macromolecule screen cloth of being produced for the 6th, 616, No. 435 with the United States Patent (USP) notification number has problem of uneven distribution, other technologies have the slow problem of throughput rate.For example, the 6th, 110, No. 590 breadboard test boards that are disclosed as of United States Patent (USP) notification number are not had continous mode production capacity.Secondly, the board that No. the 2003/0211135th, Application No., for reaching uniform requirement, speed of production is slow.Moreover, the macromolecule filament of producing with above-mentioned each technology when carrying out the production of follow-up polymer web, can't satisfy simultaneously fineness little, be evenly distributed, and increase the demand of throughput rate.
Therefore be necessary to provide the manufacture method of a kind of electric spinning equipment and macromolecule filament, wait problem slowly with skewness and the throughput rate that solves existing macromolecule filament.
Summary of the invention
One of purpose of the present invention is exactly to disclose a kind of electric spinning equipment, this electric spinning equipment utilizes rotary bogey, because the distance between the outlet of the Polymer Solution of this rotary bogey can be adjusted arbitrarily, and outlet is to move with non-linear track, so as to making the macromolecule filament form uniform WEB, this electric spinning equipment more can be provided with transport, produces uniform WEB so as to continous mode or batch, thereby the skewness and the throughput rate that overcome existing macromolecule filament wait problem slowly.
Another object of the present invention discloses a kind of rotating nozzle mechanism exactly, be applicable to electric spinning equipment, wherein this rotating nozzle mechanism moves with non-linear track, borrow to make the macromolecule filament on received vector, form uniform WEB, thereby overcome the skewness problem of existing macromolecule filament with any receiving angle.
Propose a kind of electric spinning equipment according to an aspect of the present invention, comprise: at least one rotary bogey, this rotary bogey has at least one outlet, wherein is provided with discharge electrode in this outlet and imports Polymer Solution with pipeline; And collecting electrode, this collecting electrode is the below of being located at above-mentioned rotary bogey, and has the surface in the face of above-mentioned outlet; When applying a voltage to discharge electrode, Polymer Solution is via outlet ejection and form many charged macromolecule filaments and be gathered in the received vector of collecting electrode top, simultaneously received vector is that to advance and export with a direction be to move with non-linear track, forms WEB whereby on the surface of received vector.
According to a preferred embodiment of the present invention, above-mentioned bogey can be at least one trailing arm or flat board.
According to a preferred embodiment of the present invention, above-mentioned non-linear track can for example be circular trace, elliptical path or waveform track.
According to a preferred embodiment of the present invention, an end of above-mentioned rotating shaft also is the center with the other end, carries out gyration synchronously so as to being the inclination angle with vertical direction, or fixes an angle and spray the macromolecule filament.
According to a preferred embodiment of the present invention, the spacing of being separated by between the said nozzle, the wherein movable adjustment of this spacing and be less than or equal to the length of bogey.
According to a preferred embodiment of the present invention, the shape of above-mentioned collecting electrode can for example be disc, annular, ellipse, rectangle, solid figure or its above-mentioned combination.
Propose a kind of rotating nozzle mechanism according to a further aspect of the invention, be applicable to electric spinning equipment, this rotating nozzle mechanism comprises at least: rotating shaft, this rotating shaft are to carry out spin motion around self axis; And at least one bogey is to be hubbed at rotating shaft one end, and bogey has at least one outlet, and this outlet is electrically connected to discharge electrode, and imports Polymer Solution with pipeline; When applying a voltage to discharge electrode, Polymer Solution is via outlet ejection and form many charged macromolecule filaments and be gathered in the received vector of collecting electrode top, simultaneously received vector is that to advance and export with a direction be to move with non-linear track, forms WEB whereby on the surface of received vector.
Using above-mentioned electric spinning equipment and make the macromolecule filament, is to utilize rotating nozzle mechanism to move with non-linear track, forms uniform WEB with any receiving angle so as to making superfineization macromolecule filament on received vector.The fineness that can overcome existing macromolecule filament like this is thick, skewness and throughput rate wait problem slowly.
The specific embodiment
The invention provides a kind of electric spinning equipment, it is to utilize rotating nozzle mechanism to move with non-linear track, forms uniform WEB with any receiving angle so as to making superfineization macromolecule filament on received vector.Use the manufacturing technique that above-mentioned electric spinning equipment carries out the macromolecule filament in order to further specify, the present invention is the manufacturing technique that discloses a kind of macromolecule filament, sees also Fig. 3, and it is the manufacturing process flow diagram of the macromolecule filament of a preferred embodiment of the present invention.At first, shown instep 151, provide rotating nozzle mechanism, this rotating nozzle mechanism is located in the electric spinning equipment, and comprises the end that the rotating shaft that can spin, at least one bogey are hubbed at rotating shaft at least, and bogey has at least one outlet.In another example, at least one rotary bogey also can be provided, this rotary bogey also can be located in the electric spinning equipment and have at least one outlet.Be provided with discharge electrode in the above-mentioned outlet and import Polymer Solution, and rotating shaft can carry out spin motion around self axis with pipeline.Then, shown instep 153, apply a voltage to discharge electrode, make Polymer Solution via outlet ejection and form many charged macromolecule filaments and be gathered in the received vector of collecting electrode top, the while received vector advances with a direction and nozzle is to move with non-linear track, form WEB whereby on the surface of received vector, and shown instep 155.
From the above, below cooperate Fig. 4 to Figure 14 to describe electric spinning equipment of the present invention in detail.See also Fig. 4, it is the side schematic view of the electric spinning equipment of a preferred embodiment of the present invention.Electric spinning equipment 200 comprises rotatingnozzle mechanism 210 at least, and wherein this rotatingnozzle mechanism 210 comprises rotatingshaft 211 at least, and this rotatingshaft 211 is that theaxis 213 around rotatingshaft 211 carries out spin motion with the direction of for example arrow 215.Thebogey 221 for example mid point of trailing arm is an end that is hubbed at rotating shaft 211.Another kind of mode,bogey 221 also can be a plurality of trailing arms are hubbed at rotatingshaft 211 separately with mid point same end, and this is in describing in detail after a while.Have at least one outlet on thebogey 221, its middle outlet can for example be spout or outlet (Outlet), and this outlet can be located on thebogey 221 by forexample nozzle 231 activities.Nozzle 231 is electrically connected todischarge electrode 233, and imports Polymer Solution withpipeline 241 by PolymerSolution accumulator tank 251.
In Fig. 4, the below of rotatingnozzle mechanism 210 is provided with collectingelectrode 271, collectingelectrode 271 generally is to be electrically connected to earth terminal, when utilizinghigh voltage source 261 to apply a voltage to thedischarge electrode 233 ofnozzle 231,discharge electrode 233 can form electric field with collectingelectrode 271, make the moment ofPolymer Solution 251, can form chargedmany macromolecule filaments 277 and assemble towards the direction of collectingelectrode 271 vianozzle 231 ejection.Collectingelectrode 271 can have the accumulation of exhausting air-flow guide hole (not shown) with guidingmacromolecule filament 277 in the face of the surface of rotating nozzle mechanism 210.Exhausting air-flow guide hole can be provided by a works, and wherein this works can for example be hollow and have a plurality of holes, and the material of this works can for example be metal or containing metal fabric.
As shown in Figure 4, the preset height H place of collectingelectrode 271 tops also is provided with receivedvector 273, and thesurface 275 of this receivedvector 273 is that wherein preset height H is between 0 to 1 meter in order to reception macromolecule filament 277.The received vector material that the present invention uses is not limit, and looks closely demand and decides.In addition, thesurface 275 of receivedvector 273 can for example be plane or three-dimensional face, and receivedvector 273 can have or do not have a hole.Macromoleculefilament 277 is after forming WEB on the receivedvector 273, in drying at room temperature.Because the hole that WEB stays is minimum, can be used as for example high efficiency filter material usefulness.For example, when thesurface 275 of receivedvector 273 is the plane, can be used for making plane face mask, filter net sheet etc.When thesurface 275 of receivedvector 273 is three-dimensional face, can be used for making three-dimensional mask, filtering element (cartridge), give birth to doctor's material etc.
Electric spinning equipment 200 of the present invention also can utilizetransport 280 to carry receivedvector 273 continuously with the direction of arrow 295.Configuration as shown in Figure 4,transport 280 comprises runner 281, runner 283, runner 285, runner 287,rolling wheel 289 and runner 291 at least, wherein runner 281 is in order to place the receivedvector 273 of whole winding shape,runner 283, runner 285 andforaminous conveyer 293 are in order to guide receivedvector 273 to receivemacromolecule filament 277 to collectingelectrode 271 tops with the direction ofarrow 295, to form WEB on thesurface 275 of received vector 273.Depend on the circumstances then, also can utilizerolling wheel 289lining 297 to be fitted on the receivedvector 273 with WEB,, wherein can utilizerunner 287 to place thelining 297 of whole winding shape to form combined filtration material 299.Then, the combinedfiltration material 299 that makes utilizesrunner 291 to take in immediately.Electric spinning equipment 200 of the present invention is because of havingtransport 280, thus can carry out continous mode or batch production, to reach the young demand of producing of quantizing.
See also Fig. 5, it is the profile along Fig. 4 section line AA ' gained.In one embodiment of this invention, can utilize support 300 fixing rotary nozzle mechanisms 210.Support 300 comprises top 301 at least and is used for supporting the pillar 303 on top 301, its middle and upper part 301 can be used to fixingrotary nozzle mechanism 210, and can be provided with the movable Polymer Solution accumulator tank of adjusting 251 on the pillar 303, and pillar 303 can be designed to movable being beneficial to and moves.PolymerSolution accumulator tank 251 is to be connected tonozzle 231 with pipeline (figure does not show).On top 301, also can be provided with motor 305, be used for driving the rotatingshaft 211 of rotatingnozzle mechanism 210, make rotatingshaft 211 can carry out above the rotatablely moving of one degree of freedom.
In Fig. 5, an end and the other end of thebogey 221 that articulates with rotatingshaft 211 are movably equipped withnozzle 231 respectively, the spacing d of being separated by between thenozzle 231, the wherein visual demand of spacing d and freely adjusting.For example, spacing d is the length D that is less than or equal to bogey 221.In addition, can be provided with air pressure mouth 235 atbogey 221 and the following of rotatingshaft 211 junctions, wherein air pressure mouth 235 in right amount Compressed Gas with the rate of extrusion of adjustment macromolecule filament.
In a preferred embodiment of the present invention,nozzle 231 can only be located at an end ofbogey 221, and drives and be rotated motion by rotatingshaft 211 with the direction ofarrow 215, and forms upward view as shown in Figure 6.In another embodiment,nozzle 231 can be located at two ends ofbogey 221 respectively, and drives and be rotated motion by rotatingshaft 211 with the direction ofarrow 215, and forms upward view as shown in Figure 7.In another embodiment, rotating nozzle mechanism can utilize twobogeys 221, andnozzle 231 can be located at two ends ofbogey 221 respectively, and is driven with the direction ofarrow 215 and carried out rotatablely moving of twobogeys 221 by rotatingshaft 211, and forms structure as shown in Figure 8.In like manner can push away, rotating nozzle mechanism also can utilize threebogeys 221 or fourbogeys 221, and drive with the direction ofarrow 215 and be rotated motion by rotatingshaft 211, and respectively as Fig. 9 and structure shown in Figure 10.Yet person skilled in the art scholar is understandable that, the configuration of above-mentioned rotating nozzle mechanism is only for illustrating, and nozzle of the present invention and bogey quantity and configuration thereof are not limited thereto.For example,bogey 221 of the present invention also can be the flat board of Any shape except that can be trailing arm, and the nozzle activity is located on this flat bogey.
What deserves to be mentioned is; rotating nozzle of thepresent invention mechanism 210 can carry out above the rotatablely moving of one degree of freedom; makingnozzle 231 be able to non-linear track moves; wherein non-linear track is circular trace, elliptical path or waveform track etc. for example, and prevents the beading phenomenon that the macromolecule filament is produced in the existing manufacturing technique with gravity effect and centrifugal force simultaneously.Please consult Fig. 4 again, the rotatingshaft 211 of rotatingnozzle mechanism 210 is to carry out spin motion aroundaxis 213 with the direction of forexample arrow 215, and itsaxis 213 is to become vertical.See also Figure 11, it is the rotating nozzle mechanism of another preferred embodiment of the present invention.The rotatingshaft 211 of rotatingnozzle mechanism 210 is that theaxis 213 around rotatingshaft 211 carries out spin motion with the direction of forexample arrow 215, simultaneouslyaxis 213 also can carry out spin motion with the direction that vertical line 217 is tiltangle, evenaxis 213 also can be tiltangle with vertical line 217 and carry out gyration synchronously with the direction ofarrow 218, and wherein this inclination angle can be between 0 degree between 90 degree.When the received vector of Fig. 4 or the 210 continuous conveyings in cooperation below of the illustrative rotating nozzle of Figure 11 mechanism carries out the manufacturing of macromolecule filament; macromolecule filament bynozzle 231 ejections will present circular trace for example shown in Figure 12 or elliptical path on carrier, or waveform track as shown in figure 13.
Rotating nozzle of the present invention mechanism utilizes gravity, electrostatic force and centrifugal force, makes the macromolecule filament fineness of being produced thinner, and approximately between 2 to 2000 how between the rice, and its macromolecule filament ground is heavy more than or equal to 0.3g/m2.
In above-mentioned example, can adjust the angle of inclination of rotating nozzle of thepresent invention mechanism 210 arbitrarily, make the macromolecule filament with any receiving angle, for example level, vertical or any angle, and on received vector, form uniform WEB.In another example, also can adjust the configuration of receivedvector 273 and thetransport 280 of Fig. 4, make receivedvector 273 with any receiving angle, for example level, vertical or any angle makemacromolecule filament 277 be received on the receivedvector 273 and form uniform WEB.
By the way, the organic solvent in the macromolecule filament of the present invention manufacturing also can recycle via solvent reclaimer, to meet existing environmental protection requirement.See also Figure 14, it is the schematic diagram of the solvent reclaimer of a preferred embodiment of the present invention.Macromolecule filament of the present invention manufacturing can be carried out in for example airtightmanufacturing process chamber 400, produces the waste gas that contains organic solvent in the manufacture process, can be delivered to byairduct 411 according to the direction ofarrow 401 and carry out condensation in the condensing unit 420.Can be provided withflusher 421 in thecondensing unit 420, can with exhaust gas utilization for example steam carry out condensation, and produce thewaste water 423 that contains organic solution.Waste gas after the condensation process can be delivered to gas-filteringdevice 430 byblast pipe 427 according to the direction of arrow 425.In gas-filtering device 430, the condensedfluid 435 that the waste gas after the condensation process still can produce part is recycled in thecondensing unit 420 via pipeline 437.Waste gas is again through the adsorption filtration offilter bed 433, and just becoming cleanedair 440 can directly be discharged in the atmosphere.
Below cooperate several embodiment, to illustrate the manufacture method of electric spinning equipment of the present invention and macromolecule filament.
Embodiment one
The bogey two ends of the rotating nozzle mechanism of electric spinning equipment have nozzle, wherein can utilize as No. 20 syringe needles as nozzle, and the preset height H of collecting electrode and received vector for example are 40 centimetres.The coiling speed of plane received vector is that per minute is less than 1 meter.Polymer Solution is polyacrylonitrile (Polyacrylonitrile for example; PAN) with dimethyl formamide (Dimethyl Formamide; DMF) ratio between 15 to 25 percentage by weights, yet being preferable between 15 to 20 percentage by weights.Wherein the relation of the ratio of polyacrylonitrile (PAN) and dimethyl formamide (DMF) and viscosity is shown in table 1:
Table 1
| PAN/DMF (g/ml) | Concentration (wt%) | Viscosity (cp) |
| 15/100 20/100 25/100 | 15 20 25 | 4250 12000 48000 |
At the voltage that applies about 40 kilovolts (kV) behind discharge electrode, the WEB that the macromolecule filament forms on the plane received vector and in drying at room temperature, wherein the fibre fineness of macromolecule filament is less than 0.8 micron, the macromolecule filament the speed of service of 60 centimetres of fabric widths be per minute greater than 30 centimetres, and the extruded velocity of Polymer Solution is that per minute is less than 5 milliliters.
Embodiment two
The bogey two ends of the rotating nozzle mechanism of electric spinning equipment have nozzle, wherein can utilize as No. 20 syringe needles as nozzle, and the preset height H of collecting electrode and received vector for example are 40 centimetres.The coiling speed of tubular type received vector is that per minute is 200 commentaries on classics.The Polymer Solution for example ratio of polyacrylonitrile (PAN) and dimethyl formamide (DMF) is about 15 percentage by weights.
At the voltage that applies about 40 kilovolts behind discharge electrode, the WEB that the macromolecule filament forms on the tubular type received vector and in drying at room temperature, wherein the fibre fineness of macromolecule filament is less than 0.8 micron, the extruded velocity of Polymer Solution is 5 milliliters of per minutes, and the macromolecule filament is about 4.7 centimetres an of per minute in the speed of service of 60 centimetres of fabric widths.Above-mentioned is the speed of service when producing the macromolecule filament with the single tube Polymer Solution.When carrying out young bird quantification production, also can utilize the multitube Polymer Solution to produce the macromolecule filament.For example, when utilizing 8 pipe Polymer Solutions to produce the macromolecule filament, the macromolecule filament can reach about 37.6 centimetres of per minute in the speed of service of 60 centimetres of fabric widths.
Embodiment three
The trailing arm two ends of the rotating nozzle mechanism of electric spinning equipment have nozzle, wherein can utilize No. 20 syringe needles as nozzle, and the preset height H of collecting electrode and received vector for example are 40 centimetres.Applying about 40 volts voltage behind discharge electrode, the WEB that the macromolecule filament forms on three-dimensional received vector.Compared to the three-dimensional received vector of inchoate WEB, its dioctyl phthalate (Dioctyl Phthalate; DOP) filter effect is 40 to 50 percentages.Yet after forming WEB on the three-dimensional received vector, its DOP filter effect is promoted to 85 to 88 percentages with electric spinning equipment of the present invention.
By the invention described above preferred embodiment as can be known, use the manufacture method that electric spinning equipment of the present invention carries out the macromolecule filament, its advantage is to utilize rotating nozzle mechanism to move with non-linear track, forms uniform WEB with any receiving angle so as to making the macromolecule filament on received vector.The skewness and the throughput rate that can overcome existing macromolecule filament like this wait problem slowly.
Though the present invention discloses as above with several preferred embodiments; yet it is not in order to limit the present invention; any person skilled in the art scholar without departing from the spirit and scope of the present invention; when the change that can do various equivalences and replacement, so protection scope of the present invention is when looking accompanying being as the criterion that the application's claim scope defined.