EP0608248B1 - Matiere fibreuse en ptfe et son procede de fabrication - Google Patents

Matiere fibreuse en ptfe et son procede de fabrication Download PDF

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Publication number
EP0608248B1
EP0608248B1 EP92918372A EP92918372A EP0608248B1 EP 0608248 B1 EP0608248 B1 EP 0608248B1 EP 92918372 A EP92918372 A EP 92918372A EP 92918372 A EP92918372 A EP 92918372A EP 0608248 B1 EP0608248 B1 EP 0608248B1
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EP
European Patent Office
Prior art keywords
ptfe
fibre material
cross
additives
fluidized bed
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.)
Expired - Lifetime
Application number
EP92918372A
Other languages
German (de)
English (en)
Other versions
EP0608248A1 (fr
Inventor
Bruno Klatt
Manfred Horx
Hartmut KÖLLING
Karlheinz Berndt
Gerhard Kruger
Hans-Joachim KÜNNE
Lothar Mörl
Lothar Backhauss
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.)
Magdeburger Energie und Umwelttechnik GmbH
De Nora Deutschland GmbH
Original Assignee
Heraeus Elektrochemie GmbH
Magdeburger Energie und Umwelttechnik GmbH
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 Heraeus Elektrochemie GmbH, Magdeburger Energie und Umwelttechnik GmbH filed Critical Heraeus Elektrochemie GmbH
Publication of EP0608248A1 publication Critical patent/EP0608248A1/fr
Application granted granted Critical
Publication of EP0608248B1 publication Critical patent/EP0608248B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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
    • D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
    • D01F6/12—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polymers of fluorinated hydrocarbons
    • 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
    • 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

Definitions

  • the invention relates to a fiber material made of PTFE, which has a variety of applications due to a new structure, for example for the production of diaphragms for chlor-alkali electrolysis and for filter layers of different technical uses.
  • the invention also relates to a method for producing this new fiber material.
  • PTFE fibers are known as monofilament fibers, which are suitable for the production of staple fibers of different lengths and diameters, yarns and fabrics.
  • PTFE fibers alone cannot be used to produce filter layers or diaphragms from a suitable dispersion by suction. They are too rigid for this purpose and have too much spring-back behavior.
  • Another PTFE fiber is made by grinding PTFE, sodium chloride and inorganic additives such as. B. ZrO 2 and TiO 2 , at elevated temperatures in a ball mill (DD-PS 244 365).
  • the PTFE fibers produced by this very cumbersome and complex process are principally suitable for the extraction of filter layers and diaphragms.
  • the diaphragms made from these fibers lag behind the performance of asbestos-containing diaphragms, especially in chlor-alkali electrolysis.
  • the aim of the invention is a fiber material made of PTFE, which has a wide range of applications and can be produced economically.
  • a new structure of PTFE fibers is obtained which makes it possible to use these new fibers for diaphragms in chlor-alkali electrolysis or as filter layers. They consist of fiber bundles and these of individual microfibrils, which are composed such that there are irregularly shaped spaces between the microfibrils.
  • These new structures of PTFE fibers, to which hydrophilizing additives may also be added, can be produced using an economical process.
  • a fluidized bed apparatus charged with inert bodies which has a ratio of the cross-sectional areas of discharge chamber to swirl chamber in the range of 2: 1 to 5: 1 and an inclination of the wall of the expansion chamber between discharge chamber and swirl chamber in the range of 20 to 40 ° with respect to the vertical , wherein the height of the fluidized bed apparatus above its inflow floor is 5 to 20 times the cross-sectional dimension of the swirl chamber (2) and the inflow floor has a free cross-sectional area in the range of 5 to 25%, a PTFE dispersion consisting of a salt solution with PTFE particles and optionally hydrophilizing additives, treated in a hot gas / steam stream at temperatures between 140 ° C and 210 ° C.
  • the PTFE dispersion contains a salt solution, which preferably consists of NaCl and whose concentration is between 100 g / l and the saturation limit.
  • the ratio of PTFE (calculated as a solid) to sodium chloride (also calculated as a solid) can be between 1: 1 and 1:10.
  • the fiber material according to the invention has a certain hydrophilicity.
  • additives can come from the group of inorganic substances which have long been known for this purpose (such as zirconium dioxide, titanium dioxide, silicon dioxide, kaolin, aluminum oxide, magnesium oxide, magnesium hydroxide, calcium carbonate, etc.).
  • the mixing ratio between PTFE (calculated as a solid) and the aggregate are between 20: 1 and 1: 5.
  • Another possibility of influencing the hydrophilic properties of the fiber material according to the invention is to use the principle of polymer-identical modification.
  • the mixing ratio of the PTFE (calculated as a solid) with the highly functionalized PTFE can be between 100: 1 and 3: 1.
  • the parameters to be set in the fluidized bed apparatus relate to its design and equipment, shown in FIG. 1, and to the processes running in it.
  • the use of PTFE forms surprisingly fibrous forms of different lengths. These fibrous forms consist entirely of fiber bundles, which in turn are composed of microfibrils.
  • the method according to the invention allows the fiber material according to the invention to be produced in large quantities in a technologically elegant and economical manner.
  • the mean fiber length can be set within the limits provided the process parameters according to the invention are observed.
  • the different lengths of the fibers make it possible to control the properties of the filter layers and diaphragms made from this fiber material.
  • the permeability of the filters and diaphragms as well as their mean effective pore diameter and the pore size distribution can be influenced via the mass ratio of long-fiber to short-fiber components.
  • this PTFE fiber material consists of tufts of fibers, which in turn are formed from microfibrils with irregularly shaped spaces.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention concerne une matière fibreuse en PTFE renfermant éventuellement des adjuvants conférant des propriétés hydrophiles, et offrant, de par sa structure, de grandes possibilités d'utilisation dans la fabrication de diaphragmes pour l'électrolyse de composés chloro-alcalins ainsi que pour des couches filtrantes. Conformément à l'invention, la matière fibreuse est caractérisée en ce qu'elle est constituée par des faisceaux de fibres, eux-mêmes étant formés de microfibrilles individuelles entre lesquelles sont ménagés des espaces intermédiaires de configuration irrégulière. On effectue la fabrication de cette matière fibreuse en soumettant, dans un appareil à lit fluidisé garni de corps inertes, une dispersion de PTFE composée d'une solution saline renfermant des particules de PTFE, avec addition éventuelle d'ajuvants à propriétés hydrophiles, à un traitement dans un courant de gaz chauds et de vapeur. Le procédé selon l'invention permet de fabriquer ladite matière fibreuse économiquement, de façon rationnelle sur un plan technique et en plus grandes quantités. En observant les paramètres mentionnés dans la description de l'invention, on peut agir sur la longueur des fibres.

Claims (7)

  1. Matériau fibreux constitué par du PTFE et éventuellement par des additifs conférant un caractère hydrophile, caractérisé en ce qu'il consiste en faisceaux de fibres et en ce que ceux-ci sont constitués à leur tour par des microfibrilles individuelles de telle manière qu'il existe entre les microfibrilles des interstices formés de manière irrégulière.
  2. Procédé de fabrication du matériau fibreux constitué par du PTFE et éventuellement par des additifs conférant un caractère hydrophile, caractérisé en ce qu'une dispersion de PTFE consistant en une solution de sel avec des particules de PTFE et éventuellement des additifs conférant un caractère hydrophile est traitée dans un courant gaz/vapeur chaud à des températures comprises entre 140°C et 210°C dans un appareil à couche fluidisée chargé de corps inertes, qui présente un rapport des aires de la section de la chambre d'extraction et de la chambre de fluidisation dans le domaine de 2:1 à 5:1 et une inclinaison de la paroi de la chambre d'extension entre la chambre d'extraction et la chambre de fluidisation dans le domaine de 20 à 40° par rapport à la verticale, la hauteur de l'appareil à couche fluidisée au-dessus de son fond de soufflage étant égale à 5 à 20 fois la dimension transversale de la chambre de fluidisation (2) et le fond de soufflage présentant une aire de la section libre dans le domaine de 5 à 25%.
  3. Procédé de fabrication du matériau fibreux selon la revendication 2, caractérisé en ce que la solution de sel consiste de préférence en NaCl dont la concentration est située entre 100 g/l et la limite de saturation.
  4. Procédé de fabrication du matériau fibreux selon les revendications 2 et 3, caractérisé en ce que le rapport massique PTFE:NaCl est situé entre 1:1 et 1:10.
  5. Procédé de fabrication du matériau fibreux selon la revendication 2, caractérisé en ce que les additifs conférant un caractère hydrophile contenus sont de préférence des substances inorganiques telles que le dioxyde de zirconium, le dioxyde de titane, le dioxyde de silicium, le kaolin, l'oxyde d'aluminium, l'oxyde de magnésium, le carbonate de calcium, par exemple, ou du PTFE hautement fonctionnalisé consistant en une poudre de PTFE ou en des matériaux de déchets de PTFE qui ont été préparés par irradiation avec un rayonnement riche en énergie d'une source de rayonnement gamma ou d'un accélérateur d'électrons et mélange simultané avec des sulfites, disulfites, hydrogénocarbonates d'ammonium ou alcalins ou des produits d'addition de bisulfites et de composés carbonylés jusqu'à une dose absorbée de 2000 à 10000 kGy.
  6. Procédé de fabrication du matériau fibreux selon les revendications 2 et 5, caractérisé en ce que le rapport massique :
    - du PTFE à l'additif inorganique conférant un caractère hydrophile est situé entre 20:1 et 1:5 et
    - du PTFE au PTFE hautement fonctionnalisé est situé entre 100:1 et 3:1.
  7. Procédé de fabrication du matériau fibreux selon les revendications 2 à 6, caractérisé en ce qu'un appareil à couche fluidisée dans lequel :
    - l'aire de la section de la chambre d'extraction (3) est supérieure de 2 à 5 fois à l'aire de la section de la chambre de fluidisation (2),
    - la paroi de la chambre d'extension (5) est inclinée de 20 à 40° par rapport à la verticale,
    - la hauteur de l'appareil à couche fluidisée (1) au-dessus de son fond de soufflage (4) est supérieure de 5 à 20 fois à la dimension transversale de la chambre de fluidisation (2),
    - le fond de soufflage (4) présente une aire de la section libre dans le domaine de 5 à 25%,
       - et dans lequel :
    - le diamètre des corps inertes (6) est situé dans le domaine de 1 mm à 10 mm et
    - la masse spécifique des corps inertes (6) est située dans le domaine de 2 à 10 g/cm3,
       est chargé avec une dispersion de PTFE et éventuellement des additifs conférant un caractère hydrophile,
    - la température du courant vapeur/gaz pénétrant dans la chambre de fluidisation étant de 270 à 340°C,
    - le débit spécifique étant compris entre 2 kg/m2.s et 9 kg/m2.s,
    - l'introduction massique spécifique de la dispersion de PTFE par m2 d'aire de la section de la chambre de fluidisation étant comprise entre 250 kg/h et 1500 kg/h et
    - la température de la couche fluidisée étant comprise entre 140 et 210°C.
EP92918372A 1991-09-12 1992-08-27 Matiere fibreuse en ptfe et son procede de fabrication Expired - Lifetime EP0608248B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4130356 1991-09-12
DE4130356A DE4130356C2 (de) 1991-09-12 1991-09-12 Fasermaterial aus PTFE und Verfahren zu seiner Herstellung
PCT/DE1992/000712 WO1993005213A1 (fr) 1991-09-12 1992-08-27 Matiere fibreuse en ptfe et son procede de fabrication

Publications (2)

Publication Number Publication Date
EP0608248A1 EP0608248A1 (fr) 1994-08-03
EP0608248B1 true EP0608248B1 (fr) 1997-07-30

Family

ID=6440453

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92918372A Expired - Lifetime EP0608248B1 (fr) 1991-09-12 1992-08-27 Matiere fibreuse en ptfe et son procede de fabrication

Country Status (4)

Country Link
US (1) US5700572A (fr)
EP (1) EP0608248B1 (fr)
DE (1) DE4130356C2 (fr)
WO (1) WO1993005213A1 (fr)

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US6235388B1 (en) * 1996-12-13 2001-05-22 Daikin Industries, Ltd. Fibrous materials of fluororesins and deodorant and antibacterial fabrics made by using the same
DE19746404A1 (de) * 1997-10-21 1999-04-22 Basf Ag Verfahren zur Herstellung von Kompositfasern und Disphragmen
US8262979B2 (en) 2009-08-07 2012-09-11 Zeus Industrial Products, Inc. Process of making a prosthetic device from electrospun fibers
JP5300987B2 (ja) 2009-01-16 2013-09-25 ゼウス インダストリアル プロダクツ， インコーポレイテッド 高粘度材料を含むｐｔｆｅのエレクトロスピニング
US8685424B2 (en) 2010-10-14 2014-04-01 Zeus Industrial Products, Inc. Antimicrobial substrate
US20130268062A1 (en) 2012-04-05 2013-10-10 Zeus Industrial Products, Inc. Composite prosthetic devices
EP2403982B1 (fr) * 2009-03-03 2014-10-29 Toray Fluorofibers (America) Inc. Matière polymère fluorée hydrophile et son procédé de fabrication
EP3928807A1 (fr) 2011-01-28 2021-12-29 Merit Medical Systems, Inc. Endoprothèse revêtue de ptfe électrofilé et procédé d'utilisation
WO2013109528A1 (fr) 2012-01-16 2013-07-25 Merit Medical Systems, Inc. Appareils médicaux recouverts de matériau tissé rotationnel et procédés de fabrication
US11541154B2 (en) 2012-09-19 2023-01-03 Merit Medical Systems, Inc. Electrospun material covered medical appliances and methods of manufacture
US9198999B2 (en) 2012-09-21 2015-12-01 Merit Medical Systems, Inc. Drug-eluting rotational spun coatings and methods of use
US20140205781A1 (en) * 2013-01-23 2014-07-24 Zeus Industrial Products, Inc. Silicone espun ptfe composites
CN104884694B (zh) 2013-03-13 2018-09-11 麦瑞通医疗设备有限公司 连续沉积的纤维材料以及相关联的装置和方法
US9827703B2 (en) 2013-03-13 2017-11-28 Merit Medical Systems, Inc. Methods, systems, and apparatuses for manufacturing rotational spun appliances
US9422642B2 (en) * 2013-07-29 2016-08-23 Toray Fluorofibers (America), Inc. Wear polytetrafluoroethylene (PTFE) fiber and method of making same
JP6777642B2 (ja) 2015-02-26 2020-10-28 メリット・メディカル・システムズ・インコーポレイテッドＭｅｒｉｔ Ｍｅｄｉｃａｌ Ｓｙｓｔｅｍｓ，Ｉｎｃ． 層状医療器具及び方法
CN113862821B (zh) * 2021-09-24 2022-08-05 天津工业大学 一种聚苯硫醚纤维织物型碱性水电解隔膜及其制备方法

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Also Published As

Publication number Publication date
DE4130356C2 (de) 1995-01-26
DE4130356A1 (de) 1993-04-08
US5700572A (en) 1997-12-23
EP0608248A1 (fr) 1994-08-03
WO1993005213A1 (fr) 1993-03-18

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