EP1213376A1 - Nicht nachverstreckte Polyolefinfasern mit hoher Festigkeit - Google Patents

Nicht nachverstreckte Polyolefinfasern mit hoher Festigkeit Download PDF

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Publication number
EP1213376A1
EP1213376A1 EP00126835A EP00126835A EP1213376A1 EP 1213376 A1 EP1213376 A1 EP 1213376A1 EP 00126835 A EP00126835 A EP 00126835A EP 00126835 A EP00126835 A EP 00126835A EP 1213376 A1 EP1213376 A1 EP 1213376A1
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EP
European Patent Office
Prior art keywords
propylene
weight
polyolefin fibers
melt
postdrawn
Prior art date
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Withdrawn
Application number
EP00126835A
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English (en)
French (fr)
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designation of the inventor has not yet been filed The
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Borealis AG
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Borealis AG
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Publication date
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Priority to EP00126835A priority Critical patent/EP1213376A1/de
Publication of EP1213376A1 publication Critical patent/EP1213376A1/de
Withdrawn legal-status Critical Current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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins

Definitions

  • the invention relates to non-postdrawn polyolefin fibers with high strength from propylene polymers as well as to a process for producing them.
  • Fibers from propylene polymers are known (Ullmann's Encyclopedia of Industrial Chemistry, Vol. A10, p. 536-542, Weinheim 1987).
  • Non-postdrawn polyolefin fibers with high strength comprising predominantly isotactic propylene polymers having a crystallisation temperature >116°C (DSC) and 5 to 100 ppm particles of inorganic oxides, having a particle diameter of about 0,05 to 10 ⁇ m, the fibers having tenacity values of 2,0 to 5,0 cN/dtex.
  • the predominantly isotactic propylene polymers are essentially consisting of
  • the polyolefin mixtures b) of crystalline copolymers and elastic copolymers, optionally contained in the non-postdrawn polyolefin fibers, are polymer mixtures described, for example, in the European patents 0 400 333 or 0 472 946.
  • the largely amorphous polypropylenes or propylene copolymers c), optionally contained in the non-postdrawn polyolefin fibers are, in particular, stereo block polypropylenes, which are prepared, for example, by using highly active Ziegler-Natta catalysts fixed on a metal oxide (Collette, J., Macromolecules 22 (1989), 3851 - 3858; German patent 28 30 160) or soluble Ziegler-Natta catalysts (de Candia, F., Makromol. Chem. 189 (1988), 815 - 821), optionally with subsequent reactive modification (European patent 636863) and/or degradation (European patent 640 850).
  • highly active Ziegler-Natta catalysts fixed on a metal oxide Coldlette, J., Macromolecules 22 (1989), 3851 - 3858; German patent 28 30 160
  • soluble Ziegler-Natta catalysts de Candia, F., Makromol. Chem. 189 (1988), 815 - 8
  • non-isotactic propylene homopolymers d optionally contained in the non-postdrawn polyolefin fibers are the products described p.e. in the European patent 0 475 307 or in the European patent 0 475 308.
  • the modified propylene polymers e) optionally contained in the non-postdrawn polyolefin fibers can be produced by any number of processes, e.g. by treatment of the unmodified propylene polymer with thermal decomposing radical-forming agents and/or by treatment with ionizing radiation, where both treatments may optionally be accompanied or followed by a treatment with bi- or multifunctionally unsaturated monomers, e.g. butadiene, isoprene, dimethylbutadiene or divinylbenzene. Further processes may be suitable for the production of the modified propylene polymer, provided that the resulting modified propylene polymer meets the characteristics given above.
  • modified propylene polymers e) optionally contained in the non-postdrawn polyolefin fibers are, in particular:
  • Preferred inorganic oxides are Al 2 O 3 and/or SiO 2 having a particle diameter of about 0,5 to 2 ⁇ m.
  • the auxiliary materials are 0.01 to 2.5% by weight of stabilizers, and/or 0.01 to 1% by weight of processing aids and/or optionally, 0. 1 to 1 % by weight of antistatic agents, and/or 0.2 to 3 % by weight of pigments and/or 2 to 20% by weight of flame retardants, in each case based on the sum of the polypropylenes.
  • the stabilizers, contained in the inventive non-postdrawn polyolefin fibers preferably are mixtures of 0.01% to 0.6% by weight of phenolic antioxidants, 0.01% to 0.6% by weight of 3-arylbenzofuranones, 0.01% to 0.6% by weight of processing stabilizers based on phosphites, 0.01 % to 0.6% by weight of high temperature stabilizers based on disulfides and thioethers and/or 0.01% to 0.8% by weight of sterically hindered amines (HALS).
  • HALS sterically hindered amines
  • Suitable phenolic antioxidants are 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-isoamylphenol, 2,6-di-t-butyl-4-ethylphenol, 2-t-butyl-4,6-diisopro-pylphenol, 2,6-dicyclopentyl-4-methylphenol, 2,6-di-t-butyl-4--methoxymethylphenol, 2-t-butyl-4,6-dioctadecylphenol, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-4,4-hexadecyloxyphe-nol, 2,2'-methylene-bis(6-t-butyl-4-methylphenol), 4,4'--thio-bis-(6-t-butyl-2-methylphenol), octade-
  • bis-2,2,6,6-tetramethyl-4-piperidyl sebacate and/or poly-1,1,3,3-tetra-methylbutyl)-imino)-1,3,5-triazine-2,4-diyl)(2,2,6,6-tetramethylpiperidyl)-amino)-hexamethyle-ne-4-(2,2,6,6-tetramethyl)piperidyl)-imino) are particularly suitable.
  • the inventive non-postdrawn polyolefin fibers may contain calcium stea-rate, magnesium stearate and/or waxes.
  • a still further object of the present invention is a non-postdrawn polyolefin fibers with high strength in melt spinning lines comprising of plastification extruder, melt distributor, metering pumps, spinnerets, quench box and take up device by melting of propylene polymers at temperatures of about 220 to 325°C, conveying the melt by metering pumps to the spinnerets, extrusion into the quench box and taking up the resulting hot spun fiber, characterized in that non-postdrawn polyolefin fibers comprise predominantly isotactic propylene polymers and 5 to 100 ppm particles of inorganic oxides, having a particle diameter of about 0,05 to 10 ⁇ m, the fibers being spun at spinning speed s of 1000 -6000 m/min and having tenacity values of 2,0 to 5,0 cN/dtex.
  • plasticising extruder for melting the mixtures especially single screw extruders or twin screw extruders with screw length of 28 to 30 D, preferably with flange-mounted static or dynamic mixers, are suitable. Sheer speeds can be adjusted to values of 10 2 /sec to 10 3 /sec by controlling the temperature and the rpm.
  • melt pumps preferably heated with biphenyl, are used for the melts, heated to 240° to 310°C.
  • the resulting hot spun fibers are taking up by high speed galettes, cabling the fibers into multifilament yarns and winding up the non-postdrawn polyolefin fibers containing yarns.
  • Preferred applications of the non-postdrawn polyolefin fibers are the manufacturing of nonwovens, preferred spunbond, carded or air bonded nonwovens; textile applications, or carpets.
  • extruder (1) for melting the polyolefin mixtures a single screw extruder is used with a high homogenizing effect having a screw length of 34 D with a flange-mounted static mixer.
  • the spinneret (3) has an internal diameter of 0.5 mm.
  • the pulling-off can be accomplished directly by means of the winder (6). Possible pull-off speeds are 1,000 to 6000 m/min.
  • a dry mixture consisting of 99% by weight of a metallocene propylene homopolymer (melt index of 6.2 g/10 minutes at 230°C/2.16 kg), 1% by weight of a propylene ethylene copolymer (melt index of 12 g/10 minutes at 230°C/2.16 kg, ethylene content 4,8% by weight) with fine dispersed 0,55% by weight of SiO 2 and 0,05% by weight of Al 2 O 3 , having particle diameters of 0,1 to 2 ⁇ m, and as adjuvants, the percentages in each case based on the sum of the propylene polymers, 0.25% by weight of 2-t-butyl-4,6-diisopropylphenol, 0.2% by weight of bis-2,2,6,6-tetramethyl-4-piperidyl sebacate and 0.2% by weight of calcium stearate, is melt blended at a melt temperature of 225°C in a twin screw
  • the blend is melted in the extruder at a mass tem-perature of 275 °C.
  • the melt is transferred by the extrusion pump to the spinneret and, at a spinneret temperature of 290°C, drawn off through the blast shaft, which is cooled with compressed air at a temperature of 20°C, and wound up at a speed of 4000 m/min.
  • the resulting polypropylene fiber which is not postdrawn, has a tenacity of 2.5 cN/dtex and a tensile elongation of 175%.
  • a dry mixture consisting of 95% by weight of a metallocene propylene homopolymer (melt index of 6.2 g/10 minutes at 230°C/2.16 kg), 4,5% by weight of a random heterophasic propylene ethylene blockco-polymer (melt index of 8 g/10 minutes at 230°C/2.16 kg, ethylene content 33 mol%) 0,5% by weight of a propylene ethylene copolymer (melt index of 12 g/10 minutes at 230°C/2.16 kg, ethylene content 4,8% by weight) with fine dispersed 0,50% by weight of SiO 2 , 0,05% by weight of TiO 2 and 0,05% by weight of Al 2 O 3 , having particle diameters of 0,15 to 3,5 ⁇ m, and as adjuvants, the percentages in each case based on the sum of the propylene poly-mers, 0.25% by weight of 3(3,5-di-t-buty
  • the blend is melted in the extruder at a mass tem-perature of 270 °C.
  • the melt is transferred by the extrusion pump to the spinneret and, at a spinneret temperature of 285°C, drawn off through the blast shaft, which is cooled with compressed air at a temperature of 20°C, and wound up at a speed of 3500 m/min.
  • the resulting polypropylene fiber which is not postdrawn, has a tenacity of 2.2 cN/dtex and a tensile elongation of 210%.
  • a dry mixture consisting of 95% by weight of a metallocene propylene homopolymer (melt index of 6.2 g/10 minutes at 230°C/2.16 kg), 4,8% of a propylene homopolymer having strain hardening behavior (melt index of 3,5 g/10 minutes at 230°C/2.16 kg, strain hardening according to modified propylene polymer 7 in figure 2), 0,2% by weight of a propylene homopolymer (melt index of 10,5 g/10 minutes at 230°C/2.16 kg) with fine dispersed 0,15% by weight of SiO 2 , 0,02% by weight of ZrO 2 and 0,02% by weight of MgO, having particle diameters of 0,2 to 4 ⁇ m, and as adju-vants, the percentages in each case based on the sum of the propylene polymers, 0.25% by weight of 2-t-butyl-4,6-diisopropyl
  • the blend is melted in the extruder at a mass tem-perature of 285 °C.
  • the melt is transferred by the extrusion pump to the spinneret and, at a spinneret temperature of 290°C, drawn off through the blast shaft, which is cooled with compressed air at a temperature of 20°C, and wound up at a speed of 3000 m/min.
  • the resulting polypropylene fiber which is not postdrawn, has a tenacity of 2.05 cN/dtex and a tensile elongation of 220%.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
EP00126835A 2000-12-07 2000-12-07 Nicht nachverstreckte Polyolefinfasern mit hoher Festigkeit Withdrawn EP1213376A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP00126835A EP1213376A1 (de) 2000-12-07 2000-12-07 Nicht nachverstreckte Polyolefinfasern mit hoher Festigkeit

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Application Number Priority Date Filing Date Title
EP00126835A EP1213376A1 (de) 2000-12-07 2000-12-07 Nicht nachverstreckte Polyolefinfasern mit hoher Festigkeit

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104862804A (zh) * 2015-06-03 2015-08-26 马海燕 高强耐磨聚丙烯单丝及其生产方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0569860A1 (de) * 1992-05-15 1993-11-18 Kimberly-Clark Corporation Dauerhafter Vliesstoff
EP0790262A1 (de) * 1995-08-31 1997-08-20 Chisso Corporation Äthylen-propylencopolymerzusammensetzungen und verfahren zu ihrer herstellung
EP0854155A1 (de) * 1996-07-31 1998-07-22 Japan Polyolefins Co., Ltd. Hochkristallines polypropylen
EP0878567A2 (de) * 1997-05-14 1998-11-18 PCD Polymere AG Polyolefinfasern und Polyolefingarne und daraus hergestellte textile Flächengebilde
WO1999024478A1 (en) * 1997-11-07 1999-05-20 Borealis A/S Process for preparing polypropylene
WO1999024479A1 (en) * 1997-11-07 1999-05-20 Borealis A/S Novel propylene polymers and products thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0569860A1 (de) * 1992-05-15 1993-11-18 Kimberly-Clark Corporation Dauerhafter Vliesstoff
EP0790262A1 (de) * 1995-08-31 1997-08-20 Chisso Corporation Äthylen-propylencopolymerzusammensetzungen und verfahren zu ihrer herstellung
EP0854155A1 (de) * 1996-07-31 1998-07-22 Japan Polyolefins Co., Ltd. Hochkristallines polypropylen
EP0878567A2 (de) * 1997-05-14 1998-11-18 PCD Polymere AG Polyolefinfasern und Polyolefingarne und daraus hergestellte textile Flächengebilde
WO1999024478A1 (en) * 1997-11-07 1999-05-20 Borealis A/S Process for preparing polypropylene
WO1999024479A1 (en) * 1997-11-07 1999-05-20 Borealis A/S Novel propylene polymers and products thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104862804A (zh) * 2015-06-03 2015-08-26 马海燕 高强耐磨聚丙烯单丝及其生产方法

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