EP0806500A1 - Procédé pour la fabrication de fibrilles - Google Patents

Procédé pour la fabrication de fibrilles Download PDF

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Publication number
EP0806500A1
EP0806500A1 EP97107360A EP97107360A EP0806500A1 EP 0806500 A1 EP0806500 A1 EP 0806500A1 EP 97107360 A EP97107360 A EP 97107360A EP 97107360 A EP97107360 A EP 97107360A EP 0806500 A1 EP0806500 A1 EP 0806500A1
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EP
European Patent Office
Prior art keywords
fibrils
solution
precipitation medium
polyarylene ether
mixture
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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.)
Ceased
Application number
EP97107360A
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German (de)
English (en)
Inventor
Heinz Berbner
Ulrich Dr. Eichenauer
Jürgen Göpel
Eckhard Neufeld
Hans Dieter Zettler
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BASF SE
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BASF SE
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Application filed by BASF SE filed Critical BASF SE
Publication of EP0806500A1 publication Critical patent/EP0806500A1/fr
Ceased legal-status Critical Current

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    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/66—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyethers
    • 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
    • D01D5/40—Formation of filaments, threads, or the like by applying a shearing force to a dispersion or solution of filament formable polymers, e.g. by stirring

Definitions

  • the present invention relates to a method for producing fibrils by introducing a solution of a polyarylene ether in a suitable organic solvent into a liquid precipitation medium under the simultaneous action of shear forces, a shear field with an average energy density of at least 5 when the solution is introduced into the precipitation medium in the fibril formation space W ⁇ s / cm 3 , as well as fibrils per se, which can be produced by the process according to the invention, and their use as binding fibers in the production of papers, seals, friction linings and nonwovens.
  • Fibrils of this type are used on a large scale in many areas of technology to increase the mechanical strength, in particular the rigidity, of synthetic and natural materials or moldings produced therefrom, or as binding fiber or process fiber in the production of special papers.
  • DE-A 14 69 120 describes a process for producing suspensions from fibrils when polymers are dissolved from a solution by dispersing the solution in a precipitation medium under the action of shear forces be canceled.
  • the shear effect is generated either by a stirrer (Waring-Misher) or by means of a turbulent flowing liquid.
  • These fibrils can be in the form of a tape, film or fiber, or they can be a mixture of these structures, ie they are not uniform. Fibrils made from polyarylene ethers are not described there.
  • DE-A 22 08 553 relates to a method for producing fibrils from linear polyolefins, such as e.g. Ziegler polyethylene, in which the polyolefin dissolved in a solvent above its melt dissolving temperature is subjected to flash evaporation.
  • This method requires a very large amount of energy since the melt release temperatures of polymers such as polyvinyl chloride, polyvinylidene chloride and polystyrene are very high, i.e. above 100 ° C.
  • DE-A 25 16 561 describes an improved process for the production of fibrils from polymers or copolymers of styrene, vinyl chloride or vinylidene chloride Solutions of these polymers or copolymers in methyl ethyl ketone, tetrahydrofuran or 1,4-dioxane are introduced into a liquid precipitation medium under the simultaneous action of shear forces, wherein when these solutions are introduced into the precipitation medium in the fibril formation space of the shear field, an average energy density of at least 5 W ⁇ s / cm 3 prevails. This procedure is carried out at room temperature.
  • DE-A 25 43 824 describes a complex process for the production of fibrils from poly (amide-imide) resins, in which the polymers are also dissolved in an organic solvent (a) and, before being introduced into the precipitation medium (b), with a organic, cyclic ether (c), which does not dissolve the above resin, but can be mixed homogeneously with the organic solvent (a) and the precipitation medium (b) to an unlimited extent, are mixed in a certain volume ratio.
  • This document shows that when using the process according to DE-A 26 46 332 or DE-A 25 16 561 described above on poly (amide-imide) resins, no discrete fibrils are obtained, but only finely divided powder-like particles. that show no tendency to form fleece.
  • the particles produced using the conventional method usually contain a large amount of solvent, so that the subsequent workup is difficult and time-consuming.
  • Fibrils in the sense of the invention are fibrous particles made of synthetic polymers which are morphologically similar in size and shape and in their properties to cellulose fibers.
  • the term "fibrids" is common in Anglo-Saxon usage.
  • polyarylene ether used in the context of the present invention denotes polymers and copolymers which contain the repeating units I.
  • the radicals R c and R d can also form, together with the carbon atom to which they are attached, a cycloaliphatic ring, preferably a C 5 to C 7 cycloalkyl ring.
  • This cycloalkyl ring can in turn carry one or more substituents.
  • the preferred substituents include C 1 -C 10 -alkyl radicals, such as methyl, ethyl, propyl or i-propyl, in particular methyl.
  • Preference is given to polyarylene ethers A in which T, Q and Z are -O-, -SO 2 -, C O, a chemical bond or a group of the formula -CR c R d .
  • Ar and Ar 1 are C 6 to C 18 aryl groups, such as 1,5-naphthyl, 1,6-naphthyl, 2,7-naphthyl, 1,5-anthryl, 9,10-anthryl, 2,6- Anthryl, 2,7-anthryl or biphenyl, especially phenyl. These aryl groups are preferably not substituted.
  • substituents selected from C 1 to C 10 alkyl such as methyl, ethyl, n-propyl, i-propyl, t-butyl, n-hexyl, C 6 to C 18 aryl such as phenyl or naphthyl, C 1 - to C 10 alkoxy such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy or halogen atoms.
  • Preferred substituents include methyl, phenyl, methoxy and chlorine.
  • Fibrils are preferably produced from a polyarylene sulfone or a polyarylene ether sulfone using the method according to the invention, polymers with the repeating units (I 1 ) and (I 2 ) being particularly preferred.
  • the polyarylene ethers can also be copolymers or block copolymers in which there are polyarylene ether segments and segments of other thermoplastic materials, such as polyamides, polyesters, aromatic polycarbonates, polyester carbonates, polysiloxanes, polyimides or polyetherimides.
  • the number average molecular weights M n of the block or graft arms in the copolymers are generally in the range from 1,000 to 30,000 g / mol.
  • the blocks of different structures can be arranged alternately or statistically.
  • the proportion by weight of the polyarylene ethers in the copolymers or block copolymers is generally at least 10% by weight.
  • the proportion by weight of the polyarylene ethers can be up to 97% by weight. Co or block copolymers with a weight fraction of polyarylene ether of up to 90% by weight are preferred. Copolymers and block copolymers with 20 to 80% by weight of polyarylene ether are particularly preferably used.
  • the polyarylene ethers have a number average molecular weight M n in the range from 10,000 to 60,000 g / mol, preferably 10,000 to 40,000 g / mol, and relative viscosities from 1.25 to 1.95.
  • M n number average molecular weight
  • the relative viscosities are either in 1% by weight N-methylpyrrolidone solution, in mixtures of phenol and dichlorobenzene, the mixing ratio generally being about 1: 1 v / v, or as 0.5% by weight .-% solution measured in 96% sulfuric acid at 20 ° C and 25 ° C respectively.
  • a solution of a polyarylene ether is introduced into a liquid precipitation medium under the simultaneous action of shear forces, fibrils of these polyarylene ethers being formed.
  • the process according to the invention is generally carried out at low temperature, i.e. at about 10 to about. 90 ° C, preferably at a temperature which is from about 20 to about 60 ° C.
  • Entering the solution of a polyarylene ether in a liquid precipitation medium means mixing this solution with a large excess of the precipitation medium.
  • the polyarylene ethers dissolved in a solvent at low temperature should preferably be insoluble in the precipitation medium, but the solvent used should be miscible with the precipitation medium as much as possible.
  • the volume ratio of polymer solution to precipitation medium is preferably between approximately 1: 5 to approximately 1: 100, more preferably approximately 1:10 to approximately 1:35, in particular approximately 1:10 to approximately 1:20.
  • solvents which fulfill the two properties listed above are suitable as solvents in the context of the present invention.
  • organic solvents for polyarylene ethers have been N-methylpyrrolidone (NMP), dimethylformamide (DMF), 1,3-dimethyltetrahydro-2- [1H] -pyrimidinone (DMPU), sulfolane, methylene chloride or a mixture of two or more of which has been proven, with NMP being particularly preferred.
  • the above solvents are distinguished by a particularly high solvency for the polymers in question at low temperature, by their good miscibility with the precipitation medium, in particular with water, and by their low boiling point. Some of them, such as DMF form an azeotrope with water, which has a high proportion of organic solvent, which is important for the economic recovery of the solvent.
  • the concentration of the polyarylene ethers in the solution can be 0.5 to 40, preferably 5 to 25,% by weight.
  • furans, ketones or alcohols, N-methylpyrrolidone or a mixture of two or more thereof are added to the above solution before being introduced into the precipitation medium, preferably alcohols having 1 to 4 carbon atoms, such as For example, methanol, ethanol, iso-propanol, n-propanol, iso-butanol, n-butanol and tert-butanol, ketones such as acetone and methyl ethyl ketone, and furans such as THF, the carbon atoms within the furans or THF can be substituted by methyl or ethyl groups can be used.
  • Methanol, THF and NMP are particularly preferably used.
  • the addition can take place, for example, with the aid of static or dynamic mixers.
  • These additional organic ones Solvents can be added to the polymer solution in an amount until the polymer begins to precipitate, ie they are precipitants for the polyarylene ethers in question.
  • the proportion of additional organic solvents is up to 50%, based on the total volume of the solution.
  • solvents are preferably added to the polyarylene ether solution in such a proportion that it does not precipitate out before contacting the precipitation medium.
  • the result of this addition is that the formation of fibrils from such a solution begins immediately when the solution comes into contact with the precipitation medium, whereby individual fibrils with a very large surface area are obtained.
  • the additional organic solvent is added or mixed into the solution of the polyarylene ether before it is introduced into the precipitation medium, preferably using a static or dynamic mixer.
  • Water has proven particularly useful as a liquid precipitation medium.
  • the process can also be carried out using other precipitation media, such as, for example, ethylene glycol or alcohols having 1 to 4 carbon atoms or mixtures thereof.
  • a mixture of water and at least one furan, alcohol, ketone, N-methylpyrrolidone or a mixture of two or more thereof can also be used. It is crucial that the dissolved polyarylene ether is insoluble in the precipitation medium, but the solvent used with the precipitation medium within the volume ratios used is completely miscible.
  • Fibril formation space is understood to mean the zone of a shear field generator in which the polymer solution and the liquid precipitation medium meet and in which an average energy density of at least approximately 5 W ⁇ s / cm 3 , preferably approximately 10 to approximately 100 W ⁇ s / cm 3 , is further preferred about 20 to about 50 Ws / cm 3 .
  • the volume of the fibril formation space depends on the flow rate of the precipitation medium combined with the polymer solution. Since the formation of the fibrils takes place within 1 ⁇ 10 -2 to 1 ⁇ 10 -4 s, the length of the fibril formation space at flow velocities of 5 to 50 m / s is 0.05 to 50 cm, preferably 0.1 to 5 cm.
  • Devices are preferably used as shear field generators which mechanically generate a shear field by rotating tools.
  • Commercially available machines are suitable for this, which are used for dispersing and homogenizing, for example, polymer dispersions.
  • High-speed dispersing machines or shear field generators of the Ultra-Turrax type can be used for discontinuous operation.
  • the shear field can also be generated hydraulically. If, for example, the solution of the polymer is pressed out through one or more nozzles, the liquid precipitating medium optionally being mixed intensively with the solution of the polymer in a shear field at a flow rate of at least 5 m / s, fibrils are likewise obtained.
  • the average energy density in the fibril formation space is preferably approximately 5 to approximately 50 W ⁇ s / cm 3 .
  • the apparatus shown in FIG. 1 allows continuous operation, for example.
  • a rotor (4) which is driven by a shaft (5), is located in a housing (1) with an inlet nozzle (2) and an outlet nozzle (3).
  • This rotor (4) sets the liquid precipitating medium in the housing, which is continuously fed through the inlet connection (2), in a rotating movement.
  • the kinetic energy of the rotor is transferred to the liquid precipitation medium.
  • the accelerated liquid precipitation medium is braked in an annular braking zone (6). Part of the kinetic energy is converted into heat.
  • the braking zone is formed by an annular stator that has sharp-edged openings and baffles.
  • the polymer solution is passed through a tube (7) with an inside diameter of preferably about 4 mm by means of a Dosing pump entered into the liquid precipitation medium, the outlet opening of the tube (7) being located at the location at which the liquid precipitation medium experiences its highest acceleration.
  • a fibril suspension is continuously discharged from the discharge nozzle (3), the fibrils being present as solid particles.
  • the method according to the invention can be carried out according to the so-called injector principle.
  • a device suitable for this is shown in FIG. This device and the implementation of the method are explained using the example according to the invention described below.
  • the nozzle by means of which the solution of the polyarylene ether is introduced into the precipitation medium is completely surrounded by the precipitation medium, in other words, the nozzle is located within the precipitation medium.
  • the nozzle can also be located outside the precipitation medium, but this leads to fibrils with a slightly smaller surface.
  • the pressure at the nozzle outlet is generally approximately 3 to 10 bar, or approximately 5 bar when using a rotating nozzle, although higher pressures can also be achieved and lead to good results.
  • FIG. 3 shows a longitudinal section of this device.
  • the rotor preferably a radial pump wheel (22)
  • the housing (21) consists of the front end plate (28), which has a central feed (29) for the precipitation medium, and from the periphery (25) of the peripheral part (26) surrounding the radial pump wheel (22), one over its Has circumferentially evenly distributed passage openings (27), which is shown in Fig. 4, for the formation of the fibrils.
  • These passage openings (27) in the peripheral part (26) represent the fibril formation space.
  • the housing (21) also has an open, rear end which can be covered by a removable end plate (24) which can be fastened to the housing by means of a suitable screw connection, the end plate (24) having a bushing for the shaft (23) of the radial pump wheel ( 22) is provided.
  • the radial pump wheel (22) is preferably a commercially available centrifugal pump wheel, the periphery of which may be adapted to the shape of the inner circumference of the part (26).
  • pump wheels with radial pump action can also be used, such as paddle wheels or discs or arms provided with beaters.
  • the peripheral part (26) of the housing (21) surrounding the periphery of the radial pump wheel (22) consists of elements (210), preferably rectangular in cross section, which are arranged in a circle at the same distance and which are connected to the front end plate (28) by known means. for example screwing or welding.
  • reference numeral (211) denotes inlets for the solution of the polyarylene ether
  • (212) denotes the sides of the elements (210), which can have many steps
  • reference numeral (213) denotes a collecting container for the fibril suspension
  • reference numeral (214 ) designates a discharge nozzle arranged tangentially to it, which is connected to the discharge line.
  • the intensive mixing of the flowing media takes place in a pulse exchange space upstream of the two-substance nozzle, concentrically in the flow direction.
  • FIGS. 5 and 6 Such a device has been described in DE-A 22 08 921.
  • the technical implementation of this device is shown in FIGS. 5 and 6.
  • the nozzle is installed in a larger container.
  • the nozzle and the tube (33) are shown enlarged compared to the container (34).
  • the reference number (31) denotes a central nozzle opening from which the precipitation medium emerges, (32) an outlet opening for the solution of the polyarylene ether, (33) the tube (pulse exchange space), (34) a container, (35) a feed for the precipitation medium and (36) a feed for the solution of the polyarylene ether.
  • Figure 6 shows a device in which one can do without a large container.
  • Reference number (37) represents the supply for the slower flowing liquid.
  • the fibrils are formed in the tube (33), which acts as a momentum exchange space.
  • three-component and four-component nozzles can also be used to carry out the method according to the invention.
  • Stable, discrete fibrils are obtained immediately after all process variants. They can be separated from the liquid precipitation medium and the majority of the organic solvent by filtration or centrifugation. The remaining solvent is removed by washing with water on the filter or in the centrifuge. The organic solvents used and the corresponding precipitation media can be recovered by distillation from the mother liquor and from the wash water and returned to the process.
  • the fibrils produced according to the invention can have water contents of from 60 to 99% by weight, preferably from 90 to 98% by weight, and are highly capable of forming sheets or fleece when the fibrils are deposited from an aqueous suspension on a sieve.
  • the present invention also relates to the use of the fibrils produced here as binding fibers in the production of papers, seals, friction linings and nonwovens.
  • Aqueous suspensions from the fibrils produced according to the invention are obtained by introducing the fibrils into water while stirring.
  • the consistency here is approximately 0.2 to approximately 2% and preferably approximately 0.5 to approximately 1%.
  • a dispersant may also be present in this suspension, which is generally dissolved in an amount of 0.1 to 1.0% by weight, based on the dry weight of the fibrils.
  • Suitable dispersants are, for example, surface-active substances which are composed of hydrophilic and hydrophobic segments, polyvinyl alcohols or starch.
  • the fiber pulp obtained is then worked for a further 5 to 15 minutes using a high-speed propeller stirrer.
  • the consistency is generally 0.5 to 10% and preferably 1 to 5%.
  • paper-like sheetlike structures can be obtained from the aqueous suspensions of the fibrils.
  • the fibrils according to the invention can likewise be mixed with one another in any ratio with cellulose fibers or with staple fibers of synthetic polymers and can be processed on the paper machine to form self-supporting, coherent webs.
  • a standard sheet (2.4 g) made from fibrils must have an initial wet strength of at least 80 g with a water content of 83% by weight.
  • the initial wet strengths are determined with the test equipment developed by W. Brecht and H. Fiebinger (Karl Frank, paperback paper test . 3rd extended edition, Eduard Roether Verlag, Darmstadt, 1958, p. 59).
  • the fibrils to be tested are turned on a sheet forming device by inserting a frame test strips with the dimensions 30 ⁇ 95 mm.
  • the thickness of the test strips (basis weight) is determined by the weight of the fabric. The tester then measures the load at which the test strip breaks in g.
  • the particular advantage of the method according to the invention is that discrete fibrils are obtained which are highly fibrillated and practically free of organic solvents.
  • the residual organic solvent content in the fibrils is less than 0.1% by weight.
  • highly fibrillated in the present context means that aggregates consisting of fibrils with a very high surface area according to BET up to 180 m 2 / g are obtained.
  • the present invention also relates to fibrils which can be produced by introducing a solution of a polyarylene ether in a suitable organic solvent into a liquid precipitation medium under the simultaneous action of shear forces, a shear field having an average energy density of at least 5 W when the solution is introduced into the precipitation medium in the fibril formation space.
  • s / cm 3 which preferably has a length of approximately 0.1 to approximately 10 mm, a thickness of approximately 1 to 300 ⁇ m, a Schopper-Riegler degree of grinding of approximately 15 to approximately 50 and a specific surface area of approximately 1 to approximately Have 180 m 2 / g.
  • the fibrils produced according to the invention have the structure of finely branched aggregates, as is shown by an observation through an electron microscope.
  • the extent of the fibrillation of the fibrils obtained is determined by determining the freeness according to the Schopper-Riegler method (Korn-Burgstaller, Handbuch der Werkstoff Albany , 2nd ed. 1953, 4th vol., Textil- und Zellstoff Albany, p. 388 ff, Springer Publishing house). To carry out this determination, the fibrils must be placed in an aqueous suspension with a constant consistency (2 g / l and 20 ° C). The amount of water that is retained by the suspended fibrils under certain conditions is determined. The higher the fibrillation of the fibrils, the greater the amount of water absorbed (° Schopper-Riegler, ° SR).
  • the Schopper-Riegler values of an unground sulfite pulp are between 12 and 25 ° SR.
  • the Schopper-Riegler values of the fibrils according to the present invention are, for example, approximately 15 to approximately 90 ° SR.
  • the specific surface of the fibrils according to the invention is determined by the BET method by nitrogen absorption (S. Brunnauer, TH Emmett, E. Teller, Journal of American Chemical Society , 60 (1938), p. 309).
  • the parts given in the example are parts by weight and the percentages are percentages by weight.
  • a solution of 11% polyether sulfone of the repeating unit I 1 and a molecular weight of 25,000 and 89% NMP was used as the starting material. Kurt prior to entry into the fibril formation room, based on the solution, 27% THF was homogeneously mixed in with a static mixer. The solution of the polyether sulfones obtained, consisting of 8.66% polyether sulfone, 70% NMP and 21.34% THF, was then fed to the device described in FIG. 2 by means of a metering pump. 69 kg of solution were fed via the pipeline (1) to an injector nozzle (2). At the same time, water was added via a feed (4) under a pressure of 6 bar. The water jet had an exit speed of 30 m / s. The gap at point A was 0.25 mm. The polymer solution was metered in such that 30 liters of water are used as the precipitation medium for 1 liter of solution. The resulting fibrils were collected with a sieve (6).
  • the resulting fibrils had a length of 0.5 to 1.5 mm, a thickness of 1 to 10 ⁇ m and a degree of grinding of 32 ° SR.
  • the BET specific surface area was 150 m 2 / g.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Paper (AREA)
EP97107360A 1996-05-07 1997-05-05 Procédé pour la fabrication de fibrilles Ceased EP0806500A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19618330 1996-05-07
DE1996118330 DE19618330A1 (de) 1996-05-07 1996-05-07 Verfahren zur Herstellung von Fibrillen

Publications (1)

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EP0806500A1 true EP0806500A1 (fr) 1997-11-12

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EP97107360A Ceased EP0806500A1 (fr) 1996-05-07 1997-05-05 Procédé pour la fabrication de fibrilles

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EP (1) EP0806500A1 (fr)
JP (1) JPH1060730A (fr)
DE (1) DE19618330A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015023943A1 (fr) * 2013-08-15 2015-02-19 Sabic Innovative Plastics Ip B.V. Fibres sous-micrométriques filées par cisaillement
US10119214B2 (en) 2013-07-17 2018-11-06 Sabic Global Technologies B.V. Force spun sub-micron fiber and applications

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4710344B2 (ja) * 2005-02-18 2011-06-29 東レ株式会社 電気絶縁材料

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2208921A1 (de) * 1972-02-25 1973-09-06 Basf Ag Verfahren und vorrichtung zur herstellung von kurzfasern aus thermoplastischen kunststoffen
DE2543824A1 (de) * 1975-10-01 1977-04-14 Basf Ag Verfahren zur herstellung von fibrillen aus poly(amid-imid)-harzen
JPS52121524A (en) * 1976-04-06 1977-10-13 Teijin Ltd Production of pulp like substance
JPS52124904A (en) * 1976-04-12 1977-10-20 Teijin Ltd Process for making sheets
DE2646332A1 (de) * 1976-10-14 1978-04-20 Basf Ag Verfahren zur herstellung von fibrillen aus polymerisaten
WO1996014130A1 (fr) * 1994-11-08 1996-05-17 Hoechst Aktiengesellschaft Materiau de filtration et procede d'elimination de composants de melanges gazeux et de liquides

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2208921A1 (de) * 1972-02-25 1973-09-06 Basf Ag Verfahren und vorrichtung zur herstellung von kurzfasern aus thermoplastischen kunststoffen
DE2543824A1 (de) * 1975-10-01 1977-04-14 Basf Ag Verfahren zur herstellung von fibrillen aus poly(amid-imid)-harzen
JPS52121524A (en) * 1976-04-06 1977-10-13 Teijin Ltd Production of pulp like substance
JPS52124904A (en) * 1976-04-12 1977-10-20 Teijin Ltd Process for making sheets
DE2646332A1 (de) * 1976-10-14 1978-04-20 Basf Ag Verfahren zur herstellung von fibrillen aus polymerisaten
WO1996014130A1 (fr) * 1994-11-08 1996-05-17 Hoechst Aktiengesellschaft Materiau de filtration et procede d'elimination de composants de melanges gazeux et de liquides

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 7747, Derwent World Patents Index; Class A26, AN 77-83683Y, XP002039001 *
DATABASE WPI Section Ch Week 7748, Derwent World Patents Index; Class A26, AN 77-85488Y, XP002039002 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10119214B2 (en) 2013-07-17 2018-11-06 Sabic Global Technologies B.V. Force spun sub-micron fiber and applications
WO2015023943A1 (fr) * 2013-08-15 2015-02-19 Sabic Innovative Plastics Ip B.V. Fibres sous-micrométriques filées par cisaillement
US10400355B2 (en) 2013-08-15 2019-09-03 Sabic Global Technologies B.V. Shear spun sub-micrometer fibers

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DE19618330A1 (de) 1997-11-13

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