EP1213376A1 - Non-postdrawn polyolefin fibers with high strength - Google Patents

Non-postdrawn polyolefin fibers with high strength 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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Prior art keywords
propylene
weight
polyolefin fibers
melt
postdrawn
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German (de)
French (fr)
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Borealis AG
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Borealis 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
    • D01F6/02—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)

Abstract

The invention relates to 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 µm, the fibers having tenacity values of 2,0 to 5,0 cN/dtex, a process for their production and their use.

Description

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).
Known methods for producing high tenacity fibers are oxidative chain scission degradation of hot spun fibers in conjunction with a delayed quench step (U.S. 5 281 378, US 5 318 735), the use of reactor-grade propylene polymers produced by single-site catalysis (EP 0 854 212) for producing the fibers, or the use of blends comprising of mixtures of propylene homopolymers, propylene copolymers and heterophasic propylene polymers being stabilized with organic phosphites, phenolic antioxidants or HALS-compounds for producing the fibers (EP 0 632 147). The disadvantage of these methods is, that non-postdrawn propylene polymer fibers having tenacity values of 2,0 to 5,0 cN/dtex cannot be realised.
It is the object of the present invention to provide non-postdrawn polyolefin fibers having strength values of 2,0 to 5,0 cN/dtex comprising of propylene polymers.
According to the present invention, this object is achieved by 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 µm, the fibers having tenacity values of 2,0 to 5,0 cN/dtex.
Preferably the predominantly isotactic propylene polymers are essentially consisting of
  • (a) 50 - 100 wt% propylene polymers, preferably propylene homopolymers, produced using Ziegler-Natta catalysts or metallocene catalysts, especially with an Mw/Mn ratio of 2 to 4.5, and/or copolymers of propylene, ethylene and/or α-olefins with 4 to 18 carbon atoms and a propy-lene content of 80.0 to 99.9% by weight in the form of random copolymers, block copolymers and/or random block copolymers, with a melt index of 0.5 to 40 g/10 min at 230°C/2.16 kg, preferably of 1 to 5 g/10 min at 230°C/2.16 kg,
  • (b) 0- 50 wt % of a polyolefin mixture with an Mw/Mn ratio of 2 to 6 and a melt index of 0,5 to 40 g/10 min at 230°C/2.16 kg, essentially consisting of
  • (b1) 60 to 98% by weight of a crystalline copolymer of 85 to 95% by weight of propylene and 15 to 0.5% by weight of ethylene and/or an α-olefin of the general formula CH2 = CHR, wherein R is a linear or branched alkyl group with 2 to 8 carbon atoms,
  • (b2) 2 to 40% by weight of an elastic copolymer of 20 to 70% by weight of ethylene and 80 to 30% by weight of propylene and/or an α-olefin of the general formula CH2CHR, wherein R is a linear or branched alkyl group with 2 to 8 carbon atoms,
  • (c) 0 - 30 wt% of highly amorphous polypropylenes or propylene copolymers with a crystalline poly-propylene or crystalline propylene copolymer content of less than 10% by weight, an enthalpy of melting of less than 40 J/g and a melt index of 0.5 to 40 g/10 min at 230°C/2.16 kg, the largely amorphous polypropylene being a homopolymer of propylene and/or a copolymer of propylene of at least 80 mole percent propylene and not more than 20 mol percent of one or more α-olefins of the general formula CH2CHR, wherein R is a linear or branched alkyl group with 2 to 8 carbon atoms,
  • (d) 0 - 10 wt% of non-isotactic propylene homopolymers with a melting point of 145° to 165°C, a melt viscosity of 200,000 cps at 190°C and a heat of crystallization of 4 to 10 calories per gram, 35 to 55% by weight being soluble in diethyl ether,
  • e) 0- 30 wt% of modified propylene homopolymers and/or propylene copolymers with melt indexes of 0.5 to 40 g/10 min at 230°C/2.16 kg and preferably of 2 to 5 g/10 min at 230°C/2.16 kg, and a ratio of the intrinsic viscosity of the modified propylene polymer to the intrinsic viscosity of the basic unmodified polymer (component a) with largely the same weight average molecular weight of 0,2 to 0,95.
    • 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).
    Examples for the 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.
    Examples for said modified propylene polymers e) optionally contained in the non-postdrawn polyolefin fibers, are, in particular:
    • polypropylenes modified by the reaction of polypropylenes with bismaleimido compounds in the melt (EP-A-0 574 801; EP-A-0 574 804),
    • polypropylenes modified by the treatment of polypropylenes with ionizing radiation in the solid phase (EP-A-0 190 889; EP-A-0 634 454),
    • polypropylenes modified by the treatment of polypropylenes with peroxides in the solid phase (EP-A-0-384 431) or in the melt (EP-A-0-142724),
    • polypropylenes modified by the treatment of polypropylenes with multifunctional, ethylenically unsaturated monomers using ionizing radiation (EP-A-0 678 527)
    • polypropylenes modified by the treatment of polypropylenes with multifunctional, ethylenically unsaturated monomers in the presence of peroxides in the melt (EP-A-0 688 817; EP-A-0 450 342).
    These modified polypropylene polymers normally exhibit strain hardening behaviour as usually defined in the literature.
    Preferred inorganic oxides are Al2O3 and/or SiO2 having a particle diameter of about 0,5 to 2 µm.
    According to a further embodiment, 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).
    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-cyl 3(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris(3',5'-di-t-bu-tyl-4-hydroxybenzyl)benzene and/or pentaerythritol-tetrakis-3-(3,5-di-t-butyl-4-hydroxyphenyl)pro-pionate.
    As benzofuranone derivative, 5,7-di-t-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, in particular, is suitable.
    As HALS compounds, 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.
    As processing aids, 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 µm, 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.
    As 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 102 /sec to 103/sec by controlling the temperature and the rpm.
    For uniformly metering the mixtures, which has been melted in the plasticising extruder, over the melt distributor to the capillary die, melt pumps, preferably heated with biphenyl, are used for the melts, heated to 240° to 310°C.
    According to a feature of the present invention, 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.
    Examples
    For the production of polyolefin fibers, which are not drawn subsequently, the inventive method is explained, by way of example, by a method outlined in fig. 1. In Figure 1, 1 is the extruder, 2 the extrusion pump, 3 the spinnert, 4 the blast shaft, 5 the pull-off equipment and 6 the winder
    As 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. In the pull-off equipment (5), the pulling-off can be accomplished directly by means of the winder (6). Possible pull-off speeds are 1,000 to 6000 m/min.
    Example 1
    For producing a polyolefin polymer blend with inorganic oxides, 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 SiO2 and 0,05% by weight of Al2O3, having particle diameters of 0,1 to 2 µm, 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 extruder and granulated.
    In the spinning equipment of Figure 1, 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%.
    Example 2
    For producing a polyolefin polymer blend with inorganic oxides, 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 SiO2, 0,05% by weight of TiO2 and 0,05% by weight of Al2O3, having particle diameters of 0,15 to 3,5 µm, 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-butyl-4-hydroxyphenyl)propionate, 0.2% by weight of bis-2,2,6,6-tetramethyl-4-piperidyl sebacate and 0.2% by weight of magnesium stearate, is melt blended at a melt temperature of 220°C in a twin screw extruder and granulated.
    In the spinning equipment of Figure 1, 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%.
    Example 3
    For producing a polyolefin polymer blend with inorganic oxides, 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 SiO2, 0,02% by weight of ZrO2 and 0,02% by weight of MgO, having particle diameters of 0,2 to 4 µm, 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-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 extruder and granulated.
    In the spinning equipment of Figure 1, 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%.

    Claims (10)

    1. 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 µm, the fibers having tenacity values of 2,0 to 5,0 cN/dtex.
    2. Non-postdrawn polyolefin fibers as claimed in claim 1, wherein said predominantly isotactic propylene polymers are essentially consisting of
      (c) 50 - 100 wt% propylene polymers, preferably propylene homopolymers, produced using Ziegler-Natta catalysts or metallocene catalysts, especially with an Mw/Mn ratio of 2 to 4.5, and/or copolymers of propylene, ethylene and/or α-olefins with 4 to 18 carbon atoms and a propylene content of 80.0 to 99.9% by weight in the form of random copolymers, block copolymers and/or random block copolymers, with a melt index of 0.5 to 40 g/10 min at 230°C/2.16 kg, preferably of 1 to 5 g/10 min at 230°C/2.16 kg,
      (d) 0- 50 wt % of a polyolefin mixture with an Mw/Mn ratio of 2 to 6 and a melt index of 0,5 to 40 g/10 min at 230°C/2.16 kg, essentially consisting of
      (b1) 60 to 98% by weight of a crystalline copolymer of 85 to 95% by weight of propylene and 15 to 0.5% by weight of ethylene and/or an α-olefin of the general formula CH2 = CHR, wherein R is a linear or branched alkyl group with 2 to 8 carbon atoms,
      (b2) 2 to 40% by weight of an elastic copolymer of 20 to 70% by weight of ethylene and 80 to 30% by weight of propylene and/or an α-olefin of the general formula CH2CHR, wherein R is a linear or branched alkyl group with 2 to 8 carbon atoms,
      (c) 0 - 30 wt% of highly amorphous polypropylenes or propylene copolymers with a crystalline poly-propylene or crystalline propylene copolymer content of less than 10% by weight, an enthalpy of melting of less than 40 J/g and a melt index of 0.5 to 40 g/10 min at 230°C/2.16 kg, the largely amorphous polypropylene being a homopolymer of propylene and/or a copolymer of propylene of at least 80 mole percent propylene and not more than 20 mol percent of one or more α-olefins of the general formula CH2CHR, wherein R is a linear or branched alkyl group with 2 to 8 carbon atoms,
      (d) 0 - 10 wt% of non-isotactic propylene homopolymers with a melting point of 145° to 165°C, a melt viscosity of 200,000 cps at 190°C and a heat of crystallization of 4 to 10 calories per gram, 35 to 55% by weight being soluble in diethyl ether,
      (e) 0- 30 wt% of modified propylene homopolymers and/or propylene copolymers with melt indexes of 0.5 to 40 g/10 min at 230°C/2.16 kg and preferably of 2 to 5 g/10 min at 230°C/2.16 kg, and a ratio of the intrinsic viscosity of the modified propylene polymer to the intrinsic viscosity of the basic unmodified polymer (component a) with largely the same weight average molecular weight of 0,2 to 0,95.
    3. Non postdrawn polyolefin fibers as claimed in claim 2 , wherein the polymers of component a have a melt flow index of 1 to 5 g/10 min at 230°C/2.16 kg,
    4. Non-postdrawn polyolefin fibers as claimed in one of the claims 1 to 3, wherein said predominantly isotactic propylene polymers contain 20 to 40 ppm particles of inorganic oxides selected from the group of ZnO, SnO, MgO, Al2O3, SiO2, TiO2, ZrO2 and/or HfO2.
    5. Non-postdrawn polyolefin fibers of any one of the claims 1 to 4, wherein said par-tides of inorganic oxides are Al2O3 and/or SiO2 and/or MgO having a particle diameter of about 0,5 to 2 µm.
    6. Non-postdrawn polyolefin fibers of any one of the claims 1 to 5, further comprising conventional additives such as 0.01 to 2.5% by weight of stabilizers, 0.01 to 1% by weight of processing aids and, optionally, 0. 1 to 1 % by weight of antistatic agents, 0.2 to 3 % by weight of pigments and 2 to 20% by weight of flame retardants, in each case based on the sum of the polypropylenes.
    7. Process for preparing 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 µm, 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.
    8. Process as claimed in claim 7, characterized in that the inorganic oxides are selected from the group of ZnO, SnO, MgO, Al2O3, SiO2, TiO2, ZrO2 and/or HfO2.
    9. Process for preparing non-postdrawn polyolefin fibers as claimed in claim 7, charac-terized in taking up the resulting hot spun fiber by high speed galettes, cabling the fibers into multifilament yarns and winding up the non-postdrawn polyolefin fibers containing yarns.
    10. Use of non-postdrawn polyolefin fibers of any one of the claims 1 to 6 for manufac-turing of nonwovens, preferred spunbond, carded or air bonded nonwovens for textile appli-cations and carpets.
    EP00126835A 2000-12-07 2000-12-07 Non-postdrawn polyolefin fibers with high strength Withdrawn EP1213376A1 (en)

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    Cited By (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    CN104862804A (en) * 2015-06-03 2015-08-26 马海燕 High-strength wear-resistant polypropylene monofilament and production method thereof

    Citations (6)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP0569860A1 (en) * 1992-05-15 1993-11-18 Kimberly-Clark Corporation Durable nonwoven fabric
    EP0790262A1 (en) * 1995-08-31 1997-08-20 Chisso Corporation Propylene-ethylene copolymer compositions and process for the production thereof
    EP0854155A1 (en) * 1996-07-31 1998-07-22 Japan Polyolefins Co., Ltd. Highly crystalline polypropylene
    EP0878567A2 (en) * 1997-05-14 1998-11-18 PCD Polymere AG Polyolefin fibres and polyolefin yarns and textile materials thereof
    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 (en) * 1992-05-15 1993-11-18 Kimberly-Clark Corporation Durable nonwoven fabric
    EP0790262A1 (en) * 1995-08-31 1997-08-20 Chisso Corporation Propylene-ethylene copolymer compositions and process for the production thereof
    EP0854155A1 (en) * 1996-07-31 1998-07-22 Japan Polyolefins Co., Ltd. Highly crystalline polypropylene
    EP0878567A2 (en) * 1997-05-14 1998-11-18 PCD Polymere AG Polyolefin fibres and polyolefin yarns and textile materials thereof
    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 (en) * 2015-06-03 2015-08-26 马海燕 High-strength wear-resistant polypropylene monofilament and production method thereof

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