EP0608248A1 - Ptfe fibre material and process for making it. - Google Patents
Ptfe fibre material and process for making it.Info
- Publication number
- EP0608248A1 EP0608248A1 EP92918372A EP92918372A EP0608248A1 EP 0608248 A1 EP0608248 A1 EP 0608248A1 EP 92918372 A EP92918372 A EP 92918372A EP 92918372 A EP92918372 A EP 92918372A EP 0608248 A1 EP0608248 A1 EP 0608248A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ptfe
- fiber material
- fluidized bed
- additives
- cross
- 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.)
- Granted
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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
- PTFE fibers are known as monofilament fibers, which are suitable for the production of staple fibers of different lengths and diameters, yarns and fabrics.
- 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).
- Processed PTFE fibers are principally suitable for the production of filter layers and diaphragms. However, it must be noted that the diaphragms made from these fibers are behind the
- the aim of the invention is a fiber material made of PTFE, which has a wide range of applications and can be produced economically. According to the invention, a new structure of
- a PTFE dispersion consisting of a salt solution with PTFE particles and optionally hydrophilizing additives is treated in a hot gas / steam stream at temperatures between 140 ° C. and 210 ° C. in a fluidized bed apparatus of FIG. 1 charged with inert bodies.
- the PTFE dispersion contains a saline solution that
- PTFE preferably consists of NaCl and whose concentration is between 100 g / l and the saturation limit.
- Sodium chloride (also calculated as a solid) can be between 1: 1 and 1:10. Even without the addition of special hydrophilizing agents, in contrast to other PTFE fibers, the fiber material according to the invention has a certain hydrophilicity.
- additives can be selected from the group known for a long time for this purpose
- inorganic substances such as zirconium dioxide,
- Magnesium oxide, magnesium hydroxide, calcium carbonate, etc. come.
- 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.
- a portion of a PTFE powder is added to the aqueous PTFE dispersion, which by irradiation in the
- 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 cross-sectional area of the discharge chamber 3 must be 2 to 5 times larger than the cross-sectional area of the swirl chamber 2. - Compared to the vertical, the wall of the expansion chamber 5 is inclined by 20 ° to 40 °.
- the inflow floor 4 is 5 times to 20 times the cross-sectional dimension of the swirl chamber 2.
- the inflow has a free cross-sectional area of 5 to 25%.
- the diameter of the inert body is between 1 and 10 mm.
- the temperature of the gas / steam flow entering the swirl chamber 2 should be selected between 270 and 340 ° C.
- Powders, granules, agglomerates or other compact bodies are formed when using
- 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.
- the fluidized bed apparatus 1 with a cylindrical vortex chamber 2 with a diameter of 150 mm and the processes taking place in it are characterized by the following parameters:
- the wall of the expansion chamber 5 is inclined by 30 ° with respect to the vertical.
- the fluidized bed apparatus is 2 m high.
- the inflow floor has a specific free cross-sectional area of 10%.
- this PTFE fiber material consists of tufts of fibers, which in turn are formed from microfibrils with irregularly shaped spaces.
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.The invention relates to a fibrous PTFE material possibly containing adjuvants conferring hydrophilic properties, and offering, by its structure, great possibilities of use in the manufacture of diaphragms for the electrolysis of chloro-alkaline compounds as well as for filter layers. According to the invention, the fibrous material is characterized in that it consists of bundles of fibers, themselves being formed of individual microfibrils between which are formed intermediate spaces of irregular configuration. The manufacture of this fibrous material is carried out by subjecting, in a fluidized bed apparatus furnished with inert bodies, a dispersion of PTFE composed of a saline solution containing particles of PTFE, with possible addition of additives with hydrophilic properties, to a treatment in a stream of hot gases and steam. The method according to the invention makes it possible to manufacture said fibrous material economically, rationally on a technical level and in larger quantities. By observing the parameters mentioned in the description of the invention, one can act on the length of the fibers.
Description
Fasermaterial aus PTFE und Verfahren zu seiner PTFE fiber material and process for its
HerstellungManufacturing
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Die Erfindung betrifft ein Fasermaterial aus PTFE, das durch eine neue Struktur vielfältige Anwendungsmöglichkeiten besitzt, beispielsweise für die Herstellung von Diaphragmen für die Chloralkalielektrolyse sowie für Filterschichten unterschiedlicher technischer Verwendungszwecke. Außerdem betrifft die Erfindung ein 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
Verfahren zur Herstellung dieses neuen Fasermaterials. PTFE-Fasern sind bekannt als monofile Fasern, die sich zur Herstellung von Stapelfasern unterschiedlicher Länge und Durchmesser , Garnen und Geweben , e i gnen . Process for the production of 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.
Der Nachteil dieser PTFE-Fasern besteht darin, daß es mit ihnen allein nicht gelingt, Filterschichten oder Diaphragmen durch Aufsaugen aus einer geeigneten The disadvantage of these PTFE fibers is that filter layers or diaphragms cannot be removed by suction from a suitable one
Dispersion herzustellen. Sie sind für diesen Verwendungszweck zu starr und haben ein zu starkes To produce dispersion. They are too rigid for this purpose and too strong
Rückfederungsverhalten. Springback behavior.
Eine andere PTFE-Faser wird hergestellt durch Mahlen von PTFE, Natriumchlorid und anorganischen Zuschlagstoffen, wie z. B. ZrO2 und TiO2, bei erhöhten Temperaturen in einer Kugelmühle (DD-PS 244 365). 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).
Die nach diesem sehr umständlichen und aufwendigen The after this very cumbersome and elaborate
Verfahren hergestellten PTFE-Fasern sind prinzipiell zur Gewinnung von Filterschichten und Diaphragmen geeignet. Es muß jedoch festgestellt werden, daß die aus diesen Fasern hergestellten Diaphragmen hinter den Processed PTFE fibers are principally suitable for the production of filter layers and diaphragms. However, it must be noted that the diaphragms made from these fibers are behind the
Leistungen asbesthaltiger Diaphragmen, speziell in der Chloralkalielektrolyse, zurückbleiben. Man kann vermuten, daß diese Tatsache durch die im Gegensatz zum Asbest monofile Struktur dieser PTFE-Fasern bewirkt wird. Performance of asbestos-containing diaphragms, especially in chlor-alkali electrolysis. One can assume that this fact is caused by the monofilament structure of these PTFE fibers in contrast to the asbestos.
Das Ziel der Erfindung ist ein Fasermaterial aus PTFE, das eine große Anwendungsbreite besitzt und wirtschaftlich herstellbar ist.
Erfindungsgemäß erhält man eine neue Struktur von The aim of the invention is a fiber material made of PTFE, which has a wide range of applications and can be produced economically. According to the invention, a new structure of
PTFE-Fasern, die es ermöglichen, diese neuen Fasern für Diaphragmen bei der Chlorakalielektrolyse bzw. PTFE fibers, which make it possible to use these new fibers for diaphragms in chlorakali electrolysis or
als Filterschichten zu verwenden. Sie bestehen aus to use as filter layers. they consist of
Faserbündeln und diese aus einaelnen Mikrofibrillen, die derart zusammengesetzt sind, daß sich zwischen den Mikrofibrillen unregelmäßig geformte Zwischenräume befinden. Diese neuen Strukturen von PTFE-Fasern, Fiber bundles and these from individual microfibrils, which are composed such that there are irregularly shaped spaces between the microfibrils. These new structures of PTFE fibers,
denen gegebenenfalls auch hydrophilierende Zusätze beigemischt werden, können nach einem wirtschaftlichen Verfahren hergestellt werden. Erfindungsgemäß wird in einem mit Inertkörpern beschickten Wirbelschichtapparat der FIG 1 eine PTFE-Dispersion, bestehend aus einer Salzlösung mit PTFE-Partikeln und gegebenenfalls hydrophilierenden Zusätzen, im heißen Gas/Dampf-Strom bei Temperaturen zwischen 140 °C und 210° C behandelt. Die PTFE-Dispersion enthält eine Salzlösung, die to which hydrophilizing additives may also be added, can be produced by an economical process. According to the invention, a PTFE dispersion consisting of a salt solution with PTFE particles and optionally hydrophilizing additives is treated in a hot gas / steam stream at temperatures between 140 ° C. and 210 ° C. in a fluidized bed apparatus of FIG. 1 charged with inert bodies. The PTFE dispersion contains a saline solution that
vorzugsweise aus NaCl besteht und deren Konzentration zwischen 100 g/l und der Sättigungsgrenze liegt. Das Verhältnis von PTFE (als Feststoff gerechnet) zu 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
Natriumchlorid (ebenfalls als Feststoff gerechnet) kann zwischen 1 : 1 und 1 : 10 liegen. Bereits ohne Zusatz besonderer Hydrophilierungsmittel hat das erfindungsgemäße Fasermaterial im Unterschied zu anderen PTFE- Fasern eine gewisse Hydrophilie. Sodium chloride (also calculated as a solid) can be between 1: 1 and 1:10. Even without the addition of special hydrophilizing agents, in contrast to other PTFE fibers, the fiber material according to the invention has a certain hydrophilicity.
Es kann jedoch für bestimmte Einsatzfälle zweckmäßig sein, das Fasermaterial durch geeignete Zuschlagstoffe weiter zu hydrophilieren. Diese Zuschlagstoffe können aus der Gruppe der seit langem, für diesen Zweck bekannten However, for certain applications it may be expedient to further hydrophilize the fiber material using suitable additives. These additives can be selected from the group known for a long time for this purpose
anorganischen Stoffe (wie z. B. Zirkoniumdioxid, inorganic substances (such as zirconium dioxide,
Titaniumdioxid, Siliziumdioxid, Kaolin, Aluminiumoxid, Titanium dioxide, silicon dioxide, kaolin, aluminum oxide,
Magnesiumoxid, Magnesiumhydroxid, Calciumcarbonat usw.) kommen. Magnesium oxide, magnesium hydroxide, calcium carbonate, etc.) come.
In diesen Fällen sollte das Mischungsverhältnis zwischen
PTFE (als Feststoff gerechnet) und dem Zuschlagstoff zwischen 20 : 1 und 1 : 5 liegen. In these cases, the mixing ratio between PTFE (calculated as a solid) and the aggregate are between 20: 1 and 1: 5.
Eine andere Möglichkeit, die hydrophilen Eigenschaften des erfindungsgemäßen Fasermaterials zu beeinflussen, bietet die Anwendung des Prinzips der polymeridentischen Modifizierung. Another possibility of influencing the hydrophilic properties of the fiber material according to the invention is to use the principle of polymer-identical modification.
Dabei wird der wäßrigen PTFE-Dispersion ein Anteil eines PTFE-Pulvers zugesetzt, das durch Bestrahlung im A portion of a PTFE powder is added to the aqueous PTFE dispersion, which by irradiation in the
Elektronenstrahlbeschleuniger oder in einerγ-Strahlenquelle mit einer Dosisleistung von 2 000 bis 10 000 kGy ggf. in Gegenwart von Ammonium- oder Alkalisulfiten, Electron beam accelerator or in a γ-radiation source with a dose rate of 2,000 to 10,000 kGy, if appropriate in the presence of ammonium or alkali sulfites,
-disulfiten, -hydrogensulfiten, -carbonaten, -hydrogencarbonaten oder Bisulfitaddukten von Carbonylverbindüngen oder eines Gemisches dieser Substanzen hochfunktionalisiert wurde. Diese polymeridentische Modifizierung hat die Vorteile, daß disulfites, hydrogen sulfites, carbonates, hydrogen carbonates or bisulfite adducts of carbonyl compounds or a mixture of these substances has been highly functionalized. This polymer-identical modification has the advantages that
- keine Probleme bezüglich der chemischen Beständigkeit bei dem erfindungsgemäßen Fasermaterial auftreten, no problems with regard to chemical resistance occur in the fiber material according to the invention,
- die mechanischen Eigenschaften besser sind als beim - The mechanical properties are better than that of
Zusatz der anorganischen Hydrophilierungsmittel. Addition of the inorganic hydrophilizing agents.
Das Mischungsverhältnis des PTFE (als Feststoff gerechnet) mit dem hochfunktionalisierten PTFE kann zwischen 100 : 1 und 3 : 1 liegen. Die einzustellenden Parameter im Wirbelschichtapparat betreffen dessen Gestaltung und Ausrüstung, dargestellt in FIG 1 sowie die in ihm ablaufenden Prozesse . 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.
Be i der Gestaltung des Wirbelschichtapparates 1 sind einzuhalten: When designing the fluidized bed apparatus 1, the following must be observed:
- Die Querschnittsflache der Austragskammer 3 muß 2 bis 5 mal größer als die Querschnittsflache der Wirbelkammer 2 sein.
- Gegenüber der Senkrechten ist die Wandung der Erweiterungskammer 5 um 20° bis 40° geneigt. - The cross-sectional area of the discharge chamber 3 must be 2 to 5 times larger than the cross-sectional area of the swirl chamber 2. - Compared to the vertical, the wall of the expansion chamber 5 is inclined by 20 ° to 40 °.
- Die Höhe des Wirbelschichtapparates 1 oberhalb des - The height of the fluidized bed apparatus 1 above the
Anströmbodens 4 beträgt das 5fache bis 20fache der Querschnittsabmessung der Wirbelkammer 2. The inflow floor 4 is 5 times to 20 times the cross-sectional dimension of the swirl chamber 2.
- Der Anströmbσden hat eine freie Querschnittsfläche von 5 bis 25 %. - The inflow has a free cross-sectional area of 5 to 25%.
Für die Ausrüstung des Wirbelschichtapparates 1 mit For the equipment of the fluidized bed apparatus 1 with
Inertkörpern 6 gelten folgende Bedingungen: The following conditions apply to inert bodies 6:
- Das spezifische Gewicht der Inertkörper 6 muß - The specific weight of the inert body 6 must
größer als 2 g/cm 3 sein und darf 10 g/cm3 nicht überschreiten. be greater than 2 g / cm 3 and must not exceed 10 g / cm 3 .
- Der Durchmesser der Inertkörper liegt zwischen 1 und 10 mm. - The diameter of the inert body is between 1 and 10 mm.
- Bezogen auf die Querschnittsfläche des Anströmbodens 4 müssen sich in der Wirbelkammer 2 150 kg/m2 bis 500 kg/m2 Inertkörper 6 befinden. Charakteristisch für die im Wirbelschichtapparat 1 ablaufenden Prozesse sind folgende Parameter: - In relation to the cross-sectional area of the inflow base 4, there must be 150 kg / m 2 to 500 kg / m 2 of inert bodies 6 in the swirl chamber 2. The following parameters are characteristic of the processes taking place in the fluidized bed apparatus 1:
- Die Temperatur des in die Wirbelkammer 2 eintretenden Gas/Dampf-Stromes ist zwischen 270 und 340 ° C zu wählen. - The temperature of the gas / steam flow entering the swirl chamber 2 should be selected between 270 and 340 ° C.
- In der Wirbelkammer 2 beträgt der spezifische Gas/Dampf¬- In the swirl chamber 2, the specific gas / steam is
Strom 2 kg/m 2 . s bis 9 kg/m2 . s. Current 2 kg / m 2 . s up to 9 kg / m 2 . s.
- Bezogen auf einen m2 der Querschnittsfläche der Wirbelkammer 2 werden stündlich 250 kg bis 1 500 kg der zur Faserbildung erforderlichen Dispersion eingebracht. - Based on an m 2 of the cross-sectional area of the swirl chamber 2, 250 kg to 1,500 kg of the dispersion required for fiber formation are introduced every hour.
- In der Wirbelschicht ist eine Temperatur zwischen - In the fluidized bed there is a temperature between
140 und 210 °C einzustellen.
Entgegen aller bisherigen Erfahrungen, nach der das getrocknete Gut im Wirbelschichtapparat in Form von 140 and 210 ° C. Contrary to all previous experience, according to which the dried material in the fluidized bed apparatus in the form of
Pulver, Granulaten, Agglomeraten oder anderer kompakter Körper anfällt, bilden sich bei der Verwendung von Powders, granules, agglomerates or other compact bodies are formed when using
PTFE völlig überraschend faserige Formen unterschiedlicher Länge. Diese faserigen Formen bestehen durchgängig PTFE completely surprisingly fibrous forms of different lengths. These fibrous forms are consistent
aus Faserbündeln, die ihrerseits aus Mikrofibrillen zusammengesetzt sind. Bei der Durchführung des erfindungsgemäßen Verfahrens sind sowohl die Rezeptur der oben beschriebenen Mischung als auch die einzustellenden Parameter im Wirbelschichtapparat von from fiber bundles, which in turn are composed of microfibrils. When carrying out the process according to the invention, both the formulation of the mixture described above and the parameters to be set are in the fluidized bed apparatus of
großer Bedeutung. great importance.
Überraschend und nicht vorhersehbar war auch die That was also surprising and unpredictable
Tatsache, daß mit Hilfe konzentrierter Salzlösung die erfindungsgemäßen Faserstrukturen des PTFE-Materials in einem Wirbelschichtapparat entstehen. The fact that the fiber structures of the PTFE material according to the invention are produced in a fluidized bed apparatus with the aid of concentrated salt solution.
Das erfindungsgemäße Verfahren gestattet es, The method according to the invention allows
technologisch elegant und wirtschaftlich das erfindungsgemäße Fasermaterial auch in größeren Mengen Technologically elegant and economical, the fiber material according to the invention also in larger quantities
herzustellen. manufacture.
Es hat weiter den Vorteil, daß innerhalb der Grenzen bei Einhaltung der erfindungsgemäßen Verfahrensparameter die mittlere Faserlänge eingestellt werden kann. Die unterschiedliche Länge der Fasern gestattet es, die Eigenschaften der aus diesem Fasermaterial hergestellten Filterschichten und Diaphragmen zu steuern. It also has the advantage that 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.
So kann über das Masseverhältnis lang- zu kurzfaseriger Anteile insbesondere die Durchlässigkeit der Filter und Diaphragmen sowie deren mittlerer effektiver Porendurchmesser und die Porengrößenverteilung beeinflußt werden. For example, 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.
Die Erfindung wird durch die folgenden Beispiele in ihren typischen Ausführungen beschrieben, ohne daß The invention is described in its typical embodiments by the following examples, without
sie hierdurch begrenzt wird.
Beispiel 1 it is thereby limited. example 1
Der Wirbelschichtapparat 1 mit zylindrischer Wirbelkammer 2 von 150 mm Durchmesser und die in ihm ablaufenden Prozesse werden durch folgende rameter charakterisiert: The fluidized bed apparatus 1 with a cylindrical vortex chamber 2 with a diameter of 150 mm and the processes taking place in it are characterized by the following parameters:
- Die Querschnittsfläche der Austragskammer 3 beträgt - The cross-sectional area of the discharge chamber 3 is
0,47 m2. 0.47 m 2 .
- Gegenüber der Senkrechten ist die Wandung der ErWeiterungskammer 5 um 30 º geneigt. - The wall of the expansion chamber 5 is inclined by 30 ° with respect to the vertical.
- Oberhalb des Anströmbodens 4 ist der Wirbelschichtapparat 2 m hoch. - Above the inflow floor 4, the fluidized bed apparatus is 2 m high.
- Der Anströmboden besitzt eine spezifische freie Querschnittsfläche von 10 %. - The inflow floor has a specific free cross-sectional area of 10%.
- Verwendet werden 5 kg Inertkörper (283 kg/m2) mit 3 mm- 5 kg inert body (283 kg / m 2 ) with 3 mm are used
Durchmesser und 7,8 g/cm3 spezifischem Gewicht. Diameter and 7.8 g / cm 3 specific weight.
- In die Wirbelkammer treten 283 kg/h eines Gas/Dampfstromes (Luft) mit 290 °C ein, der die Inertkörper in den Wirbelzustand versetzt. - 283 kg / h of a gas / vapor stream (air) at 290 ° C. enters the vortex chamber, which brings the inert bodies into the vortex state.
- In die Wirbelschicht werden 12 kg/h (679 kg/m2 . h) einer wäßrigen PTFE-Dispersion, in der 0,6 kg PTFE- Teilchen (Teilchengröße <1 μm), 3,8 kg Natriumchlorid und 0,72 kg Zirkoniumdioxid enthalten sind, eingebracht.- In the fluidized bed 12 kg / h (679 kg / m 2. H) of an aqueous PTFE dispersion in which 0.6 kg of PTFE particles (particle size <1 microns), 3.8 kg of sodium chloride and 0.72 kg Zirconium dioxide are included.
- In der Wirbelschicht stellt sich eine Temperatur von - A temperature of
160 °C ein. 160 ° C.
- Aus der Wirbelschicht werden stündlich ca. 5 kg PTFE- faserhaltiges Material ausgetragen. - Approx. 5 kg of material containing PTFE fibers are discharged from the fluidized bed every hour.
Wie eine rasterelektronenmikroskopische Analyse zeigt, besteht dieses PTFE-Fasermaterial aus Faserbüscheln, die ihrerseits aus Mikrofibrillen mit unregelmäßig geformten Zwischenräumen gebildet werden.
Beisp iel 2 As a scanning electron microscopic analysis shows, this PTFE fiber material consists of tufts of fibers, which in turn are formed from microfibrils with irregularly shaped spaces. Example 2
Wie Beispiel 1, aber 7. Anstrich verändert: Like example 1, but 7th coat changed:
- In die Wirbelschicht werden 12 kg/h (679 kg/m2. h) einer wäßrigen PTFE-Dispersion, in der 1,2 kg PTFE- Teilchen (Teilchengröße <1 μm) 3,8 kg Natriumchlorid und 0,1 kg hochfunktionalisiertes PT enthalten sind, eingebracht. Beispiel 3 - 12 kg / h (679 kg / m 2 h) of an aqueous PTFE dispersion in which 1.2 kg of PTFE particles (particle size <1 μm), 3.8 kg of sodium chloride and 0.1 kg of highly functionalized are placed in the fluidized bed PT are included. Example 3
Wie Beispiel 1, aber 7. Anstrich verändert: Like example 1, but 7th coat changed:
- In die Wirbelschicht werden 12 kg/h (679 kg/m2 . h) einer wäßrigen PTFE-Dispersion, in der 1,3 kg PTFE- Teilchen (Teilchengröße <1 μm) und 3,8 kg Natriumchlorid enthalten sind, eingebracht.
- 12 kg / h (679 kg / m 2 h) of an aqueous PTFE dispersion, in which 1.3 kg of PTFE particles (particle size <1 μm) and 3.8 kg of sodium chloride, are introduced into the fluidized bed.
Bezugszeichen zu FIGUR 1 Reference number for FIGURE 1
1 - Wirbelschichtapparat 1 - fluidized bed apparatus
2 - Wirbelkammer 2 - swirl chamber
3 - Austragsksmmer 3 - Delivery quarters
4 - Anströmboden 4 - Inflow floor
5 - Erweiterungskammer 5 - expansion chamber
6 - Inertkörper 6 - inert body
7 - eintretender Dampf7 - steam entering
8 - PTFE-Dispersion8 - PTFE dispersion
9 - austretender Gas/Dampf -Strom
9 - escaping gas / steam flow
Claims
Patentansprüche 1. Faserrnaterial aus PTFE und gegebenenfalls hydrophilierenden Zusätzen, gekennzeichnet dadurch, daß es aus Faserbündeln besteht und diese wiederum aus einzelnen 1. Fiber material made of PTFE and optionally hydrophilizing additives, characterized in that it consists of fiber bundles and these in turn from individual
Mikrofibrillen derart zusammengesetzt sind, daß sich zwischen den Mikrofibrillen unregelmäßig geformte Microfibrils are composed such that irregularly shaped between the microfibrils
Zwischenräume befinden. Spaces.
2. Verfahren zur Herstellung des Fasermaterials aus PTFE 2. Process for producing the fiber material from PTFE
und gegebenenfalls hydrophilierenden Zusätzen, gekennzeichnet dadurch, daß in einem mit Inertkörpern beschickten Wirbelschichtapparat der FIG 1 eine PTFE- Dispersion, bestehend aus einer Salzlösung mit PTFE- Partikeln und gegebenenfalls hydrophilierten Zusätzen, im heißen Gas/Dampf-Strom bei Temperaturen zwischen 140 °C und 210 °C behandelt wird. and optionally hydrophilizing additives, characterized in that in a fluidized bed apparatus of FIG. 1 charged with inert bodies, a PTFE dispersion, consisting of a salt solution with PTFE particles and optionally hydrophilized additives, in a hot gas / steam stream at temperatures between 140 ° C. and 210 ° C is treated.
3. Verfahren zur Herstellung des Fasermaterials nach 3. Process for the production of the fiber material according to
Anspruch 2, gekennzeichnet dadurch, daß die Salzlösung vorzugswe i se aus Na Cl besteht , deren Konzentr a tion zwischen 100 g/l und der Sättigungsgrenze liegt. Claim 2, characterized in that the saline solution preferably consists of Na Cl, the concentration of which is between 100 g / l and the saturation limit.
4. Verfahren zur Herstellung des Fasermatsrials nach 4. Process for the production of the fiber material according to
Ansprüchen 2 und 3, gekennzeichnet dadurch, daß das Claims 2 and 3, characterized in that the
Masseverhältnis PTFE : NaCl zwischen 1 : 1 und Mass ratio PTFE: NaCl between 1: 1 and
1 : 10 liegt. 1:10 lies.
5. Verfahren zur Herstellung des Fasermaterials nach 5. Process for the production of the fiber material according to
Anspruch 2, gekennzeichnet dadurch, daß als Claim 2, characterized in that as
hydrophilierende Zusätze vorzugsweise Preferably hydrophilizing additives
- anorganische Stoffe wie z. 3. Zirkoniumdioxid, - inorganic substances such as 3. zirconium dioxide,
Titaniumcioxid, Siliziumdioxid, Kaolin, Aluminiumoxid. Maαnesiumoxid, Calciumcarbonat oder - hochfunktionalisiertes PTFE aus PTFE-Pulver oder PTFE-Abfallmaterialien, die durch Bestrahlen und energiereicher Strahlung einer j -Strahlenquelle oder eines Eiektronenösschleunigers bei gleichzeitiger Vermischung mit Ammonium- oder Alkalisulfiten, -disulfiten, -hydrαgensulfiten, -carbonaten, -hydrogencarbonaten oder Bisulfitaddukten von Carbonylverbindungen bis zu einer absorbierten Dosis von 2 000 bis 10 000 kGy hergestellt wurden, enthalten sind. Titanium dioxide, silicon dioxide, kaolin, aluminum oxide. Magnesium oxide, calcium carbonate or - Highly functionalized PTFE made of PTFE powder or PTFE waste materials, which are exposed to radiation and high-energy radiation j radiation source or an electron accelerator with simultaneous mixing with ammonium or alkali sulfites, disulfites, hydrogen sulfides, carbonates, bicarbonates or bisulfite adducts of carbonyl compounds up to an absorbed dose of 2,000 to 10,000 kGy were contained.
6. Verfahren zur Herstellung des Fasermaterials nach 6. Process for the production of the fiber material according to
Ansprüchen 2 und 5. gekennzeichnet dadurch, daß das Massevsrhältnis von Claims 2 and 5. characterized in that the mass ratio of
- PTFE zum anorganischen hydrophilierenden Zusatz zwischen 20 : 1 und 1 : 5 und von - PTFE for the inorganic hydrophilizing additive between 20: 1 and 1: 5 and from
- PTFE zu hochfunktionalisierten PTFE zwischen - PTFE to highly functionalized PTFE between
100 : 1 und 3 : 1 liegt. 100: 1 and 3: 1.
7. Verfahren zur Herstellung des Faserma'terials nach 7. Process for the production of the fiber material according to
Ansprüchen 2 bis 6. gekennzeichnet dadurch, daß ein Wirbeischichtapparat entsprechend FIG 1, für den außerdem gilt: Claims 2 to 6, characterized in that a fluidized bed apparatus according to FIG 1, for which the following also applies:
- die Querscnnittsfläche der Austracskammer (3) muß - The cross-sectional area of the exit chamber (3) must
2 bis 5 mal größer als die Querschnittsfläche der 2 to 5 times larger than the cross-sectional area of the
Wirbelkammer (2) sein, Swirl chamber (2),
- gegenüber der Senkrechten ist die Wandung der - The wall is opposite the vertical
Erweiterungskammer (5) um 20 bis 40 geneigt, Expansion chamber (5) inclined by 20 to 40,
- die Höhe des Wirbeischichtapparates (1) oberhalb des Anströmbodens (4) beträgt das 5fache bis - The height of the fluidized bed apparatus (1) above the inflow floor (4) is 5 times to
20fache der Querschnittsabmessung der Wirbelkammer (2), - der Anströmboden (4) hat eine freie Querschnittsfläche von 5 bis 25 %, 20 times the cross-sectional dimension of the swirl chamber (2), - The inflow floor (4) has a free cross-sectional area of 5 to 25%,
- der Durchmesser der Inertkörper (6) liegt zwischen 1 mm und 10 mm, - The diameter of the inert body (6) is between 1 mm and 10 mm,
- das spezifische Gewicht der Inertkörper (6) liegt zwischen 2 und 10 g/cm3 - The specific weight of the inert body (6) is between 2 and 10 g / cm 3
beaufschlagt wird mit einer PTFE-Dispersion und gegebenenfalls hydrophilierenden Zusätzen, wobeiis loaded with a PTFE dispersion and optionally hydrophilizing additives, wherein
- die Temperatur des in die Wirbelkammer e intretenden Damo f /Gas- Stromes 270 b i s 340 °C, the temperature of the damo f / gas stream intruding into the swirl chamber 270 to 340 ° C.,
- der spezifische Durchsatz zwischen 2 kg/m2 . s bis 9 kg/m2 . s, - the specific throughput between 2 kg / m 2 . s up to 9 kg / m 2 . s,
- der spezifische Mengeneintrag der PTFE-Dispersion pro m 2 Querschnittsfläche der Wirbelkammsr zwischen 250 kg/h und 1 500 kg/h - The specific amount of PTFE dispersion per m 2 cross-sectional area of the vertebral comb between 250 kg / h and 1,500 kg / h
- und die Wirbelschichttemperatur zwischen 140 °C und 210 °C beträgt. - And the fluidized bed temperature is between 140 ° C and 210 ° C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4130356 | 1991-09-12 | ||
| DE4130356A DE4130356C2 (en) | 1991-09-12 | 1991-09-12 | PTFE fiber material and process for its manufacture |
| PCT/DE1992/000712 WO1993005213A1 (en) | 1991-09-12 | 1992-08-27 | Ptfe fibre material and process for making it |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0608248A1 true EP0608248A1 (en) | 1994-08-03 |
| EP0608248B1 EP0608248B1 (en) | 1997-07-30 |
Family
ID=6440453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92918372A Expired - Lifetime EP0608248B1 (en) | 1991-09-12 | 1992-08-27 | Ptfe fibre material and process for making it |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5700572A (en) |
| EP (1) | EP0608248B1 (en) |
| DE (1) | DE4130356C2 (en) |
| WO (1) | WO1993005213A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69716643T2 (en) * | 1996-12-13 | 2003-06-26 | Daikin Ind Ltd | FIBER MATERIALS FROM FLUORINE RESIN AND DESODORING AND ANTIBACTERIAL SURFACES MADE THEREOF |
| DE19746404A1 (en) * | 1997-10-21 | 1999-04-22 | Basf Ag | Process for the production of composite fibers and disphragmas |
| EP2384375B1 (en) | 2009-01-16 | 2017-07-05 | Zeus Industrial Products, Inc. | Electrospinning of ptfe with high viscosity materials |
| US20130268062A1 (en) | 2012-04-05 | 2013-10-10 | Zeus Industrial Products, Inc. | Composite prosthetic devices |
| MX2011009216A (en) * | 2009-03-03 | 2011-10-10 | Toray Fluorofibers America Inc | Hydrophilic fluoropolymer material and method of making same. |
| WO2011017695A1 (en) | 2009-08-07 | 2011-02-10 | Zeus, Inc. | Multilayered composite |
| EP2563956A4 (en) | 2010-10-14 | 2013-09-18 | Zeus Ind Products Inc | Antimicrobial substrate |
| CN103561682A (en) | 2011-01-28 | 2014-02-05 | 梅瑞特医药体系股份有限公司 | Electrospun PTFE coated stent and method of use |
| EP2804637B1 (en) | 2012-01-16 | 2019-09-25 | Merit Medical Systems, Inc. | Rotational spun material covered medical appliances and methods of manufacture |
| 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 |
| EP2967929B1 (en) | 2013-03-13 | 2017-11-29 | Merit Medical Systems, Inc. | Methods, systems, and apparatuses for manufacturing rotational spun appliances |
| EP2971320B1 (en) | 2013-03-13 | 2021-09-29 | Merit Medical Systems, Inc. | Serially deposited fiber materials and associated devices and methods |
| US9422642B2 (en) * | 2013-07-29 | 2016-08-23 | Toray Fluorofibers (America), Inc. | Wear polytetrafluoroethylene (PTFE) fiber and method of making same |
| WO2016138221A1 (en) | 2015-02-26 | 2016-09-01 | Merit Medical Systems, Inc. | Layered medical appliances and methods |
| CN113862821B (en) * | 2021-09-24 | 2022-08-05 | 天津工业大学 | Polyphenylene sulfide fiber fabric type alkaline water electrolysis diaphragm and preparation method thereof |
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| US3043652A (en) * | 1951-05-18 | 1962-07-10 | Metallgesellschaft Ag | Fluid bed process for granulating fine-grained materials |
| US2760917A (en) * | 1951-09-28 | 1956-08-28 | Gulf Research Development Co | Fluidized catalytic process for the destructive hydrogenation of hydrocarbons |
| SE392582B (en) * | 1970-05-21 | 1977-04-04 | Gore & Ass | PROCEDURE FOR THE PREPARATION OF A POROST MATERIAL, BY EXPANDING AND STRETCHING A TETRAFLUORETENE POLYMER PREPARED IN AN PASTE-FORMING EXTENSION PROCEDURE |
| DE2646332B2 (en) * | 1976-10-14 | 1979-04-12 | Basf Ag, 6700 Ludwigshafen | Process for the production of fibrils from fluorine-containing polymers |
| US4184939A (en) * | 1977-09-26 | 1980-01-22 | Olin Corporation | Diaphragms for use in the electrolysis of alkali metal chlorides |
| US4278524A (en) * | 1977-09-26 | 1981-07-14 | Olin Corporation | Diaphragms for use in the electrolysis of alkali metal chlorides |
| US4207164A (en) * | 1977-10-03 | 1980-06-10 | Olin Corporation | Diaphragms for use in the electrolysis of alkali metal chlorides |
| DE3045333A1 (en) * | 1980-12-02 | 1982-07-01 | Dynamit Nobel Ag, 5210 Troisdorf | "FIBRIDS AND FIBRILLES MADE OF VINYLIDENE FLUORIDE POLYMERS" |
| IL67047A0 (en) * | 1981-10-28 | 1983-02-23 | Eltech Systems Corp | Narrow gap electrolytic cells |
| US4544474A (en) * | 1981-12-21 | 1985-10-01 | Olin Corporation | Porous diaphragms for electrolytic cells having non-uniform hydrophobicity |
| US4468360A (en) * | 1981-12-21 | 1984-08-28 | Olin Corporation | Preparing porous diaphragms for electrolytic cells having non-uniform hydrophobicity |
| DD244365A5 (en) * | 1984-09-17 | 1987-04-01 | Eltech Systems Corporation,Us | NON-ISOTROPER, ORGANIC PLUS NON-ORGANIC FIBER COMPOUND AND METHOD FOR THE PRODUCTION THEREOF |
| MX169225B (en) * | 1984-09-17 | 1993-06-24 | Eltech Systems Corp | COMPOSITE OF NON-ORGANIC FIBERS / POLYMER METHOD FOR PREPARING IT AND USING IT, INCLUDING A DIMENSIONALLY STABLE SEPARATOR |
| US4853189A (en) * | 1987-01-23 | 1989-08-01 | Phillips Petroleum Company | Apparatus for conversion of oils to hydrocarbon products |
| US5009971A (en) * | 1987-03-13 | 1991-04-23 | Ppg Industries, Inc. | Gas recombinant separator |
| US5266276A (en) * | 1988-07-15 | 1993-11-30 | Bp Chemicals Limited | Apparatus for the gas-phase polymerization of olefins in a fluidized-bed reactor |
| US5030403A (en) * | 1989-01-17 | 1991-07-09 | Ppg Industries, Inc. | Method for making polymeric fibrils |
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| US5188712A (en) * | 1991-01-03 | 1993-02-23 | Ppg Industries, Inc. | Diaphragm for use in chlor-alkali cells |
| EP0545068A3 (en) * | 1991-11-08 | 1993-12-22 | Du Pont | Wetting of diaphragms |
-
1991
- 1991-09-12 DE DE4130356A patent/DE4130356C2/en not_active Expired - Fee Related
-
1992
- 1992-08-27 EP EP92918372A patent/EP0608248B1/en not_active Expired - Lifetime
- 1992-08-27 US US08/325,285 patent/US5700572A/en not_active Expired - Lifetime
- 1992-08-27 WO PCT/DE1992/000712 patent/WO1993005213A1/en active IP Right Grant
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| Title |
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| EP-A- 0 418 155 * |
| GB-A- 1 355 373 * |
| See also references of WO9305213A1 * |
| US-A- 5 009 971 * |
| WO-A-86/01841 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4130356A1 (en) | 1993-04-08 |
| US5700572A (en) | 1997-12-23 |
| WO1993005213A1 (en) | 1993-03-18 |
| EP0608248B1 (en) | 1997-07-30 |
| DE4130356C2 (en) | 1995-01-26 |
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