WO2011029777A1 - Procédés de production de fibres polymères enduites - Google Patents

Procédés de production de fibres polymères enduites Download PDF

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Publication number
WO2011029777A1
WO2011029777A1 PCT/EP2010/062936 EP2010062936W WO2011029777A1 WO 2011029777 A1 WO2011029777 A1 WO 2011029777A1 EP 2010062936 W EP2010062936 W EP 2010062936W WO 2011029777 A1 WO2011029777 A1 WO 2011029777A1
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Prior art keywords
fibers
polymer
water
polymer fibers
dispersion
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PCT/EP2010/062936
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German (de)
English (en)
Inventor
Evgueni Klimov
Peter Przybylski
Burghard Liebmann
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Basf Se
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Publication of WO2011029777A1 publication Critical patent/WO2011029777A1/fr

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/08—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin
    • D06M14/10—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/2246—Esters of unsaturated carboxylic acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/345—Nitriles
    • D06M13/348—Nitriles unsaturated, e.g. acrylonitrile
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/31—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated nitriles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/06—Processes in which the treating agent is dispersed in a gas, e.g. aerosols

Definitions

  • the present invention relates to processes for the production of coated polymer fibers in which fibers of a diameter in the range from 10 nm to 10 ⁇ m are produced from a solution, dispersion or melt of a polymer. Furthermore, the invention relates to coated polymer fibers, their use and fiber fabrics comprising the coated polymer fibers.
  • Fibers with a diameter of a few nm to a few ⁇ m can be carried out better in other ways, for example after electrospinning or centrifuge spinning processes, to name but a few.
  • Centrifuge spinning processes suitable for the production of nanofibers are disclosed, for example, in EP 624 665 A and EP 1 088 918 A.
  • the polymer-containing solution or dispersion is placed in a rotating container and discharged by centrifugal forces from the container in the form of fibers.
  • the fibers obtained by means of these electrospinning or centrifuge spinning processes can also be deposited and obtained directly, for example by deposition on a support, in the form of fibrous sheets, for example nonwovens.
  • polymer fibers such as fabrics or nonwovens. These are widely used, for example in mass applications such as textiles, as technical devices such as filters or for special applications such as wound dressings in the medical sector.
  • polymers commonly referred to as water-insoluble, for example styrene-acrylic ester copolymers often have the disadvantage that fibrous sheet formed from them can lose stability or strength at least during prolonged exposure to water or moisture.
  • polymers for example naturally occurring polymers based on polysaccharides, which likewise do not dissolve under the action of water, but which can absorb and incorporate water, so that fibers or surface fiber structures produced from these polymers, for example, swell and thus also have a mechanical or chemical effect. especially in filters - be changed in their permeability.
  • fibers from water-soluble polymers can be rendered insoluble by cross-linking or restructuring (post-crystallization).
  • the stability of polyvinyl alcohol fibers to water could be e.g. by treatment with methanol (see Yao L. et al., Chem. Mater. 15 (2003) 1860-1864), crosslinking with polyacrylic acid (see Zeng J. et al., e-polymers 78 (2004)) or UV crosslinking of modified polyvinyl alcohol (see Zeng J. et al., Macromol Rapid Commun. 26 (2005) 1557-1562).
  • the crosslinker was already added to the polymer-containing spinning solution and co-spun. It is a thermal or radiation-induced aftertreatment required, which is usually complex and expensive.
  • WO 2006/089522 A1 discloses processes for producing polymer fibers, wherein a dispersion of a water-insoluble polymer is electrospun in an aqueous medium.
  • this process it has been possible for the first time to spin water-insoluble polymers without the use of organic solvents by means of an electrospinning process, polymer fibers, in particular nano- or mesofibres, being obtained.
  • One possibility for improving the water stability of fibers obtained from aqueous dispersions by electrospinning of water-insoluble polymers consists in the interparticle crosslinking of the fibers according to WO 2009/074630, another in the specific coordination of the glass transition temperature of the polymer and the processing temperature during electrospinning according to WO 2009/010443 ,
  • 6,126,776 discloses a process in which a solid, UV or plasma pretreated polymer substrate, for example films or nonwovens, is treated with 2-cyanoacrylate vapors to improve the adhesion of a post-applied organic material .
  • 2-cyanoacrylate monomers which can be converted to polymers with improved water stability.
  • polycyanoacrylates and adhesions with cyanoacrylate adhesives are not permanently moisture-stable, since under appropriate conditions the polymer can be split again (see http://de.wikipedia.org/wiki/Klebstoff dated 17.07.2009, chapter 4.2, cyanoacrylate - adhesives).
  • more favorable and more efficient methods are desirable in order to improve the water or moisture resistance of polymer fibers, in particular the so-called nanofibers.
  • the use of organic solvents should be largely avoided in the production of such water or moisture-stable fibers and fiber fabrics for toxicological, occupational safety and regulatory reasons.
  • coated polymer fibers and fiber sheets which can be produced by the process according to the invention have an improved water or moisture resistance compared with known nanofibers, i. they have a reduced solubility, swelling and / or change in the mechanical properties and / or the flow properties and / or the fiber structure under the action of moisture or moisture.
  • organic solvents is largely avoided in the inventive method.
  • copolymers encompasses both homopolymers and copolymers Suitable copolymers include both random and alternating systems, block copolymers or graft copolymers
  • copolymers encompasses polymers which are composed of two or more different monomers or in which The incorporation of at least one monomer into the polymer chain can be implemented in various ways, as is the case, for example, with the stereo block copolymers., Blends of homopolymers and copolymers can also be used.
  • the homopolymers and copolymers can be miscible or immiscible with one another
  • the polymers suitable for the processes according to the invention can be of synthetic origin, but they can also be naturally occurring polymers, for example based on polysaccharides.
  • Preferred polymers for use in the process according to the invention are those which are not water or moisture-resistant, in particular those which are water-soluble or water-swellable.
  • water-soluble is to be understood as meaning all polymers whose solubility in water is higher than 0.1% by weight (based on the total weight of the solution) at 23 ° C.
  • water-swellable means all polymers whose weight gain after storage for 6 hours at 50 ° C in a convection oven and subsequent storage in water at 23 ° C for 30 minutes is more than 5% (based on the weight of the polymer after storage for 6 hours at 50 ° C).
  • Particularly preferred water-soluble or water-swellable polymers suitable for use in the processes of this invention are polyvinyl alcohol, poly-N-vinylpyrrolidone, polyvinylformamide, polyethylene oxide, polyvinylamine, polyvinylacetate, polyacrylic acid, polyacrylic acid esters, polyacrylamide, polyaccharides such as cellulose, cellulose ethers such as e.g. Methyl cellulose (with a degree of substitution of 3 to 40%), ethyl cellulose, butyl cellulose, hydroxymethylcelluloses; hydroxyethylcelluloses; Hydroxypropylcelluloses, isopropylcellulose, cellulose esters, e.g. Cellulose acetate, starches, modified starches such as e.g. Methyl ether starch and alginate.
  • Particularly preferred water-soluble or water-swellable polymers are polyvinyl alcohol and polyvinylformamide.
  • Fibers from the melt are preferably suitable polymers as known in the art and described in the literature synthetic polyamides and polyesters.
  • Suitable methods known to the person skilled in the art for producing polymer fibers of the stated diameter from solution are described, for example, in A. Echte, Handbuch der Technischen Polymerchemie, VCH Verlagsgesellschaft mbH, Weinheim, 1993, Chap. 9.6.3.2 "Dry Spinning” and 9.6.3.3 “Wet Spinning” p. 575-577.
  • the preferred polymers are cellulose acetates and polyacrylonitrile known to the person skilled in the art and described in the literature.
  • Preferred methods of preparation of solutions are those in which water is used as the solvent, since thereby possible toxicological, labor-safety-related and approval-related difficulties can be avoided.
  • suitable polymers are preferably polyvinyl alcohols known to the person skilled in the art and described in the literature.
  • electrospinning or centrifugal spinning processes in particular electrospinning processes.
  • Methods for electrospinning are described, for example, in D.H. Reneker and H.D. Chun, Nanotechn. 7 (1996) 216 f., A. Greiner and J. Wendorff, Angew. Chemistry Int. Ed. 1 19 (2007) 5770-5805, WO 2006/089522 A1, WO 2009/074630, WO 2009/010443.
  • Centrifuge spinning processes in which the polymer-containing melt, solution or dispersion is placed in a rotating container and discharged from the container in the form of fibers by centrifugal forces are described, for example, in EP 624 665 A and EP 1 088 918 A.
  • the preferred polymers are cellulose acetates and polyacrylonitrile known to the person skilled in the art and described in the literature.
  • Preferred methods of preparation by means of electrospinning from solutions are those in which water is used as the solvent, since this makes it possible to avoid possible toxicological, labor-safety-related and approval-related difficulties.
  • suitable polymers are preferably polyvinyl alcohols known to the person skilled in the art and described in the literature.
  • electrospinning processes for the production of fibers of the stated size from dispersions, in particular aqueous dispersions can be used.
  • a dispersion of at least one water-insoluble polymer is electrospun in an aqueous medium.
  • a dispersion in the sense of the present invention in accordance with textbook knowledge, denotes a mixture of at least two immiscible phases, one of the at least two phases being liquid.
  • dispersions are subdivided into aerosols, emulsions and suspensions, the second or further phase being gaseous in the case of aerosols, solid in the case of emulsions and solid in the case of suspensions.
  • the polymer dispersions can be prepared by all methods known to the person skilled in the art for this purpose.
  • All of the abovementioned polymers can be used in the dispersions to be used according to the invention individually or in any combination with one another and in any desired mixing ratio.
  • homopolymers or copolymers based essentially on acrylates, styrenes, vinyl acetates, vinyl ethers, butadienes, isoprenes, methacrylates, alpha-methylstyrenes, acrylamide, vinylsulfonic acid, vinylsulfonic acid esters, vinyl esters, vinyl alcohol, acrylonitrile, vinylsulfones and / or vinyl halides good results are achieved.
  • the average particle diameter of the at least one water-insoluble polymer preferably being between 100 nm and 1 ⁇ m.
  • the average particle diameter of the suspended particles is between 0.03 ⁇ m and 2.5 ⁇ m, preferably between 0.05 ⁇ m and 1.2 ⁇ m (determined according to W. Scholtan and H. Lange in Kolloid-Z. 1972), pp. 782-796 by means of ultracentrifuge).
  • the dispersion for electrospinning additionally contains at least one water-soluble polymer in addition to the at least one water-insoluble polymer.
  • at least one water-soluble polymer in addition to the at least one water-insoluble polymer.
  • all water-soluble polymers known to the person skilled in the art may be added to the dispersion of at least one water-insoluble polymer in an aqueous medium.
  • the preparation of the dispersions of at least one water-insoluble polymer in an aqueous medium further comprising at least one water-soluble polymer according to the further embodiment of the invention can be carried out in any way known to those skilled in the art, for example by emulsion polymerization.
  • the solids content of the dispersion to be used according to the invention-based on the total weight of the dispersion- is preferably 2 to 80% by weight, more preferably 10 to 60% by weight and most preferably 15 to 50% by weight.
  • the weight fraction of the water-soluble polymer is usually 0.1 to 120 wt .-%, more preferably 2 to 70 wt .-% and most preferably 5 to 50 wt .-%.
  • the melt, solution or dispersion to be used in electrospinning can be electrospun in any manner known to those skilled in the art.
  • the mass transport in the form of a jet takes place on the opposite electrode.
  • the optionally present solvent evaporates in the intermediate electrode space and the polymer-containing solid is then present in the form of fibers on the counter electrode.
  • Spinning can be done in both vertical directions (bottom to top and top to bottom) and in horizontal direction.
  • a cycler-based device for example Nanospider from Elmarco (Czech Rep.), Is used.
  • the solution, dispersion or melt used is in a container in which a metal roller rotates permanently or the spin formulation is metered onto the roller with a separate device.
  • the roll can be smooth, structured or provided with metal wires. In this case, part of the formulation is resistant to the roll surface.
  • the electric field between the roller and the counter electrode (above the roller) causes the formulation to form liquid jets first, which then lose any solvent present on the way to the counter electrode or solidify the melt.
  • a nanofiber nonwoven fabric is formed on the substrate (eg polypropylene, polyester or cellulose), which is passed between the two electrodes.
  • the electric field generally has a strength between 0.01 to 10 kV / cm, preferably between 1 and 6 kV / cm and more preferably between 2 and 4 kV / cm.
  • the electric field has a magnitude of 2.1 kV / cm (82 kV at 25 cm electrode spacing). Spinning can be done in both vertical directions (bottom to top and top to bottom) and in horizontal direction.
  • Additives may be added to the solution, dispersion or melt of the polymer to alter, for example, the viscosity or surface tension, resulting in e.g. specifically influences the fiber formation or fiber morphology.
  • Preferred additives are thickeners and surfactants known to the person skilled in the art and described in the literature.
  • active substances which have a targeted effect on a living organism, in particular a pharmacological, agrochemical, medicinal or cosmetic effect.
  • active substances may be active pharmaceutical ingredients, cosmetic effect substances, agrochemical active substances (fungicides, herbicides, insecticides), food or feed additives, biological active substances (peptides, growth factors, bacteria) or a combination of several of these active substances.
  • the aim of the addition of the active substances mentioned is that they are released or released after the application of the coated polymer fibers or fiber fabrics according to the invention on or on living organisms, and specifically develop a desired specific action on or in the living organism.
  • the fibers which can be produced from the solution, dispersion or melt of a polymer by the abovementioned processes generally have a diameter in the region of 10 nm to 10 ⁇ , preferably from 20 nm to 5 ⁇ , particularly preferably from 50 nm to 2 ⁇ .
  • Essential to the invention is that these fibers are contacted during or after their preparation with a 2-cyanoacrylic acid ester.
  • Suitable 2-cyanoacrylic acid esters which are generally known to the person skilled in the art and are described in the literature, are, for example, methyl, ethyl, n-butyl, octyl, allyl or methoxyethyl esters of 2-cyanoacrylic acid, in particular ethyl 2-cyanoacrylate.
  • the contacting of the polymer fibers can be carried out according to the invention by exposing the fibers to an atmosphere containing gaseous 2-cyanoacrylic acid esters during their preparation.
  • the partial pressure of the 2-cyanoacrylic acid esters in the gas phase is equal to or less than the vapor pressure of the 2-cyanoacrylic ester used at the particular processing temperature.
  • the partial pressure of the 2-cyanoacrylic esters used is generally in the range of 1 mbar to 1 bar, preferably in the range of 50 mbar to 800 mbar, more preferably in the range of 100 mbar to 500 mbar.
  • the partial pressures of the 2-cyanoacrylic acid esters used can also be significantly higher than these values.
  • the contacting of the polymer fibers with gaseous 2-cyanoacrylic acid ester is preferably carried out by exposing the fibers to an atmosphere containing gaseous 2-cyanoacrylic acid esters after their preparation. That In a first step, the polymer fibers are produced by the processes described above, and the contacting of the polymer fibers with gaseous 2-cyanoacrylic acid ester takes place only in a second separate step.
  • the advantage of this variant is that the temperature-dependent vapor pressures of the 2-cyanoacrylic esters can be chosen independently of the temperature of the polymer fiber production.
  • the partial pressure of the 2-cyanoacrylic esters used is generally in the range from 1 mbar to 1 bar, preferably in the range from 50 mbar to 800 mbar, more preferably in the range from 100 mbar to 500 mbar.
  • the partial pressures of the 2-cyanoacrylic acid esters used can also be significantly higher than these values.
  • the contacting of the polymer fibers with gaseous 2-cyanoacrylic acid both during and after their preparation is usually carried out over a period of 1 s to 60 min, preferably from 10 s to 30 min, more preferably from 1 min to 10 min.
  • the contacting of the polymer fibers with 2-cyanoacrylic acid ester can also be carried out by the 2-cyanoacrylic acid esters be added to the melt, solution or dispersion of the polymer from which the polymer fibers are prepared (of course, this embodiment is not possible if the ingredients of the melt, solution or dispersion chemically react with or cause the polymerization of the 2-cyanoacrylic acid esters, for example aqueous solutions is the case).
  • the concentration of 2-cyanoacrylic acid esters be added to the melt, solution or dispersion of the polymer from which the polymer fibers are prepared
  • Cyanacrylklader in the melt, solution or dispersion is in this embodiment of the invention usually in the range of 0.1 to 10 wt .-%, preferably from 0.5 to 5 wt .-%, particularly preferably from 1 to 5 wt .-%, in each case based on the total weight of the melt, solution or dispersion.
  • the contacting of the polymer fibers with 2-cyanoacrylic acid ester may also be effected by treating the fibers after their preparation with a solution containing the 2-cyanoacrylic acid esters.
  • Suitable solvents for 2-cyanoacrylic acid esters are, for example, acetone or 2-butanone.
  • the concentration of 2-cyanoacrylic acid esters in this solution is usually in the range from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, particularly preferably from 1 to 5% by weight, in this embodiment of the invention. , in each case based on the total weight of the solution.
  • the temperature at which the contacting takes place is usually in the range from 5 to 90.degree. C., preferably from 15 to 50.degree.
  • the contacting of the polymer fibers with the solution of the 2-cyanoacrylic acid ester is generally carried out over a period of 1 second to 60 minutes, preferably from 10 seconds to 30 minutes, more preferably from 1 minute to 10 minutes.
  • the contacting of the polymer fibers with 2-cyanoacrylic acid ester is preferred in which the
  • Fibers are exposed after or during their manufacture to an atmosphere containing gaseous 2-cyanoacrylic acid ester.
  • the described coatings of the polymer fibers with 2-cyanoacrylic acid ester are not limited to the fibers as such, but can also be carried out accordingly on the fibrous sheets formed from the polymer fibers.
  • the polymer fibers which can be prepared in the course of the process according to the invention have a diameter in the range from 10 nm to 10 ⁇ m, preferably from 20 nm to 5 ⁇ m, particularly preferably from 50 nm to 2 ⁇ m.
  • the length of the fibers depends on the purpose and is usually 50 ⁇ up to several kilometers.
  • 2-cyanoacrylic acid ester By contacting the polymer fibers or the fiber fabrics with 2-cyanoacrylic acid ester separates from monomeric 2-cyanoacrylate and is polymerized to poly-2 cyanoacrylates.
  • the deposition is usually in the form of a coating adhering to the polymer fiber, particularly preferably complete. However, the coating can also take place partially, ie the surface of the polymer fibers is not completely coated. Depending on the morphology of the fibers, it is also possible that the poly-2-cyanoacrylates formed are not or only partially in the form of a coating on the fiber adhere, but instead or in the fiber or on the fiber adhere.
  • coated polymer fibers according to the invention can be prepared by the processes according to the invention.
  • Preferred inventive coated polymer fibers comprising polymer fibers having a diameter in the range of 10 nm to 10 ⁇ , preferably from 20 nm to 5 ⁇ , particularly preferably from 50 nm to 2 ⁇ , and adhering to the polymer fibers coating of poly-2-cyanoacrylic, wherein the thickness of the coating is particularly preferably in the range from 1 to 200 nm, in particular from 10 to 100 nm.
  • the coated polymer fibers of the invention are particularly suitable for the production of fibrous sheets.
  • the production of the fiber fabrics can be carried out either in the same process step as the preparation of the polymer fibers, for example as described above in the direct production of fiber fabrics by electrospinning, or in a separate process step known in the art and described in the literature following the preparation the coated polymer fibers according to the invention.
  • fibrous sheets of the invention can be used in many different applications, for example for the production of filters or filter parts, in particular for gas / air and liquid filtration, non-wovens or nonwovens, especially nonwovens for use in cosmetic products, textiles, especially household textiles , Cleaning products, medical devices (such as wound dressings or face masks), hygiene products, cell culture carriers or catalyst carriers.
  • the said objects may consist wholly or partly of the fibrous sheets, e.g. in the form of coatings and / or components.
  • the fibrous sheets according to the invention are preferably used as filters and medical carriers.
  • coated polymer fibers and fiber sheets which can be produced by the process according to the invention have an improved water or moisture resistance compared with known nanofibers, i. they have a reduced solubility, swelling and / or change in the mechanical properties and / or the flow properties and / or the fiber structure under the action of moisture or moisture.
  • the use of organic solvents is largely avoided in the inventive method.
  • a further advantage of the coated polymer fibers according to the invention is that polymerized
  • Cyanacryl Acidester from a medical or toxicological point of view are harmless (see, for example, Handbook of Adhesive Technology, 2nd Ed., A. Pizzi, K. Mittal, Mar- Decker (Ed.), 2003, p. 809) and for many applications, for example in the medical sector.
  • Example V-1 is a photomicrograph of the polymer fibers obtained in Example V-1 (polyvinyl alcohol fibers, not contacted before water treatment)
  • Figure 2 is a photomicrograph of the coated polymer fibers obtained in Example 1 (polyvinyl alcohol fibers contacted with ethyl 2-cyanoacrylate prior to water treatment).
  • Figure 3 is a photomicrograph of the coated polymer fibers obtained in Example 1 (polyvinyl alcohol fibers contacted with ethyl 2-cyanoacrylate after water treatment) a scanning electron micrograph of the polymer fibers obtained in Example V-2 (polystyrene-co-acrylate-polyvinyl alcohol fibers, not contacted, before water treatment) a scanning electron micrograph of the polymer fibers obtained in Example V-2 (polystyrene-co-acrylate-polyvinyl alcohol fibers, not contacted, after water treatment)
  • Example 6 is a scanning electron micrograph of the polymer fibers obtained in Example 2 (polystyrene-co-acrylate-polyvinyl alcohol fibers, contacted with ethyl-2-cyanoacrylate, after water treatment)
  • the polymer fibers described in the Examples were prepared by the following either tip-based or roller-based electrospinning techniques. Further specific details are given in the individual examples.
  • Tip-based electrospinning process For producing the polymer fibers by the tip-based electrospinning method, an apparatus has been used in which a capillary nozzle connected to one pole of a power source is used to atomize the polymer melt, dispersion or solution. Opposite the outlet of the capillary nozzle, a square counterelectrode connected to the other pole of the voltage source is arranged at a distance of about 20 cm, which acts as a collector for the fibers formed. During operation of the device, a voltage between 15 kV and 35 kV is set at the electrodes and the polymer melt, dispersion or solution is discharged through the capillary nozzle under a low pressure.
  • coated polymer fibers according to the invention were contacted either with gaseous or dissolved in a solvent 2-Cyanacrylklaestern. Further specific details are given in the individual examples.
  • the polymer fibers and coated polymer fibers according to the invention prepared according to the examples and comparative examples were introduced into quiescent water at a temperature of 23 ° C. for a period of 24 hours to determine the resistance to water or moisture. After subsequent drying, light or electron microscope images were taken (see Fig.). By comparing them visually with corresponding electron micrographs of the identical polymer fiber samples prior to water treatment, it can be seen whether and how much the fibers, their morphology or microstructure has changed under the action of water, ie how water- or moisture-resistant the fibers are.
  • Example V-1 and 1
  • the polymer was made into polymer fibers by the tip-based electrospinning process, with the following process parameters chosen:
  • Example V-1 A part of the polymer fibers obtained in Example V-1 was tested for water and moisture resistance as described above. The fibers completely dissolved. Another portion of the polymer fibers obtained in Example V-1 was contacted with ethyl 2-cyanoacrylate as follows:
  • Example 1 Sigma Aldrich 0.5g of ethyl 2-cyanoacrylate was placed in a 50ml glass vial and then gasified at a temperature of 150 ° C. evaporated. Subsequently, the substrate was contacted with the polymer fibers obtained in Example V-1 for a period of 5 minutes in this gas phase.
  • the thus-obtained coated polymer fibers (Example 1) are shown in FIG. A part of the coated polymer fibers obtained in Example 1 was tested for water and moisture resistance as described above. Fig. 3 shows these coated polymer fibers after the test.
  • Example V-2 and 2 The following polymer dispersion was used:
  • the polymer dispersion was processed into polymer fibers by the roll-based electrospinning method, with the following process parameters chosen: voltage: 82 kV
  • Example V-2 The polymer fibers thus obtained (Example V-2) are shown in FIG. A part of the polymer fibers obtained in Example V-2 was tested for water resistance and moisture resistance as described above. Fig. 5 shows these polymer fibers after the test.
  • Example V-2 Another portion of the polymer fibers obtained in Example V-2 was contacted with ethyl 2-cyanoacrylate as follows:
  • Example 2 coated polymer fibers (Example 2) were obtained.
  • Example 2 A part of the coated polymer fibers obtained in Example 2 was tested for water resistance as described above.
  • Fig. 6 shows these coated polymer fibers after the test.
  • coated polymer fibers which can be produced by the process according to the invention and also fibrous webs have improved water or moisture resistance compared with known nanofibers, ie. they have a reduced solubility, swelling and / or change in the mechanical properties and / or the flow properties and / or the fiber structure under the action of moisture or moisture.

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

Abstract

L'invention concerne des procédés de production de fibres polymères enduites, selon lesquels des fibres d'un diamètre de 10 nm à 10 μm sont produites à partir d'une solution, d'une dispersion ou d'une masse fondue d'un polymère. Selon l'invention, les fibres sont mises en contact avec un ester de l'acide 2-cyanoacrylique pendant ou après leur production. L'invention concerne également des fibres polymères enduites, leur utilisation ainsi que des structures fibreuses planes comprenant lesdites fibres polymères enduites.
PCT/EP2010/062936 2009-09-11 2010-09-03 Procédés de production de fibres polymères enduites WO2011029777A1 (fr)

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EP09170029.4 2009-09-11
EP09170029 2009-09-11

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WO2011029777A1 true WO2011029777A1 (fr) 2011-03-17

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WO (1) WO2011029777A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105568555A (zh) * 2016-02-19 2016-05-11 江苏亿茂滤材有限公司 一种空气过滤石墨烯纤维膜的制备方法

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105568555A (zh) * 2016-02-19 2016-05-11 江苏亿茂滤材有限公司 一种空气过滤石墨烯纤维膜的制备方法
CN105568555B (zh) * 2016-02-19 2018-02-02 江苏亿茂滤材有限公司 一种空气过滤石墨烯纤维膜的制备方法

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