EP2171136B1 - Procédé pour produire des nanofibres et des mésofibres par électrofilage de dispersions colloïdales contenant au moins un polymère pratiquement insoluble dans l'eau - Google Patents

Procédé pour produire des nanofibres et des mésofibres par électrofilage de dispersions colloïdales contenant au moins un polymère pratiquement insoluble dans l'eau Download PDF

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Publication number
EP2171136B1
EP2171136B1 EP20080786037 EP08786037A EP2171136B1 EP 2171136 B1 EP2171136 B1 EP 2171136B1 EP 20080786037 EP20080786037 EP 20080786037 EP 08786037 A EP08786037 A EP 08786037A EP 2171136 B1 EP2171136 B1 EP 2171136B1
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Prior art keywords
copolymers
polymer
weight
water
fibers
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EP2171136A2 (fr
Inventor
Rajan Venkatesh
Evgueni Klimov
Michel Pepers
Walter Heckmann
Andreas Greiner
Aleksandar Stoiljkovic
Jürgen Schmidt-Thümmes
Vijay Immanuel Raman
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BASF SE
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BASF SE
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    • 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
    • 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
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • 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
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/36—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated carboxylic acids or unsaturated organic esters as the major constituent
    • 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
    • D01F6/52—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 of polymers of unsaturated carboxylic acids or unsaturated esters
    • 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
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • 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
    • Y10T428/298—Physical dimension

Definitions

  • the present invention relates to a process for the preparation of polymer fibers, in particular of nano- and mesofibers, wherein a colloidal dispersion of at least one substantially water-insoluble polymer is electrospun in an aqueous medium, as well as fibers obtainable by this process, textile fabrics containing the fibers according to the invention, and the use of the fibers according to the invention and of the textile fabrics according to the invention.
  • the skilled person knows a large number of methods, of which the electrospinning method (electrospinning) currently has the greatest significance.
  • electrospinning electrospinning
  • this method for example, by DH Reneker, HD Chun at Nanotechn. 7 (1996), page 216 f , Usually, a polymer melt or a polymer solution is exposed to a high electric field at an edge serving as an electrode. This can be achieved, for example, by extruding the polymer melt or polymer solution in an electric field under low pressure through a cannula connected to one pole of a voltage source.
  • DE-A1-101 33 393 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 electro-spun.
  • a solution of a water-insoluble polymer for example a poly-L-lactide solution in dichloromethane or a polyamide 46 solution in pyridine
  • DE-A1-10 2004 009 887 relates to a process for the production of fibers with a diameter of ⁇ 50 microns by electrostatic spinning or spraying 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 mesofibers are required with a diameter of less than 1 micron, which can be produced by the known electrospinning process only by using polymer solutions.
  • WO 2004/080681 A1 relates to apparatus 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 suitable for electrospinning are mentioned.
  • WO 2004/048644 A2 discloses the electrosynthesis of nanofibers and nano-composite films.
  • solutions also encompasses heterogeneous mixtures such as suspensions or dispersions.
  • Fibers are made of electrically conductive polymers. These are according to WO 2004/048644 A2 preferably obtained from the solutions containing the corresponding monomers.
  • WO 2006 / 089522A1 relates to a process for producing polymer fibers wherein a colloidal dispersion of at least one substantially water-insoluble polymer is electrospun in an aqueous medium.
  • aqueous polymer dispersions by means of an electrospinning process, polymer fibers, in particular nano- or mesofibers, being obtained.
  • WO 2006 / 089522A1 is a latex of a partially crosslinked poly (n-butyl acrylate) having a glass transition temperature of -43 ° C (according to Polymer Handbook (4th Edition), Edited by: Brandrup, J .; Immergut, Edmund H .; Grulke, Eric A .; Abe, Akihiro; Bloch, Daniel R. ⁇ 1999; 2005 John Wiley & Sons ) electro-spun at a temperature of 20 ° C.
  • the object of the present invention is to provide a process for the electrospinning of aqueous polymer dispersions, with which polymer fibers with respect to those in WO 2006 / 089522A1 disclosed polymer fibers optimized structural and / or mechanical properties can be obtained.
  • the object is achieved by providing a process for producing polymer fibers in which a colloidal dispersion of at least one substantially water-insoluble polymer is electrospun in an aqueous medium at 5 to 90 ° C.
  • the process according to the invention is then characterized in that the at least one essentially water-insoluble polymer has a glass transition temperature T g , measured by means of DSC, which lies in a range from a maximum of 15 ° C. above to a maximum of 15 ° C. below the process temperature.
  • T g glass transition temperature
  • fibers with a high water resistance can be obtained, which are characterized by a good mechanical stability. It is possible to produce nano- and mesofibers with a diameter of less than 1 .mu.m from aqueous dispersions with the method according to the invention, so that the use of non-aqueous toxic, combustible, irritating, explosive and / or corrosive solvents can be avoided. Since the fibers produced by the process according to the invention of substantially water-insoluble Polymers are constructed, a subsequent process step for water stabilization of the fibers is not required.
  • a colloidal dispersion of at least one substantially water-insoluble polymer is electrospun in an aqueous medium.
  • substantially water-insoluble polymers are, for the purposes of the present invention, in particular polymers having a solubility in water of less than 0.1% by weight.
  • 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.
  • Suspensions are preferably used in the process according to the invention.
  • the colloidal polymer dispersions preferably used according to the invention are also referred to in the technical language as latex.
  • the glass transition temperature T g is the temperature at which fully or partially amorphous polymers change from the liquid or rubber-elastic, flexible state to the glassy or hard-elastic, brittle state. It is an important parameter for plastics and is specific to each plastic.
  • the measurement of the glass transition temperature T g can, for. B. by Dynamic Mechanical Analysis (DMA), Differential Scanning Calorimetry (DSC) or dilatometry done.
  • DMA Dynamic Mechanical Analysis
  • DSC Differential Scanning Calorimetry
  • the values mentioned in the present application for the glass transition temperatures of various polymers were the Polymer Handbook (4th Edition), Edited by: Brandrup, J .; Immergut, Edmund H .; Grulke, Eric A .; Abe, Akihiro; Bloch, Daniel R. ⁇ 1999; 2005 John Wiley & Sons taken or - unless they are mentioned in the Polymer Handbook - determined by DSC (DIN 53765, ISO 11357-2).
  • the at least one essentially water-insoluble polymer has a glass transition temperature T g which is in a range from a maximum of 15 ° C. above to a maximum of 15 ° C. below the process temperature, preferably in a range of not more than 10 ° C. above to not more than 10 ° C. below the process temperature, particularly preferably in a range from a maximum of 5 ° above to a maximum of 5 ° C below the process temperature.
  • polymer fibers having excellent properties are obtained by the method of the present invention because the processing temperature of the polymers is in the range of the film-forming temperature (MFFT) of the polymers.
  • MFFT film-forming temperature
  • the film-forming temperature generally corresponds approximately to T g or is slightly below this value ( Emulsion polymerization and emulsion polymers, Edited by. P. Lovell, M. EI-Aasser, J. Wiley, 1997 ; Waterbased Acrylates for Decorative Coatings, Authors M. Schwartz, R. Baumstark, 2001 )).
  • At least one essentially water-insoluble polymer is understood as meaning both individual homopolymers and copolymers as well as mixtures of different homopolymers or copolymers.
  • the term "at least one substantially water-insoluble polymer” also polymer blends understood that in addition to the at least one homo- or copolymer z.
  • B. contain a plasticizer. It is known to the person skilled in the art that the glass transition temperature (and the film-forming temperature) of polymers can be reduced by adding a plasticizer or by crosslinking of the polymer. Suitable plasticizers are generally dependent on the homo- or copolymer used. Usual plasticizers are z.
  • plasticizers are further z. B. hexahydrophthalic. In principle, it is known to the person skilled in the art which plasticizers are suitable for which polymers or polymer blends.
  • the inventive method is carried out at a temperature of 5 to 90 ° C.
  • the electrospinning process according to the invention preferably takes place at a temperature of from 10 to 70.degree. C., more preferably at from 15 to 50.degree.
  • the process temperature depends, inter alia, on the essentially water-insoluble polymer used, since the essentially water-insoluble polymer has, according to the invention, a glass transition temperature T g in the range from a maximum of 15 ° C. above to a maximum of 15 ° C. below the process temperature.
  • the process temperature is to be understood as meaning the ambient temperature during the electrospinning process between the spinning source and the counterelectrode.
  • the spinning source may be e.g. to act as a cannula (e.g., a needle) or roller.
  • the colloidal polymer dispersions used according to the invention can be prepared by all processes known to the person skilled in the art for this purpose.
  • the colloidal dispersions are prepared by emulsion polymerization of suitable monomers to give the corresponding latices.
  • the latex obtained by emulsion polymerization is used directly in the process of the invention without further workup.
  • colloidal polymer dispersions z.
  • secondary dispersions are used. These are prepared from polymers already prepared by dispersing in an aqueous medium. In this way, for. As dispersions of polyethylene or polyesters can be produced.
  • the aqueous medium in which the substantially water-insoluble polymer is present is generally water.
  • the aqueous medium may contain other additives in addition to water, eg. B. additives used in the emulsion polymerization of suitable monomers to produce a latex. Suitable additives are known in the art.
  • Suitable substantially water-insoluble polymers are, for. B. selected from the group consisting of homo- and copolymers of aromatic vinyl compounds, homopolymers and copolymers of alkyl acrylates, homopolymers and copolymers of alkyl methacrylates, homopolymers and copolymers of ⁇ -olefins, homo- and copolymers of aliphatic dienes, homo- and Copolymers of vinyl halides, homo- and copolymers of vinyl acetates, homopolymers and copolymers of Acrylonitriles, homopolymers and copolymers of urethanes, homopolymers and copolymers of vinylamides and copolymers composed of two or more of the monomer units forming the abovementioned polymers.
  • Suitable homo- and copolymers of aromatic vinyl compounds are homopolymers and copolymers based on poly (alkyl) styrenes, z.
  • Suitable polyalkyl acrylates are, for. B. polyalkyl acrylates based on iso-butyl acrylate, tert-butyl acrylate, ethyl acrylate. When copolymers containing polyalkyl acrylates are used, further suitable are methyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate and n-butyl acrylate.
  • Suitable poly (alkyl) methacrylates are, for. B. polyalkyl methacrylates based on n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, ethylhexyl methacrylate, glycidyl methacrylate, methyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-pentyl methacrylate. If copolymers are used which contain poly (alkyl) methacrylates, z. As hydroxypropyl methacrylate suitable.
  • Suitable homopolymers and copolymers of ⁇ -olefins are, for. As polyethylene, polypropylene, poly (ethylene / propylene) (EPDM) and olefin / vinyl acetate copolymers, for. Ethylene / vinyl acetate copolymers, and olefin / acrylate copolymers, e.g. B. ethylene / acrylate copolymers.
  • Suitable homopolymers and copolymers of vinyl halides are, for.
  • polyvinyl chloride polytrichlorethylene, polytrifluoroethylene or polyvinyl fluoride.
  • homopolymers and copolymers are homopolymers and copolymers based on melamine-containing compounds, 1,3-butadiene, isoprene or vinyl alcohols (insofar as they are essentially water-insoluble and have a T g in the range according to the invention).
  • copolymers of acrylates, methacrylates, vinyl alcohols, polyalcohols and / or vinylaromatic compounds with acrylic acid, maleic acid, fumaric acid, methacrylic acid and / or itaconic acid (insofar as they are essentially water-insoluble and have a T g in the range according to the invention).
  • the at least one essentially water-insoluble polymer is preferably selected from the group consisting of polystyrene, poly- ⁇ -methylstyrene, styrene / alkyl acrylate copolymers, in particular styrene / n-butyl acrylate copolymers, styrene / alkyl methacrylate copolymers, ⁇ -methylstyrene / alkyl acrylate copolymers.
  • Copolymers ⁇ -methylstyrene / alkyl methacrylate copolymers, poly (alkyl) methacrylates, polyethylene, ethylene-vinyl acetate copolymers, ethylene / acrylate copolymers, polyvinyl chloride, polyalkylnitrile and polyvinyl acetate, polyurethanes, styrene-butadiene copolymers and styrene-acrylonitrile-butadiene copolymers.
  • the at least one substantially water-insoluble polymer selected from styrene / alkyl acrylate copolymers, in particular styrene / n-butyl acrylate copolymers, and styrene / alkyl methacrylate copolymers.
  • Suitable alkyl acrylates used in the styrene / alkyl acrylate copolymers are e.g. N-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, lauryl acrylate, methyl acrylate and n-propyl acrylate, with n-butyl acrylate, ethyl acrylate, methyl acrylate and 2- Ethylhexyl acrylate are preferred.
  • Suitable alkyl methacrylates used in the styrene / alkyl methacrylate copolymers are e.g. N-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, ethylhexyl methacrylate, Glycidyl methacrylate, hydroxymethacrylate, hydroxypropyl methacrylate, n-propyl acrylate, i-propyl acrylate and n-pentyl methacrylate, preferably n-butyl methacrylate, ethylhexyl methacrylate and methyl methacrylate.
  • the proportion of the various monomer units in the above-mentioned copolymers is variable (and depends on the desired glass transition temperature).
  • the proportion of styrene in the copolymers is generally from 30 to 100% by weight, preferably from 40 to 95% by weight, and the proportion of n-butyl acrylate from 0 to 70% by weight. , preferably 5 to 60 wt .-%, wherein the total amount of styrene and alkyl acrylate or alkyl methacrylate is 100 wt .-%.
  • substantially water-insoluble polymers are commercially available or can be prepared according to processes known to those skilled in the art.
  • substantially water-insoluble polymers are used which are prepared by emulsion polymerization.
  • the polymer latex obtained in the emulsion polymerization can be used directly in the electrospinning process according to the invention as a colloidal dispersion.
  • the at least one essentially water-insoluble polymer can be used in uncrosslinked, partially crosslinked or completely crosslinked form in the colloidal dispersion, provided that its solubility in water is less than 0.1% by weight.
  • the at least one essentially water-insoluble polymer used in the colloidal dispersion in the process according to the invention is partially or completely crosslinked, the crosslinking taking place by intraparticulate crosslinking.
  • Intraparticulate crosslinking of the at least one substantially water-insoluble polymer is generally accomplished by adding at least one crosslinker (crosslinking monomer) during the preparation of the substantially water-insoluble polymer by polymerization of the corresponding monomers to the monomer mixture.
  • crosslinkers and suitable amounts of crosslinker are known in the art and z. In Emulsion polymerization and emulsion polymers, Edited by. P. Lovell, M. EI-Aasser, J. Wiley, 1997 called.
  • Suitable crosslinkers are generally monomers which contain two, optionally also three or more, ethylenic double bonds which are capable of copolymerization and which are not conjugated in the 1,3-positions.
  • Suitable crosslinkers are compounds having two or more ethylenically unsaturated groups, such as diacrylates or dimethacrylates of at least dihydric saturated alcohols, such as. Ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, Butanediol-1,4-diacrylate, butanediol-1,4-dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methylpentanediol diacrylate and 3-methylpentanediol dimethacrylate.
  • Ethylene glycol diacrylate ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate
  • the acrylic acid and methacrylic acid esters of alcohols having more than 2 OH groups can also be used as crosslinking agents, eg. B. trimethylolpropane triacrylate or trimethylolpropane trimethacrylate.
  • Another class of crosslinkers are diacrylates or dimethacrylates of polyethylene glycols or polypropylene glycols having molecular weights of from 200 to 9,000, respectively.
  • oligomers of ethylene oxide or propylene oxide are suitable for the preparation of crosslinking agents, for.
  • diethylene glycol diacrylate diethylene glycol dimethacrylate, triethylene glycol diacrylate, Triehtylenglykoldimethacrylat, tetraethylene glycol diacrylate and / or tetraethylene glycol dimethacrylate.
  • crosslinking agents are vinyl acrylate, vinyl methacrylate, vinyl itaconate, divinyl adipate, butanediol divinyl ether, trimethylolpropane trivinyl ether, allyl acrylate, allyl methacrylate, pentaerythritol triallyl ether, triallyl sucrose, pentaallylsucrose, methylenebis (meth) acrylamide, divinylethyleneurea, divinylpropyleneurea, divinylbenzene, divinyldioxane, triallylcyanourate, tetraallylsilane, tetravinylsilane and bis or polyacrylic siloxanes (eg Tegomere® from Th. Goldschmidt AG).
  • Preferred crosslinkers are for. B. divinyl compounds such as divinyl benzene, diallyl and triallyl compounds such as diallyl maleate, diallyl fumarate, diallyl phthalate, triallyl cyanurate or triallyl isocyanurate, polyallyl compounds such as polyallyl methacrylate, allyl esters of acrylic and methacrylic acid, Dihydrodicyclopentadienylacrylat (DCPA), divinyl esters of dicarboxylic acids such as Succinic acid and adipic acid, diallyl and divinyl ethers of functional alcohols such as ethylene glycol and butane-1,4-diol such as ethylene glycol dimethacrylate, pentaerythritol tetraacrylate.
  • DCPA Dihydrodicyclopentadienylacrylat
  • functional alcohols such as ethylene glycol and butane-1,4-diol
  • the amount of suitable crosslinker is generally 0.01 to 20 wt .-%, preferably 0.01 to 10 wt .-%.
  • the resulting polymer may be fully crosslinked, that is, all (100%) of the crosslinkable groups of the polymer are crosslinked, or partially crosslinked, ie, only a few 50 to 100%, preferably 60 to 98%) of the polymer suitable for crosslinking are networked.
  • the average weight-average particle diameter of the at least one essentially water-insoluble polymer generally being from 1 nm to 2.5 ⁇ m, preferably from 10 nm to 1.2 ⁇ m, particularly preferably from 15 nm to 1 micron.
  • the average weight-average particle diameter of emulsion-produced latex particles which are used in a preferred embodiment in the method according to the invention is generally from 30 nm to 2.5 .mu.m, preferably from 50 nm to 1.2 .mu.m (determined according to W. Scholtan and H. Lange in Kolloid-Z. and Polymers 250 (1972), pp. 782-796 by means of ultracentrifuge).
  • colloidal polymer suspensions, in particular latexes in which the polymer particles have a weight-average particle diameter of 20 nm to 500 nm, in particular very particularly preferably 30 nm to 250 nm.
  • the colloidal suspension preferably used according to the invention may have particles with monomodal particle size distribution of the polymer particles or with bimodal or polymodal particle size distribution.
  • mono-, bi- and polymodal particle size distribution are known to the person skilled in the art.
  • the latex particles can be arranged in any manner known to the person skilled in the art. For example, only particles with gradient structure, core-shell structure, salami structure, multi-core structure, multi-layer structure and raspberry morphology are mentioned.
  • latex also means the mixture of two or more latices.
  • the preparation of the mixture can be carried out by any known method, e.g. by mixing two latices at any time prior to spinning.
  • the colloidal dispersion in addition to the at least one water-insoluble polymer, additionally contains at least one water-soluble polymer, wherein water-soluble polymer in the sense of the present invention means a polymer having a solubility in water of at least 0.1% by weight becomes.
  • the at least one water-soluble polymer which is preferably additionally present in the colloidal dispersions can serve as a template polymer.
  • the template polymer serves as a kind of "thickener” for the essentially water-insoluble polymers of the colloidal dispersion.
  • water-insoluble polymer fibers in particular nano- and microfibers, are obtained, without disintegration of the polymer fibers.
  • the water-soluble polymer may be a homopolymer, copolymer, block polymer, 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 water-soluble polymers known to those skilled in the art may be added to the colloidal dispersion of at least one substantially water-insoluble polymer in an aqueous medium, in particular with polyvinyl alcohol, polyvinylformamide, polyvinylamine, polycarboxylic acid (polyacrylic acid, polymethacrylic acid), polyacrylamide, polyitaconic acid, poly (2 -hydroxyethyl acrylate), poly (N-isopropylacrylamide), polysulfonic acid (poly (2-acrylamido-2-methyl-1-propanesulfonic acid) or PAMPS), polymethacrylamide, polyalkylene oxides, e.g.
  • polyethylene oxides Poly-N-vinylpyrrolidone; hydroxymethylcelluloses; hydroxyethylcelluloses; hydroxypropyl; carboxymethyl; maleic; alginates; collagens; Gelatin, poly (ethyleneimine), polystyrenesulfonic acid; Combinations composed of two or more of the monomeric units constituting the above-mentioned polymers, copolymers composed of two or more monomer units constituting the aforementioned polymers, graft copolymers composed of two or more of the monomeric units constituting the aforementioned polymers, star polymers composed of two or more of them above-mentioned polymer-forming monomer units, highly branched polymers composed of two or more of the above-mentioned polymer-forming monomer units and dendrimers composed of two or more of the group of the above-mentioned polymer-forming monomer units selected water-soluble polymers selected particularly good results.
  • the water-soluble polymer is selected from polyvinyl alcohol, polyethylene oxides, polyvinylformamide, polyvinylamine and poly-N-vinylpyrrolidone.
  • 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 colloidal dispersion to be used according to the invention-based on the total weight of the dispersion- is preferably from 5 to 60% by weight, particularly preferably from 10 to 50% by weight and very particularly preferably from 10 to 40% by weight.
  • the colloidal dispersion to be used in the process according to the invention comprises at least one substantially water-insoluble polymer and optionally at least one water-soluble polymer in an aqueous medium, based on the total weight of the dispersion, 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 weight ratio of essentially water-insoluble polymer to the water-soluble polymer preferably present in the colloidal dispersion depends on the polymers used.
  • the substantially water-insoluble polymer and the preferably used water-soluble polymer can be used in a weight ratio of 300: 1 to 1: 5, preferably 100: 1 to 1: 2, particularly preferably 40: 1 to 1: 1.5 become.
  • the colloidal dispersion to be used according to the invention can be electrospun in any manner known to the person skilled in the art, for example by extrusion of the dispersion, preferably of the latex, under low pressure through a cannula connected to one pole of a voltage source at a distance from the cannula outlet arranged counter electrode.
  • the distance between the cannula and the counterelectrode acting as a collector and the voltage between the electrodes is adjusted such that between the electrodes an electric field of preferably 0.1 to 9 kV / cm, particularly preferably 0.3 to 6 kV / cm and most preferably 0.5 to 3 kV / cm forms.
  • the fibers produced 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, based on the inventive selection of substantially water-insoluble polymers in relation to the process temperature compared to fibers having polymers, the glass transition temperature of more than +/- 15 ° C above or below the process temperature of the electrospinning process have optimized structural and / or mechanical properties, in particular with respect to uniformity, compactness, elasticity and mechanical and thermal 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.
  • An essential aspect with regard to the use of the polymer fibers according to the invention is - in addition to good structural and mechanical properties as well as thermal stability - the fiber diameter of the polymer fibers according to the invention.
  • the fiber diameter has a significant influence, for example, on the porosity of the filter media produced from the polymer fibers according to the invention and on the optical and haptic properties of z.
  • textile fabrics such as Vliessen, which are made from the fibers of the invention. It has been found that the fiber diameter, which depends inter alia on the process parameters such as flow rate and the field strength of the electric field and possibly on the diameter of the inserted cannula, further from the material properties, eg. B. the diameter of the polymer particles used in the inventive Electro-spinning process used essentially water-insoluble polymers and the ratio of the components used in the electrospinning process is dependent on each other.
  • the fiber diameter is proportional to the average weight average particle diameter of the substantially water-insoluble polymer used in the method of the invention.
  • the diameter of the polymer particles used it is possible to control the fiber diameter of the polymer fibers of the present invention and to selectively manufacture polymer fibers having specific fiber diameters.
  • Suitable particle sizes (average weight-average particle diameter) of the substantially water-insoluble polymer are mentioned above.
  • Very particularly preferred average weight-average particle diameters are 10 to 500 nm, preferably 10 to 200 nm, particularly preferably 10 to 100 nm.
  • the polymer fibers of the invention are suitable for further processing e.g. by interweaving the polymer fibers according to the invention into textile fabrics.
  • Another object of the present invention are therefore textile fabrics containing polymer fibers according to the present invention.
  • Preferred embodiments of the polymer fibers according to the invention are mentioned above.
  • the textile fabrics can be constructed exclusively from the polymer fibers according to the invention or, in addition to the polymer fibers according to the invention, contain conventional fibers known to the person skilled in the art. It is e.g. possible that the textile fabric according to the invention is constructed from conventional fibers and has a support (layer) containing the polymer fibers according to the invention. It is further e.g. possible that the textile fabric is made up of a mixture of conventional fibers and polymer fibers according to the invention.
  • Preferred applications are selected from the group consisting of the use in the following applications: filters or filter parts, non-wovens, nonwovens, in particular for gas, air and / or liquid filtration, technical or household textiles or components or coatings of such textiles such as wipes, facial tissues, clothing, medical textiles, etc., coatings of packaging, e.g. B. coatings of paper, for use in wound healing, or as a wound dressing, for the transport or release of active ingredients and effect substances, eg.
  • the polymer fibers according to the invention are used in the form of textile fabrics.
  • the production of textile fabrics from the polymer fibers according to the invention is known to the person skilled in the art and can be carried out by all customary processes. However, it is also possible to use the fibers according to the invention itself, for. As additives (fillers) for polymers or as precursors for the preparation of other fibers and continuous layers.
  • the output of the capillary 2 is at a distance of about 20 cm arranged a connected to the other pole of the voltage source 1 square counter electrode 5, which acts as a collector for the fibers formed.
  • a voltage of 30 kV is set at the electrodes 2, 5 and the colloidal dispersion 4 is discharged through the capillary nozzle 2 of the syringe 3 at a low pressure. Due to the electrostatic charge of the essentially water-insoluble polymers in the colloidal dispersion, which occurs due to the strong electric field of 0.1 to 10 kV / cm, a material flow directed towards the counterelectrode 5, which solidifies on the way to the counterelectrode 5 with fiber formation 6, arises. As a result, 5 fibers 7 are deposited with diameters in the micro and nanometer range on the counter electrode.
  • a colloidal dispersion of at least one essentially water-insoluble polymer and at least one nonionic surfactant is electrospun in an aqueous medium using the aforementioned device.
  • the determination of the solids content within the dispersion is carried out gravimetrically by means of a Mettler Toledo HR73 Halogen Moisture Analyzer by heating about 1 ml of the sample to 200 ° C. within 2 minutes and drying the sample to constant weight and then weighing it.
  • the mean particle size is the weight average d 50 , determined by means of an analytical ultracentrifuge (according to W. Scholtan and H. Lange in Kolloid-Z. and Polymers 250 (1972), pp. 782-796 ).
  • the size, i. the diameter and length of the fibers is determined by evaluation of electron micrographs.
  • the polymer latex used in the following examples contains a styrene / n-butyl acrylate copolymer in an amount of about 40% by weight (Example 1: 38.9% by weight, Example 2: 37.5% by weight, Example V3: 38.6 wt .-%), based on the total weight of the polymer latex.
  • the mean particle size (weight average, d 50 ) is 131 nm (Example 1), 137 nm (Example 2) or 149 nm (Example V3).
  • the copolymers are from 35% by weight of styrene and 65% by weight of n-butyl acrylate (Example 1), 50% by weight of styrene and 50% by weight of n-butyl acrylate (Example 2) and 70% by weight of styrene and 30% by weight of n-butyl acrylate (Example V3).
  • Example V3 is a comparative example in the present process. While the copolymer of Example 1 has a T g of 6.8 ° C and the copolymer in Example 2 has a T g of 27.2 ° C, the copolymer of Example V3 a T g of 64.2 ° C on. The process is at 19 ° C carried out so that the T g of the copolymer according to Example V3 is outside the claimed range.
  • polymer latices containing the said copolymers is carried out by customary methods known to the person skilled in the art.
  • a polymer latex is usually obtained with a content of styrene / n-butyl acrylate copolymer of> 30 wt .-%, which is then diluted with water to the desired concentration.
  • water-soluble polymer is poly (vinyl alcohol) (PVA) is having a weight average molecular weight (M w) of 145,000 g / mol, which is hydrolyzed to 99% - used (Mowiol ® 28 99 from Kuraray Specialties Europe KSE).
  • PVA poly (vinyl alcohol)
  • M w weight average molecular weight
  • the preparation of the electrospinning used colloidal dispersions is carried out by mixing a styrene / n-butyl acrylate copolymer-containing latex with water.
  • the solids content of the dispersion to be spun is 19.4% by weight.
  • To the polymer latex is added the above-mentioned polyvinyl alcohol, in aqueous solution (10% strength by weight), so that the colloidal dispersion to be spun contains about 4.8% by weight PVA and the weight ratio of styrene / n-butyl acrylate Copolymer to polyvinyl alcohol (PVA) in the mixture is about 80:20.
  • Table 1 summarizes the colloidal dispersions to be spun: example Amount of copolymer 2) Amount PVA 2) [% by weight] T g [° C] 3) 1 19.4% by weight 4.8% by weight 6.8 ° C 2 19.4% by weight 4.8% by weight 27.2 ° C V3 1) 19.4% by weight 4.8% by weight 64.2 ° C V4 1) 17.9 4.5 107 ° C 1) comparison 2) Styrene / n-butyl acrylate copolymer according to Examples 1, 2, V3 and polystyrene according to Example V4 based on the total weight of the dispersion 3) The modulus of elasticity was measured by means of a Minimat microtensile tester (Polymer Laboratories Ltd., UK) on samples of 10 mm length and a distance of 5 mm at room temperature at a speed of 0.2 mm / min.
  • Minimat microtensile tester Polymer Laboratories Ltd., UK
  • colloidal dispersions 1, 2, V3 and V4 prepared according to paragraph 1 are used in the in FIG. 1 electro-spun apparatus shown.
  • the dispersion is conveyed at a temperature of 19 ° C. through a syringe 3 with a capillary nozzle 2 provided at its tip with an inner diameter of 0.3 mm with a sample advance of 0.5 ml / h, the distance between the electrodes 2, 5 200 mm and between the electrodes, a voltage of 30 kV is applied.
  • the resulting fibers are treated with water for 17 hours at room temperature to remove the water-soluble polymer.
  • FIG. 2 are the scanning electron micrographs of the colloidal dispersions 1 (left, Fig. 2a ), 2 (middle, Fig. 2b ) and V3 (right, Fig. 2c ) produced fibers.
  • FIG. 2 it can be seen that when using copolymers which have a T g in a range from a maximum of 15 ° C above to a maximum of 15 ° C below the process temperature, more uniform polymer fibers are obtained ( Fig. 2a, Fig. 2b ) than when copolymers whose T g is outside the stated range ( Fig. 2c ).
  • the modulus of elasticity of the fibers of Example 1 according to the invention is 9 MPa, while the modulus of elasticity of fibers according to Example V4 is 1.2 MPa.
  • the fibers of the invention are thus characterized by a high elasticity.

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  • 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)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (16)

  1. Procédé pour la préparation de fibres polymères, où une dispersion colloïdale d'au moins un polymère essentiellement insoluble dans l'eau est filé électriquement dans un milieu aqueux à une température de 5 à 90°C, caractérisé en ce que ledit au moins un polymère essentiellement insoluble dans l'eau présente une température de transition vitreuse Tg, mesurée par DSC, qui se situe dans une plage d'au maximum 15°C au-dessus à au maximum 15°C au-dessous de la température de procédé.
  2. Procédé selon la revendication 1, caractérisé en ce que ledit au moins un polymère essentiellement insoluble dans l'eau présente une Tg dans une plage d'au moins -10°C à au maximum 105°C, la Tg du polymère se situant dans une plage d'au maximum 15°C au-dessus à au maximum 15°C au-dessous de la température de procédé.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que ledit au moins un polymère essentiellement insoluble dans l'eau est choisi dans le groupe constitué par les homopolymères et les copolymères de composés de vinyle aromatiques, les homopolymères et les copolymères d'acrylates d'acryle, les homopolymères et les copolymères de méthacrylates d'alkyle, les homopolymères et les copolymères d'α-oléfines, les homopolymères et les copolymères de diènes aliphatiques, les homopolymères et les copolymères d'halogénures de vinyle, les homopolymères et les copolymères d'acétates de vinyle, les homopolymères et les copolymères d'acrylonitriles, les homopolymères et les copolymères d'uréthanes, les homopolymères et les copolymères de vinylamides et les copolymères formés à partir d'une ou de plusieurs des unités monomères formant les polymères susmentionnés.
  4. Procédé selon la revendication 3, caractérisé en ce que ledit au moins un polymère essentiellement insoluble dans l'eau est choisi parmi les copolymères de styrène/acrylate d'alkyle et les copolymères de styrène/méthacrylate d'alkyle.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que ledit au moins un polymère essentiellement insoluble dans l'eau est utilisé sous forme non réticulée, partiellement réticulée ou complètement réticulée dans la dispersion colloïdale.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le diamètre moyen pondéral des particules dudit au moins un polymère essentiellement insoluble dans l'eau est situé entre 1 nm et 2,5 µm.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la dispersion colloïdale contient en outre au moins un polymère soluble dans l'eau présentant une solubilité dans l'eau d'au moins 0,1% en poids.
  8. Procédé selon la revendication 7, caractérisé en ce que le polymère soluble dans l'eau est choisi dans le groupe constitué par les homopolymères, les copolymères, les copolymères greffés, les polymères en étoile, les polymères hautement ramifiés et les dendrimères.
  9. Procédé selon la revendication 7 ou 8, caractérisé en ce que le polymère soluble dans l'eau est choisi dans le groupe constitué par le poly(alcool vinylique), le polyvinylformamide, la polyvinylamine, le poly(acide carboxylique), le polyacrylamide, le poly(acide itaconique), le poly(acrylate de 2-hydroxyéthyle), le poly(N-isopropylacrylamide), le poly(acide sulfonique), le polyméthacrylamide, les poly(oxydes d'alkylène) ; la poly-N-vinylpyrrolidone ; les hydroxyméthylcelluloses ; les hydroxyéthylcelluloses ; les hydroxypropylcelluloses ; les carboxyméthylcelluloses ; les acides maléiques ; les alginates ; les collagènes ; les gélatines, la poly(éthylèneimine), le poly(acide styrènesulfonique); les combinaisons formées par deux ou plus de deux des unités monomères formant les polymères susmentionnés, les copolymères formés par deux ou plus de deux des unités monomères formant les polymères susmentionnés, les copolymères greffés formés par deux ou plus de deux des unités monomères formant les polymères susmentionnés, les polymères en étoile formés par deux ou plus de deux des unités monomères formant les polymères susmentionnés, les polymères hautement ramifiés formés par deux ou plus de deux des unités monomères formant les polymères susmentionnés et les dendrimères formés par deux ou plus de deux des unités monomères formant les polymères susmentionnés.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que la teneur en solides de la dispersion colloïdale, par rapport au poids total de la dispersion, est de 5 à 60% en poids, de préférence de 10 à 50% en poids, de manière particulièrement préférée de 10 à 40% en poids.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que la dispersion colloïdale contient, par rapport au poids total de la dispersion, 0 à 25% en poids, de préférence 0,5 à 20% en poids, de manière particulièrement préférée 1 à 15% en poids d'un polymère soluble dans l'eau.
  12. Fibre pouvant être obtenue par un procédé selon l'une quelconque des revendications 1 à 11.
  13. Fibre selon la revendication 12, caractérisée en ce qu'elle présente un diamètre de 10 nm à 50 µm, de préférence de 50 nm à 2 µm et de manière tout particulièrement préférée de 100 nm à 1 µm.
  14. Fibre selon la revendication 12 ou 13, caractérisée en ce qu'elle présente une longueur d'au moins 50 µm.
  15. Structure textile plane, contenant des fibres selon l'une quelconque des revendications 12 à 14.
  16. Utilisation de fibres selon l'une quelconque des revendications 12 à 14 ou de structures textiles planes selon la revendication 15 pour une utilisation dans les applications suivantes : les filtres ou les parties de filtres, les non-tissés, les nattes, les textiles techniques ou, selon le cas, domestiques ou, selon le cas, les constituants ou les revêtements de ces textiles, les textiles médicaux, les revêtements ou, selon le cas, les constituants d'emballages, pour une utilisation dans la guérison de plaies, ou, selon le cas, comme pansement, pour le transport ou, selon le cas, la libération de substances actives ou conférant un effet, les supports de culture cellulaire, les supports de catalyseur, les capteurs ou, selon le cas, leurs composants, les amortisseurs acoustiques, les précurseurs pour la fabrication d'autres fibres, ainsi que les couches continues, comme additifs pour polymères, les revêtements pour améliorer le toucher, les propriétés optiques et l'aspect, la fabrication de membranes ainsi que les adsorbants et les absorbants de milieux solides, liquides et gazeux.
EP20080786037 2007-07-18 2008-07-10 Procédé pour produire des nanofibres et des mésofibres par électrofilage de dispersions colloïdales contenant au moins un polymère pratiquement insoluble dans l'eau Not-in-force EP2171136B1 (fr)

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EP20080786037 EP2171136B1 (fr) 2007-07-18 2008-07-10 Procédé pour produire des nanofibres et des mésofibres par électrofilage de dispersions colloïdales contenant au moins un polymère pratiquement insoluble dans l'eau

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