CN100360725C - Ultra-hydrophobic conductive macromolecular nano fiber and method for preparing same and use thereof - Google Patents

Ultra-hydrophobic conductive macromolecular nano fiber and method for preparing same and use thereof Download PDF

Info

Publication number
CN100360725C
CN100360725C CNB2005100766596A CN200510076659A CN100360725C CN 100360725 C CN100360725 C CN 100360725C CN B2005100766596 A CNB2005100766596 A CN B2005100766596A CN 200510076659 A CN200510076659 A CN 200510076659A CN 100360725 C CN100360725 C CN 100360725C
Authority
CN
China
Prior art keywords
nano fiber
hydrophobic
polymer
ultra
super
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB2005100766596A
Other languages
Chinese (zh)
Other versions
CN1880526A (en
Inventor
朱英
张敬畅
翟锦
郑咏梅
万梅香
江雷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Chemical Technology
Institute of Chemistry CAS
Original Assignee
Beijing University of Chemical Technology
Institute of Chemistry CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing University of Chemical Technology, Institute of Chemistry CAS filed Critical Beijing University of Chemical Technology
Priority to CNB2005100766596A priority Critical patent/CN100360725C/en
Publication of CN1880526A publication Critical patent/CN1880526A/en
Application granted granted Critical
Publication of CN100360725C publication Critical patent/CN100360725C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

The present invention relates to nanometer fiber of super-hydrophobic conducting polymers, which is the coaxial nanometer fiber with a core-shell structure. A core is the polymer fiber of which the diameter is from 80 to 300 nanometers, and a coaxial shell is a conducting polymer layer of which the thickness is from 80 to 200 nanometers and is composed of the granules of the conducting polymers of which the granule sizes are from 20 to 40 nanometers. The polymer is polyvinyl cyanide, poly oxirene, polyvinylpyrrolidone, polymethyl methacrylate, polyvinyl alcohol, cellulose acetate, polycarbonate, etc. The conducting polymers are polyaniline, polythiophene or polypyrrole. The nanometer fiber of super-hydrophobic conducting polymers is prepared by using the polymerization method of electrostatic spinning and original-position chemical oxidation, and has the property of the super-hydrophobic and super-hydrophilic inverse transformation of pH value responses. The present invention can be used for intelligent micro-fluid switches, controllable separating technology, controllable medical release, the stealth technology which can be rapidly switched, electromagnetic shielding, antistatic purpose, sensors, etc.

Description

Ultra-hydrophobic conductive macromolecular nano fiber and its production and use
Technical field
The invention belongs to field of functional materials; specifically relate to a kind of ultra-hydrophobic conductive macromolecular nano fiber; it has the characteristic to the super-hydrophobic and quick reversible conversion of Superhydrophilic of pH value response; and the preparation method who utilizes electrostatic spinning and in-situ chemical oxidation polymerization this ultra-hydrophobic conductive macromolecular nano fiber technology, that be produced on a large scale, and uses thereof.
Background technology
Structure that conducting polymer is special and excellent physical chemistry make it become the focus of material science research, as one of irreplaceable emerging functional material, conducting polymer is at the energy, opto-electronic device, information, sensor, molecular wire and molecular device, and extensive, tempting application prospect is arranged on electromagnetic shielding, anti-corrosion of metal and the stealth technology.But because intermolecular strong effect and delocalized electron structure cause the strand rigidity big, make conducting polymer be dissolved in any solvent hardly, heating is until decomposing still not fusion, comprehensive mechanical property is relatively poor, make it be difficult to processing method, seriously hindered the large-scale promotion application of conducting polymer in every field with traditional moulding.Therefore, how the conducting polymer Direct Spinning is made for conductive fiber and becomes one of main target of present material educational circles research.
Along with reducing of research material size, the surface of material and interfacial property become extremely important, especially surface wettability.The infiltrating adjusting and the fields such as microfluid, biological medicine, Gene Isolation that are controlled at have important use value and have caused common concern.At present, can adopt to add and induce, induce adjusting and the control that realizes surface wettability as temperature, light, electric field etc.A kind of thin polymer film of temperature-responsive is disclosed among the Chinese invention patent CN 1569933A, it is to make by the atom transfer radical surface initiated polymerization on the surface with enough roughness to have the temperature-responsive macromolecule, and this film has been realized super-hydrophobic and reversible conversion Superhydrophilic.But the time that the reversible wettability of its temperature-responsive transforms is long, and its preparation method is not suitable for scale preparation.
Summary of the invention
The objective of the invention is to overcome the thin polymer film of existing temperature-responsive; when realizing the reversible conversion of super-hydrophobic and Superhydrophilic; long to the time that the reversible wettability of temperature-responsive transforms; and the preparation method is not suitable for the defective of scale preparation, thereby a kind of super-hydrophobic and super hydrophilic quick reversible conversion and ultra-hydrophobic conductive macromolecular nano fiber easy to prepare of the pH of having value response are provided.
But another object of the present invention is to provide a kind of method of utilizing the above-mentioned conductive macromolecular nano fiber of scale preparation of electrostatic spinning and in-situ chemical oxidation polymerization technology.
A further object of the present invention is to provide the purposes of above-mentioned conductive macromolecular nano fiber.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of ultra-hydrophobic conductive macromolecular nano fiber, it is the co-axial nano fiber with nucleocapsid structure, described " nuclear " is that diameter is the polymer fiber of 80~300 nanometers, and coaxial with it " shell " is 80~200 nanometer thickness electroconductive polymer layers, it is that 20~40 conductivity high molecule nanometer particles are formed by particle diameter.
Described polymer is polyacrylonitrile, poly-oxireme, polyvinylpyrrolidone, polymethyl methacrylate, polyvinyl alcohol, cellulose acetate, Merlon, polyacrylamide, PLA or polyvinyl chloride.
Described conducting polymer is polyaniline, polythiophene or polypyrrole.
The ultra-hydrophobic conductive macromolecular nano fiber of this nucleocapsid structure has the characteristic to the super-hydrophobic and quick reversible conversion of Superhydrophilic of pH value response, in neutral solution performance super-hydrophobicity, in acid solution, show hydrophobicity, in alkaline solution, show water-wet behavior.
The invention provides a kind of preparation method of above-mentioned ultra-hydrophobic conductive macromolecular nano fiber, it has utilized electrostatic spinning and in-situ chemical oxidation polymerization method, specifically comprises the steps:
1) polymer is dissolved in the solvent, makes the polymer solution of 5~20wt%;
Described polymer is polyacrylonitrile, poly-oxireme, polyvinylpyrrolidone, polymethyl methacrylate, polyvinyl alcohol, cellulose acetate, Merlon, polyacrylamide, PLA or polyvinyl chloride;
Described solvent is deionized water, ethanol, acetone, chloroform, N, dinethylformamide, oxolane or acetic acid;
2) during the polymer solution that step 1) is made was packed the device for storing liquid of existing device for spinning into, electrospinning operating distance (needle point is to the distance between the receiving device) was 8~20cm; Open high voltage source, regulate spinning voltage to 10~26kV, polymer electrospinning solution sprays from injection apparatus, and forms the Taylor awl at the spinning nozzle place, solvent evaporates subsequently, the diameter that obtains solidifying on receiving system is the polymer nanofiber of 80~300 nanometers;
Described existing electric spinning equipment comprises high-voltage DC power supply, device for storing liquid, injection apparatus and receiving system four parts; The output voltage of employed high-voltage DC power supply is 0~30kV, device for storing liquid is vertically placed, injection apparatus adopts single injector head to spray, receiving system be with different conductive metal sheet, wire netting, metallic film or electro-conductive glass as the conduction gatherer, or on above-mentioned conduction gatherer, load a nonconducting receiver (for example sheet glass).
3) 1~2mL conductive high polymer monomer is joined in 50mL 1mol/L hydrochloric acid or the sulfuric acid, fully stirring and evenly mixing; With step 2) in the polymer nanofiber that obtains of electrospinning be immersed in the acid solution of this conductive high polymer monomer;
Described conductive high polymer monomer is aniline, thiophene or pyrroles;
4) 0.6~5 gram oxidant is dissolved in the hydrochloric acid or sulfuric acid solution of 1mol/L of 50mL, slowly be added drop-wise in the system of step 3), evenly stir, make conductive high polymer monomer at polymer nanofiber surface polymerization reaction take place, after the polymerization 1~24 hour, obtain conductive macromolecular nano fiber;
Described oxidant is ammonium persulfate, sodium peroxydisulfate, ferric trichloride, manganese oxide, hydrogen peroxide, potassium bichromate or dichloride copper;
5) with the conductive macromolecular nano fiber that obtains in step 4) 1mol/L alkaline solution dedoping, use fluorine-containing this fiber of organic sulfonic acid solute doping of 1wt% then, can obtain ultra-hydrophobic conductive macromolecular nano fiber of the present invention;
Described alkaline solution comprises: ammoniacal liquor, sodium hydrate aqueous solution, potassium hydroxide aqueous solution;
Described fluorine-containing organic sulfonic acid comprises: perfluorooctane sulfonate, perfluor ethylsulfonic acid;
Solvent in the described fluorine-containing organic sulfonic acid solution comprises: deionized water, chloroform, ethanol.
The invention provides a kind of purposes of above-mentioned conductive macromolecular nano fiber.This ultra-hydrophobic conductive macromolecular nano fiber has the characteristic of the super-hydrophobic and super hydrophilic reversible conversion of pH value response, can be used for intelligence and prays for fluid switch, controlled isolation technics, controlled drug, the stealth technology that can switch fast, electromagnetic shielding, antistatic, anticorrosive, sensor etc.
Ultra-hydrophobic conductive macromolecular nano fiber provided by the invention is the co-axial nano fiber with nucleocapsid structure, and wherein " nuclear " is about the polymer nanofiber of 80~300 nanometers for diameter; " shell " is the electroconductive polymer layer of 80~200 nanometer thickness, and it is that the conducting polymer particle of 20~40 nanometers is formed by particle diameter.The contact angle of this conductive fiber and water is higher than 150 °, shows super-hydrophobicity.This nanofiber has the characteristic of the super-hydrophobic and super hydrophilic reversible conversion of pH value response simultaneously.The pattern of this conductive macromolecular nano fiber can be by the control of electric spinning polymer template fiber, and the thickness of the shell of fiber can be controlled by polymerization time.
The present invention mixes with the reversible soda acid of polyaniline and the dedoping characteristic is a foundation, utilize electrostatic spinning and in-situ chemical oxidation polymerization technology, prepared ultra-hydrophobic conductive macromolecular nano fiber, it has the characteristic of the super-hydrophobic and super hydrophilic quick reversible conversion of pH value response.Its basic principle is: with the organic polymer soln is raw material, applies high-pressure electrostatic in polymer solution, and electrospinning obtains polymer nanofiber.In acid medium, be template with above-mentioned polymer nanofiber, utilize chemical oxidization method, carry out in-situ polymerization at the electric spinning polymer fiber surface, the coaxial fiber of the high molecular nanometer that obtains conducting electricity.With aqueous slkali dedoping obtain the insulating conductive macromolecular nano fiber of attitude, then with fluorine-containing organic sulfonic acid this high polymer nanometer fiber that mixes once more, can obtain super-hydrophobic conductive macromolecular nano fiber, this fiber has the characteristic of the super-hydrophobic and super hydrophilic quick reversible conversion of pH value response.
Characteristics of the present invention are:
1) ultra-hydrophobic conductive macromolecular nano fiber provided by the invention has nucleocapsid structure, and its center is a polymer nanofiber, and shell is the conducting high polymers thing.
2) this ultra-hydrophobic conductive macromolecular nano fiber has the characteristic to the super-hydrophobic and super hydrophilic reversible conversion of pH value response, in neutrality, show super-hydrophobic, in acid solution, show hydrophobicity, in alkaline solution, show the excess of export water-wet behavior.
3) can obtain having the conductive-nano-fibers of the characteristic of super-hydrophobic fast and super hydrophilic reversible conversion, it has long-term stability and repeated.
4) pattern of this ultra-hydrophobic conductive macromolecular nano fiber is controlled, and the pattern of its center is by the control of electrospinning parameter, and the shell of fiber was controlled by the in-situ polymerization time.
5) the present invention utilizes electrostatic spinning and in-situ polymerization technology, utilizes the reversible soda acid of conducting polymer to mix and the dedoping characteristic cleverly, has prepared the wettability of the super-hydrophobic and super hydrophilic reversible conversion with the response of pH value.This square law device is simple, easy to operate, and cost is low, applicability is wide.
Description of drawings
Fig. 1 is the stereoscan photograph of the ultra-hydrophobic conductive polyaniline nano fiber of embodiment 1 preparation.
Fig. 2 is the transmission electron microscope photo of the ultra-hydrophobic conductive polyaniline nano fiber of embodiment 1 preparation.
Fig. 3 is the X-photoelectron spectroscopy of N element of the ultra-hydrophobic conductive polyaniline nano fiber of embodiment 1 preparation.
Fig. 4 is the static contact angle photo of water droplet on the ultra-hydrophobic conductive polyaniline nano fiber surface of embodiment 1 preparation.
Fig. 5 is that 7 neutral solutions and pH are the contact angle that 13 aqueous slkali circulates and records for the ultra-hydrophobic conductive polyaniline nano fiber of embodiment 1 preparation and pH.
Fig. 6 is that 1 acid solution and pH are the contact angle that 13 aqueous slkali circulates and records for the ultra-hydrophobic conductive polyaniline nano fiber of embodiment 1 preparation and pH.
The specific embodiment
Embodiment 1,
1) polyacrylonitrile is dissolved in N, in the dinethylformamide, makes the polyacrylonitrile solution of 8wt%.
2) polyacrylonitrile solution in the step 1) is packed in the device for storing liquid of existing device for spinning, electrospinning operating distance (needle point is to the distance between the receiving device) is 8cm; Open high voltage source, regulate spinning voltage to 10kV, the average diameter that obtains solidifying on receiving system is the polyacrylonitrile nano fiber of 100 nanometers.
Described existing device for spinning comprises high-voltage DC power supply, liquid dispensing apparatus, injection apparatus and receiving system four parts; The output voltage of employed high-voltage DC power supply is 0~30Kv, and liquid dispensing apparatus is by gravity feeding, and injection apparatus adopts single injector head to spray, and receiving system is one to be placed on the rectangular slide on the aluminium platinum.
3) 1mL aniline is joined in the hydrochloric acid solution of 50mL 1mol/L, fully stirring and evenly mixing; With step 2) the polyacrylonitrile nano fiber 3g that obtains of electrospinning is immersed in the hydrochloric acid solution of this aniline; 0.6 gram ammonium persulfate is dissolved in the hydrochloric acid solution of 1mol/L of 50mL, slowly is added drop-wise in this system, evenly stir, make aniline at polyacrylonitrile nano fiber surface polymerization reaction take place, polymerization obtained electrically conductive polyaniline nano fiber after 1 hour.
4) electrically conductive polyaniline nano fiber that step 3) obtained is with 1mol/L ammoniacal liquor dedoping, with 1wt% perfluorooctane sulfonate this fiber that mixes, can obtain ultra-hydrophobic conductive polyaniline nano fiber of the present invention then.
The stereoscan photograph of the electrically conductive polyaniline nano fiber that this is super-hydrophobic and transmission electron microscope photo are distinguished as depicted in figs. 1 and 2, and as seen this nanofiber has nucleocapsid structure, and wherein " nuclear " is that diameter is the polyacrylonitrile nano fiber of 80 nanometers; Coaxial with it is the electrically conductive polyaniline " shell " of 80 nanometer thickness, and it is that 30 nano-conductive polyaniline particles are formed by particle diameter.
The X-photoelectron spectroscopy of the N element of the electrically conductive polyaniline nano fiber that this is super-hydrophobic as shown in Figure 3, this fiber shell is a doped polyaniline as can be known.
Water droplet at the static contact angle photo on this super-hydrophobic electrically conductive polyaniline nano fiber surface as shown in Figure 4, the contact angle of water and this electrically conductive polyaniline is 162.1 °, electrically conductive polyaniline nano fiber shows superhydrophobic characteristic.
This super-hydrophobic electrically conductive polyaniline nano fiber and 7 neutral solutions that at pH are and pH be the contact angle that records of 13 aqueous slkali circulation as shown in Figure 5, show the characteristic of super-hydrophobic and super hydrophilic reversible conversion.
This super-hydrophobic electrically conductive polyaniline nano fiber and 1 acid solution that is at pH and pH be the contact angle that records of 13 aqueous slkali circulation as shown in Figure 6, show the characteristic of hydrophobic and super hydrophilic reversible conversion.
Embodiment 2,
1) will gather oxireme and be dissolved in the chloroform, make the poly-oxireme solution of 10wt%.
2) the poly-oxireme solution in the step 1) is packed in the device for storing liquid of existing device for spinning, electrospinning operating distance (needle point is to the distance between the receiving device) is 10cm; Open high voltage source, regulate spinning voltage to 20kV, the average diameter that obtains solidifying on receiving system is the poly-oxireme nanofiber of 140 nanometers.
Described existing device for spinning comprises high-voltage DC power supply, liquid dispensing apparatus, injection apparatus and receiving system four parts; The output voltage of employed high-voltage DC power supply is 0~30Kv, and liquid dispensing apparatus is by gravity feeding, and injection apparatus adopts single injector head to spray, and receiving system is one to be placed on the rectangular slide on the aluminium platinum.
3) 1mL aniline is joined in the sulfuric acid solution of 50mL 1mol/L, fully stirring and evenly mixing; With step 2) the poly-oxireme nanofiber 3g that obtains of electrospinning is immersed in the sulfuric acid solution of this aniline; 3 gram ferric trichlorides are dissolved in the sulfuric acid solution of 1mol/L of 50mL, slowly are added drop-wise in this system, evenly stir, make aniline at the surperficial polymerization reaction take place of poly-oxireme nanofiber, polymerization obtained electrically conductive polyaniline nano fiber after 4 hours.
4) electrically conductive polyaniline nano fiber that step 3) is obtained is used this fiber of 1wt% perfluorooctane sulfonate solute doping then with 1mol/L sodium hydrate aqueous solution dedoping, can obtain ultra-hydrophobic conductive polyaniline nano fiber of the present invention.
This super-hydrophobic polyaniline nano fiber has nucleocapsid structure, and wherein " nuclear " is that diameter is the poly-oxireme nanofiber of 140 nanometers; Coaxial with it is the electrically conductive polyaniline " shell " of 100 nanometer thickness, and it is that 30 nano-conductive polyaniline particles are formed by particle diameter.
Water droplet is 160.4 ° at the static contact angle on this super-hydrophobic electrically conductive polyaniline nano fiber surface, shows superhydrophobic characteristic.
This super-hydrophobic electrically conductive polyaniline nano fiber with at 7 neutral solutions that pH is and pH be the characteristic that shows super-hydrophobic and super hydrophilic reversible conversion in 13 the aqueous slkali.
This super-hydrophobic electrically conductive polyaniline nano fiber and 1 acid solution that is at pH and pH are the characteristic that shows hydrophobic and super hydrophilic reversible conversion in 13 the aqueous slkali.
Embodiment 3,
1) polyvinylpyrrolidone is dissolved in the ethanol, makes the polyvinylpyrrolidonesolution solution of 12wt%.
2) the poly-oxireme solution in the step 1) is packed in the device for storing liquid of existing device for spinning, electrospinning operating distance (needle point is to the distance between the receiving device) is opened high voltage source for 12cm, regulate spinning voltage to 18kV, the average diameter that obtains solidifying on receiving system is the polyvinylpyrrolidonenanometer nanometer fiber of 160 nanometers.
Described existing device for spinning comprises high-voltage DC power supply, liquid dispensing apparatus, injection apparatus and receiving system four parts; The output voltage of employed high-voltage DC power supply is 0~30Kv, and liquid dispensing apparatus is by gravity feeding, and injection apparatus adopts single injector head to spray, and receiving system is one to be placed on the rectangular slide on the aluminium platinum.
3) 2mL aniline is joined in the sulfuric acid solution of 50mL 1mol/L, fully stirring and evenly mixing; With step 2) the poly-polyvinylpyrrolidonenanometer nanometer fiber 3g that obtains of electrospinning is immersed in the sulfuric acid solution of this aniline; 3 grammes per square metre potassium chromates are dissolved in the sulfuric acid solution of 1mol/L of 50mL, slowly are added drop-wise in this system, evenly stir, make aniline at polyvinylpyrrolidonenanometer nanometer fiber surface polymerization reaction take place, polymerization obtained electrically conductive polyaniline nano fiber after 8 hours.
4) electrically conductive polyaniline nano fiber that step 3) is obtained is used this fiber of 1wt% perfluorooctane sulfonate solute doping then with 1mol/L sodium hydrate aqueous solution dedoping, can obtain ultra-hydrophobic conductive polyaniline nano fiber of the present invention.
This super-hydrophobic polyaniline nano fiber has nucleocapsid structure, and wherein " nuclear " is that diameter is the polyvinylpyrrolidonenanometer nanometer fiber of 160 nanometers; Coaxial with it is the electrically conductive polyaniline " shell " of 130 nanometer thickness, and it is that 30 nano-conductive polyaniline particles are formed by particle diameter.
Water droplet is 163.5 ° at the static contact angle on this super-hydrophobic electrically conductive polyaniline nano fiber surface, shows superhydrophobic characteristic.
This super-hydrophobic electrically conductive polyaniline nano fiber with at 7 neutral solutions that pH is and pH be the characteristic that shows super-hydrophobic and super hydrophilic reversible conversion in 13 the aqueous slkali.
This super-hydrophobic electrically conductive polyaniline nano fiber and 1 acid solution that is at pH and pH are the characteristic that shows hydrophobic and super hydrophilic reversible conversion in 13 the aqueous slkali.
Embodiment 4,
1) polymethyl methacrylate is dissolved in the acetone, makes the polymethyl methacrylate solution of 15wt%.
2) the poly-oxireme solution in the step 1) is packed in the device for storing liquid of existing device for spinning, electrospinning operating distance (needle point is to the distance between the receiving device) is 10cm; Open high voltage source, regulate spinning voltage to 22kV, the average diameter that obtains solidifying on receiving system is the polymethyl methacrylate nano fiber of 150 nanometers.
Described existing device for spinning comprises high-voltage DC power supply, liquid dispensing apparatus, injection apparatus and receiving system four parts; The output voltage of employed high-voltage DC power supply is 0~30Kv, and liquid dispensing apparatus is by gravity feeding, and injection apparatus adopts single injector head to spray, and receiving system is one to be placed on the rectangular slide on the aluminium platinum.
3) 2mL aniline is joined in the hydrochloric acid solution of 50mL 1mol/L, fully stirring and evenly mixing; With step 2) the polymethyl methacrylate nano fiber 3g that obtains of electrospinning is immersed in the hydrochloric acid solution of this aniline; 4 gram hydroperoxide dissolutions in the hydrochloric acid solution of the 1mol/L of 50mL, slowly are added drop-wise in this system, evenly stir, make aniline at polymethyl methacrylate nano fiber surface polymerization reaction take place, polymerization obtained electrically conductive polyaniline nano fiber after 9 hours.
4) electrically conductive polyaniline nano fiber that step 3) is obtained is used this fiber of 1wt% perfluorooctane sulfonate solute doping then with 1mol/L sodium hydrate aqueous solution dedoping, can obtain ultra-hydrophobic conductive polyaniline nano fiber of the present invention.
This super-hydrophobic polyaniline nano fiber has nucleocapsid structure, and wherein " nuclear " is that diameter is the polyvinylpyrrolidonenanometer nanometer fiber of 150 nanometers; Coaxial with it is the electrically conductive polyaniline " shell " of 140 nanometer thickness, and it is that 30 nano-conductive polyaniline particles are formed by particle diameter.
Water droplet is 164.2 ° at the static contact angle on this super-hydrophobic electrically conductive polyaniline nano fiber surface, shows superhydrophobic characteristic.
This super-hydrophobic electrically conductive polyaniline nano fiber with at 7 neutral solutions that pH is and pH be the characteristic that shows super-hydrophobic and super hydrophilic reversible conversion in 13 the aqueous slkali.
This super-hydrophobic electrically conductive polyaniline nano fiber and 1 acid solution that is at pH and pH are the characteristic that shows hydrophobic and super hydrophilic reversible conversion in 13 the aqueous slkali.
Embodiment 5,
1) polyvinyl alcohol is dissolved in the deionized water, makes the solution of 10wt% polyvinyl alcohol.
2) poly-vinyl alcohol solution in the step 1) is packed in the device for storing liquid of existing device for spinning, electrospinning operating distance (needle point is to the distance between the receiving device) is 20cm; Open high voltage source, regulate spinning voltage to 26kV, the average diameter that obtains solidifying on receiving system is the polyvinyl alcohol nano of 130 nanometers.
Described existing device for spinning comprises high-voltage DC power supply, liquid dispensing apparatus, injection apparatus and receiving system four parts; The output voltage of employed high-voltage DC power supply is 0~30Kv, and liquid dispensing apparatus is by gravity feeding, and injection apparatus adopts single injector head to spray, and receiving system is an electro-conductive glass.
3) 1mL pyrroles is joined in the sulfuric acid solution of 50mL 1mol/L, fully stirring and evenly mixing; With step 2) the polyvinyl alcohol nano 4g that obtains of electrospinning is immersed in this pyrroles's the hydrochloric acid solution; 5 grammes per square metre potassium chromates are dissolved in the sulfuric acid solution of 1mol/L of 50mL, slowly are added drop-wise in this system, evenly stir, make the pyrroles at polyvinyl alcohol nano surface polymerization reaction take place, polymerization obtained the electric polypyrrole nano fiber after 8 hours.
4) the electric polypyrrole nano fiber that step 3) is obtained is used this fiber of 1wt% perfluor ethylsulfonic acid solute doping then with 1mol/L sodium hydrate aqueous solution dedoping, can obtain ultra-hydrophobic conductive polypyrrole nanofiber of the present invention.
This ultra-hydrophobic conductive polypyrrole nanofiber has nucleocapsid structure, and wherein " nuclear " is that diameter is the polyvinyl alcohol nano of 130 nanometers; That coaxial with it is conduction pyrroles's " shell " of 120 nanometer thickness, and it is that 30 conductive nano polypyrrole particles are formed by particle diameter.
Water droplet is 157.8 ° at the static contact angle of this super-hydrophobic electric polypyrrole nano fiber surface, shows superhydrophobic characteristic.
This super-hydrophobic electric polypyrrole nano fiber with at 7 neutral solutions that pH is and pH be the characteristic that shows super-hydrophobic and super hydrophilic reversible conversion in 13 the aqueous slkali.
This super-hydrophobic electric polypyrrole nano fiber and 1 acid solution that is at pH and pH are the characteristic that shows hydrophobic and super hydrophilic reversible conversion in 13 the aqueous slkali.
Embodiment 6,
1) with in the molten ethanolic solution of cellulose acetate, makes the cellulose acetate solution of 15wt%.
2) cellulose acetate solution in the step 1) is packed in the device for storing liquid of existing device for spinning, electrospinning operating distance (needle point is to the distance between the receiving device) is 10cm; Open high voltage source, regulate spinning voltage to 20kV, the average diameter that obtains solidifying on receiving system is the cellulose acetate nanofiber of 200 nanometers.
Described existing device for spinning comprises high-voltage DC power supply, liquid dispensing apparatus, injection apparatus and receiving system four parts; The output voltage of employed high-voltage DC power supply is 0~30Kv, and liquid dispensing apparatus is by gravity feeding, and injection apparatus adopts single injector head to spray receiving system one electro-conductive glass.
3) 2mL pyrroles is joined in the hydrochloric acid solution of 50mL lmol/L, fully stirring and evenly mixing; With step 2) the cellulose acetate nanofiber 4g that obtains of electrospinning is immersed in this pyrroles's the hydrochloric acid solution; 5 gram manganese dioxide are dissolved in the hydrochloric acid solution of 1mol/L of 50mL, slowly are added drop-wise in this system, evenly stir, make the pyrroles at cellulose acetate fibre surface polymerization reaction take place, polymerization obtained the electric polypyrrole nano fiber after 24 hours.
4) the electric polypyrrole nano fiber that step 3) obtained is with 1mol/L ammoniacal liquor dedoping, with 1wt% perfluor ethylsulfonic acid this fiber that mixes, can obtain ultra-hydrophobic conductive polypyrrole nanofiber of the present invention then.
This ultra-hydrophobic conductive polypyrrole nanofiber has nucleocapsid structure, and wherein " nuclear " is that diameter is the cellulose acetate nanofiber of 200 nanometers; That coaxial with it is conduction pyrroles's " shell " of 200 nanometer thickness, and it is that 40 conductive nano polypyrrole particles are formed by particle diameter.
Water droplet is 154.3 ° at the static contact angle of this super-hydrophobic electric polypyrrole nano fiber surface, shows superhydrophobic characteristic.
This super-hydrophobic electric polypyrrole nano fiber with at 7 neutral solutions that pH is and pH be the characteristic that shows super-hydrophobic and super hydrophilic reversible conversion in 13 the aqueous slkali.
This super-hydrophobic electric polypyrrole nano fiber and 1 acid solution that is at pH and pH are the characteristic that shows hydrophobic and super hydrophilic reversible conversion in 13 the aqueous slkali.
Embodiment 7,
1) with in the molten tetrahydrofuran solution of Merlon, makes the polycarbonate solution of 17wt%;
2) polycarbonate solution in the step 1) is packed in the device for storing liquid of existing device for spinning, electrospinning operating distance (needle point is to the distance between the receiving device) is 18cm; Open high voltage source, regulate spinning voltage to 22kV, the average diameter that obtains solidifying on receiving system is the polycarbonate nano fiber of 180 nanometers.
Described existing device for spinning comprises high-voltage DC power supply, liquid dispensing apparatus, injection apparatus and receiving system four parts; The output voltage of employed high-voltage DC power supply is 0~30Kv, and liquid dispensing apparatus is by gravity feeding, and injection apparatus adopts single injector head to spray receiving system one electro-conductive glass.
3) 1mL pyrroles is joined in the sulfuric acid solution of 50mL 1mol/L, fully stirring and evenly mixing; With step 2) the polycarbonate nano fiber 3g that obtains of electrospinning is immersed in this pyrroles's the sulfuric acid solution; 3 gram sodium peroxydisulfates are dissolved in the sulfuric acid solution of 1mol/L of 50mL, slowly are added drop-wise in this system, evenly stir, make the pyrroles at polycarbonate nano fiber surface polymerization reaction take place, polymerization obtained the electric polypyrrole nano fiber after 12 hours.
4) the electric polypyrrole nano fiber that step 3) obtained is with 1mol/L potassium hydroxide solution dedoping, with 1wt% perfluor ethylsulfonic acid this fiber that mixes, can obtain ultra-hydrophobic conductive polypyrrole nanofiber of the present invention then.
This ultra-hydrophobic conductive polypyrrole nanofiber has nucleocapsid structure, and wherein " nuclear " is that diameter is the polycarbonate nano fiber of 180 nanometers; That coaxial with it is conduction pyrroles's " shell " of 150 nanometer thickness, and it is that 30 conductive nano polypyrrole particles are formed by particle diameter.
Water droplet is 154.7 ° at the static contact angle of this super-hydrophobic electric polypyrrole nano fiber surface, shows superhydrophobic characteristic.
This super-hydrophobic electric polypyrrole nano fiber with at 7 neutral solutions that pH is and pH be the characteristic that shows super-hydrophobic and super hydrophilic reversible conversion in 13 the aqueous slkali.
This super-hydrophobic electric polypyrrole nano fiber and 1 acid solution that is at pH and pH are the characteristic that shows hydrophobic and super hydrophilic reversible conversion in 13 the aqueous slkali.
Embodiment 8,
2) polyacrylamide is dissolved in the deionized water, makes the polyacrylamide solution of 5wt%.
2) polyacrylamide solution in the step 1) is packed in the device for storing liquid of existing device for spinning, electrospinning operating distance (needle point is to the distance between the receiving device) is 14cm; Open high voltage source, regulate spinning voltage to 18kV, the average diameter that obtains solidifying on receiving system is the polyacrylamide nano fiber of 80 nanometers.
Described existing device for spinning comprises high-voltage DC power supply, liquid dispensing apparatus, injection apparatus and receiving system four parts; The output voltage of employed high-voltage DC power supply is 0~30Kv, and liquid dispensing apparatus is by gravity feeding, and injection apparatus adopts single injector head to spray receiving system one electro-conductive glass.
3) 2mL pyrroles is joined in the hydrochloric acid solution of 50mL 1mol/L, fully stirring and evenly mixing; With step 2) the polyacrylamide nano fiber 3g that obtains of electrospinning is immersed in this pyrroles's the hydrochloric acid solution; Restrained the dichloride copper dissolution in the hydrochloric acid solution of the 1mol/L of 50mL with 4, and slowly be added drop-wise in this system, and evenly stirred, and made the pyrroles at polyacrylamide nano fiber surface polymerization reaction take place, polymerization obtained the electric polypyrrole nano fiber after 11 hours.
4) the electric polypyrrole nano fiber that step 3) obtained is with 1mol/L ammoniacal liquor dedoping, with 1wt% perfluor ethylsulfonic acid this fiber that mixes, can obtain ultra-hydrophobic conductive polypyrrole nanofiber of the present invention then.
This ultra-hydrophobic conductive polypyrrole nanofiber has nucleocapsid structure, and wherein " nuclear " is that diameter is the polycarbonate nano fiber of 80 nanometers; That coaxial with it is conduction pyrroles's " shell " of 140 nanometer thickness, and it is that 30 conductive nano polypyrrole particles are formed by particle diameter.
Water droplet is 154.7 ° at the static contact angle of this super-hydrophobic electric polypyrrole nano fiber surface, shows superhydrophobic characteristic.
This super-hydrophobic electric polypyrrole nano fiber with at 7 neutral solutions that pH is and pH be the characteristic that shows super-hydrophobic and super hydrophilic reversible conversion in 13 the aqueous slkali.
This super-hydrophobic electric polypyrrole nano fiber and 1 acid solution that is at pH and pH are the characteristic that shows hydrophobic and super hydrophilic reversible conversion in 13 the aqueous slkali.
Embodiment 9,
1) PLA is dissolved in the ethanol, makes the PLA solution of 20wt%.
2) the PLA solution in the step 1) is packed in the device for storing liquid of existing device for spinning, electrospinning operating distance (needle point is to the distance between the receiving device) is 10cm; Open high voltage source, regulate spinning voltage to 20kV, the average diameter that obtains solidifying on receiving system is the polylactic acid nano fiber of 300 nanometers.
Described existing device for spinning comprises high-voltage DC power supply, liquid dispensing apparatus, injection apparatus and receiving system four parts; The output voltage of employed high-voltage DC power supply is 0~30Kv, and liquid dispensing apparatus is by gravity feeding, and injection apparatus adopts single injector head to spray, and receiving system is one to be placed on the rectangular slide on the aluminium platinum.
3) the 1mL thiophene is joined in the hydrochloric acid solution of 50mL 1mol/L, fully stirring and evenly mixing; With step 2) the polylactic acid nano fiber 4g that obtains of electrospinning is immersed in the hydrochloric acid solution of this thiophene; 1 gram ammonium persulfate is dissolved in the hydrochloric acid solution of 1mol/L of 50mL, slowly is added drop-wise in this system, evenly stir, make thiophene at polylactic acid nano fiber surface polymerization reaction take place, polymerization obtained the conductive polythiophene nanofiber after 2 hours.
4) the conductive polythiophene nanofiber that step 3) obtained is with 1mol/L ammoniacal liquor dedoping, with 1wt% perfluorooctane sulfonate this fiber that mixes, can obtain ultra-hydrophobic conductive polythiophene nanofiber of the present invention then.
This ultra-hydrophobic conductive polythiophene nanofiber has nucleocapsid structure, and wherein " nuclear " is that diameter is the polylactic acid nano fiber of 300 nanometers; Coaxial with it is the conduction thiophene " shell " of 100 nanometer thickness, and it is that 30 conductive nano polythiophene particles are formed by particle diameter.
Water droplet is 156.5 ° at the static contact angle on this super-hydrophobic conductive polythiophene nanofiber surface, shows superhydrophobic characteristic.
This super-hydrophobic conductive polythiophene nanofiber with at 7 neutral solutions that pH is and pH be the characteristic that shows super-hydrophobic and super hydrophilic reversible conversion in 13 the aqueous slkali.
This super-hydrophobic conductive polythiophene nanofiber and 1 acid solution that is at pH and pH are the characteristic that shows hydrophobic and super hydrophilic reversible conversion in 13 the aqueous slkali.
Embodiment 10,
1) polyvinyl chloride is dissolved in the acetic acid, makes the polyvinyl chloride solution of 8wt%.
2) polyvinyl chloride solution in the step 1) is packed in the device for storing liquid of existing device for spinning, electrospinning operating distance (needle point is to the distance between the receiving device) is 12cm; Open high voltage source, regulate spinning voltage to 18kV, the average diameter that obtains solidifying on receiving system is the polyvinyl chloride nano fiber of 110 nanometers.
Described existing device for spinning comprises high-voltage DC power supply, liquid dispensing apparatus, injection apparatus and receiving system four parts; The output voltage of employed high-voltage DC power supply is 0~30Kv, and liquid dispensing apparatus is by gravity feeding, and injection apparatus adopts single injector head to spray, and receiving system is one to be placed on the rectangular slide on the aluminium platinum.
3) the 2mL thiophene is joined in the sulfuric acid solution of 50mL 1mol/L, fully stirring and evenly mixing; With step 2) the polyvinyl chloride nano fiber 3g that obtains of electrospinning is immersed in the sulfuric acid solution of this thiophene; 5 gram hydroperoxide dissolutions in the sulfuric acid solution of the 1mol/L of 50mL, slowly are added drop-wise in this system, evenly stir, make thiophene, behind the polyase 13 hour, obtain the conductive polythiophene nanofiber at polyvinyl chloride nano fiber surface polymerization reaction take place.
4) the conductive polythiophene nanofiber that step 3) obtained is with 1mol/L ammoniacal liquor dedoping, with 1wt% perfluorooctane sulfonate this fiber that mixes, can obtain ultra-hydrophobic conductive polythiophene nanofiber of the present invention then.
This ultra-hydrophobic conductive polythiophene nanofiber has nucleocapsid structure, and wherein " nuclear " is that diameter is the polylactic acid nano fiber of 110 nanometers; Coaxial with it is the conduction thiophene " shell " of 100 nanometer thickness, and it is that 30 conductive nano polythiophene particles are formed by particle diameter.
Water droplet is 154.9 ° at the static contact angle on this super-hydrophobic conductive polythiophene nanofiber surface, shows superhydrophobic characteristic.

Claims (10)

1, a kind of ultra-hydrophobic conductive macromolecular nano fiber, it is the co-axial nano fiber with nucleocapsid structure, described " nuclear " is that diameter is the polymer fiber of 80~300 nanometers, and coaxial with it " shell " is 80~200 nanometer thickness electroconductive polymer layers, it is that 20~40 conductivity high molecule nanometer particles are formed by particle diameter.
2, ultra-hydrophobic conductive macromolecular nano fiber as claimed in claim 1 is characterized in that: described polymer is polyacrylonitrile, poly-oxireme, polyvinylpyrrolidone, polymethyl methacrylate, polyvinyl alcohol, cellulose acetate, Merlon, polyacrylamide, PLA or polyvinyl chloride.
3, ultra-hydrophobic conductive macromolecular nano fiber as claimed in claim 1 is characterized in that: described conducting polymer is polyaniline, polythiophene or polypyrrole.
4, the preparation method of the described ultra-hydrophobic conductive macromolecular nano fiber of a kind of claim 1, it has utilized electrostatic spinning and in-situ chemical oxidation polymerization method, specifically comprises the steps:
1) polymer is dissolved in the solvent, makes the polymer solution of 5~20wt%;
Described polymer is polyacrylonitrile, poly-oxireme, polyvinylpyrrolidone, polymethyl methacrylate, polyvinyl alcohol, cellulose acetate, Merlon, polyacrylamide, PLA or polyvinyl chloride;
2) during the polymer solution that step 1) is made was packed the device for storing liquid of existing device for spinning into, the electrospinning operating distance was 8~20cm; Open high voltage source, regulate spinning voltage to 10~26kV, polymer electrospinning solution sprays from injection apparatus, and forms the Taylor awl at the spinning nozzle place, solvent evaporates subsequently, the diameter that obtains solidifying on receiving system is the polymer nanofiber of 80~300 nanometers;
3) 1~2mL conductive high polymer monomer is joined in the hydrochloric acid or sulfuric acid of 50mL 1mol/L, fully stirring and evenly mixing; With step 2) in the polymer nanofiber that obtains of electrospinning be immersed in the acid solution of this conductive high polymer monomer;
Described conductive high polymer monomer is aniline, thiophene or pyrroles;
4) 0.6~5 gram oxidant is dissolved in the hydrochloric acid or sulfuric acid of 50mL 1mol/L, slowly is added drop-wise in the system of step 3), evenly stir, conductive high polymer monomer obtains conductive macromolecular nano fiber at polymer nanofiber surface polymerization reaction take place;
5) with the conductive macromolecular nano fiber that obtains in step 4) 1mol/L alkaline solution dedoping, use fluorine-containing this fiber of organic sulfonic acid solute doping of 1wt% then, obtain ultra-hydrophobic conductive macromolecular nano fiber of the present invention.
5, the preparation method of ultra-hydrophobic conductive macromolecular nano fiber as claimed in claim 4, it is characterized in that: the solvent of described step 1) is that described solvent is deionized water, ethanol, acetone, chloroform, N, dinethylformamide, oxolane or acetic acid.
6, the preparation method of ultra-hydrophobic conductive macromolecular nano fiber as claimed in claim 4 is characterized in that: electric spinning equipment described step 2) comprises high-voltage DC power supply, device for storing liquid, injection apparatus and receiving system four parts; The output voltage of employed high-voltage DC power supply is 0~30kV, device for storing liquid is vertically placed, injection apparatus adopts single injector head to spray, receiving system be with different conductive metal sheet, wire netting, metallic film or electro-conductive glass as the conduction gatherer, or on above-mentioned conduction gatherer, load a nonconducting receiver.
7, the preparation method of ultra-hydrophobic conductive macromolecular nano fiber as claimed in claim 4 is characterized in that: the oxidant of described step 4) is ammonium persulfate, sodium peroxydisulfate, ferric trichloride, manganese oxide, hydrogen peroxide, potassium bichromate or dichloride copper.
8, the preparation method of ultra-hydrophobic conductive macromolecular nano fiber as claimed in claim 4 is characterized in that: the alkaline solution of described step 5) is ammoniacal liquor, sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
9, the preparation method of ultra-hydrophobic conductive macromolecular nano fiber as claimed in claim 4 is characterized in that: the fluorine-containing organic sulfonic acid of described step 5) is perfluorooctane sulfonate or perfluor ethylsulfonic acid; Its solvent is deionized water, chloroform or ethanol.
10, the described ultra-hydrophobic conductive macromolecular nano fiber of claim 1 is in the application that is used on intelligent microfluid switch, controlled isolation technics, controlled drug, the stealth technology that can switch fast, electromagnetic shielding, antistatic, the anticorrosive or sensor.
CNB2005100766596A 2005-06-13 2005-06-13 Ultra-hydrophobic conductive macromolecular nano fiber and method for preparing same and use thereof Expired - Fee Related CN100360725C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2005100766596A CN100360725C (en) 2005-06-13 2005-06-13 Ultra-hydrophobic conductive macromolecular nano fiber and method for preparing same and use thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2005100766596A CN100360725C (en) 2005-06-13 2005-06-13 Ultra-hydrophobic conductive macromolecular nano fiber and method for preparing same and use thereof

Publications (2)

Publication Number Publication Date
CN1880526A CN1880526A (en) 2006-12-20
CN100360725C true CN100360725C (en) 2008-01-09

Family

ID=37518872

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2005100766596A Expired - Fee Related CN100360725C (en) 2005-06-13 2005-06-13 Ultra-hydrophobic conductive macromolecular nano fiber and method for preparing same and use thereof

Country Status (1)

Country Link
CN (1) CN100360725C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108396561A (en) * 2018-04-10 2018-08-14 天津工业大学 A kind of core-shell structural conductive nanofiber and preparation method thereof

Families Citing this family (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100526524C (en) * 2007-02-02 2009-08-12 吉林大学 No-solvent electrically spinning process for preparing micron and nanometer fiber
RU2490738C2 (en) * 2007-11-27 2013-08-20 Мария СТРЕММЕ Composite materials containing internally conducting polymer and method and apparatus
CN101200510B (en) * 2007-11-27 2012-05-23 南京大学 Soluble organic macromolecule conducting material and method for producing the same
CN101226161B (en) * 2008-01-31 2010-11-03 浙江大学 Preparation method of polymethyl methacrylate/polyaniline nano fibre composite resistor type film gas sensor
CN101266225B (en) * 2008-04-28 2010-12-29 吉林大学 Electric spinning method for preparing high performance ceramic base nanometer fibre gas-sensitive sensor
TWI414345B (en) * 2010-01-04 2013-11-11 Taiwan Textile Res Inst A nanofiber-containing membrane, a composite membrane, a process for producing them and their use
CN101805940A (en) * 2010-03-23 2010-08-18 浙江大学 Polymer electrospun fibers, preparation method thereof and application thereof
CN101892530B (en) * 2010-07-15 2012-06-13 东华大学 Preparation of polyaniline/polypyrrole composite nano fiber electrode materials with core-shell structure
CN102212210B (en) * 2011-04-29 2014-06-11 南京理工大学 Method for preparing polyaniline-coated bacteria cellulose nano conductive composite by in-situ polymerization
CN102443870B (en) * 2011-09-13 2013-07-24 青岛大学 Method for preparing ordered coaxial structural micro and nano fibers
CN102517670B (en) * 2011-11-08 2013-11-06 上海理工大学 Method for preparing polyacrylonitrile nano-fibers by circulation and coaxial electrospinning of surface active agent solution
CN102517690B (en) * 2011-12-14 2013-09-04 燕山大学 Method for preparing polyaniline composite conductive fiber
CN102561042A (en) * 2012-01-10 2012-07-11 青岛大学 Preparation method for dendritic-nanometer-structure polyaniline air-sensitive sensor
CN102605554A (en) * 2012-03-16 2012-07-25 北京化工大学 Preparation method for super-hydrophobic and super-hydrophilic electrostatic spinning nanofiber composite membranes
CN103572606B (en) * 2012-08-07 2016-04-20 嘉兴学院 There is compound porous fiber and the double-hole structural membrane preparation method of nucleocapsid structure
CN103572408B (en) * 2012-08-07 2015-11-25 嘉兴学院 The electroactive composite fibre of nucleocapsid structure and tissue engineering bracket preparation method
CN103668529B (en) * 2012-09-06 2015-10-21 北京服装学院 Prepare composite conducting fiber method, the composite conducting fiber obtained thus and application thereof
CN102967715B (en) * 2012-10-25 2014-09-03 杭州普施康生物科技有限公司 Novel ELISA biochemical optical disk detection system
CN103047485A (en) * 2012-11-16 2013-04-17 李宏江 Manufacturing method and application scheme for super drain pipes capable of reducing hydraulic resistance
CN103243481B (en) * 2013-05-20 2016-06-08 东华大学 A kind of electrospinning process prepared containing micro-nano ball fiber
CN103255634B (en) * 2013-05-23 2015-08-12 中原工学院 A kind of preparation method of polyacrylonitrile/pocompounde compounde micro-nano conductive fiber
CN103243563B (en) * 2013-05-23 2015-09-02 中原工学院 A kind of preparation method of polylactic acid/polyaniline composite conductive fiber
CN105200658B (en) * 2014-06-30 2019-03-26 天津工业大学 A kind of composite nano-fiber membrane and preparation method thereof for electromagnetic shielding
CN106555242B (en) * 2015-09-25 2019-02-19 中国石油化工股份有限公司 A kind of conductive polymer fibers and its preparation method and application
CN105388198B (en) * 2015-10-16 2018-08-10 武汉纺织大学 A kind of preparation of bundles of nanofibers based transistor and its application in ion sensor
CN105536052A (en) * 2015-12-28 2016-05-04 北京航空航天大学 Preparing method of magnetic-electro dual function nanofiber membrane
CN105624830B (en) * 2016-01-06 2017-12-22 东华大学 A kind of uvioresistant PAN/GO Coaxial Nanofibers and preparation method thereof
CN105696110A (en) * 2016-02-26 2016-06-22 哈尔滨工业大学深圳研究生院 Conductive nanofiber and preparation method and application thereof
CN105696197B (en) * 2016-03-22 2018-01-19 东华大学 A kind of c-type core-shell nano tunica fibrosa and its eccentric shaft electrostatic spinning preparation method
CN105820372B (en) * 2016-03-30 2019-04-09 青岛大学 A kind of conduction aeroge and preparation method thereof
CN106189604A (en) * 2016-08-25 2016-12-07 阜南县天亿工艺品有限公司 A kind of wood artwork water paint containing antistatic multiple cellulose acetate nanofiber and preparation method thereof
CN108193500B (en) * 2016-12-08 2020-04-24 中国科学院大连化学物理研究所 Composite nanofiber, composite nanofiber supported catalyst, preparation method and application thereof
CN106992418A (en) * 2017-03-08 2017-07-28 宁波高新区远创科技有限公司 A kind of preparation method of corrosion-resistant substation grounding material
CN106916255A (en) * 2017-04-08 2017-07-04 新沂市中诺新材料科技有限公司 A kind of preparation method of novel C e PPy/PMMA nano core-shell composite conducting materials
CN107699974A (en) * 2017-09-13 2018-02-16 铜陵海源超微粉体有限公司 A kind of preparation method of modified oxidized iron Vingon electrospun material
CN110655768A (en) * 2017-12-06 2020-01-07 雷珊珊 Polylactic acid fiber fused polypyrrole material and preparation method thereof
CN109913971A (en) * 2017-12-12 2019-06-21 中国科学院大连化学物理研究所 A kind of porous composite nano fiber and its preparation method and application
CN108385206A (en) * 2018-02-01 2018-08-10 福建农林大学 A kind of konjaku glucomannan electroresponse spiral bionic fiber and preparation method thereof
CN108677274B (en) * 2018-04-08 2020-10-02 中国科学院深圳先进技术研究院 Polymer fiber with fluorine-doped surface and preparation method thereof
CN108771977A (en) * 2018-07-04 2018-11-09 南京林业大学 A kind of preparation method of the super-hydrophobic super-oleophylic nano fibrous membrane based on layer-by-layer for oil water mixture separation
CN109762186A (en) * 2019-01-04 2019-05-17 华南理工大学 A kind of fibre-reinforced high molecular basis material and the preparation method and application thereof based on interface response
CN109795001B (en) * 2019-02-25 2021-02-26 山东农业大学 Preparation method of humidity stimulation response type transparent cellulose membrane driver
CN109880127B (en) * 2019-03-05 2022-02-08 中原工学院 Preparation method of high-strength triple-network polypyrrole-based conductive composite hydrogel material
CN109856295B (en) * 2019-03-25 2022-04-26 东南大学 Method for extracting fluoroquinolone veterinary drug residues in animal derived food
CN110409058B (en) * 2019-07-24 2022-03-04 武汉理工大学 Preparation method of polyacrylonitrile/polyaniline/nickel nanofiber membrane for artificial nerve conduit
CN110396730B (en) * 2019-07-30 2022-05-03 江苏锵尼玛新材料股份有限公司 Conductive polyaniline blend fiber and preparation method and application thereof
CN112695437B (en) * 2020-12-19 2022-11-04 杭州文宇纺织有限公司 Pillowcase fabric and processing technology thereof
CN113026209B (en) * 2021-02-08 2021-12-21 东华大学 Self-driven piezoelectric response surface hydrophilicity and hydrophobicity regulating fiber membrane and preparation method thereof
CN116904073A (en) * 2023-07-13 2023-10-20 江阴纳力新材料科技有限公司 Preparation method of water-resistant carbon-coated slurry and carbon-coated current collector

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1408082A (en) * 1973-01-04 1975-10-01 Ici Ltd Filaments
JPS6175810A (en) * 1984-09-21 1986-04-18 Unitika Ltd Electrically conductive regenerated cellulosic fiber
CN1450210A (en) * 2003-04-29 2003-10-22 东华大学 Polyaniline/polyacrylonitrile composite conductive fibre and preparation process thereof
JP2004225214A (en) * 2003-01-24 2004-08-12 Toray Ind Inc Electroconductive conjugated fiber
WO2005005696A1 (en) * 2003-06-30 2005-01-20 The Procter & Gamble Company Coated nanofiber webs
CN1569933A (en) * 2003-07-16 2005-01-26 中国科学院化学研究所 Soakage reversibly variable temperature-responsive copolymer film preparation method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1408082A (en) * 1973-01-04 1975-10-01 Ici Ltd Filaments
JPS6175810A (en) * 1984-09-21 1986-04-18 Unitika Ltd Electrically conductive regenerated cellulosic fiber
JP2004225214A (en) * 2003-01-24 2004-08-12 Toray Ind Inc Electroconductive conjugated fiber
CN1450210A (en) * 2003-04-29 2003-10-22 东华大学 Polyaniline/polyacrylonitrile composite conductive fibre and preparation process thereof
WO2005005696A1 (en) * 2003-06-30 2005-01-20 The Procter & Gamble Company Coated nanofiber webs
CN1569933A (en) * 2003-07-16 2005-01-26 中国科学院化学研究所 Soakage reversibly variable temperature-responsive copolymer film preparation method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
二氧化硅@聚合物同轴纳米纤维. 洪友良,商铁存,靳玉伟,杨帆,王策.高等学校化学学报,第26卷第5期. 2005 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108396561A (en) * 2018-04-10 2018-08-14 天津工业大学 A kind of core-shell structural conductive nanofiber and preparation method thereof

Also Published As

Publication number Publication date
CN1880526A (en) 2006-12-20

Similar Documents

Publication Publication Date Title
CN100360725C (en) Ultra-hydrophobic conductive macromolecular nano fiber and method for preparing same and use thereof
CN103255634B (en) A kind of preparation method of polyacrylonitrile/pocompounde compounde micro-nano conductive fiber
Ju et al. Redox‐active iron‐citrate complex regulated robust coating‐free hydrogel microfiber net with high environmental tolerance and sensitivity
Wu et al. Electrospinning of multilevel structured functional micro-/nanofibers and their applications
Laforgue et al. Production of conductive PEDOT nanofibers by the combination of electrospinning and vapor-phase polymerization
CN105696110A (en) Conductive nanofiber and preparation method and application thereof
CN101133104B (en) Conductive polymer composed of particles having anisotropic morphology
CN103192074B (en) Highly dispersed sliver powder and conductive silver paste for film batteries
CN107819095B (en) A kind of high security complex lithium electric separator and preparation method thereof
CN103361885B (en) A kind of preparation method of antibacterial fibroin fiber film
CN103213350B (en) Transparent conductive film and preparation method thereof
Mu et al. Electroless silver plating on PET fabric initiated by in situ reduction of polyaniline
CN103219090B (en) A kind of preparation method of Nano Silver coated high molecular microsphere composite conductive silver slurry
CN105332092B (en) A kind of flexible micro nanometer fiber twisted wire with electromagnetic performance and preparation method thereof
Liu et al. Hollow nanostructured polyaniline: preparation, properties and applications
CN104911719A (en) Method for preparing conducting polymer micro-nanofibers in magnetic spinning mode
KR101816761B1 (en) Oxidation resistant hybrid structure including metal thin film coated on conductive polymer structure, and method of preparing the same
CN101275299A (en) Thermal bubble spinning method and device for nano-fiber production
CN105506783A (en) Preparation method for barium titanate nanofiber arrayed in orientation mode
CN108726485B (en) Porous hollow oxide nano-microsphere and preparation method and application thereof
CN111253914A (en) Phase change microcapsule with core-shell structure and preparation method and application thereof
CN106001583A (en) Preparation method of silver nanowire
CN104538121B (en) Photo-electro-magnetic three-function banded coaxial nano cable array and preparation method thereof
CN105332136A (en) Conductive micro-nanometer fiber stranded wire based on solvent-free electrospinning and preparing method thereof
CN107910097B (en) A kind of transparent conductive electrode and preparation method thereof with sunk structure

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080109

Termination date: 20130613