CN105332136A - Conductive micro-nanometer fiber stranded wire based on solvent-free electrospinning and preparing method thereof - Google Patents
Conductive micro-nanometer fiber stranded wire based on solvent-free electrospinning and preparing method thereof Download PDFInfo
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Abstract
The invention discloses a conductive micro-nanometer fiber stranded wire based on solvent-free electrospinning and a preparing method thereof. The conductive micro-nanometer fiber stranded wire comprises a photocuring material template stranded wire and a conductive macromolecule layer. The photocuring material template stranded wire is formed by winding micro-nanometer fiber cured by solvent-free electrospinning ultraviolet light. The conductive macromolecule layer is manufactured through an in-situ polymerization method and comprises conductive macromolecule layer bodies permeating into the template stranded wire and wrapping the template stranded wire. According to the conductive micro-nanometer fiber stranded wire, conductivity of the fiber stranded wire is further improved while excellent stretchability is kept, organic solvent does not need to be added in the electrostatic spun yarn preparing process, the preparing process is safer and more environmentally friendly, and the stranded wire is suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of conduction micro nanometer fiber twisted wire based on solvent-free electrospinning and preparation method thereof, belong to field of nano material preparation.
Background technology
Electrostatic spinning technique is a kind of method simply effectively preparing micro/nano-fibre, the nanofiber using electrostatic spinning technique to prepare, and can be made into the structure that how abundant twisted wire etc. is more, to expand its range of application.But traditional electrostatic spinning technique, owing to can play most organic solvent in spinning process, cause the very large wasting of resources and environmental pollution, even some organic solvent is also toxic, can damage the health of people.And solvent-free spining technology does not need solvent in spinning process, thus solve the drawback that tradition has solvent spinning contaminated environment.Current solvent-free spinning has melt spinning, heat cure spinning, UV photocuring spinning etc.The spendable material of UV photocuring is a lot, wherein urethane acrylate (PUA) is a kind of ideal UV-cured resin, be usually used in coating and adhesive area, film after its solidification or fiber have the high-wearing feature of polyurethane, adhesion, pliability and excellent resistance to low temperature, are a kind of radiation curing materials of high comprehensive performance.Chinese patent (CN104532367A) is only limitted at present for the spinning of UV photocuring and obtains polyurethane micro nanometer fiber by the method for ultra-violet curing, Chinese patent (CN101021017A) also obtains polyurethanes micro nanometer fiber by the method for ultra-violet curing, but it needs with reactive diluent used in combination according to certain ratio, precursor liquid is prepared cumbersome, and the fiber of preparation is generally shorter and irregular, solidification not exclusively, length maximum is 1 centimetre, and toughness is poor, the structure that twisted wire etc. is more complicated can not be processed to, and these fibers do not possess electric conductivity, limit the range of application of material.
The develop rapidly of society electronic equipment, also more and more higher to the requirement of electronic equipment internal, especially the appearance of wearable electronic etc., make the requirement of conductive material except excellent electric conductivity, also need goodish pliability, this just makes flexible conducting material more and more be subject to concern and the attention of people.But the nanofiber obtained with method of electrostatic spinning or nano fiber twisted mostly exist the problem that electrical conductivity is too low or pliability is poor, the application demand of microelectronic device well can not be adapted to.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of conductive-nano-fibers twisted wire based on solvent-free electrospinning and preparation method thereof is provided, this conduction micro nanometer fiber twisted wire further increases the electric conductivity of fiber strands while maintaining excellent tensility, simultaneously in electrostatic spinning preparation process without the need to adding organic solvent, preparation process is safety and environmental protection more, matters large-scale production.
To achieve these goals, technical scheme provided by the invention is as follows:
A kind of conduction micro nanometer fiber twisted wire based on solvent-free electrospinning, described conduction micro nanometer fiber twisted wire comprises photo-curing material template twisted wire and electroconductive polymer layer, described photo-curing material template twisted wire is that micro nanometer fiber is entwined by solvent-free electrospinning ultraviolet light polymerization, described electroconductive polymer layer is obtained by situ aggregation method, comprises and permeates the inner electroconductive polymer layer with being coated on template twisted wire outside in template twisted wire.
Template twisted wire of the present invention is under few oxygen environment, utilize electrostatic spinning technique, using ultraviolet light as light source, cause the photocuring prepolymer with chemical reactivity and be rapidly converted into solid-state micro/nano-fibre, because raw materials all in spinning precursor liquid all participates in polymerisation, whole process organic solvent-free participates in, non-volatility organic compound VOC discharges, safety and environmental protection, suitability for scale production, under few oxygen environment, oxygen inhibition phenomenon is not obvious, photo-curing material polymerization completely, gained micro nanometer fiber is longer and regular homogeneous, pliability is good, template twisted wire is made by this fiber, gained conduction micro nanometer fiber twisted wire is made to have excellent stretch recovery energy, template fiber is dipped in conduction high polymer in-situ polymerization precursor solution, high polymer also enters in the fibre gap of twisted wire inside and forms electroconductive polymer layer while template surface polymerization, effectively improve the electrical conductivity of material, this conduction micro nanometer fiber twisted wire is made to have excellent extension recovery and electric conductivity, can be used for preparing optics, electronic device etc.
Further, the maximum tension rate of described conduction micro nanometer fiber twisted wire is more than or equal to 200%.
Further, the electrical conductivity of described conduction micro nanometer fiber twisted wire is 10
2the S/cm order of magnitude, under extended state, electrical conductivity reduces with the increase of extensibility.
The invention also discloses the preparation method of described a kind of conduction micro nanometer fiber twisted wire based on solvent-free electrospinning, comprise the following steps:
(1) configure spinning precursor liquid: mixed under light protected environment with light trigger by the liquid prepolymer of photo-curing material, more standingly under natural light environment make its pre-polymerization, obtain spinning precursor liquid;
(2) template twisted wire is prepared: the spinning precursor liquid that step (1) is joined is placed in the liquid storage mechanism that electrostatic spinning apparatus is communicated with spinning nozzle, and carry out electrospinning under the spinning nozzle of described electrostatic spinning apparatus and collector being placed in few oxygen environment, described electrostatic spinning apparatus is the electric spinning equipment preparing orderly micro nanometer fiber, the jet sprayed spinning nozzle with ultraviolet source in electrospinning process and the collector of electrostatic spinning apparatus irradiate, collect ordered arrangement photo-curing material micro nanometer fiber on collector, be wound in the twisted wire of even thickness as template twisted wire,
(3) in-situ polymerization precursor solution is configured: the monomer of conducting polymer, oxidant, dopant acid are dissolved in deionized water and make in-situ polymerization precursor solution;
(4) conductive layer is coated: immersed by the template twisted wire of step (2) gained in the in-situ polymerization precursor solution of step (3) gained, leaves standstill taking-up after the complete coated die plate twisted wire of conducting polymer and is drying to obtain conduction micro nanometer fiber twisted wire.
Inventor thinks, method of electrostatic spinning prepares the solidification of UV curing materials micro nanometer fiber not exclusively, the general shorter and irregular reason of fiber is: electrostatic spinning is as a kind of method preparing micro nanometer fiber, use it for and prepare photo-curing material micro nanometer fiber, the large feature of specific area of its obtained micro nanometer fiber, this fibre morphology increases the contact area of prepolymer and oxygen, it is made to contact more abundant with the oxygen in air, be exaggerated the effect of UV curing materials oxygen inhibition phenomenon in the curing process, hinder the polymerizing curable of prepolymer, thus cause obtained photo-curing material micro nanometer fiber solidification not exclusively, poor toughness, fiber is generally shorter and irregular, have impact on large-scale production and the application prospect of fiber.Preparation method of the present invention, select to carry out electrospinning process under few oxygen environment that oxygen concentration is low and prepare micro nanometer fiber, in spinning process, pre-polymer solution is under action of high voltage, jet is formed from spinneret ejection, light trigger in jet absorbs the energy of ultraviolet light and produces living radical, living radical causes prepolymer polymerization reaction take place, with the splitting of fiber in the process that jet falls, finally on collector, form polymer micro-nanometer fiber, thus realize solvent-free electrostatic spinning.The spinning environment of few oxygen; effectively prevent the oxygen inhibition phenomenon at electrostatic spinning; thus obtained completion of cure, form rule and continuous print micro nanometer fiber in a large number; and organic solvent-free participates in spinning process; effectively prevent organic solvent to volatilize the environmental pollution caused; safety and environmental protection, the large-scale industrial that the method is applicable to photo-curing material micro nanometer fiber is produced.
Further, the photo-curing material of described step (1) is one or more in urethane acrylate, epoxy acrylate, polyether acrylate, polyester acrylate, acrylic resin.
Further, the photo-curing material of described step (1) is urethane acrylate, and the mass ratio of described light trigger and urethane acrylate is 1:10 ~ 30, and the standing pre-polymerization time of described step (1) is 1 ~ 2 day.
In numerous photo-curing material, urethane acrylate (PUA) is the ideal UV-cured resin of a class, be usually used in coating and adhesive area, film after its solidification or fiber have the high-wearing feature of polyurethane, adhesion, pliability, the optical property of high-peeling strength and excellent resistance to low temperature and polyacrylate brilliance and weatherability, are a kind of radiation curing materials of high comprehensive performance.As the various acrylates that coating and adhesive use, be easy to carry out bulk polymerization, oxygen inhibition phenomenon more easily overcomes.
Further, described step (3) preparation in-situ polymerization precursor solution is for be dissolved in obtained solution A in ionized water by ammonium persulfate, sulfosalicylic acid and aniline are joined the even obtained solution B of deionized water for stirring, at room temperature respectively with after magnetic stirrer, solution A is dropwise added drop-wise in solution B and stirs, namely obtain in-situ polymerization precursor solution; Described step (4) puts into 4 DEG C of refrigerators for being immersed in in-situ polymerization precursor solution by template twisted wire after sealing, and namely the standing natural air drying that takes out after 24 ~ 36 hours obtains conduction micro nanometer fiber twisted wire.
The in-situ polymerization conducting solutions such as polyaniline all have very high compatibility with urethane acrylate material, urethane acrylate nanofiber being made twisted wire is immersed in in-situ polymerization conductive polyaniline solution, high performance composite can be formed, while keeping tensility, improve the electric conductivity of fiber strands further.
Further, few oxygen environment of described step (2) be oxygen concentration lower than 5% spinning environment, the spinning voltage of the electrospinning process of described step (2) is 10 ~ 30 kilovolts, spinning distance is 5 ~ 50 centimetres, the power of ultraviolet source is 300 ~ 500 watts, and the spacing between ultraviolet source and collector is 10 ~ 20 centimetres.
Further, electrostatic spinning apparatus in described step (2) comprises high voltage source, liquid storage mechanism, spinning nozzle, oxygen barrier mechanism, ultraviolet source and cylinder collector, described high-voltage power cathode connects spinning nozzle, spinning nozzle is communicated with the liquid storage mechanism of storage spinning precursor liquid, described cylinder collector connects high voltage source negative pole or direct ground connection, described oxygen barrier mechanism comprises seal box, described spinning nozzle and cylinder collector are positioned at seal box, ultraviolet source is positioned at seal box or its ultraviolet light launched can inject seal box, ultraviolet source can irradiate spinning nozzle and cylinder collects interelectrode space, described seal box is provided with air inlet and gas outlet, described air inlet connects gas source, described gas source is source nitrogen, carbon dioxide source or inert gas source, also be provided with in described seal box and hinder gas to be directly blown into baffle plate in case, described baffle plate is between air inlet and collector, the shadow shield of the jet preventing ultraviolet light direct irradiation spinning nozzle ejection end place is provided with in described seal box, described shadow shield is between ultraviolet source and spinning nozzle ejection end, press close to spinning nozzle ejection end to arrange, the described collection cylinder of cylinder collector docks with the output shaft of DC brushless motor and links, the central axis of the output shaft of collection cylinder and DC brushless motor coincides, the electric machine controller of DC brushless motor electric connection of power supply and control motor speed.
This device is provided with oxygen barrier mechanism, oxygen barrier mechanism need be first opened when this device uses, reduce the concentration of oxygen in seal box, to build the spinning environment of few oxygen, and then solvent-free spinning precursor liquid is injected liquid storage mechanism, open ultraviolet source and high voltage source, under few oxygen oxygen atmosphere, carry out electrostatic spinning, effectively can overcome the impact of oxygen inhibition phenomenon on photo-curing material micro nanometer fiber forming process.
To volatilize the environmental pollution that causes and be unfavorable for the problem that large-scale commercial applications is produced to eliminate organic solvent in conventional electrostatic spinning, under designing the few oxygen environment built at nitrogen or two sample carbon, inert gas, utilize electrostatic spinning technique, using ultraviolet light as light source, cause the acrylic ester prepolymer with chemical reactivity and be rapidly converted into solid-state micro/nano-fibre, because raw materials all in spinning precursor liquid all participates in polymerisation, achieve solvent-free electrostatic spinning.And obtain by cylinder collector the micro nanometer fiber that longer arrangement is orderly, good toughness, diameter are more regular, because gained fiber has enough length, toughness and homogeneity, the good twisted wire structure of pattern can be made into, as masterplate twisted wire.
Further, described step (2) is before electrospinning process starts, employing internal diameter is the wireway of 8 ~ 12 millimeters, first open gas source and pass into gas in seal box, gas flow rate 3 ~ 9 cubic millimeters/second, open electrostatic spinning apparatus after passing into 3 ~ 5 minutes and reaching few oxygen environment again and open spinning, spinning nozzle is 5 ~ 50 centimetres to the spacing of collection cylinder, collection cylinder radius 3 ~ 8 centimetres, DC brushless motor drives the rotating speed of drum rotating to be 180 ~ 300 revs/min.
Beneficial effect of the present invention is: the invention provides a kind of conductive-nano-fibers twisted wire based on solvent-free electrospinning and preparation method thereof, this conduction micro nanometer fiber twisted wire further increases the electric conductivity of fiber strands while maintaining excellent tensility, simultaneously in electrostatic spinning preparation process without the need to adding organic solvent, preparation process is safety and environmental protection more, matters large-scale production.Specifically:
(1) the method is selected under few oxygen environment that oxygen concentration is low, to carry out electrospinning process prepare photo-curing material micro nanometer fiber, in spinning process, pre-polymer solution is under action of high voltage, jet is formed from spinneret ejection, light trigger in jet absorbs the energy of ultraviolet light and produces living radical, living radical causes prepolymer polymerization reaction take place, with the splitting of fiber in the process that jet falls, finally on collector, form polymer micro-nanometer fiber, thus realize solvent-free electrostatic spinning.The spinning environment of few oxygen, effectively prevent the oxygen inhibition phenomenon at electrostatic spinning, thus obtain completion of cure in a large number, pliability is good, form rule and continuous print photo-curing material micro nanometer fiber, template twisted wire is made by this fiber, gained conduction micro nanometer fiber twisted wire is made to have excellent stretch recovery energy, template fiber is dipped in conduction high polymer in-situ polymerization precursor solution, high polymer also enters in the fibre gap of twisted wire inside and forms electroconductive polymer layer while template surface polymerization, effectively improve the electrical conductivity of material, this conduction micro nanometer fiber twisted wire is made to have excellent extension recovery and electric conductivity, the electrical conductivity of this conduction micro nanometer fiber twisted wire is up to 10
2the S/cm order of magnitude, maximum tension rate, up to more than 200%, can be used for preparing optics, electronic device etc.
(2) precursor liquid used in spinning process is made up of the prepolymer of light trigger and photo-curing material, and not containing other organic solvents, the utilization rate of raw material can reach 100%, and non-volatility organic compound VOC discharges, environmental friendliness.
(3) preparation method of this conduction micro nanometer fiber twisted wire is simple, equipment is easy to operate, reproducible, be convenient to promote.
Accompanying drawing explanation
Fig. 1 is the structural representation of the electrostatic spinning apparatus that embodiment 1 to 3 uses.
The electron micrograph of conduction micro nanometer fiber twisted wire prepared by Fig. 2 embodiment 1.
The extension test curve of conduction micro nanometer fiber twisted wire prepared by Fig. 3 embodiment 1.
The extension recovery curve of conduction micro nanometer fiber twisted wire prepared by Fig. 4 embodiment 1.
In Fig. 1,1-high voltage source, 2-ultraviolet source, 3-gas cylinder, 31-gas cylinder pressure-reducing valve, 4-DC brushless motor, 41-electric machine controller, 5-air inlet, 6-gas outlet, 7 collection cylinders, 8-spinning nozzle, 9-baffle plate, 10-shadow shield, 11-wireway, 12-liquid storage mechanism, 13-wire, 14-seal box.
Detailed description of the invention
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, concrete material proportion, process conditions and result thereof described by embodiment only should can not limit the present invention described in detail in claims yet for illustration of the present invention.
The electrostatic spinning apparatus that the embodiment of the present invention 1 to 3 uses as shown in Figure 1, comprise high voltage source 1, liquid storage mechanism 12, spinning nozzle 8, oxygen barrier mechanism, ultraviolet source 2 and collector, described high voltage source 1 positive pole connects spinning nozzle 8, spinning nozzle 8 is communicated with the liquid storage mechanism 12 of storage spinning precursor liquid, described liquid storage mechanism 12 is plastic injector needle tubing, described collector connects high voltage source 1 negative pole, described oxygen barrier mechanism comprises the seal box 14 of inner anaerobic or few oxygen, described spinning nozzle 8 and collector are positioned at seal box 14, ultraviolet source 2 is positioned at outside seal box 14, its ultraviolet light launched can be injected in seal box 14, ultraviolet source 2 can irradiate between spinning nozzle 8 and collector, the seal box 14 of described oxygen barrier mechanism is provided with air inlet 5 and gas outlet 6, described seal box 14 is lucite case, air inlet 5 and gas outlet 6 are separately positioned on two relative sidewalls of seal box 14, described air inlet 5 connects gas source, described gas source is gas cylinder 3, nitrogen is filled with in the gas cylinder 3 of embodiment 1, also be provided with in described seal box 14 and hinder nitrogen to be directly blown into baffle plate 9 in case, described baffle plate 9 is between air inlet 5 and collector, described collection is cylinder collector very, the collection cylinder 7 of described cylinder collector docks with the output shaft of DC brushless motor 4 and links, the central axis of the output shaft of collection cylinder 7 and DC brushless motor 4 coincides, the electric machine controller 41 of DC brushless motor 4 electric connection of power supply and control motor speed, the shadow shield 10 of the jet preventing ultraviolet light direct irradiation spinning nozzle 8 ejection end place is provided with in described seal box 14, described shadow shield 10 is between ultraviolet source 2 and spinning nozzle 8 ejection end, press close to spinning nozzle 8 ejection end to arrange.
Embodiment 1
Based on a preparation method for the conduction micro nanometer fiber twisted wire of solvent-free electrospinning, comprise the following steps:
(1) spinning precursor liquid is configured: the Liquid photoinitiators (photoinitiator1173 adding 0.4 gram in conical flask, 2-hydroxy-2-methyl-1-phenyl-1-acetone, Aldrich), add the urethane acrylate (DR-U301 of 8 grams again, Changxing chemical engineering industry joint-stock company (Taiwan)), carry out shading stirring with magnetic stirring apparatus, adopt 45 degree of heating water baths, stir 2 hours, light trigger is mixed with urethane acrylate; Under room temperature available light, leave standstill 2 days, the pre-polymerization that urethane acrylate is occurred to a certain extent obtains precursor solution;
(2) template twisted wire is prepared: the spinning precursor solution that step (1) is joined being poured into internal diameter is in the aluminum spinneret of 1.2 centimetres, the most advanced and sophisticated size 3 millimeters of spinneret, nitrogen is passed in airtight casing, nitrogen flow rate 3 cubic millimeters/second, electrostatic spinning is carried out again after reaching oxygen barrier effect after passing into 5 minutes, spinneret is 10 centimetres to the distance of cylinder collector, spinning voltage 22 kilovolts, collection cylinder radius 5 centimetres, motor speed 180 revs/min, ultraviolet source power 300 watts, the fiber of spinneret ejection is irradiated, it is 15 centimetres that ultraviolet source collects distance to cylinder, through 10 minutes, cylinder collector is collected the continuous micro nanometer fiber that arrangement is orderly, gained micro nanometer fiber is wound in the twisted wire of diameter distribution 0.04 ~ 0.10 millimeter,
(3) in-situ polymerization precursor solution is configured: 2.33 grams of ammonium persulfates (APS, Mw:228.20) joined in 50 ml deionized water, be denoted as solution A; 3.89 grams of sulfosalicylic acids (SSA, Mw:254.20) and 1.13 grams of aniline (Mw:93.13) are joined in 50 ml deionized water, is denoted as solution B; At room temperature use magnetic stirrer after 90 minutes respectively, solution A is dropwise added drop-wise in solution B, about 30 minutes used times; Again by gained solution stir about 10 minutes, namely obtain in-situ polymerization precursor solution;
(4) conductive layer is coated: immersed by the template twisted wire of step (2) gained in the in-situ polymerization precursor solution of step (3) gained and seal, put into refrigerator, temperature is adjusted to 2 DEG C, leaves standstill taking-up after 24 hours and is drying to obtain conduction micro nanometer fiber twisted wire.As shown in Figure 2, as shown in Figure 3, the computing formula of the extensibility described in figure is the shape characteristic of gained conduction micro nanometer fiber twisted wire in the change of this twisted wire current strength in drawing process:
The maximum tension rate calculating this conduction micro nanometer fiber twisted wire is after tested greater than 200%, and electrical conductivity is 10
2the S/cm order of magnitude.Fig. 3 is the extension test curve of conduction micro nanometer fiber twisted wire prepared by embodiment 1, as seen from Figure 3, the electric property of this twisted wire changes along with the increase of extensibility, Fig. 4 is the extension recovery curve of conduction micro nanometer fiber twisted wire prepared by embodiment 1, as seen from Figure 4, after fiber stretches by different ratio, reply former length, electric current recovers initial value rapidly, fast response time has and well responds recoverability, to sum up analyze, this conduction micro nanometer fiber twisted wire useful application is in equipment such as miniature force-sensing sensors.
Embodiment 2
Based on a preparation method for the conduction micro nanometer fiber twisted wire of solvent-free electrospinning, comprise the following steps:
(1) spinning precursor liquid is configured: the solid-state light initator (184 adding 0.5 gram in conical flask, 1-hydroxy-cyclohexyl-phenyl ketone, Aldrich), add the urethane acrylate (DR-U301 of 9 grams again, Changxing chemical engineering industry joint-stock company (Taiwan)), carry out shading stirring with magnetic stirring apparatus, adopt 50 degree of heating water baths, stir 1 hour, make solid-state light initator and urethane acrylate mixed dissolution even; Under room temperature available light, leave standstill 1 day, the pre-polymerization that urethane acrylate is occurred to a certain extent obtains precursor solution;
(2) template twisted wire is prepared: the spinning precursor solution that step (1) is joined being poured into internal diameter is in the aluminum spinneret of 1.2 centimetres, the most advanced and sophisticated size 2 millimeters of spinneret, nitrogen is passed in airtight casing, nitrogen flow rate 9 cubic millimeters/second, electrostatic spinning is carried out again after reaching oxygen barrier effect after passing into 3 minutes, spinneret is 5 centimetres to the distance of cylinder collector, spinning voltage 24 kilovolts, collection cylinder radius 3 centimetres, motor speed 300 revs/min, ultraviolet source power 500 watts, the fiber of spinneret ejection is irradiated, it is 10 centimetres that ultraviolet source collects distance to cylinder, through 5 minutes, cylinder collector is collected the continuous micro nanometer fiber that arrangement is orderly, gained micro nanometer fiber is wound in the twisted wire of diameter distribution 0.04 ~ 0.10 millimeter,
(3) configure in-situ polymerization precursor solution: by 0.3 milliliter of hydrochloric acid, 1.2 milliliters of EDOT, 60 ml deionized water mixing, are denoted as solution B; By 2.16 grams of ammonium persulfates, 30 ml deionized water mixing, are denoted as solution A, at room temperature use magnetic stirrer after 10 minutes respectively, solution A be dropwise added drop-wise in solution B; Again by gained solution stir about 10 minutes, namely obtain in-situ polymerization precursor solution;
(4) conductive layer is coated: immersed by the template twisted wire of step (2) gained in the in-situ polymerization precursor solution of step (3) gained and seal, put into refrigerator, temperature is adjusted to 4 DEG C, leave standstill after 36 hours and take out, can stretch the PEDOT/PUA just obtaining having electric conductivity after the twisted wire natural air drying of taking-up twisted wire.The maximum tension rate calculating this conduction micro nanometer fiber twisted wire is after tested greater than 320%, and electrical conductivity is 10
2the S/cm order of magnitude.
Embodiment 3
Based on a preparation method for the conduction micro nanometer fiber twisted wire of solvent-free electrospinning, comprise the following steps:
(1) spinning precursor liquid is configured: the Liquid photoinitiators (photoinitiator1173 adding 0.05 gram in conical flask, 2-hydroxy-2-methyl-1-phenyl-1-acetone, Aldrich), add the polyester acrylate (CN750 of 1 gram again, Sartomer (Guangzhou) Chemical Co., Ltd.), carry out shading stirring with magnetic stirring apparatus, adopt 30 degree of heating water baths, stir 1 hour, make light trigger and urethane acrylate mixed dissolution even; Under room temperature available light, leave standstill 2 days, the pre-polymerization that urethane acrylate is occurred to a certain extent obtains precursor solution;
(2) template twisted wire is prepared: the spinning precursor solution that step (1) is joined being poured into internal diameter is in the aluminum spinneret of 1.2 centimetres, the most advanced and sophisticated size 1.2 millimeters of spinneret, nitrogen is passed in airtight casing, nitrogen flow rate 5 cubic millimeters/second, electrostatic spinning is carried out again after reaching oxygen barrier effect after passing into 4 minutes, spinneret is 6 centimetres to the distance of cylinder collector, spinning voltage 24 kilovolts, collection cylinder radius 8 centimetres, motor speed 200 revs/min, ultraviolet source power 350 watts, the fiber of spinneret ejection is irradiated, it is 50 centimetres that ultraviolet source collects distance to cylinder, through 10 minutes, cylinder collector is collected the continuous micro nanometer fiber that arrangement is orderly, gained micro nanometer fiber is wound in the twisted wire of diameter distribution 0.04 ~ 0.10 millimeter,
(3) configure in-situ polymerization precursor solution: by 0.003 mole of sodium lignin sulfonate, 0.040 gram of pyrroles PY monomer, 100 ml deionized water mixing, are denoted as solution B; By 2.16 grams of ammonium persulfates, 100 ml deionized water mixing, are denoted as solution A; At room temperature use magnetic stirrer after 50 minutes respectively, solution A is dropwise added drop-wise in solution B; Again by gained solution stir about 20 minutes, namely obtain in-situ polymerization precursor solution;
(4) conductive layer is coated: immersed by the template twisted wire of step (2) gained in the in-situ polymerization precursor solution of step (3) gained and seal, put into refrigerator, temperature is adjusted to 4 DEG C, leave standstill after 36 hours and take out, can stretch the PPY/PUA just obtaining having electric conductivity after the twisted wire natural air drying of taking-up twisted wire.The maximum tension rate calculating this conduction micro nanometer fiber twisted wire is after tested greater than 400%, and electrical conductivity is 10
2the S/cm order of magnitude.
The above, be only explanation embodiment of the present invention, not to any formal and substantial restriction of the present invention, should be understood that, for those skilled in the art, under the prerequisite not departing from the inventive method, the some improvement made and supplement also should be considered as protection scope of the present invention, the present invention place of not elaborating is prior art known in those skilled in the art, all those skilled in the art, without departing from the spirit and scope of the present invention, utilize a little change that disclosed above technology contents is made, modify and the equivalent variations developed, be Equivalent embodiments of the present invention, meanwhile, all according to substantial technological of the present invention to the change of any equivalent variations that above-described embodiment does, modify and differentiation, all still belong to the scope of technical scheme of the present invention.
Claims (10)
1. the conduction micro nanometer fiber twisted wire based on solvent-free electrospinning, it is characterized in that, described conduction micro nanometer fiber twisted wire comprises photo-curing material template twisted wire and electroconductive polymer layer, described photo-curing material template twisted wire is that micro nanometer fiber is entwined by solvent-free electrospinning ultraviolet light polymerization, described electroconductive polymer layer is obtained by situ aggregation method, comprises and permeates the inner electroconductive polymer layer with being coated on template twisted wire outside in template twisted wire.
2., as claimed in claim 1 based on the conduction micro nanometer fiber twisted wire of solvent-free electrospinning, it is characterized in that, the maximum tension length of described conduction micro nanometer fiber twisted wire is more than or equal to 200%.
3., as claimed in claim 1 based on the conduction micro nanometer fiber twisted wire of solvent-free electrospinning, it is characterized in that, the electrical conductivity of described conduction micro nanometer fiber twisted wire is 10
2the S/cm order of magnitude, under extended state, electrical conductivity reduces with the increase of extensibility.
4. the preparation method of a kind of conduction micro nanometer fiber twisted wire based on solvent-free electrospinning as described in claims 1 to 3, is characterized in that, comprise the following steps:
(1) configure spinning precursor liquid: mixed under light protected environment with light trigger by the liquid prepolymer of photo-curing material, more standingly under natural light environment make its pre-polymerization, obtain spinning precursor liquid;
(2) template twisted wire is prepared: the spinning precursor liquid that step (1) is joined is placed in the liquid storage mechanism that the electrostatic spinning apparatus preparing orderly micro nanometer fiber is communicated with spinning nozzle, and carry out electrospinning under the spinning nozzle of described electrostatic spinning apparatus and collector being placed in few oxygen environment, the jet sprayed spinning nozzle with ultraviolet source in electrospinning process and the collector of electrostatic spinning apparatus irradiate, collect ordered arrangement photo-curing material micro nanometer fiber on collector, be wound in the twisted wire of even thickness as template twisted wire;
(3) in-situ polymerization precursor solution is configured: the monomer of conducting polymer, oxidant, dopant acid are dissolved in deionized water and make in-situ polymerization precursor solution;
(4) conductive layer is coated: immersed by the template twisted wire of step (2) gained in the in-situ polymerization precursor solution of step (3) gained, leaves standstill taking-up after the complete coated die plate twisted wire of conducting polymer and is drying to obtain conduction micro nanometer fiber twisted wire.
5. the preparation method of a kind of conduction micro nanometer fiber twisted wire based on solvent-free electrospinning as claimed in claim 4, it is characterized in that, the photo-curing material of described step (1) is one or more in urethane acrylate, epoxy acrylate, polyether acrylate, polyester acrylate, acrylic resin.
6. the preparation method of a kind of conduction micro nanometer fiber twisted wire based on solvent-free electrospinning as claimed in claim 5, it is characterized in that, the photo-curing material of described step (1) is urethane acrylate, the mass ratio of described light trigger and urethane acrylate is 1:10 ~ 30, and the standing pre-polymerization time of described step (1) is 1 ~ 2 day.
7. the preparation method of a kind of conduction micro nanometer fiber twisted wire based on solvent-free electrospinning as claimed in claim 6, it is characterized in that, described step (3) preparation in-situ polymerization precursor solution is for be dissolved in obtained solution A in ionized water by ammonium persulfate, sulfosalicylic acid and aniline are joined the even obtained solution B of deionized water for stirring, at room temperature respectively with after magnetic stirrer, solution A is dropwise added drop-wise in solution B and stirs, namely obtain in-situ polymerization precursor solution; Described step (4) puts into 4 DEG C of refrigerators for being immersed in in-situ polymerization precursor solution by template twisted wire after sealing, and namely the standing natural air drying that takes out after 24 ~ 36 hours obtains conduction micro nanometer fiber twisted wire.
8. the preparation method of a kind of conduction micro nanometer fiber twisted wire based on solvent-free electrospinning as claimed in claim 4, it is characterized in that, few oxygen environment of described step (2) be oxygen concentration lower than 5% spinning environment, the spinning voltage of the electrospinning process of described step (2) is 10 ~ 30 kilovolts, spinning distance is 5 ~ 50 centimetres, the power of ultraviolet source is 300 ~ 500 watts, and the spacing between ultraviolet source and collector is 10 ~ 20 centimetres.
9. the preparation method of a kind of conduction micro nanometer fiber twisted wire based on solvent-free electrospinning as claimed in claim 4, it is characterized in that, electrostatic spinning apparatus in described step (2) comprises high voltage source, liquid storage mechanism, spinning nozzle, oxygen barrier mechanism, ultraviolet source and cylinder collector, described high-voltage power cathode connects spinning nozzle, spinning nozzle is communicated with the liquid storage mechanism of storage spinning precursor liquid, described cylinder collector connects high voltage source negative pole or direct ground connection, described oxygen barrier mechanism comprises seal box, described spinning nozzle and cylinder collector are positioned at seal box, ultraviolet source is positioned at seal box or its ultraviolet light launched can inject seal box, ultraviolet source can irradiate spinning nozzle and cylinder collects interelectrode space, described seal box is provided with air inlet and gas outlet, described air inlet connects gas source, described gas source is source nitrogen, carbon dioxide source or inert gas source, also be provided with in described seal box and hinder gas to be directly blown into baffle plate in case, described baffle plate is between air inlet and collector, the shadow shield of the jet preventing ultraviolet light direct irradiation spinning nozzle ejection end place is provided with in described seal box, described shadow shield is between ultraviolet source and spinning nozzle ejection end, press close to spinning nozzle ejection end to arrange, the described collection cylinder of cylinder collector docks with the output shaft of DC brushless motor and links, the central axis of the output shaft of collection cylinder and DC brushless motor coincides, the electric machine controller of DC brushless motor electric connection of power supply and control motor speed.
10. the preparation method of a kind of conduction micro nanometer fiber twisted wire based on solvent-free electrospinning as claimed in claim 9, it is characterized in that, described step (2) is before electrospinning process starts, employing internal diameter is the wireway of 8 ~ 12 millimeters, first open gas source and pass into gas in seal box, gas flow rate 3 ~ 9 cubic millimeters/second, open electrostatic spinning apparatus after passing into 3 ~ 5 minutes and reaching few oxygen environment again and open spinning, spinning nozzle is 5 ~ 50 centimetres to the spacing of collection cylinder, collection cylinder radius 3 ~ 8 centimetres, DC brushless motor drives the rotating speed of drum rotating to be 180 ~ 300 revs/min.
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