EP0398094A2 - Procédé pour la fabrication de mono- et multifilaments ou de fibres courtes de polyarylène-sulfide et fibres de polyarylène-sulfide à haute ténacité - Google Patents

Procédé pour la fabrication de mono- et multifilaments ou de fibres courtes de polyarylène-sulfide et fibres de polyarylène-sulfide à haute ténacité Download PDF

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Publication number
EP0398094A2
EP0398094A2 EP90108480A EP90108480A EP0398094A2 EP 0398094 A2 EP0398094 A2 EP 0398094A2 EP 90108480 A EP90108480 A EP 90108480A EP 90108480 A EP90108480 A EP 90108480A EP 0398094 A2 EP0398094 A2 EP 0398094A2
Authority
EP
European Patent Office
Prior art keywords
multifilaments
sec
stretching
fibers
dtex
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
Application number
EP90108480A
Other languages
German (de)
English (en)
Other versions
EP0398094B1 (fr
EP0398094A3 (fr
Inventor
Wolfgang Dipl.-Ing. Anderheggen
Michael Dr Krämer
Roland Dr. Vogelsgesang
Wolfram Dr. Wagner
Wolfgang Dipl.-Ing. Olges
Thomas Dipl.-Ing. Dragovic
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0398094A2 publication Critical patent/EP0398094A2/fr
Publication of EP0398094A3 publication Critical patent/EP0398094A3/fr
Application granted granted Critical
Publication of EP0398094B1 publication Critical patent/EP0398094B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • 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
    • D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
    • D01F6/765—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products from polyarylene sulfides

Definitions

  • Processes for the production of mono- and multifilaments and staple fibers made of multifilaments based on polyarylene sulfides are specified by means of melt spinning, multiple stretching and, if appropriate, crimping and fixing.
  • the chain molecules are oriented by treating the stabilized filaments in the first drawing stages at temperatures ⁇ 100 ° C. (preferably in drawing baths, in particular in boiling water);
  • the orientation and crystallinity required for high strengths is achieved by post-stretching (in hot air) at elevated temperature.
  • the dwell times in the first stage necessary for the effective stretching according to the invention can only be relatively narrow Ranges are varied in order to subsequently achieve the calculated orientations and effects, in particular high strengths, crystallinities and densities. Dwell times that are too long at temperatures> 100 ° C result in elongation of the material without additional orientation and thus an insufficient increase in strength.
  • crimping is also carried out, (tensionless) fixed and cut.
  • an aerodynamic crimping nozzle it must be stretched according to the invention in such a way that the sliver remains with a sufficiently high shrinkage which is important for the crimping and further processing.
  • the crimp is improved with the tension-free fixation. Tear-resistant fibers with a sufficiently high residual crimp for further processing are obtained.
  • Fibers, textile titers (up to approx. 20 dtex) hitherto unknown strength of> 6 cN / dtex, preferably> 6.2 cN / dtex, in particular> 6.4 cN / dtex, are claimed.
  • the various process steps in the stretching stages or aftertreatments require certain conditions in order to achieve the desired material strengthening in the selected area with the stretching.
  • the multistage drawing according to the invention leads to highly oriented, highly crystalline and high-strength mono- and multifilaments and not to plastically deformed thread structures of inferior quality.
  • Essentially linear polyarylene sulfides, in particular polyphenylene sulfides, are preferred, and those having an essentially linear structure are particularly preferred.
  • Another subject of the invention are highly oriented polyarylene sulfide fibers, preferably polyphenylene sulfide fibers of an essentially linear structure, with strengths> 6.0 cN / dtex, preferably ⁇ 6.4 cN / dtex and in particular ⁇ 7.0 cN / dtex. They generally also have high birefringence values> 0.46, densities ⁇ 1.37 and crystallinities ⁇ 40%.
  • the predried granules of polyarylene sulfides preferably poly-p-phenylene sulfide, have an essentially linear structure (ie without the use of a trifunctional starting compound) and without a curing process during production (drying at 140 ° C. for 4 hours) is carried out in an extruder at 330 ° C. melted, metered via a spinning pump and extruded through a 1-hole or multi-hole nozzle.
  • the extruder is placed under a vacuum above a storage container. Monofilaments are cooled in a water bath, multifilaments are blown with warm air or another gas below the nozzle in order to adjust the spinnability and the subsequent stretching behavior.
  • the take-off speeds are between 10 and 5000 m / min, preferably between 20 and 300 m / min. The slower speed applies to spinning in a water bath.
  • the material is therefore not initially fully stretched in a first stretching stage combination at a lower temperature, and a further stretching stage is connected. This means that the stretching speeds can be reduced overall and the material can be stretched sufficiently gently.
  • the post-stretching c3) is carried out at temperatures above 150 ° C., preferably between 180 ° C. and 240 ° C., in hot gaseous media (hot air), with a higher degree of crystallinity than after the stretching at the lower temperatures (stages c1) and c2 )) is reached. It was found that the filament tempera tur during the stretching according to step 3) passes through that temperature range in which the half-life of the crystallization has a minimum and thus takes place particularly quickly and effectively. Post-drawing by contact hot drawing (eg over metal plates) is usually less effective and also leads to uneven treatment (especially with thicker filaments).
  • the multiple stretching can be carried out continuously or discontinuously with an interruption after the two-stage stretching at a low temperature, but is preferably carried out continuously.
  • Continuous drawing results in short dwell times (e.g. 0.4 to 0.7 seconds) in the high-temperature drawing field due to the limited dimensions of the apparatus.
  • the material strength can be further improved.
  • the fixation can be combined with this drawing step because of the longer dwell time in the high-temperature drawing step.
  • the process is completed after stretching or fixing.
  • the multifilaments (given if several spinning positions, combined as a cable) a tension-free fixation and a cutting process.
  • Crimping of the material is possible with a mechanical, but preferably with a hydro- or aerodynamic process, the latter being the more gentle, preferred process.
  • a device is used for crimping, which emerges from a channel for the transport of filaments through a surrounding gas or. Steam flow exists, to which a rod cage concentrically connects as a stuffer box (eg DE 27 14 610 A1).
  • a sufficiently high crimp can be impressed on this material with a crimping nozzle under the action of hot air or saturated steam at a temperature of 100 ° C to 240 ° C, preferably from 140 ° C to 220 ° C. Since, with increasing shrinkage values of the drawn fibers, the crimp increases after the shrinkage is triggered, but the tensile strength decreases significantly, should the shrinkage should not be set to> 70%, preferably not more than 15%.
  • a subsequent tension-free fixation at a temperature of 150 ° C to 250 ° C and a residence time of 30 to 600 sec can improve the crimp.
  • FIG. 2 shows the dependence of the fiber strength and the residual crimp values on the fixing temperature.
  • the residual crimp values were determined in accordance with DIN 53 840; they result from where l2 is the crimped length at a voltage of 10 mN / dtex and l3 is the crimped length at a voltage of 0.1 mN / dtex following the load with 10 mN / dtex.
  • the residual crimp values increase continuously with the fixing temperature and can be increased from 4% to over 12% in the example shown with a fixing time of 300 sec. At very high fixing temperatures above 220 ° C, the residual crimp values increase even further, but the fiber strengths decrease too much.
  • the crimped tape produced in this way can be easily cut and processed into staple fibers of variable length on one cutting edge.
  • Essentially linear PPS connections to be used according to the invention can e.g. according to DE-A-3 428 984/5/6, which processes are characterized by polycondensation with the use of highly polar solvents.
  • the fibers by the process according to the invention can preferably be used in the technical sector, for example in hot gas dedusting, dry and wet filtration to dry felts for paper machines, in particular in the hot passage, friction linings, seals and packings, sewing threads and electrical applications in corresponding further technical fields of application.
  • Heat protection clothing can be constructed in the textile sector on the basis of polyarylene sulfide, in particular polyphenylene sulfide fibers.
  • the granules, dried at 140 ° C. for 4 hours, of an essentially linear poly-p-phenylene sulfide not exposed to a thermal curing process (produced by a process in highly polar solvents) with a melt viscosity of 90 Pa.s (measured at 306 ° C. and a shear rate of ⁇ 1/1000 s) is melted in an extruder at approx. 310 ° C, extruded through a single-hole nozzle with a bore diameter of 0.3 to 1.6 mm and quenched in a water bath.
  • the take-off speed is 100 m / min.
  • Example 2 The dried granules from Example 1 are melted in an extruder at approx. 310 ° C. and extruded through a 100-hole die.
  • a dried granulate of essentially linear poly-p-phenylene sulfide with a melt viscosity of 120 Pa.s is melted in an extruder at approx. 315 ° C and extruded through a 400-hole die.
  • the multifilament band is fed to a crimping nozzle, crimped at 150 ° C and then fixed without tension at 190 ° C before the cutting process with a dwell time of 240 sec.
  • the following individual fiber values result: Titer: 3.4 dtex Strength: 5.5 cN / dtex Elongation at break: 20% Boiling shrink: 0% Thermal shrink at 200 ° C: 4% Residual ripple: 10%
  • the fixation stabilizes the crimped threads against changes in length under the influence of temperature.
  • the wide-angle diagrams from various stages of PPS fiber production generally show that the spun material after spinning is amorphous and not oriented is.
  • the diffraction experiments on stretched and fixed PPS according to the invention show that this material is highly oriented and highly crystalline.
  • the filaments are re-drawn by 19% at an inlet speed of 30 m / min.
  • the optical birefringence on the highly oriented fiber is 0.468. This is a particularly high value, as it appears to be generally valid (> 0.460) for the high-strength fibers produced according to the invention.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
EP90108480A 1989-05-17 1990-05-05 Procédé pour la fabrication de mono- et multifilaments ou de fibres courtes de polyarylène-sulfide et fibres de polyarylène-sulfide à haute ténacité Expired - Lifetime EP0398094B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3916010 1989-05-17
DE3916010 1989-05-17
DE4006397A DE4006397A1 (de) 1989-05-17 1990-03-01 Verfahren zur herstellung von mono- und multifilamenten sowie stapelfasern auf basis von polyarylensulfiden, sowie hochfeste polyarylensulfid-fasern
DE4006397 1990-03-01

Publications (3)

Publication Number Publication Date
EP0398094A2 true EP0398094A2 (fr) 1990-11-22
EP0398094A3 EP0398094A3 (fr) 1991-10-23
EP0398094B1 EP0398094B1 (fr) 1995-12-27

Family

ID=25880946

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90108480A Expired - Lifetime EP0398094B1 (fr) 1989-05-17 1990-05-05 Procédé pour la fabrication de mono- et multifilaments ou de fibres courtes de polyarylène-sulfide et fibres de polyarylène-sulfide à haute ténacité

Country Status (4)

Country Link
US (1) US5024797A (fr)
EP (1) EP0398094B1 (fr)
JP (1) JPH0340812A (fr)
DE (2) DE4006397A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0574789A1 (fr) * 1992-06-18 1993-12-22 Hoechst Aktiengesellschaft Procédé pour la fabrication de fibres de polyphénylènesulfide et multifilaments ainsi obtenus
EP1834683A1 (fr) * 2006-03-14 2007-09-19 Diolen Industrial Fibers B.V. Tissu de support et élément filtrant le comprenant
EP2246463B1 (fr) * 2008-01-09 2017-03-22 Toray Industries, Inc. Fibre de poly(sulfure de phénylène) et son procédé de fabrication

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101142347B (zh) * 2005-03-18 2010-05-19 戴奥伦工业纤维有限公司 聚苯硫醚单丝纱的制造方法
JP5464813B2 (ja) * 2008-03-21 2014-04-09 旭化成せんい株式会社 耐熱性繊維不織布
EP2716800A4 (fr) * 2011-06-02 2014-11-05 Toray Industries Fibres de poly(sulfure de phénylène) et tissu non tissé
WO2015031591A1 (fr) 2013-08-29 2015-03-05 Teleflex Medical Incorporated Suture à éléments multiples à haute résistance

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE214471C (fr) *
US3898204A (en) * 1973-04-27 1975-08-05 Phillips Petroleum Co Production of fibers from phenylene sulfide polymers
US3895091A (en) * 1973-04-27 1975-07-15 Phillips Petroleum Co Production of fibers from phenylene sulfide polymers
US3912695A (en) * 1974-04-08 1975-10-14 Phillips Petroleum Co Fibrous articles from phenylene sulfide polymers
US4098776A (en) * 1976-05-28 1978-07-04 Phillips Petroleum Company Poly(arylene sulfide) fibers
DE2714610A1 (de) * 1977-04-01 1978-10-05 Karl Rabenseifner Belag zur digitalen-elektronischen weitenmessung beim kugelstossen
JPS5716954A (en) * 1980-06-27 1982-01-28 Toray Industries Long fiber nonwoven fabric comprising aromatic sulfide polymer fiber and method
JPS5818409A (ja) * 1981-07-24 1983-02-03 Toray Ind Inc ポリフエニレンスルフイド繊維の製造方法
DE3526066A1 (de) * 1985-07-20 1987-01-22 Bayer Ag Fasern und filamente aus polyarylensulfiden
DE3428984A1 (de) * 1984-08-07 1986-02-20 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von hochmolekularen, gegebenenfalls verzweigten polyarylensulfiden
EP0171021B1 (fr) * 1984-08-07 1993-07-21 Bayer Ag Poly(sulfures de phénylène), procédé pour la préparation de poly(sulfures de phénylène) et leur utilisation
US4645825A (en) * 1984-08-07 1987-02-24 Bayer Aktiengesellschaft Fibres and filaments of polyarylene sulphides
JPH0796724B2 (ja) * 1985-03-22 1995-10-18 呉羽化学工業株式会社 高物性ポリアリーレンチオエーテル繊維およびその製造法
DE3529501A1 (de) * 1985-08-17 1987-02-19 Bayer Ag Verfahren zur herstellung von hochmolekularen, gegebenenfalls verzweigten polyarylensulfiden
JPS62242517A (ja) * 1986-04-14 1987-10-23 Kureha Chem Ind Co Ltd ポリパラフェニレンスルフィド２軸延伸フィルム及びその製造方法
DE3788642T2 (de) * 1986-09-26 1994-05-19 Toray Industries Polyphenylensulfon-faser und verfahren zur herstellung.

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0574789A1 (fr) * 1992-06-18 1993-12-22 Hoechst Aktiengesellschaft Procédé pour la fabrication de fibres de polyphénylènesulfide et multifilaments ainsi obtenus
EP1834683A1 (fr) * 2006-03-14 2007-09-19 Diolen Industrial Fibers B.V. Tissu de support et élément filtrant le comprenant
EP2246463B1 (fr) * 2008-01-09 2017-03-22 Toray Industries, Inc. Fibre de poly(sulfure de phénylène) et son procédé de fabrication

Also Published As

Publication number Publication date
JPH0340812A (ja) 1991-02-21
DE4006397A1 (de) 1990-11-29
EP0398094B1 (fr) 1995-12-27
DE59009996D1 (de) 1996-02-08
US5024797A (en) 1991-06-18
EP0398094A3 (fr) 1991-10-23

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