EP1213376A1 - Non-postdrawn polyolefin fibers with high strength - Google Patents
Non-postdrawn polyolefin fibers with high strength Download PDFInfo
- 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
- Authority
- EP
- European Patent Office
- Prior art keywords
- propylene
- weight
- polyolefin fibers
- melt
- postdrawn
- 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.)
- Withdrawn
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- 239000000835 fiber Substances 0.000 title claims abstract description 48
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 35
- 229920001155 polypropylene Polymers 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 16
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- -1 propylene, ethylene Chemical group 0.000 claims description 25
- 239000004743 Polypropylene Substances 0.000 claims description 24
- 239000000155 melt Substances 0.000 claims description 22
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 20
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 14
- 229920001384 propylene homopolymer Polymers 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 238000009987 spinning Methods 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 238000002074 melt spinning Methods 0.000 claims description 2
- 239000012968 metallocene catalyst Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 238000004804 winding Methods 0.000 claims description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- 239000000654 additive Substances 0.000 claims 1
- 229940095050 propylene Drugs 0.000 description 11
- 238000011282 treatment Methods 0.000 description 8
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 4
- 229920002959 polymer blend Polymers 0.000 description 4
- 229940116351 sebacate Drugs 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002671 adjuvant Substances 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 229940078456 calcium stearate Drugs 0.000 description 3
- 230000005865 ionizing radiation Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 238000005482 strain hardening Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- DQCLZKINSGKBFP-UHFFFAOYSA-N 2-tert-butyl-4,6-di(propan-2-yl)phenol Chemical compound CC(C)C1=CC(C(C)C)=C(O)C(C(C)(C)C)=C1 DQCLZKINSGKBFP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
- FRAQIHUDFAFXHT-UHFFFAOYSA-N 2,6-dicyclopentyl-4-methylphenol Chemical compound OC=1C(C2CCCC2)=CC(C)=CC=1C1CCCC1 FRAQIHUDFAFXHT-UHFFFAOYSA-N 0.000 description 1
- WUHPLKWATBYDFS-UHFFFAOYSA-N 2,6-ditert-butyl-4-(3-methylbutyl)phenol Chemical compound CC(C)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WUHPLKWATBYDFS-UHFFFAOYSA-N 0.000 description 1
- SCXYLTWTWUGEAA-UHFFFAOYSA-N 2,6-ditert-butyl-4-(methoxymethyl)phenol Chemical compound COCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SCXYLTWTWUGEAA-UHFFFAOYSA-N 0.000 description 1
- NOLLYPZAEJVJBX-UHFFFAOYSA-N 2-tert-butyl-4,6-dioctadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC(CCCCCCCCCCCCCCCCCC)=C(O)C(C(C)(C)C)=C1 NOLLYPZAEJVJBX-UHFFFAOYSA-N 0.000 description 1
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 description 1
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical class C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 description 1
- CWTMUDGIRYDDHJ-UHFFFAOYSA-N 4-hexadecoxyphenol Chemical compound CCCCCCCCCCCCCCCCOC1=CC=C(O)C=C1 CWTMUDGIRYDDHJ-UHFFFAOYSA-N 0.000 description 1
- CYHYIIFODCKQNP-UHFFFAOYSA-N 5,7-ditert-butyl-3-(3,4-dimethylphenyl)-3h-1-benzofuran-2-one Chemical compound C1=C(C)C(C)=CC=C1C1C(C=C(C=C2C(C)(C)C)C(C)(C)C)=C2OC1=O CYHYIIFODCKQNP-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- CJSBUWDGPXGFGA-UHFFFAOYSA-N dimethyl-butadiene Natural products CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Images
Classifications
-
- 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
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.
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.
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%.
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%.
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)
- 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.
- 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.
- 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,
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP00126835A EP1213376A1 (en) | 2000-12-07 | 2000-12-07 | Non-postdrawn polyolefin fibers with high strength |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP00126835A EP1213376A1 (en) | 2000-12-07 | 2000-12-07 | Non-postdrawn polyolefin fibers with high strength |
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| Publication Number | Publication Date |
|---|---|
| EP1213376A1 true EP1213376A1 (en) | 2002-06-12 |
Family
ID=8170599
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| Application Number | Title | Priority Date | Filing Date |
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| EP00126835A Withdrawn EP1213376A1 (en) | 2000-12-07 | 2000-12-07 | Non-postdrawn polyolefin fibers with high strength |
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Cited By (1)
| 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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| 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 |
| WO1999024479A1 (en) * | 1997-11-07 | 1999-05-20 | Borealis A/S | Novel propylene polymers and products thereof |
| WO1999024478A1 (en) * | 1997-11-07 | 1999-05-20 | Borealis A/S | Process for preparing polypropylene |
-
2000
- 2000-12-07 EP EP00126835A patent/EP1213376A1/en not_active Withdrawn
Patent Citations (6)
| 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 |
| WO1999024479A1 (en) * | 1997-11-07 | 1999-05-20 | Borealis A/S | Novel propylene polymers and products thereof |
| WO1999024478A1 (en) * | 1997-11-07 | 1999-05-20 | Borealis A/S | Process for preparing polypropylene |
Cited By (1)
| 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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