EP2084312A2 - Procédé de fabrication de fibres nano- et mésopolymères par électrofilage de polyélectrolytes de charges opposées - Google Patents

Procédé de fabrication de fibres nano- et mésopolymères par électrofilage de polyélectrolytes de charges opposées

Info

Publication number
EP2084312A2
EP2084312A2 EP07817714A EP07817714A EP2084312A2 EP 2084312 A2 EP2084312 A2 EP 2084312A2 EP 07817714 A EP07817714 A EP 07817714A EP 07817714 A EP07817714 A EP 07817714A EP 2084312 A2 EP2084312 A2 EP 2084312A2
Authority
EP
European Patent Office
Prior art keywords
water
fibers
polymer
solution
electrospinning
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.)
Granted
Application number
EP07817714A
Other languages
German (de)
English (en)
Other versions
EP2084312B1 (fr
Inventor
Andreas Greiner
Lisa Hamel
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.)
Philipps Universitaet Marburg
Original Assignee
Philipps Universitaet Marburg
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 Philipps Universitaet Marburg filed Critical Philipps Universitaet Marburg
Publication of EP2084312A2 publication Critical patent/EP2084312A2/fr
Application granted granted Critical
Publication of EP2084312B1 publication Critical patent/EP2084312B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds

Definitions

  • the present invention relates to a process for the preparation of polymer fibers, in particular of nano- and mesofasem, wherein an aqueous solution of oppositely charged polyelectrolytes is electro-spun, and fibers obtainable by this process. After subsequent contact with water there is no disintegration of the fibers according to the invention.
  • the present invention relates to the fields of macromolecular chemistry, process engineering and materials science.
  • a polymer melt or a polymer solution is usually exposed to a high electric field at an edge serving as an electrode, which can be achieved, for example, by subjecting the polymer melt or polymer solution in an electric field under low pressure to a pole Due to the resulting electrostatic charging of the polymer melt or polymer solution, a material flow directed onto the counterelectrode, which solidifies on the way to the counterelectrode, is produced with this method depending on the electrode geometries called nonwovens or ensembles of ordered fibers.
  • DE 101 33 393 A1 discloses a process for producing hollow fibers having an inner diameter of 1 to 100 nm, in which a solution of a water-insoluble polymer-for example a poly-L-lactide solution in dichloromethane or a polyamide-46 Solution in pyridine - is electrospun.
  • a solution of a water-insoluble polymer-for example a poly-L-lactide solution in dichloromethane or a polyamide-46 Solution in pyridine - is electrospun.
  • a similar method is also known from WO 01/09414 A1 and DE 103 55 665 A1.
  • DE 196 00 162 A1 discloses a process for producing lawn mower wire or textile fabrics in which polyamide, polyester or polypropylene as a thread-forming polymer, a maleic anhydride-modified polyethylene / polypropylene rubber and one or more aging stabilizers are combined, melted together and melted together are mixed before this melt is melt-spun.
  • DE 10 2004 009 887 A1 relates to a process for the production of fibers with a diameter of ⁇ 50 ⁇ m by electrostatic spinning or spraying of a melt of at least one thermoplastic polymer.
  • the electrospinning of polymer melts allows only fibers with diameters greater than 1 ⁇ m to be produced.
  • nano- and / or mesofasem are required with a diameter of less than 1 micron, which can be prepared by the known electrospinning process only by using polymer solutions.
  • WO 2004/080681 A1 relates to devices and methods for the electrostatic processing of polymer formulations.
  • the polymer formulations may be solutions, dispersions, suspensions, emulsions, mixtures thereof or polymer melts.
  • electrospinning is mentioned.
  • no concrete polymer formulations are mentioned which are suitable for electrospinning.
  • WO 2004/048644 A2 discloses the electrosynthesis of nanofibers and nano-composite films.
  • solutions also encompasses heterogeneous mixtures such as suspensions or dispersions, inter alia, fibers from electrically conductive polymers can be produced according to WO 2004/048644 A2 2004/046644 A2 preferably obtained from the solutions containing the corresponding monomers.
  • EP 06119248.0 dated 21.08.2006 which has priority over prior unpublished applications, describes a process optimized for the electrospinning of aqueous polymer dispersions which is optimized with respect to DE 10 2005 008 926 A1 and with which polymer fibers having optimized structural and / or mechanical properties can be obtained.
  • a colloidal dispersion of at least one substantially water-insoluble polymer in an aqueous medium electrospun.
  • the process according to EP 06119248.0 is characterized in that the colloidal dispersion contains at least one nonionic surfactant.
  • fibers with a high water resistance can be obtained, which are characterized by a good mechanical stability. It is possible with the method according to EP 06119248.0 to produce nano- and mesofasem with a diameter of less than 1 ⁇ m from aqueous dispersions, so that the use of non-aqueous, toxic, combustible, irritating, explosive and / or corrosive solvents can be avoided , Since the fibers produced according to the process according to EP 06119248.0 are composed of essentially water-insoluble polymers, a subsequent process step for water stabilization of the fibers is not required.
  • the object of the present invention is to provide a process for electrospinning aqueous polymer systems which can be used to obtain water-stable polymer fibers in which there is no disintegration of the fibers after subsequent contact with water.
  • This object is achieved according to the invention by a process in which aqueous solutions comprising oppositely charged polyelectrolytes are electrospun.
  • water-soluble polymers can now also be spun with the aid of polyelectrolytes from aqueous systems, without any further after-treatment, eg. As thermal or photochemical crosslinking is necessary.
  • thermal or photochemical crosslinking is necessary.
  • the use of corrosive, toxic, combustible, irritating, explosive, etc. solvents is obsolete.
  • the often necessary use of water-soluble polymers with subsequent crosslinking step becomes unnecessary, resulting in significant technical advantages.
  • Polyelectrolytes are polymers that carry ionic groups at each repeat unit. In order for the electrolyte properties to emerge, dissociation must occur, but this may be limited even in water. By appropriate additives, for. As acids or bases, the dissociation ability and thus the Polyektrolytrich can be increased. If oppositely charged posi- When electrolytes are used, charge balance can lead to the formation of polyelectrolyte complexes, which are generally difficult to rehydrolysable.
  • Positively charged polyelectrolytes polyvinylamine, poly (diallyldimethylammonium chloride), polypyridine, polyethylenimine.
  • Negatively charged polyelectrolytes polyacrylic acid, polyalcohol, polystyrenesulfonic acid.
  • Suitable bases by means of which the polyelectrolyte strength of the negatively charged polyelectrolytes to be used according to the invention can be adjusted, for example, but not exhaustively, LiOH, NaOH, KOH, Ca (OH) 2 , Mg (OH) 2 and Ba (OH) 2 .
  • charge-carrying groups of the polyacids used are neutralized to from 0.01 to 99.99% before electrospinning, preferably from 0.1 to 10% and particularly preferably from 0.1 to 1%.
  • Suitable acids are, for example but not exhaustive, HCl, HBr, Hl, H 2 SO 4 .
  • impurity additives are removed before the solution is electrospun.
  • the person skilled in the art knows how to remove foreign ions, for example with the aid of ion exchangers.
  • the molar ratio of the negatively charged to the positively charged polyelectrolytes is 6: 4 to 4: 6, more preferably 1: 1.
  • the aqueous medium in which the polyelectrolytes are present is generally water.
  • the aqueous medium can in addition to water more Contain additives, such as additives for the neutralization of charge-carrying groups or for changing the conductivity and surface tension of the solution to be spun. Suitable additives are known in the art.
  • the aqueous solution of polyelectrolyte used for electrospinning may contain at least one nonionic surfactant.
  • nonionic surfactants physical properties of the aqueous polyelectrolyte solutions to be spun can be specifically changed, for example viscosity, surface tension and conductivity. Furthermore, nonionic surfactants influence the process conditions of electrospinning and the stability and morphology of the resulting fibers, especially in the case of meso- and nanofibers.
  • any surfactants known to the person skilled in the art can be used in the process according to the invention.
  • nonionic surfactants provides steric stabilization of the polyelectrolytes. Thereby, the mechanical stability of the fibers obtained by the method according to the invention can be improved. Furthermore, it has been found that the use of nonionic surfactants can improve the formation of fibers by electrospinning compared with spraying the aqueous polyelectrolyte solution. Furthermore, it has been found that by the presence of ionic surfactants, a decrease in the viscosity of the colloidal dispersion can be achieved, whereby the production of thinner and more compact fibers than without addition of nonionic surfactants is possible. Furthermore, an increase in the conductivity of the dispersions and a decrease in the surface tension can be detected.
  • Suitable nonionic surfactants are known to those skilled in the art and are e.g. selected from the group consisting of (oligo) oxyalkylene-containing surfactants, carbohydrate-containing surfactants and amine oxides.
  • (oligo) oxyalkylene - (OR 1 ) n - is to be understood that the (OH go) oxyalkylene groups containing surfactants one or more Oxyalkylengrup- may have pen.
  • R 1 is an alkylene group, preferably an alkylene group having 2 to 4 carbon atoms and n is a natural number greater than or equal to 1, preferably 3 to 30. In this case, n is usually a When n is greater than 1, the radicals R 1 in the oxalkylene groups may be the same or different.
  • the surfactants containing (oligo) oxyalkylene groups are preferably selected from the group consisting of fatty alcohol alkoxylates, alkoxylated triglycerides and polyalkylene glycol ethers alkylated on both sides.
  • Suitable alkoxylates or alkoxylated compounds are e.g. Ethoxylates, propoxylates, butoxylates, or random or block copolymers (or oligomers) composed of two or more different alkoxylates, e.g. Ethoxylates and propoxylates.
  • Suitable carbohydrate group-containing surfactants are e.g. selected from the group consisting of alkyl polyglycosides, sucrose esters, sorbitan esters (sorbitans), e.g. Polyoxyethylene sorbitan trioleate, and fatty acid N-methylglucamides (fatty acid glucamides).
  • the nonionic surfactants suitable according to the invention may contain either (ON-go) oxyalkylene groups or carbohydrate groups or both (OH) oxyalkylene groups and carbohydrate groups.
  • Suitable amine oxides are, in particular, alkyldimethylamine oxides.
  • nonionic surfactants are known to the person skilled in the art and are commercially available or can be prepared by processes known to the person skilled in the art.
  • the nonionic surfactants according to the invention can in principle be present in amounts in the aqueous solutions which do not lead to coagulation.
  • the optimum quantities depend, among other things, on the surfactant used and the application temperature.
  • the at least one nonionic surfactant is preferably present in the aqueous solutions in an amount of from 0.5 to 10% by weight, particularly preferably from 0.3 to 5% by weight, based on the total weight of the polyelectrolyte used. It has been found that particularly good process results - both in terms of the formation of polymer fibers and in terms of quality, e.g.
  • the mechanical stability of the polymer fibers is achieved when 0.3 to 1% by weight, preferably 0.5 to 1% by weight, based on the total weight of the aqueous solution, of the nonionic surfactant, e.g. a block copolymer based on various alkylene oxides, e.g. based on propylene oxide and ethylene oxide.
  • the nonionic surfactant e.g. a block copolymer based on various alkylene oxides, e.g. based on propylene oxide and ethylene oxide.
  • the at least one nonionic surfactant contained in the aqueous polyelectrolyte solutions according to the process of the invention can either be added during the preparation of the aqueous polyelectrolyte solutions or subsequently after the preparation of the aqueous polyelectrolyte solutions. In a preferred embodiment, the at least one nonionic surfactant is added subsequently to the final aqueous polyelectrolyte solution prior to the start of the electrospinning process.
  • a particular advantage of the present invention is that the polyelectrolytes to be spun do not necessarily have to be crosslinked and crosslinking after electrospinning is not absolutely necessary.
  • the solution comprising reversely charged polyelectrolytes in addition to the oppositely charged polyelectrolyte and the at least one nonionic surfactant additionally at least one water-soluble polymer, wherein water-soluble polymer according to the present invention, a polymer having a solubility in water of at least 0.1 wt .-% is understood.
  • At least one water-soluble polymer be used as the so-called template polymer in addition to the solutions comprising oppositely charged polyelectrolytes.
  • the fiber formation from the solution comprising oppositely charged polyelectrolytes is further favored over spraying (electrospraying).
  • the template polymer serves as a kind of "glue" for the polyelectrolytes in the spinning solution.
  • the water-soluble polymer may be a homopolymer, copolymer, block copolymer, graft copolymer, star polymer, hyperbranched polymer, dendrimer, or a mixture of two or more of the foregoing types of polymers. According to the findings of the present invention, the addition of at least one water-soluble polymer not only accelerates / promotes fiber formation. Rather, the quality of the resulting fibers is significantly improved.
  • the solution comprising oppositely charged polyelectrolytes in an aqueous medium may be admixed with all the water-soluble polymers known to the person skilled in the art, in particular with those of polyvinyl alcohol; Polyalkylene oxides, eg polyethylene oxides; Poly-N-vinylpyrrolidone; Hydroxymethylcelluloses; hydroxyethylcelluloses; hydroxypropyl; Carboxymethylcelluloses; maleic; alginates; collagens; Combinations made up of two or more of the above-mentioned polymer-forming monomer units, copolymers composed of two or more of the above-mentioned polymer-forming monomer units, graft copolymers composed of two or more of the above-mentioned polymers forming monomer units, star polymers formed from two or more of the above-mentioned polymers Monomer units and dendrimers composed of two or more of the aforementioned polymer-forming monomer units existing group selected water-soluble polymers particularly good results
  • the water-soluble polymer is selected from polyvinyl alcohol, polyethylene oxides and poly-N-vinylpyrrolidone.
  • the abovementioned water-soluble polymers are commercially available or can be prepared according to processes known to those skilled in the art.
  • the solids content of the solution to be used according to the invention comprising oppositely charged polyelectrolytes - based on the total weight of the solution - preferably 5 to 60 wt .-%, more preferably 10 to 50 wt .-% and most preferably 10 to 40 wt. -%.
  • the solution comprising oppositely charged polyelectrolytes in the process according to the invention contains at least one nonionic surfactant and optionally at least one water-soluble polymer in an aqueous medium, based on the total weight of the solution, from 0 to 25% by weight preferably 0.5 to 20 wt .-% and most preferably 1 to 15 wt .-%, of at least one water-soluble polymer.
  • the solutions used according to the invention comprise oppositely charged polyelectrolytes in a preferred embodiment, in each case based on the total amount of the solution,
  • Hi. 0 to 25 wt .-% preferably 0.5 to 20 wt .-%, particularly preferably 1 to 15 wt .-% of at least one water-soluble polymer, and iv. 5 to 94.9 wt .-%, preferably 10 to 89.2 wt .-%, particularly preferably 15 to 88.5 wt .-% water.
  • the weight ratio of oppositely charged polyelectrolytes to the water-soluble polymer preferably present in the aqueous solutions depends on the polymers used.
  • the oppositely charged polyelectrolytes and the water-soluble polymer preferably used in a weight ratio of 10: 1, preferably 9: 1, more preferably 8: 2 to 2: 8 are used.
  • the solution to be used according to the invention comprising oppositely charged polyelectrolytes, can be electrospun in any manner known to the person skilled in the art, for example by extruding the solution under low pressure through a cannula connected to one pole of a voltage source to a counter electrode arranged at a distance from the cannula outlet.
  • the distance between the cannula and the counterelectrode acting as a collector and the voltage between the electrodes is set such that between the electrodes an electric field of preferably 0.5 to 2 kV / cm, particularly preferably 0.75 to 1.5 kV / cm and very particularly preferably 0.8 to 1 kV / cm is formed.
  • the fibers obtained it may be expedient to subsequently chemically bond them together or, for example, through a chemical intermediary to network with each other.
  • a fiber layer formed by the fibers can be further improved, in particular with regard to water and temperature resistance.
  • Another object of the present invention are fibers, in particular nano- and mesofibers, which are obtainable by the method according to the invention.
  • the fibers according to the invention are distinguished by the fact that the addition of the nonionic surfactant according to the invention to fibers prepared without addition of the nonionic surfactant has optimized structural and / or mechanical properties, in particular uniformity, compactness and stability.
  • the diameter of the fibers according to the invention is preferably 10 nm to 50 ⁇ m, particularly preferably 50 nm to 2 ⁇ m and very particularly preferably 100 nm to 1 ⁇ m.
  • the length of the fibers depends on the purpose and is usually 50 microns to several kilometers.
  • the present invention relates to solutions comprising oppositely charged polyelectrolytes in an aqueous medium, which also contain at least 0.5 wt .-% of a water-soluble polymer having a solubility in water of at least 0.1 wt .-% and at least one nonionic surfactant.
  • the solutions according to the invention comprise comprehensively charged polyelectrolytes, in each case based on the total weight of the solution, i. 5 to 60 wt .-%, preferably 10 to 50 wt .-%, particularly preferably 10 to 40 wt .-% oppositely charged polyelectrolytes, ii. 0 to 10 wt .-%, preferably 0.3 to 5 wt .-%, particularly preferably 0.3 to
  • nonionic surfactant iii. 0 to 25 wt .-%, preferably 0.5 to 20 wt .-%, particularly preferably 1 to
  • Suitable oppositely charged polyelectrolytes, aqueous media, water-soluble polymers and nonionic surfactants and suitable amounts of these components in the solutions comprising oppositely charged polyelectrolytes are mentioned above.
  • the solutions according to the invention comprising oppositely charged polyelectrolytes are preferably used in the process according to the invention.
  • the present invention relates to the use of nonionic surfactants in a process for producing polymer fibers by an electrospinning process.
  • an improvement in the electrospinning process can be achieved with a view to favoring fiber formation (electrospinning) over spraying the colloidal dispersion preferably used in the electrospinning process.
  • the structural and mechanical properties of the polymer fibers produced according to the electrospinning process can be improved, in particular with regard to the fiber quality, uniformity and stability and the spinnability of the fibers.
  • polyacrylic acid PAS
  • poly (diallyldimethylammonium chloride) poly (DADMAC)
  • a 25% by weight solution of PAS and a solution containing 20% by weight of poly (DADMAC) were prepared.
  • an aqueous NaOH solution with 4 wt .-% NaOH was prepared. 1 g of this solution was taken and made up to 20 g with H 2 O.
  • PAS / poly (DADMAC) solutions were prepared in the ratio 1: 1, i. 1 g
  • Each PAS solution was mixed with 1.25 g of poly (DADMAC) solution and electrospun.
  • the fibers were each treated with water after electrospinning for 1 h at 20 ° C to determine the extent of possible disintegration of the electrospun fibers.
  • the fibers of the control experiment were after the water treatment under the
  • Fiq. 1 shows a schematic representation of a device suitable for carrying out the electrospinning process according to the invention.
  • the device comprises a syringe 3, at the tip of which is a capillary nozzle 2.
  • This capillary nozzle 2 is connected to a pole of a voltage source 1.
  • the syringe 3 receives the polyelectrolyte solutions 4 to be spun.
  • a counterelectrode 5 connected to the other pole of the voltage source 1 is arranged at a distance of about 20 cm, which acts as a collector for the fibers formed.
  • a voltage between 18 kV and 35 kV is set at the electrodes 2 and 5, and the polyelectrolyte solution 4 is discharged through the capillary nozzle 2 of the syringe 3 at a low pressure.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention concerne un procédé de fabrication de fibres polymères, notamment de nano- et mésofibres par électrofilage, une solution aqueuse contenant des polyélectrolytes portant des charges opposées étant électrofilée. Les fibres ainsi obtenues sont résistantes à l'eau. La solution à filer selon l'invention peut éventuellement contenir au moins un tensioactif non-ionique et/ou au moins un polymère soluble dans l'eau. L'invention concerne également les fibres pouvant être obtenues au moyen de ce procédé.
EP07817714.4A 2006-10-23 2007-10-22 Procédé de fabrication de fibres nano- et mésopolymères par électrofilage de polyélectrolytes de charges opposées Not-in-force EP2084312B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200610050279 DE102006050279A1 (de) 2006-10-23 2006-10-23 Verfahren zur Herstellung von Nano- und Mesopolymerfasern durch Elektrospinnen von Polyelektrolyten gegensätzlicher Ladung
PCT/DE2007/001880 WO2008049397A2 (fr) 2006-10-23 2007-10-22 Procédé de fabrication de fibres nano- et mésopolymères par électrofilage de polyélectrolytes de charges opposées

Publications (2)

Publication Number Publication Date
EP2084312A2 true EP2084312A2 (fr) 2009-08-05
EP2084312B1 EP2084312B1 (fr) 2014-06-25

Family

ID=39244279

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07817714.4A Not-in-force EP2084312B1 (fr) 2006-10-23 2007-10-22 Procédé de fabrication de fibres nano- et mésopolymères par électrofilage de polyélectrolytes de charges opposées

Country Status (3)

Country Link
EP (1) EP2084312B1 (fr)
DE (1) DE102006050279A1 (fr)
WO (1) WO2008049397A2 (fr)

Families Citing this family (10)

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Publication number Priority date Publication date Assignee Title
DE102009015226A1 (de) 2009-04-01 2010-10-14 Kim, Gyeong-Man, Dr. Template-gestütztes Musterbildungsverfahren von Nanofasern im Electrospinn-Verfahren und deren Anwendungen
EP2292309A1 (fr) * 2009-08-07 2011-03-09 Ahlstrom Corporation Nanofibres dotées de stabilité chimique et physique améliorée et voile contenant lesdites nanofibres
JP5569826B2 (ja) * 2010-05-10 2014-08-13 独立行政法人物質・材料研究機構 高分子ファイバーとその製造方法および製造装置
US20130146810A1 (en) 2011-12-08 2013-06-13 Basf Se Process for Producing Water-Absorbing Polymer Fibres
EP2607382A1 (fr) 2011-12-22 2013-06-26 Philipps Universität Marburg Fibres à dispersion électrofilées fonctionnalisées de manière chimique pour des revêtements couche par couche
US9725827B2 (en) 2012-10-02 2017-08-08 Basf Se Process for producing water-absorbing polymer fibers
CN108385278B (zh) * 2018-02-01 2021-02-19 重庆中纳科技有限公司 一种抗水解的电纺pva/paa交联纳米纤维膜及其制备方法
CN108796825B (zh) * 2018-06-22 2019-08-27 南京邮电大学 检测潮湿环境爆炸物蒸气的多孔纳米纤维薄膜及其制备方法与应用
EP3999126A1 (fr) * 2019-07-15 2022-05-25 Symrise AG Fibres coaxiales contenant un liquide
US20220218053A1 (en) * 2021-01-13 2022-07-14 University Of Central Florida Research Foundation, Inc. Antiviral electrospun fibers and methods of reducing airborne pathogen spread

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DE4402857C2 (de) * 1994-01-31 1996-11-28 Freudenberg Carl Fa Verfahren zum Herstellen eines Mikrofaser-Vliesstoffs, Mikrofaser-Vliesstoff und dessen Verwendung
DE10003397A1 (de) * 2000-01-27 2001-08-09 Hartmann Paul Ag Polyelektrolyt-Feststoffsystem, Verfahren zur Herstellung desselben sowie Wundverband
US6596678B2 (en) * 2000-05-09 2003-07-22 The Procter & Gamble Co. Laundry detergent compositions containing a polymer for fabric appearance improvement
DE102005008926A1 (de) * 2005-02-24 2006-11-16 Philipps-Universität Marburg Verfahren zur Herstellung von Nano- und Mesofasern durch Elektrospinning von kolloidalen Dispersionen
JP2007327148A (ja) * 2006-06-06 2007-12-20 Tokyo Institute Of Technology 高分子電解質繊維およびその製造方法

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Also Published As

Publication number Publication date
WO2008049397A3 (fr) 2008-11-20
WO2008049397A2 (fr) 2008-05-02
DE102006050279A1 (de) 2008-04-30
EP2084312B1 (fr) 2014-06-25

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