EP0119185B1 - Méthode pour la fabrication de fibres en polyimide hautement résistantes à la flamme et aux hautes températures - Google Patents

Méthode pour la fabrication de fibres en polyimide hautement résistantes à la flamme et aux hautes températures Download PDF

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Publication number
EP0119185B1
EP0119185B1 EP84890036A EP84890036A EP0119185B1 EP 0119185 B1 EP0119185 B1 EP 0119185B1 EP 84890036 A EP84890036 A EP 84890036A EP 84890036 A EP84890036 A EP 84890036A EP 0119185 B1 EP0119185 B1 EP 0119185B1
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Prior art keywords
spinning
temperature
polyimide
solution
dry
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Expired
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EP84890036A
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German (de)
English (en)
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EP0119185A2 (fr
EP0119185A3 (en
Inventor
Klaus Dipl.-Ing. Dr. Weinrotter
Thomas Dipl.-Chem. Dr. Jeszenszky
Heinrich Dr. Schmidt
Siegfried Baumann
Johann Kalleitner
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IMI-TECH FIBRES GMBH
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Lenzing AG
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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
    • D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
    • 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
    • Y10T428/2904—Staple length fiber
    • 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
    • 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

Definitions

  • the invention relates to a method for producing flame-retardant, high-temperature-resistant polyimide fibers by the dry spinning method from a solution in aprotic organic solvents.
  • Heat-resistant polymers have been known for a long time. They contain aromatic groups in their molecular chains, so that highly conjugated binding systems are created which are essential for high temperature resistance. Examples of this are aromatic polyamides and polyimides, in which the temperature resistance could be significantly increased by substituting the aliphatic chain with benzene residues.
  • the mixed polyimides described therein are soluble in polar, aprotic organic solvents, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone or dimethyl sulfoxide.
  • the polymers are prepared by the solution codification of benzophenonetetracarboxylic acid dianhydride with a mixture of tolylene diisocyanate and diphenylmethane diisocyanate in one of the aforementioned solvents.
  • the polymer can be processed directly from the solutions.
  • DE-A-2 442 203 further describes that fibers can be produced from the solutions, in particular by wet spinning, the fiber cross section being able to be designed differently by selecting the spinning bath.
  • the fiber cross section is round or elliptical.
  • polar aprotic solvent e.g. dimethylformamide, dimethylacetamide, N-methylpyrrolidone or similar
  • the fiber cross section is round or elliptical.
  • z. B. Glycerin in the precipitation bath pseudo hollow fibers with a narrow longitudinal slot and a serrated outside.
  • DE-A-2442 203 only contains general information without any statement about the fiber properties that can be achieved.
  • the object of the invention is to produce fibers from flame-retardant, high-temperature-resistant polyimide polymers according to the dry spinning method, which have improved performance properties, in particular an irregular fiber cross-section, which, with the same basis weight as fibers of round cross-section, ensure much better coverage, a pleasant feel and a high level To have shine.
  • the preparation of the polymers can be carried out by reacting benzophenonetetracarboxylic acid dianhydride, tolylene diisocyanate and diphenylmethane diisocyanate in an aprotic organic solvent, giving a solution of the polymer.
  • the solid powdery polymer can also be brought into solution continuously or discontinuously in an aprotic solvent such as dimethylacetamide, N-methylpyrrolidone, or dimethyl sulfoxide, preferably dimethylformamide.
  • the dissolving temperature is chosen between 30 and 120 ° C, preferably a solution with a content between 25 and 35 wt.% Is prepared.
  • the solution obtained is degassed, can be filtered one or more times and is fed to the spinning head of a dry spinning device via a spinning pump.
  • the individual shaft output can expediently be between 20 and 400 kg fiber / d, preferably between 150 and 300 kg / d.
  • spinning shafts can be combined to form a so-called “spinning machine " .
  • the technical design of the spinning head, the spinning shaft or the entire spinning machine can be similar to that which is common in the dry spinning of acrylic fibers.
  • the cross-sections are irregular and have - to use alphabetical letters as a comparison - strongly profiled shapes such as W, U, C, Y, E, V, T, X.
  • These fiber cross-sectional shapes which also apply to the The following fiber aftertreatment is not a property that has long been desired by textile technicians and which brings about the improvement in use properties mentioned above.
  • the typical fiber bundle cross sections shown in FIG. 1 do not change when different numbers of nozzle holes are used, provided that the nozzle holes are only round.
  • the same typical cross-sectional shapes were obtained when using 100-hole nozzles as well as 200, 400, 600 and 800-hole nozzles.
  • the shaft cables obtained in the manner described by means of dry spinning, spooled in between or deposited in cans are advantageously washed with water at a speed of 2 to 20 m / min at first at temperatures of 80 to 100 ° C. for the aftertreatment, then previved, using a sieve drum or calender dryer dried at temperatures between 120 and 300 ° C until the cable moisture after the dryer is less than 5%, the cable tape is then stretched in one or more stages in a ratio of 1: 2 to 1:10 at temperatures between 315 to 450 ° C, then post-finished with a conventional preparation, crimped in a compression crimping machine at room temperature and finally cut into staple fibers or, in the case of the production of continuous filaments, wound up after the stretching process.
  • the fibers are freed of residual solvent by intensive washing with hot water. Preavivation involves the application of a commercially available antistatic in order to be able to pass the sliver through the dryer without any problems. Maintaining the moisture content of less than 5% after drying is important in order to carry out the subsequent high-temperature drawing without difficulty can. This high temperature drawing is carried out either over heated rolls, a heating table or over a hot air oven, and it can be carried out in one or more stages. Maintaining temperatures between 315 and 450 ° C during stretching is necessary because of the high glass transition point of the polyimide fibers (about 315 ° C).
  • a satisfactory crimp can be applied with conventional stuffer box crimping machines at temperatures ⁇ 100 ° C, which enables the later processing of the staple fibers on conventional textile machines.
  • the re-finishing takes place by means of commercially available finishing agents for synthetic fibers, which can have a cationic and / or anionic and / or non-ionic character.
  • the point in time of the re-activation does not necessarily have to be after the high-temperature stretching, but can also be selected after the crimping.
  • the cutting into staple fibers is done with commercially available cutting machines. In the case of the production of continuous yarns, the cable strips with the desired cable thickness are passed separately through the aftertreatment system and are wound up on spools after the high-temperature stretching and possibly after-aging.
  • the spinning gas temperature at the height of the nozzle package is 295 ° C and at the end of the 8 m long spinning shaft is 115 ° C, the amount of spinning gas is 60 m 3 / h (based on normal conditions).
  • the shaft output is set to 150 kg fiber / d.
  • the spun material with a total titer of 2640 dtex, which has a residual DMF content of 15% by weight, based on polymer solids, is collected on spools and folded into a cable band with a total titer of 184800 dtex.
  • the cable band is then washed in water at 90 ° C, provided with an antistatic finish in a dip tank, dried at 180 ° C using a sieve drum dryer and then stretched over a heating bracket in a ratio of 1: 5.
  • the surface temperature of the heating bracket is 380 ° C.
  • the stretched cable tape is provided with a mixture of cationic / nonionic preparation, crimped in a stuffer box at room temperature and cut into staple fibers of 40 mm in length.
  • the fibers which have a final titer of 2.2 dtex, have a strength of 28 cN / tex, the fiber elongation is 34%, the loop strength 15 cN / tex, the knot strength 20 cN / tex, the boiling shrinkage is 0.4%.
  • the fibers have a pronounced lobed or serrated shape in cross section (as shown in FIG. 1) and the LOI value, measured on a knitted stocking with a weight per unit area of 150 g / m 2 , is 37% 0 2 . If the fibers are exposed to a temperature of 260 ° C for a period of 250 hours, the specified fiber data will not change, ie the fiber is thermostable at the specified temperature. The water absorption of the fibers is 20 ° C and 65% relative humidity 2.7%.
  • the spinning gas temperature at the height of the nozzle pack is 320 ° C and at the end of the spinning shaft 120 ° C, the amount of spinning gas is 70 m 3 / h (based on normal conditions).
  • the shaft output is set to 200 kg fiber / d.
  • the spun material with a total titre of 7140 dtex, which has a residual DMF content of 17% by weight, based on polymer solids, is collected on spools and folded into a cable band with a total titre of 357,000 dtex.
  • the cable band is washed, pre-treated, dried and then stretched in two stages over heated rollers.
  • the total stretch ratio is 1: 7, the surface temperature of the heated rolls is 340 ° C.
  • the cable tape is crimped at room temperature in a compression crimping chamber, then treated with a nonionic finishing agent by spraying and cut into staple fibers.
  • the fibers which have a final titer of 1.7 dtex, have a strength of 30 cN / tex, the fiber elongation is 30%, the boiling shrinkage is 0.45%.
  • the fibers show in cross section the characteristic shape shown in FIG. 1 or described in Example 1.
  • the further treatment of the solution is as in Example 1.
  • the solution is spun using a 240-hole nozzle, the nozzle hole shape is circular and has a hole diameter of 175 kt m.
  • the spinning solution temperature is 60 ° C before entering the nozzle pack.
  • the spinning gas temperature at the level of the nozzle package is 260 ° C and at the end of the spinning shaft 110 ° C, the amount of spinning gas is 55 m 3 / h (based on normal conditions).
  • the shaft output is set to 130 kg fiber / d.
  • the spun material with a total titre of 6240 dtex which has a residual DMF content of 20% by weight, based on polymer solids, is collected on bobbins and several bobbins are submitted to the aftertreatment process.
  • the individual cable tapes, each with a total titer of 6240 dtex, are passed through the post-treatment process separately, i.e. washed, pre-aged and dried.
  • the drawing takes place in one step in a hot air oven, the drawing ratio be carries 1: 4.7.
  • the air temperature during stretching is 420 ° C.
  • the stretched cable tapes are then individually wound on cross-wound bobbins as an endless filament bundle.
  • the individual filaments, which have a final titer of 5.5 dtex, have a strength of 24 cN / tex, the fiber elongation is 40%, the boiling shrinkage is 0.3%.
  • the filaments show in cross section the characteristic shape shown in FIG. 1.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)

Claims (3)

1. Procédé pour préparer des fibres de polyimide difficiles à enflammer, capables de résister à des températures élevées, ayant une composition répondant à la formule générale
Figure imgb0011
dans laquelle R est présent en partie sous la forme d'un groupe de formule
Figure imgb0012
et le reste est présent sous forme d'un groupe de formule
Figure imgb0013
selon le procédé de filature à sec, à partir d'une solution dans des solvants organiques aprotiques, procédé caractérisé en ce qu'on conduit les opérations de filature à sec dans une cellule de filature, en filant une solution contenant 20 à 40% du polyimide que l'on fait passer par des filières à orifices de section ronde, comportant de 20 à 800 orifices et ayant un diamètre d'orifice de filière de 100 à 300 lim, en opérant à une vitesse d'injection comprise entre 20 et 100 m/min, une vitesse de retrait ou d'appel comprise entre 100 et 800 m/ min, avec une quantité de gaz de filature comprise entre 40 et 100 m3/h (quantité rapportée aux conditions normales) et à une température de gaz de filature comprise entre 200 et 350°C, on lave le câble ainsi obtenu, présentant une teneur en solvant résiduel de 5 à 25% en poids - teneur rapportée à la matière polymère solide - et ayant un titre de filament individuel compris entre 3,5 et 35 dtex, en opérant le lavage dans l'eau chaude, puis on sèche jusqu'à une teneur en humidité inférieure à 5%, on étire ensuite à température élevée et enfin on éventuellement frise et l'on découpe pour obtenir des fibres discontinues.
2. Procédé selon la revendication 1, caractérisé en ce que les câbles enroulés sur des bobines ou déposés dans des pots, que l'on obtient ainsi pour le traitement ultérieur à des vitesses d'introduction de 2 à 20 m/min, tout d'abord à l'eau à des températures de 80 à 100°C, puis soumis à avivage préliminaire, séchés à l'aide d'un sécheur à tambour perforé ou à calandres à des températures comprises entre 120 et 300°C, jusqu'à ce qu'après le sécheur, l'humidité des câbles soit inférieure à 5%, le ruban est ensuite étiré en une ou plusieurs étapes à un taux ou rapport d'étirage de 1:2 jusqu'à 1: 10 à des températures comprises entre 315 et 450°C, puis le ruban est soumis à un avivage ultérieur à l'aide d'une préparation usuelle, il est frisé à la température ambiante dans une machine de frisage avec compression et enfin il est découpé en des fibres discontinues ou, dans le cas de la production de filaments sans fin, il est enroulé sur des bobines après le processus d'étirage.
3. Procédé selon l'une des revendications 1 et 2, ou selon ces deux revendications, caractérisé en ce qu'on file une solution du polyimide dans du diméthylacétamide, du diméthylsulfoxyde, de la N-méthylpyrrolidone ou avantageusement dans du diméthylformamide.
Figure imgb0014
EP84890036A 1983-03-09 1984-03-01 Méthode pour la fabrication de fibres en polyimide hautement résistantes à la flamme et aux hautes températures Expired EP0119185B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT820/83 1983-03-09
AT0082083A AT377016B (de) 1983-03-09 1983-03-09 Verfahren zur herstellung von schwer entflammbaren, hochtemperaturbestaendigen polyimidfasern

Publications (3)

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EP0119185A2 EP0119185A2 (fr) 1984-09-19
EP0119185A3 EP0119185A3 (en) 1986-11-26
EP0119185B1 true EP0119185B1 (fr) 1989-01-18

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US (1) US4801502A (fr)
EP (1) EP0119185B1 (fr)
JP (1) JPS59168120A (fr)
AT (1) AT377016B (fr)
CA (1) CA1229209A (fr)
DE (1) DE3476227D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT17296U1 (de) * 2019-07-23 2021-11-15 Evonik Fibres Gmbh Polyimidfasern für die Heißgasfiltration

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4758649A (en) * 1986-05-21 1988-07-19 Kuraray Co., Ltd. Heat resistant organic synthetic fibers and process for producing the same
AT391710B (de) * 1988-02-26 1990-11-26 Chemiefaser Lenzing Ag Schwer entflammbare hochtemperaturbestaendige polyimidfasern und formkoerper daraus
AT395188B (de) * 1989-04-13 1992-10-12 Chemiefaser Lenzing Ag Verfahren zur herstellung schwer entflammbaren, hochtemperaturbestaendigen, papierartigen materials auf basis von polyimidfasern
JPH0247308A (ja) * 1988-08-03 1990-02-16 Kyoto Kogei Seni Univ 導電性アルミナ質繊維及びその製造方法
US5051210A (en) * 1988-08-03 1991-09-24 Kyoto Institute Of Technology Alumina fiber and a method of producing the same
FI89526C (fi) * 1988-11-29 1993-10-11 Chemiefaser Lenzing Ag Svaorantaendbara, hoegtemperaturbestaendiga pappersartade material baserade pao termostabila polymerer
AT392974B (de) * 1989-07-13 1991-07-25 Chemiefaser Lenzing Ag Mischpolyimide sowie verfahren zu ihrer herstellung
AT395178B (de) * 1990-10-15 1992-10-12 Chemiefaser Lenzing Ag Schwer entflammbare, hochtemperaturbestaendige polyimidfasern, sowie verfahren zu ihrer herstellung
AT399882B (de) * 1993-11-03 1995-08-25 Chemiefaser Lenzing Ag Monoaxial verstreckter formkörper aus polytetrafluorethylen und verfahren zu seiner herstellung
JPH07310232A (ja) * 1994-05-13 1995-11-28 Toyobo Co Ltd バグフィルター用ポリアミドイミド繊維
RU2062309C1 (ru) * 1994-08-01 1996-06-20 Мусина Тамара Курмангазиевна Нити, выполненные из полностью ароматического полиимида, и способ их получения
US6610242B1 (en) 2000-11-13 2003-08-26 Malcolm Swanson Method for treating polymeric fiber mats and for making filters from such treated fiber mats
US6782185B2 (en) 2002-07-03 2004-08-24 Sumitomo Electric Industries, Ltd. Optical variable attenuator and optical module
US20050129764A1 (en) * 2003-12-11 2005-06-16 Vergez Juan A. Osmotic device containing licofelone
US20060248651A1 (en) * 2005-05-05 2006-11-09 Creative Bedding Technologies, Inc. Stuffing, filler and pillow
JP5086764B2 (ja) * 2007-10-17 2012-11-28 株式会社カネカ 非熱可塑性不織布及びその利用、並びに当該非熱可塑性不織布の製造方法。
WO2009054349A1 (fr) 2007-10-26 2009-04-30 Kaneka Corporation Masse de fibres de polyimide, matériau absorbant les sons, matériau d'isolation thermique, nappe ignifuge, tissu de filtre, vêtement résistant à la chaleur, tissu non-tissé, matériau d'isolation thermique/absorbant les sons pour avion, et filtre de sac résistant à la chaleur
JP5254593B2 (ja) * 2007-11-05 2013-08-07 株式会社カネカ 非熱可塑性ポリイミド繊維を含む繊維集合体を含む断熱・吸音材および航空機
CA2739033C (fr) 2008-10-17 2017-06-20 Solvay Advanced Polymers, L.L.C. Fibre ou feuille composee de polymeres a haute tg et son processus de fabrication
CN102471486B (zh) 2009-07-03 2014-07-02 罗地亚经营管理公司 改性聚酰胺、其制备方法及由所述聚酰胺获得的制品
KR101898455B1 (ko) * 2016-03-31 2018-09-13 가부시키가이샤 아이.에스.티 폴리이미드 섬유 및 폴리이미드 섬유의 제조 방법
CN111254505B (zh) * 2020-02-19 2021-10-08 江苏恒科新材料有限公司 一种大有光聚酯纤维及其纺丝所用的喷丝板及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1603108A (fr) * 1968-06-04 1971-03-22
CA1035496A (fr) * 1973-10-12 1978-07-25 Upjohn Company (The) Fibres de copolyimides resistant aux fortes chaleurs
US3985934A (en) * 1974-07-26 1976-10-12 The Upjohn Company Polyimide fiber having a serrated surface and a process of producing same
JPS56159314A (en) * 1980-05-09 1981-12-08 Ube Ind Ltd Preparation of polyimide fiber
JPS57205517A (en) * 1981-06-11 1982-12-16 Ube Ind Ltd Preparation of polyimide hollow fiber

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT17296U1 (de) * 2019-07-23 2021-11-15 Evonik Fibres Gmbh Polyimidfasern für die Heißgasfiltration

Also Published As

Publication number Publication date
EP0119185A2 (fr) 1984-09-19
JPS59168120A (ja) 1984-09-21
CA1229209A (fr) 1987-11-17
JPS6327444B2 (fr) 1988-06-03
DE3476227D1 (en) 1989-02-23
ATA82083A (de) 1984-06-15
US4801502A (en) 1989-01-31
EP0119185A3 (en) 1986-11-26
AT377016B (de) 1985-01-25

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