EP2598232A1 - Fibre creuse poreuse - Google Patents

Fibre creuse poreuse

Info

Publication number
EP2598232A1
EP2598232A1 EP11775726.0A EP11775726A EP2598232A1 EP 2598232 A1 EP2598232 A1 EP 2598232A1 EP 11775726 A EP11775726 A EP 11775726A EP 2598232 A1 EP2598232 A1 EP 2598232A1
Authority
EP
European Patent Office
Prior art keywords
hollow fiber
range
calcium carbonate
pores
carbonate particles
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Withdrawn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
EP11775726.0A
Other languages
German (de)
English (en)
Inventor
Roland Vogel
Claudia Hinüber
Marijan Vucak
Christoph Nover
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.)
Schaefer Kalk GmbH and Co KG
Original Assignee
Schaefer Kalk GmbH and Co KG
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 Schaefer Kalk GmbH and Co KG filed Critical Schaefer Kalk GmbH and Co KG
Priority to EP11775726.0A priority Critical patent/EP2598232A1/fr
Publication of EP2598232A1 publication Critical patent/EP2598232A1/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Withdrawn legal-status Critical Current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
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247—Discontinuous hollow structure or microporous structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
    • B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • 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
    • 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
    • D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/08—Specific temperatures applied
    • B01D2323/081—Heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/0283—Pore size
    • 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
    • Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
    • 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 present invention relates to porous hollow fibers comprising at least one preferably semicrystalline polymer, and to processes for their
  • Hollow fibers are already known and refer to filament yarns or staple fibers made of viscose or synthetic fibers with air pockets, which by special
  • Hollow fibers are generally more bulky than ordinary fibers and show greater thermal insulation capacity.
  • hollow fibers of cellulose acetate, polysulfone, polyacrylonitrile, polymethyl methacrylate, polyamide, polybenzimidazole or glass are also produced.
  • Preferred applications of hollow fibers include fillings for
  • porous hollow fibers For the production of porous hollow fibers, various methods are known.
  • the conventional way is the stretching process.
  • many crystalline polymers can be transferred by stretching into a highly-oriented morphological state.
  • the resulting fibers are characterized in particular by an increased modulus, improved strength, a significantly increased
  • TIPS thermally induced phase separation
  • the structure of the hollow fibers depends to a large extent on the thermodynamic interactions between the polymer and the solvent, the
  • Phase growth affect as soon as a phase separation has occurred.
  • the fibers available by TIPS are comparatively brittle and glued together. Their permeability is lower in comparison with porous hollow fibers obtained by stretching.
  • porous hollow fibers are also described in the patent literature and in other publications.
  • polypropylene is mainly used as the starting material.
  • US Pat. No. 5,232,642 relates to a process for the production of porous hollow-fiber membranes made of polypropylene. These hollow fibers have large, rectangular pores with pore diameters of 1 pm to 10 pm. The production takes place by melt spinning with a hollow fiber nozzle. The pores are produced by multiple stretching at different temperatures with intermediate annealing at different temperatures.
  • the patent US 6,890,436 describes hollow fiber membranes with openings of 1 pm to 10 pm. These hollow fiber membranes are produced in a wet spinning process. The spinning solution of polymer, solvent and a phase separation additive in the spin bath are added to microparticles which in the
  • Solvents of the spinning solution are insoluble. After the spinning process, the microparticles are dissolved out with a selective solvent.
  • microparticles are metal oxides such as silica, zinc oxide and alumina, metallic microparticles such as silicon, zinc, copper, iron and aluminum, and inorganic compounds such as sodium chloride,
  • Particle size of the microparticles should preferably be in the range of 1 pm to 20 pm, and more preferably in the range of 2 pm to 10 pm.
  • the patent application EP 0 168 783 A1 discloses asymmetric microporous hollow fibers for hemodialysis and processes for their preparation.
  • Hollow fiber consists of 90 wt .-% to 99 wt .-% of a hydrophobic polymer and 10 wt .-% to 1 wt .-% of a hydrophilic polymer having a water absorbency of 3 wt .-% to 10%, wherein the Hollow fiber is prepared by an extruded solution of 12 wt .-% to 20 wt .-% first polymer, 2 wt .-% to 10 wt .-% second polymer remainder solvent from the inside out while simultaneously dissolving a portion of the
  • Pore former is precipitated from the extrudate and then washed out the leached part of the pore-forming agent and the remaining organic components and then the resulting fiber is fixed in a washing bath.
  • Temperature range of 110 ° C to 155 ° C are generated.
  • the draw rate is less than 10% / min.
  • porous hollow fibers are made by a stretching process of double-layered hollow fibers containing polymethylsilsesquioxane (PMSO) fillers.
  • PMSO polymethylsilsesquioxane
  • relatively small filler particles are present in the inner and relatively large filler particles in the outer layer.
  • Elongated pores with an average length of 10 ⁇ m and a mean width of 2 ⁇ m are formed in the outer layer.
  • the inner layer comprises elongated pores with an average length of 5 pm and a mean width of 1 pm.
  • Microporous hollow fiber membranes formed from blends of isotactic and atactic polypropylene Journal of Membrane Science 164 (2000) 59-65 discloses microporous hollow fibers spun from blends of isotactic and atactic polypropylene become. The atactic polypropylene is removed after melt spinning by extraction. Then the hollow fiber is stretched cold. The membranes have smaller ones
  • Pore diameters and higher permeabilities than hollow fibers produced by traditional stretching processes are 0.017 ⁇ m.
  • Film strips are stretched after melt spinning in a hot air oven with a draw ratio of ⁇ greater than 10 after (overdrawing). At these extreme draw ratios, the morphology of the Fo Kunststoffmixchen changes. The color changes from transparent to opaque. After etching with permanganate, elongated pores having an average length of 1 ⁇ m and a width of 0.2 ⁇ m are visible on the surface.
  • Textile fibers, in particular hollow fibers, are not mentioned in this document.
  • the property profile of the resulting hollow fibers should be further improved if possible.
  • the aim was to achieve a pore shape which was as well defined as possible and controllable as well as possible a uniform pore distribution.
  • the object of the invention was, in particular, to make accessible porous hollow fibers which have both a continuous porosity, preferably a microporosity, for the flow through with gases or liquids as well as pores, preferably nanopores, with suitable pore geometries
  • porous hollow fiber having all the features of present claim 1. Furthermore, a particularly advantageous process for the production of the porous hollow fiber, particularly suitable intermediates and particularly expedient fields of application of the porous hollow fiber put under protection.
  • ⁇ an average length in the range of 0.045 pm to 120 pm
  • the hollow fiber further comprises second pores, which
  • ⁇ an average length in the range of 0.1 nm to 99 nm
  • the porous hollow fiber according to the invention has on the one hand a continuous porosity, in particular a microporosity, for the flow through with gases or liquids. On the other hand, it also includes pores, in particular nanopores, with suitable
  • Pore geometries for the adsorption of gases or liquid substances are described.
  • the solution according to the invention can be implemented in a comparatively simple manner, extremely cost-effectively and efficiently, on an industrial scale.
  • porous hollow fiber according to the invention can be used in a particularly advantageous manner in many fields of application.
  • the present invention relates to a first
  • Hollow fiber which is particularly suitable for producing the porous hollow fiber according to the invention.
  • fiber refers to the thin strand primarily formed during production, which has a large length-to-cross-section ratio.
  • filament is understood to mean a bundle of individual fibers.
  • the first hollow fiber comprises at least one polymer, preferably at least one thermoplastically processable polymer which is furthermore preferably semicrystalline.
  • polymers include
  • Cellulosic polymers in particular cellulose acetates, polyacrylates, poly (aryl ether ether ketones), polymethacrylates, in particular polymethyl methacrylates,
  • Polyacrylonitriles polyimides, in particular polybenzimidazoles, polyamides,
  • Polyesters polysulfones, polyolefins, especially polypropylenes, polylactic acid, polybutyric acid, and mixtures thereof.
  • the first hollow fiber comprises at least one polyolefin, in particular at least one polypropylene, expediently at least one isotactic polypropylene or at least one syndiotactic polypropylene.
  • the polymer used in the invention preferably the thermoplastically processable polymer, especially the polypropylene, preferably has a melt index (MI) of 0.5 to 30, measured according to the procedure described in ASTM D-1238. Particularly preferred is the
  • the first hollow fiber further comprises calcium carbonate particles, preferably precipitated calcium carbonate particles (PCC), with specific properties.
  • PCC precipitated calcium carbonate particles
  • crystallites includes crystallites or
  • Crystallite or primary particles are defined as the smallest individual particles found in
  • calcium carbonate particles in the context of the present invention denotes particles which, based on their total weight, at least 95.0% by weight, preferably at least 99.0% by weight, in particular at least 99.5% by weight. CaC0 3 included.
  • the calcium carbonate particles of the present invention are preferably substantially crystalline. Conveniently, at least 50 wt .-%, preferably at least 75 wt .-%, in particular at least 90 wt .-% of
  • the calcium carbonate particles as a crystalline material.
  • the calcium carbonate particles particularly preferably comprise calcite and / or aragonite fractions, the calcite fraction advantageously being greater than 30% by weight, preferably greater than 50% by weight, in particular greater than 90% by weight.
  • the crystallites of the calcium carbonate particles have a form factor of less than 5, preferably less than 4, preferably less than 3, particularly preferably less than 2, in particular less than 1.7. Furthermore, the form factor of the crystallites is preferably greater than 1, preferably greater than 1, 1, in particular greater than 1.3.
  • the aspect ratio is defined by the ratio of the largest dimension and the smallest dimension of the crystallites (primary particles). It is preferably by means of
  • Scanning electron microscopy suitably determined by the largest dimension and the smallest dimension of the crystallites for at least 10
  • Crystallites determined in a photograph and averaged each arithmetically.
  • the calcium carbonate particles preferably in
  • a rhombohedral crystal morphology Conveniently, at least 50%, preferably at least 75%, more preferably at least 90%, suitably at least 95%, in particular at least 99%, of the crystallites have a rhombohedral form.
  • the shape of the crystallites is preferably determined by means of scanning electron microscopy.
  • Calcium carbonate particles moreover have a BET specific surface of at least 0, 1 m 2 / g, preferably of at least 1, 0 m 2 / g, more preferably of at least 3.0 m 2 / g, suitably of at least 4.0 m 2 / g, particularly preferably of at least 5.0 m 2 / g, in particular of at least 10.0 m 2 / g, on.
  • the BET specific surface area of the calcium carbonate particles is preferably less than 30.0 m / g, preferably less than 25.0 m / g, more preferably less than 20.0 m 2 / g, favorably less than 15.0 m 2 / g.
  • the BET specific surface area of the calcium carbonate particles is expediently determined in accordance with ISO 9277-1995.
  • the calcium carbonate particles in the context of the present invention preferably have an average primary particle size of at least 10 nm, preferably of at least 30 nm, particularly preferably of at least 50 nm,
  • the average primary particle size is preferably at most 20 ⁇ , preferably at most 10 m, particularly preferably at most 1 ⁇ , very particularly preferred at most 0.75 ⁇ , conveniently at most 0.6 ⁇ , in particular at most 0.5 ⁇ .
  • the primary particle size is preferably determined by scanning tunneling microscopy (SEM).
  • the particle size and the particle size distribution of the calcium carbonate particles is preferably determined by means of sedimentation analysis, expediently using the Sedigraphs 5100 (Micromeritics GmbH).
  • the average size of the calcium carbonate particles (corresponds to the d 50 % value defined below) is at least 0.030 ⁇ m, preferably at least 0.050 ⁇ m, particularly preferably at least 0.070 ⁇ m, advantageously at least 0.100 ⁇ m, very particularly preferably at least 0.150 ⁇ m, advantageously at least 0.250 ⁇ , in particular at least 0.350 ⁇ . Furthermore, the average size of the calcium carbonate particles is at most 20 ⁇ , preferably at most 10 ⁇ , more preferably at most 5 ⁇ , advantageously at most 3 ⁇ , most preferably at most 2 ⁇ , advantageously at most 1, 2 ⁇ , in particular at most 0.8 ⁇ .
  • the value dso% is the
  • Particle size value at which 50% by weight of the particles have a particle size less than or equal to the d 50% value is a Particle size value at which 50% by weight of the particles have a particle size less than or equal to the d 50% value.
  • the width of the particle size distribution is preferably determined by the
  • granulometric factor (ds4% - di 6% ) / d 5 o%, where
  • d 84 % denotes the particle size value at which 84% by weight of the particles have a particle size less than or equal to the de4 % value
  • di 6 % denotes the particle size value at which 16% by weight of the particles have a particle size less than or equal to the di 6 % value.
  • the granulometric factor of the particle size distribution of the calcium carbonate particles is preferably at most 3.5, preferably at most 2.5, in particular at most 1. Furthermore, the granulometric factor is the
  • Particle size distribution of the calcium carbonate particles preferably
  • the calcium carbonate particles are at least one
  • Coating agents include silanes, carboxylic acids, carboxylic acid salts, polyacrylic acids, polyacrylic acid salts, and mixtures thereof.
  • the salts mentioned preferably do not comprise sodium salts.
  • the carboxylic acids may be aliphatic or aromatic, with aliphatic carboxylic acids being particularly preferred.
  • the aliphatic carboxylic acids may be linear, branched or cyclic, substituted or unsubstituted, saturated or unsaturated, aliphatic carboxylic acids. They preferably comprise at least 4, preferably at least 8, particularly preferably at least 10, in particular at least 14 carbon atoms. Furthermore, they preferably comprise at most 32, preferably at most 28, particularly preferably at most 24, in particular at most 22 carbon atoms.
  • very particularly preferred aliphatic carboxylic acids include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid,
  • Stearic acid isostearic acid, hydroxystearic acid, arachic acid, behenic acid, lignorceric acid, hexacosanoic acid, montanic acid, triacontanoic acid, 9-tetradecenoic acid, palmitoleic acid, cis-6-octadecenoic acid, (Z) octadec-9- acid, oleic acid, elaidic acid, linoleic acid, trans-9, trans-12-octadecadienoic acid, linolenic acid, trans-9, trans-12-octadecadienoic acid, ⁇ -elaeostearic acid, ⁇ -elaeostearic acid, gadoleic acid, Arachidonic acid, erucic acid, trans-13-docosenoic acid and all-cis-7,10,13,16,19-docosapentaenoic acid. Furthermore, mixture
  • Mixtures comprising substantially palmitic, stearic and oleic acids are most preferred.
  • Mixtures called "stearins" containing from 30% to 40% by weight stearic acid, from 40% to 50% by weight Palmitic acid and 13 wt .-% to 20 wt .-% oleic acid, are particularly suitable for the purposes of the present invention.
  • Suitable aliphatic carboxylic acids include rosin acids,
  • Carboxylic acids include potassium, ammonium and calcium salts, more preferably calcium salts, the carboxylic acids.
  • Preferred polyacrylic acids for the purposes of the present invention have a weight average molecular weight of at least 500 g / mol, preferably of at least 700 g / mol, in particular of at least 1000 g / mol.
  • the molecular weight is preferably at most 15,000 g / mol, preferably at most 4000 g / mol, in particular at most 2000 g / mol. Furthermore, mixtures and / or salts of these polyacrylic acids are particularly advantageous.
  • Preferred salts of the polyacrylic acids include potassium, ammonium and calcium salts, more preferably calcium salts, polyacrylic acids.
  • the proportion of the coating agent can in principle be chosen freely. It is preferably at least 0.0001 wt .-%, preferably at least 0.001 wt .-%, particularly preferably at least 0.01 wt .-%, in particular at least 0.05 wt .-%, each based on the total weight of the coated
  • Calcium carbonate particles is preferably at most 60 wt .-%, preferably at most 25 wt .-%, particularly preferably at most 10 wt .-%, in particular at most 6 wt .-%, each based on the total weight of the coated calcium carbonate particles.
  • Calcium carbonate particles can be carried out in a manner known per se. It is described in detail in particular in the patent application WO 2007/068593, the disclosure of which in this respect by reference in the present
  • the relative proportions of the components on the first hollow fiber are not particularly limited and can be freely selected.
  • the Weight ratio of polymer to calcium carbonate in the range of 95: 5 to 50:50, preferably in the range of 90:10 to 60:40, in particular in the range of 80:20 to 70:30, is located.
  • the first hollow fiber preferably comprises at least 25.0% by weight, preferably at least 50.0% by weight, in particular at least 60.0% by weight, of polymer and preferably at least 1.0% by weight, preferably at least 5 , 0 wt .-%, particularly preferably at least 10.0 wt .-%, in particular
  • the first hollow fiber preferably comprises at most 50.0% by weight, preferably at most 40.0% by weight, in particular at most 35.0% by weight of calcium carbonate particles, in each case based on the total weight of the
  • the preparation of the first hollow fiber can be carried out in a manner known per se. Conveniently, one starts from a composition comprising the polymer and the calcium carbonate. Particularly advantageous is the admixture of an organic nucleating agent, as this significantly reduces the calcium carbonate crystallites in the polymer and the crack propagation is much more homogeneous.
  • Particularly suitable nucleating agents for the purposes of the present invention include polyhydric alcohols which preferably comprise at least 2, preferably at least 3, more preferably at least 4, conveniently at least 5, in particular at least 6 hydroxyl groups, which are preferably present in each case as CHOH groups.
  • nucleating agents include ethylene glycol, glycerin, threitol, erythritol, arabitol, ribitol, adonite, xylitol, sorbitol, mannitol, dulcitol, with compounds having more than 4, preferably 6, carbon atoms being particularly preferred.
  • the proportion of the nucleating agent in the composition is preferably at most 5% by weight, preferably in the range from 0.1% by weight to at most 3% by weight, particularly preferably in the range from 0.2% by weight to at most 1 , 5 wt .-%, in particular in the range of 0.3 wt .-% to 0.75 wt .-%, each based on the total weight of the composition, wherein the proportion of polymer, calcium carbonate and nucleating agent to the composition, based on their weight, preferably at least 85.0 wt .-%, preferably, at least 90.0 wt .-%, particularly preferably at least 95.0 wt .-%, in particular at least 99.0 wt .-%, is.
  • the composition comprising the polymer and the calcium carbonate particles is melt-spun using a hollow fiber-forming die. Obtained in this way a non-stretched hollow fiber, which is preferably oriented and highly crystallized.
  • nozzles for the formation of hollow fibers is on the standard literature, in particular on Franz Fourne Synthetic fibers: manufacturing, machinery and apparatus, properties; Manual for Plant Design, Machine Design and Operation Kunststoff, Vienna; Hanser Verlag, 1995 and the references cited therein.
  • a nozzle having a double-tube construction is preferred because it may give a substantially uniform section
  • a horseshoe-shaped nozzle or other structure may also be used.
  • the air introduced into the hollow fiber to maintain its hollow shape can be spontaneously or forcibly supplied.
  • the spinning temperature be 20 ° C to 150 ° C higher than the melting point of the polymer.
  • the extruded at a suitable spinning temperature polymer is preferably taken at a spinning delay of 5 to 5000.
  • the resulting first hollow fiber is preferably highly oriented in the longitudinal direction of the fiber and preferably has an inside diameter of 100 ⁇ m to 2000 ⁇ m and a wall thickness of 15 ⁇ m to 800 ⁇ m.
  • ⁇ an average length in the range of 0.045 pm to 120 pm, preferably in
  • Range from 0.105 ⁇ m to 60 ⁇ m preferably in the range from 0.150 ⁇ m to 30 ⁇ m, particularly preferably in the range from 0.225 ⁇ m to 18 ⁇ m,
  • ⁇ an average width in the range of 0.030 pm to 20 pm, preferably in
  • Range of 0.050 pm to 10 pm preferably in the range of 0.070 pm to 5 pm, more preferably in the range of 0.100 pm to 3 pm, advantageously in the range of 0.150 pm to 2 pm, most preferably in the range of 0.250 ⁇ to 1, 2 [im, in particular in the range of 0.350 ⁇ to 0.8 ⁇ , each measured in the fiber direction, have,
  • the ratio of the mean length of the first pores to the mean width of the first pores is at least 1.5: 1, preferably at least 2: 1, preferably at least 3: 1, more preferably at least 5: 1, advantageously at least 7.5: 1, in particular at least 10: 1, is.
  • porous hollow fiber comprises second pores, which
  • ⁇ an average length in the range of 0.1 nm to 99 nm, preferably in the range of 0.2 nm to 90 nm, preferably in the range of 0.3 nm to 80 nm, particularly preferably in the range of 0.4 nm to 70 nm, suitably in the range of 0.5 nm to 60 nm, in particular in the range of 0.75 nm to 50 nm, and
  • ⁇ an average width in the range of 1 nm to 20,000 nm, preferably in
  • the corresponding values for the mean length and width of the respective pores are preferably determined by means of electron microscopy, in which case an arithmetic agent is preferably formed over at least 5, preferably at least 10, in particular at least 15, pores.
  • the first hollow fiber is preferably stretched to an elongation greater than 50%, preferably greater than 100%, particularly preferably greater than 200%, in particular in the range of 300% to 600%, in each case based on the initial length of the hollow fiber, measured at 25 ° C.
  • this first hollow fiber is desirably heat treated at a temperature in the range of 100 ° C to 165 ° C, preferably in the range of 1 10 ° C to 155 ° C prior to stretching.
  • the heat treatment (or annealing) time is preferably 30 minutes or more.
  • the stretching of the hollow fiber itself is preferably carried out at a temperature in the range of 100 ° C to 165 ° C, preferably in the range of 110 ° C to 155 ° C.
  • the deformation rate during drawing is preferably set to not more than 10% per second. Furthermore, the stretching speed is suitably in the range of 10 cm / min to 110 cm / min.
  • deformation rate means a value obtained by dividing the amount of stretch (in%) in a draw range by the time (in seconds) required for the hollow fiber to pass the draw range.
  • the calcium carbonate particles are at least partially removed after hiding from the porous hollow fiber.
  • a suitable solvent is preferably used, preferably an aqueous solvent
  • Composition more preferably an acidic aqueous
  • the residual calcium carbonate content of the porous hollow fiber after the at least partial removal of the calcium carbonate particles is less than 30 wt .-%, preferably less than 20 wt .-%, particularly preferably less than 10 wt .-%,
  • the resulting porous hollow fibers have a substantially stabilized shape and do not necessarily require a thermal fixing step for fixing the porous structure. However, if desired, they may be thermally fixed under constant length under tensile stress or under relaxed conditions in the same temperature range as used for hiding.
  • Preferred fields of application of the porous hollow fiber according to the invention include their use in fillings for duvets, pillows, sleeping bags,
  • Reverse osmosis for desalting, concentrating, fractionating proteins, enzymes and the like, for decomposing gas mixtures, as an oxygenator in artificial lung, for plasma separation during dialysis, at
  • porous hollow fiber according to the invention in the icrofiltration is very particularly preferred in this context.
  • Form factor 1: 5; Edge length about 350 nm; particle size distribution
  • the samples were mixed in ten batches in a microcompounder at 210 ° C at a speed of 80 revolutions per minute for a period of four minutes after reflow.
  • the finished mixture was spun in a piston spinning device with hollow nozzle at 240 ° C at a take-off speed of 100 m / min.
  • the spun hollow fiber was set at a temperature of 130 ° C at a speed of 50 cm / min (original fiber length: 5 cm) on a
  • the hollow fiber thus produced shows elongated over the entire volume
  • the micropores show a consistent
  • the hollow fibers produced in this way show nanopores with an average pore width of 100 nm and an average pore length of 10 nm, in each case in the stretch direction.
  • the calcium carbonate particles were removed from the hollow fibers with a mixture (50:50) of methanol and hydrochloric acid.
  • FIG. 1 shows a scanning tunneling micrograph of a stretched hollow fiber which contains first pores in the yarn direction, second pores perpendicular to the yarn direction and calcium carbonate particles.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention concerne une fibre creuse poreuse, comprenant des premiers pores qui présentent ▪ une longueur moyenne dans la plage de 0,045 μm à 120 μm et ▪ une largeur moyenne dans la plage de 0,030 μm à 20 μm, mesurées chacune dans la direction de la fibre, le rapport de la longueur moyenne des premiers pores à la largeur moyenne des premiers pores valant au moins 1,5:1, la fibre creuse comprenant en outre des deuxièmes pores qui présentent ▪ une longueur moyenne dans la plage de 0,1 nm à 99 nm et ▪ une largeur moyenne dans la plage de 1 nm à 20 000 nm, mesurées chacune dans la direction de la fibre, le rapport de la longueur moyenne des deuxièmes pores à la largeur moyenne des deuxièmes pores valant au plus 1:1,5. Des domaines d'utilisation préférés des fibres creuses poreuses comprennent leur utilisation dans des remplissages, dans des membranes perméables sélectives, pour l'immobilisation d'enzymes et/ou de cellules, pour l'hémodialyse ainsi que pour l'accumulation d'hydrogène.
EP11775726.0A 2010-07-30 2011-07-28 Fibre creuse poreuse Withdrawn EP2598232A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11775726.0A EP2598232A1 (fr) 2010-07-30 2011-07-28 Fibre creuse poreuse

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP10007958 2010-07-30
EP10008206A EP2412426A1 (fr) 2010-07-30 2010-08-06 Fibre creuse poreuse
EP11775726.0A EP2598232A1 (fr) 2010-07-30 2011-07-28 Fibre creuse poreuse
PCT/EP2011/003775 WO2012013345A1 (fr) 2010-07-30 2011-07-28 Fibre creuse poreuse

Publications (1)

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EP2598232A1 true EP2598232A1 (fr) 2013-06-05

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EP10008206A Withdrawn EP2412426A1 (fr) 2010-07-30 2010-08-06 Fibre creuse poreuse
EP11775726.0A Withdrawn EP2598232A1 (fr) 2010-07-30 2011-07-28 Fibre creuse poreuse

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EP (2) EP2412426A1 (fr)
CA (1) CA2805927A1 (fr)
WO (1) WO2012013345A1 (fr)

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US8975305B2 (en) 2012-02-10 2015-03-10 Kimberly-Clark Worldwide, Inc. Rigid renewable polyester compositions having a high impact strength and tensile elongation
WO2014097007A1 (fr) * 2012-12-19 2014-06-26 Kimberly-Clark Worldwide, Inc. Fibres de faible densité et leurs procédés de formation
JP6436591B2 (ja) * 2013-06-12 2018-12-12 キンバリー クラーク ワールドワイド インコーポレイテッド 包装用ポリオレフィンフィルム
US11965083B2 (en) 2013-06-12 2024-04-23 Kimberly-Clark Worldwide, Inc. Polyolefin material having a low density
MX363276B (es) * 2013-06-12 2019-03-15 Kimberly Clark Co Tejido multifuncional.
US9957369B2 (en) 2013-08-09 2018-05-01 Kimberly-Clark Worldwide, Inc. Anisotropic polymeric material
KR102224569B1 (ko) 2013-08-09 2021-03-08 킴벌리-클라크 월드와이드, 인크. 중합체 물질의 다공성을 선택적으로 제어하기 위한 기술
BR112017009619B1 (pt) 2014-11-26 2021-10-05 Kimberly-Clark Worldwide, Inc. Material de poliolefina, fibra, trama não tecida, artigo absorvente, e, método para formação de um material de poliolefina
EP3037156A1 (fr) * 2014-12-22 2016-06-29 Gambro Lundia AB Séchage de membranes creuses en ligne
CA3219268A1 (fr) * 2019-06-27 2020-12-30 W. L. Gore & Associates, Inc. Systemes de culture pour algues marines
AU2020303888A1 (en) * 2019-06-27 2022-01-27 W.L. Gore & Associates, Inc. Biointerfaces for growing seaweed
CN112030254A (zh) * 2020-08-28 2020-12-04 平湖爱之馨环保科技有限公司 一种微孔纤维及其制造方法
KR20240038096A (ko) 2021-08-05 2024-03-22 더블유. 엘. 고어 앤드 어소시에이트스, 인코포레이티드 해조류 부착근의 포획 및 부착을 촉진하는 복합 재료
CN114887486B (zh) * 2022-05-09 2023-04-18 中国海洋大学 一种基于甘露醇的聚酯疏松复合纳滤膜及其制备方法与应用
CN119593081B (zh) * 2023-09-08 2025-10-10 中国石油化工股份有限公司 一种贯通孔型超高分子量聚乙烯纤维、其制造方法及其应用

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US20130118981A1 (en) 2013-05-16
EP2412426A1 (fr) 2012-02-01
WO2012013345A1 (fr) 2012-02-02

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