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EP1311715A1 - Fabrication de fibres polymeres a morphologies nanometriques - Google Patents

Fabrication de fibres polymeres a morphologies nanometriques

Info

Publication number
EP1311715A1
EP1311715A1 EP01974154A EP01974154A EP1311715A1 EP 1311715 A1 EP1311715 A1 EP 1311715A1 EP 01974154 A EP01974154 A EP 01974154A EP 01974154 A EP01974154 A EP 01974154A EP 1311715 A1 EP1311715 A1 EP 1311715A1
Authority
EP
European Patent Office
Prior art keywords
porous
porous fibers
fiber
fibers
polymer
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.)
Withdrawn
Application number
EP01974154A
Other languages
German (de)
English (en)
Inventor
Lothar Heinrich
Martin Steinhart
Joachim H. Wendorff
Johannes Averdung
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.)
Transmit Gesellschaft fuer Technologietransfer mbH
Original Assignee
Creavis Gesellschaft fuer Technologie und Innovation mbH
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 Creavis Gesellschaft fuer Technologie und Innovation mbH filed Critical Creavis Gesellschaft fuer Technologie und Innovation mbH
Publication of EP1311715A1 publication Critical patent/EP1311715A1/fr
Withdrawn legal-status Critical Current

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
    • 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
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247—Discontinuous hollow structure or microporous structure
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2935—Discontinuous or tubular or cellular core
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2973—Particular cross section
    • Y10T428/2975—Tubular or cellular

Definitions

  • the invention relates to a method for producing nanoscale polymeric fibers with morphologies and textures, in particular with open porous structures, and to their modification and use.
  • nanoscale materials Due to the high surface volume / volume ratio and the deviations from typical order structures in macroscopic systems, nanoscale materials have special physical and chemical properties, as described, for example, in Gleitner, H .; "Nanostructured Materials", in Encyclopedia of Physical Science and Technology, Nol. 10, p. 561 ff. These include short-range magnetic properties of metallic or oxidic materials, slight field-induced tunneling of electrons from filament tips or particularly advantageous biocompatibility properties caused by nanoscale microdomains.
  • these property profiles which have changed compared to maloscopic materials, new technological developments in microelectronics, display technology, surface technology, in the production of catalysts and in medical technology, in particular as carrier materials for cell and tissue cultures, have now been achieved.
  • fiber materials with filament diameters that are smaller than 300 nm and can reach dimensions of a few 10 nm are suitable as field electron emission electrodes according to WO 98/1588.
  • semiconductor systems too, described in US Pat. No. 5,627,140, they offer technological advantages, likewise as catalyst systems with improved activity profiles, as set out in WO 98/26871.
  • Such fibers can be chemically modified and provided with chemical functions, for example by chemical etching or by plasma treatment, processed into fabrics or compressed into felt-like materials.
  • Fibers with diameters smaller than 3000 nm can be produced according to WO 00/22207 with the help of relaxing pressure gases from special nozzles.
  • State of the art are also electrostatic spinning processes, described in DE 100 23 456.9.
  • GB 2 142 870 describes such a method which is used for the production of woven vascular implants.
  • Nanofibers can be used as templates for coatings that are applied to the fibers from solutions or by vapor deposition, for example.
  • polymeric, ceramic, oxidic, glass-like or even metallic materials can be deposited on the fibers as closed layers.
  • tubes of various materials can be obtained in this way, whose inner diameters can be adjusted from 10 nm to a few ⁇ m depending on the filament diameter, and their wall thicknesses in nm or depending on the coating conditions ⁇ m range.
  • the production of such nano or mesotubes is described in DE 10 23 456.9.
  • fibers can be provided with a porous coating. After a subsequent pyrolysis treatment, fibers with high porosity are available, which are advantageous, for example, for catalytic uses.
  • porous fiber materials offer additional technical advantages over closed, solid fibers because they have a significantly higher surface area.
  • nanotubes have a very large surface area, they are quite complex to manufacture due to the pyrolysis step.
  • EP 0 047 795 describes polymeric fibers which have a solid core and a porous, foam-like sheathing of the core.
  • the fiber core is said to have a high mechanical
  • the porous shell has a high surface.
  • very surface-active applications such as B. Filtration, the porous structure produced according to EP 0 047 795 is not sufficient in many cases.
  • the invention was therefore based on the object of making nano- and mesoscale polymer fibers with a very large surface area accessible by a simple process.
  • the present invention therefore relates to porous fibers made of polymeric materials, the fibers having a diameter of 20 to 4000 nm and pores in the form of channels extending at least to the fiber core and / or through the fiber.
  • Another object of the invention is a process for the production of porous fibers from polymeric materials, wherein a 3 to 20 wt .-% solution of a polymer in an easily evaporable organic solvent or solvent mixture by means of electrospinning at an electric field above 10 5 V / m is spun, the resulting fiber having a diameter of 20 to 4000 nm and pores in the form of channels extending at least to the fiber core and / or through the fiber.
  • Electrospinning processes are e.g. B. in Fong, H .; Reneker, D.H .; J. Polym. Sci., Part B, 37 (1999), 3488 and in DE 100 23 456.9.
  • Porous fiber structures according to the invention contain polymer blends or copolymers, preferably polymers such as polyethylene, polypropylene, polystyrene, polysulfone, polylactide, polycarbonate, polyvinyl carbazole, polyurethanes, polymethacrylates, PVC, polyamides, polyacrylates, polyvinyl pyrrolidone, polyethylene oxide, polypropylene oxide, polysaccharide and / or soluble polysaccharides and / or soluble polymers as the polymeric material , such as B. Cellulose Acetate.
  • polymers such as polyethylene, polypropylene, polystyrene, polysulfone, polylactide, polycarbonate, polyvinyl carbazole, polyurethanes, polymethacrylates, PVC, polyamides, polyacrylates, polyvinyl pyrrolidone, polyethylene oxide, polypropylene oxide, polysaccharide and / or soluble polysaccharides and
  • polymers can be used individually or in the form of their blends.
  • at least one water-soluble and at least one water-insoluble polymer is used.
  • the mass ratio can in each case be between 1: 5 and 5: 1, preferably 1: 1.
  • 3-20% by weight, preferably 3-10% by weight, particularly preferably 3-6% by weight, of at least one polymer are dissolved in an organic solvent and spun into a porous fiber by means of electrospinning.
  • the fibers according to the invention have diameters of 20 to 1500 nm, preferably 20 to 1000, particularly preferably 20 to 500, very particularly preferably 20 to 100 nm.
  • Dimethyl ether, dichloromethane, chloroform, ethylene glycol dimethyl ether, ethyl glycol isopropyl ether, ethyl acetate, acetone or mixtures thereof, optionally supplemented with further solvents, can be used as the easily evaporable organic solvent.
  • the evaporation step can be carried out at normal pressure or in a vacuum. If necessary, the pressure must be adjusted to the boiling points of the solvents.
  • solvents or solvent mixtures in the process which represent a theta solvent for the polymer / polymer blend in question.
  • the theta state of the polymer solutions can also be run through during the electrospinning process. This is e.g. B. during the evaporation step of the solvent.
  • a feature of the high surface area of the porous fibers according to the invention is the surface area, which is over 100 m 2 / g, preferably over 300 m 2 / g, in particular over 600 m 2 / g, very particularly preferably over 700 m 2 / g.
  • These surfaces can be calculated on the basis of the dimensions resulting from the scanning electron microscope images or measured by nitrogen adsorption using the BET method.
  • porous fibers produced by the process according to the invention can be processed into woven fabrics, knitted fabrics and shaped and structured pressed material, modified wet-chemically and plasma-chemically, or loaded with materials of different objectives, for example pharmaceutical active ingredients or catalytic precursors, by impregnation and subsequent drying.
  • porous fibers according to the invention can be used as an adsorbent or absorbent, in the biological field (biomaterial) and as a template for producing highly porous solids (e.g. ceramics by molding and burning out the polymeric templates).
  • porous fibers according to the invention by means of a surface modification by means of a low-temperature plasma or chemical reagents, such as, for example, aqueous sodium hydroxide solution, inorganic acids, acid anhydrides or halides or, depending on the surface functionality, with silanes, isocyanates, organic acid halides or anhydrides , Alcohols, aldehydes or alkylation chemicals including the corresponding catalysts.
  • a surface modification enables the porous fibers to have a more hydrophilic or hydrophobic surface, which is advantageous when used in the biological or biomedical field.
  • Porous fibers according to the invention can be used as reinforcing composite components in polymeric materials, as filter materials, as supports for catalysts, for. B.
  • porous fibers according to the invention which can be recognized by optical birefringence. They are therefore particularly suitable as a reinforcing component in fiber composite materials, the large inner surface, in particular after suitable surface modification, ensuring effective binding and strength of the polymer matrix.
  • ternary mixtures of two polymers and an easily evaporable solvent or solvent mixture are spun, one of the polymer components being water-soluble, for example polyvinylpyrrolidone, polyethylene oxide, polypropylene oxide, polysaccharides or methyl cellulose.
  • These ternary solutions were spun electrostatically in the same way as the binary mixtures set out above. This resulted in nano and meso fibers, which, however, showed no porous morphology.
  • a non-porous structure of the fiber is obtained using conventional electrospinning processes. It is expedient to work with polymer solutions that are far from the theta state and do not pass through it during the spinning process.
  • This fiber material can also be woven, knitted and shaped as well as structured Compacts processed, superficially modified and functionalized and the uses listed above.
  • PLLA Semi-crystalline poly-L-lactide
  • FLUKA dichloromethane
  • the dosage rate of the solution to the outlet cannula which had an inner diameter of 0.5 mm, was varied between 0.3 and 2 cm 3 / s.
  • the temperature of the solution was set at 25 ° C.
  • the distances between the cannula tip and counter electrodes were between 10 and 20 cm, the working voltage was set to 35 kV.
  • the spinning process produced porous fibers with diameters from 100 nm to 4 ⁇ m.
  • the scanning electron microscopic images show uniformly shaped fibers, as shown in FIG. 1, which show the continuous, open porous structure at higher SEM resolution (FIG. 2).
  • SEM scanning electron microscopic images
  • FIG. 1 show the continuous, open porous structure at higher SEM resolution (FIG. 2).
  • FIG. 2 shows the continuous, open porous structure at higher SEM resolution
  • the BET surface areas of these porous fibers were between 200 and 800 m 2 / g, one Calculation of the surface from the SEM images even resulted in surfaces up to 1,500 m 2 / g.
  • the SEM image in FIG. 3 shows a porous PLLA fiber which was produced with a metering rate of the solution of 0.8 cm 3 / s.
  • the BET surface area of this fiber was measured at 650 m 2 / g, the value calculated from the SEM absorption was 1,200 m 2 / g.
  • Example 2 6% by weight of an aromatic polyurethane (Tecoflex TM, manufacturer: Thermetics, USA) with the average molecular weight of 180,000 g / mol was dissolved in acetone (FLUKA, Germany; pure chromatography). The temperature of the solution was set at 23 ° C.
  • Tecoflex TM aromatic polyurethane
  • Example 2 The conditions of the electrostatic spinning corresponded to those of Example 1. Anisotropic, porous threads with diameters from 120 nm to 4 ⁇ m were also obtained, the BET surface area of which was between 150 and 600 m 2 / g.
  • the SEM image in FIG. 4 shows such polyurethane threads which were obtained at a dosage of 1.2 cm 3 / s (BET: 490 m 2 / g).
  • a 13% by weight solution of polycarbonate with an average molecular weight of 230,000 g / mol in dichloromethane according to Example 1 was spun electrostatically at an inlet temperature of 20 ° C. at a metering rate of 1.5 cm 3 / s.
  • the electric field strength was 30 kV / m.
  • the following example describes the production of ultra-thin porous fibers from blends of water-insoluble and water-soluble polymers.
  • Example 4 Atactic, amorphous poly-D, L-lactide (PDLLA) with an average molecular weight of 54,000 g / mol and a glass transition temperature of 52 ° C (manufacturer: Bschreibinger Ingelheim, Germany) and polyvinylpyrroUdon with an average molecular weight of 360,000 g / mol (type K90; FLUKA, Germany) were dissolved in dichloromethane in the mass ratios 5: 1, 1: 1 and 1: 5. The concentrations of the polymer mixtures in dichloromethane were between 2 and 5% by weight.
  • PLLA amorphous poly-D, L-lactide
  • a working voltage of 40 kV was set at an electrode spacing of 23 cm.
  • the metering rates were 0.5 to 2 cm 3 / s.
  • Threads with diameters of 80 nm to 4 ⁇ m were obtained which showed no porosity in the SEM.
  • the water-soluble polyvinylpyrroUdon (PVP) can be completely removed by treating the fibers produced in this way or the nonwovens made therefrom with water at room temperature. After 15 minutes of ultrasound, the removal of PVP was complete.
  • PVP-PDLLA ratios 1: 1 and 1: 5 decreasing porosities were obtained with BET surface areas of 210 m 2 / g and 170 m 2 / g.
  • porous threads produced according to the invention can be deposited randomly in the form of balls.
  • flat or ribbon-like arrangements of the staple fibers can also be produced.
  • Porous, spinal fibers arranged in the form of a lumen according to Example 1 were poured into a cylindrical aluminum mold with a diameter of 20 mm, edge height also 20 mm, and pressed together by hand, so that a layer height of 5 mm was obtained. Subsequently, the porous fibers introduced were compressed at 50 ° C. over a period of 15 minutes with a compressive force of 30 kp using a fit-for-purpose aluminum piston.
  • the porous fiber described in Example 1 produced at a metering rate of 0.8 cm 3 / s, was pressed in several stages in the manner described above and in the last phase with a contact pressure of 60 kp over a period of 60 minutes at 50 ° C compressed. The result was a compact of 1.2 mm thickness with a BET surface area of 380 m 2 / g.
  • the wettability of the compacts with water was average, the contact angles were between 45 and 58 degrees.
  • the plate produced in this way was used as an adsorbent and absorbent in a laboratory suction filter with a tight seal between the filling cylinder and the glass frit underneath.
  • the amount of 100 ml of a 0.1% sugar solution was converted into a sugar single pass-through completely retained by the sorption layer produced from the porous fibers according to the invention.
  • Application example 2 The spherical, porous fibers produced according to example 2 were activated in a microwave plasma and under the action of an argon / oxygen mixture.
  • Hexagon was obtained from Technics Plasma, Germany.
  • the microwave power was set to 300 W, the system pressure was 0.02 bar and the two gases were metered in continuously via a defined leak at 4 • 10 "3 normal liters / min.
  • the activated porous threads were stirred into an aqueous solution of 5% by weight hydroxyethyl methacrylate (manufacturer: Röhm, Germany) and filtered after an exposure time of 15 minutes and dried under water jet vacuum at 50 ° C. for 24 hours.
  • hydroxyethyl methacrylate manufactured by Röhm, Germany
  • the fibers treated in the manner set out above were then treated with UV rays with repeated turning.
  • An arrangement of 4 Ultra-Vitalux lamps (manufacturer: Osram, Germany) served as the UV source.
  • the duration of the radiation exposure was 30 minutes, the mean distance to the source was 20 cm.
  • the compacts produced therefrom according to Application Example 1 had a BET surface area of 680 m / g and were characterized by very good wettability with water.
  • the compacts obtained from application examples 1 and 2 were examined for their behavior towards living cells.
  • the samples were inoculated with human umbilical cord endothelial cells (HUVEC) and then their growth behavior was examined.
  • HUVEC human umbilical cord endothelial cells
  • Application Example 3 Fiber materials according to Examples 2 and 3 were twisted and compacted into threads similar to the Idassian spinning process, for which the fibers were slightly moistened. Thread material similar to wool fiber was obtained, with a thread thickness of 0.3 to 0.4 mm. After drying, the threads widened to 0.6 to 1 mm thread thickness.
  • This thread material from the porous primary fibers according to the invention can be wound up and processed into simple fabrics in the laboratory.
  • the use of adhesives, binders and strength-promoting crosslinking agents for surface-activated fibers improve both the processability of the fiber materials obtained from the primary fiber according to the invention and their tear strength.
  • the tissues produced in this way are particularly suitable for the production of highly porous catalyst supports, heat insulation materials, absorbers and filters, as scaffolding material in tissue engineering and for blood vessel and bone implantology.
  • the high porosities promote vascularization, support both the cell supply with nutrients and the disposal of metabolic products and offer advantages for cell differentiation as well as osseofication and tissue integration.
  • Fibers according to Examples 1 and 3 were in a plasma system (manufacturer: Eltro, Baesweiler, Germany), in a rotating glass drum according to Application Example 2, at a pressure of 15 Pa, a microwave power of 2 kW and 2.45 GHz, a pulse duration of 500 ⁇ s and period of 2 s exposed to an argon atmosphere exposed to nickel carbonyl (FLUKA).
  • FLUKA nickel carbonyl
  • argon flowed at 5 l / h over a nickel tetracarbonyl heated to 40 ° C.
  • the supply lines to the plasma chamber were thermostatted at 100 ° C to exclude deposition of Ni (CO) 4 .
  • porous threads treated in this way were pressed into sheets of 1 mm thickness in accordance with Application Example 1 and cut into square parts of 5 mm edge length. They were then further reduced with hydrogen in a thermostated glass tube at 50 ° C. for 3 hours. The flow rate of the hydrogen was 101 / h.
  • Ethylene was then mixed in at a constant temperature at a flow rate of 1 l / h. There was complete hydrogenation of the ethylene to ethane.

Landscapes

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

Abstract

L'invention concerne des fibres poreuses en matériaux polymères qui présentent un diamètre de 20 à 4000 nm et des pores sous forme de canaux s'étendant au moins jusqu'au coeur de la fibre et/ou traversant la fibre. Le procédé de fabrication des fibres poreuses consiste à soumettre une solution contenant 5 à 20 % en poids d'au moins un polymère et un solvant organique à un électrofilage en présence d'un champ électrique supérieur à 10<5>V/m, la fibre obtenue présentant un diamètre de 20 à 4000 nm et des pores sous forme de canaux s'étendant au moins jusqu'au coeur de la fibre et/ou traversant la fibre. Ces fibres poreuses peuvent être utilisées en tant que supports de catalyseurs, produits adsorbants ou absorbants ou en tant que biomatériaux, elles peuvent être modifiées ou fonctionnalisées chimiquement ou utilisées en tant que modèles pour fabriquer des corps solides très poreux.
EP01974154A 2000-08-18 2001-08-10 Fabrication de fibres polymeres a morphologies nanometriques Withdrawn EP1311715A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10040897A DE10040897B4 (de) 2000-08-18 2000-08-18 Nanoskalige poröse Fasern aus polymeren Materialien
DE10040897 2000-08-18
PCT/EP2001/009236 WO2002016680A1 (fr) 2000-08-18 2001-08-10 Fabrication de fibres polymeres a morphologies nanometriques

Publications (1)

Publication Number Publication Date
EP1311715A1 true EP1311715A1 (fr) 2003-05-21

Family

ID=7653201

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01974154A Withdrawn EP1311715A1 (fr) 2000-08-18 2001-08-10 Fabrication de fibres polymeres a morphologies nanometriques

Country Status (5)

Country Link
US (1) US6790528B2 (fr)
EP (1) EP1311715A1 (fr)
AU (1) AU2001293750A1 (fr)
DE (1) DE10040897B4 (fr)
WO (1) WO2002016680A1 (fr)

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WO2002016680A1 (fr) 2002-02-28

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