EP1356142A1 - Non-postdrawn polyolefin fibers with high tenacity - Google Patents
Non-postdrawn polyolefin fibers with high tenacityInfo
- Publication number
- EP1356142A1 EP1356142A1 EP01991772A EP01991772A EP1356142A1 EP 1356142 A1 EP1356142 A1 EP 1356142A1 EP 01991772 A EP01991772 A EP 01991772A EP 01991772 A EP01991772 A EP 01991772A EP 1356142 A1 EP1356142 A1 EP 1356142A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- propylene
- polymers
- polyolefin fibers
- fibers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- D01F6/44—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
-
- 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
- D01F6/02—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
Definitions
- the invention relates to non-postdrawn polyolefin fibers with high tenacity 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 consisting 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.
- non-postdrawn polyolefin fibers consisting essentially of predominantly isotactic propylene polymers having a crystallisation temperature of > 116 °C (DSC) and 0,001 to 2 % by weight, based on the propylene polymers used, of ⁇ -nucleating agents which are selected from the group consisting of polymers which are different from isotactic propylene polymers, which are selected from the group consisting of tetrafluoroethylene polymers, polycarbonates, polybutyleneterephthalate, polyethyleneterephthalate, 3-methylbutene polymers, 4-methylpentene-1 - polymers, syndiotactic propylene polymers, polyphenyleneoxides, propylene-methylbutene copolymers, styrene-acrylonitrile copolymers, polyallyltrimethylsilanes and hydrolysed ethylene vinylacetate copolymers, and benzoic acid, benzoic acid
- the predominantly isotactic propylene polymers are essentially consisting of
- 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 ⁇ -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 melt indexes of 0.5 to 40 g/10 min at 230 °C/2.16 kg and preferably of 1 to 5 g/10 min at 230 °C/2.16 kg,
- 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.
- 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 0400333 or 0472 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 640850).
- 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 - 821
- non-isotactic propylene homopolymers d optionally contained in the non-postdrawn polyolefin fibers are the products described p.e. in the European patent 0 475307 or in the European patent 0475308.
- 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 :
- modified polypropylenes have 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.
- modified poylpropylene polymers normally exhibit strain hardening behaviour as usually defined in the literature.
- tetrafluoroethylene polymers optionally contained in the non-postdrawn poly-olefin fibers, are polytetrafluoroethylene, tetrafluoroethylene propylene copolymers and tetrafluoroethylene isobutylene copolymers.
- polycarbonates optionally contained in the non-postdrawn polyolefin fibers
- polycarbonates are poly(4,4'-isopropylidenediphenylene carbonate) and copolycondensates based on 4,4'-isopropylidenebisphenol, 4,4'-tetrabromoisopropylidenebisphenol and/or 4,4'- hexabromoiso-propylidenebisphenol.
- polyphenyleneoxides optionally contained in the non-postdrawn polyolefin fibers, are poly-2,6-dimethylphenyleneoxide, poly-2,6-diisopropylphenyleneoxide or poly- 2,6-diphenylphenyleneoxide.
- C 7 -C 13 benzoic acid derivatives optionally contained in the non-postdrawn polyolefin fibers, are benzoic anhydride, o-toluic acid and 2,6-dimethylbenzoic acid.
- sorbitol derivatives optionally contained in the non-postdrawn polyolefin fibers, are di-(p-methylbenzylidene) sorbitol, trinaphthylidenesorbitol and naphthylmethylenesorbitol.
- salts of C 7 -C 13 aromatic carbonic acids are sodium benzoate and tertiary- butylbenzoic acid aluminium salt.
- a preferred aromatic carbonic acid is sodium benzoate.
- Examples for phosphoric acid derivatives are ammonium polyphosphate, cyclic calcium phosphate compounds, sodium-2,2'-methylenebis-(4,6-di-tert.-butylphenyl)phosphate and bis-(tertiary-butyl) phos-phoric acid sodium salt.
- a preferred cyclic calcium phosphate compound, optionally contained in the non- postdrawn polyolefin fibers, is bis(2,6-di-tert.butyl-1-hydroxy)methane calcium phosphate.
- a further ⁇ -nucleation method, which is also suitable, is a special reactor technique, where the catalyst is prepolymerised with monomers like vinylcyclohexane (VCH). This method is described in greater detail in e.g. EP 0316 187 A2.
- Preferred 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-methyl- phenol, 2,6-di-t-butyl-4-isoamylphenol, 2,6-di-t-butyl-4-ethyIphenol, 2-t-butyl-4,6-diisopro- pylphenol, 2,6-dicyclopentyI-4-methylphenol, 2,6-di-t-butyl-4-methoxymethyIphenol, 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-methyIphenol), 4,4'-thio-bis-(6-t-butyl- 2-methylphen
- 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-tetrar ⁇ ethyl)piperidyl)-imino) are particularly suitable.
- the inventive non-postdrawn polyolefin fibers may contain calcium stea-rate, magnesium stearate and/or waxes.
- the predominantly isotactic propylene polymers comprise from 5 - 100 ppm of particles of inorganic oxides having a particle diameter from about 0.05 - 10 ⁇ m.
- Inorganic oxides selected from the group consisting of ZnO, SnO, MgO, AI 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , HfO 2 and mixtures thereof in amounts of from 20 -40 ppm are preferred. Still more preferred are particles of inorganic oxides of AI 2 O 3 and/or SiO 2 and/or MgO having a particle diameter from about 0.5 to 2.0 ⁇ m.
- a still further object of the present invention is a process for preparing the inventive non- postdrawn polyolefin fibers having tenacity values of 2,0 to 5,0 cN/dtex , characterized by melting of predominantly isotactic propylene polymers having a crystallisation temperature of > 116 °C (DSC) and 0,001 to 2 % by weight, based on the propylene polymers used, of ⁇ -nucleating agents which are selected from the group consisting of polymers which are different from isotactic propylene polymers, which are selected from the group consisting of tetrafluoroethylene polymers, polycarbonates, polybutyleneterephthalate, polyethyleneterephthalate, 3-methylbutene polymers, 4-methylpentene-1 - polymers, syndiotactic propylene polymers, polyphenyleneoxides, propylene-methylbutene copolymers, styrene-acrylonitrile copolymers, polyallyltrimethyls
- 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
- the melts heated to 240° to 310 °C.
- the resulting hot spun fibers are taken up by high speed galettes, cabling the fibers into multifilament yarns and winding up the non- postdrawn polyolefin fibers-containing yarns.
- non-postdrawn polyolefin fibers are the manufacturing of nonwovens, preferred spunbond, carded or air bonded nonwovens; textile applications, carpets.
- T is the extruder
- 2 the extrusion pump
- 3 the spinneret
- 4 the blast shaft
- 5 the pull-off equipment
- 6 the winder.
- extruder (1 ) for melting the polyolefin mixtures a single screw extruder is used with a high homogenizing effect with a screw length of 34 D and 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 1000 to 6000 m/min.
- the melt indices for propylene polymers were measured with a load of 2.16 kg at 230 °C.
- the melt index is that quantity of polymer in grams which the test apparatus standardized to DIN 53735 extrudes within 10 minutes at a temperature of 230 °C under a weight of 2.16 kg.
- a dry mixture consisting of 85 % by weight of a metallocene propylene homopolymer (melt index of 6.2 g/10 minutes at 230 °C/2.16 kg), 13 % by weight of a propylene ethylene copolymer (melt index of 4,2 g/10 minutes at 230 °C/2.16 kg, ethylene content 4,8 % by weight), 2 % by weight of a 4-methylpentene-1 propylene copolymer (melt index of 0,25 g/10 minutes at 230 °C/5 kg, propylene content 6,8 % by weight), 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
- the blend is melted in the extruder at a mass temperature 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 3.6 cN/dtex and a tensile elongation of 105 %.
- a dry mixture consisting of 90 % by weight of a metallocene propylene homopolymer (melt index of 6.2 g/10 minutes at 230 °C/2.16 kg), 5 % by weight of a random heterophasic propylene ethylene blockcopolymer (melt index of 8 g/10 minutes at 230 °C/2.16 kg, ethylene content 33 mol%) 5 % by weight of a propylene ethylene copolymer (melt index of 4,2 g/10 minutes at 230 °C/2.16 kg, ethylene content 4,8 % by weight) and, the percentages in each case based on the sum of the propylene polymers, 0,2 % by weight of dibenzylidene sorbitol, 0.25 % by weight of 3(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 0.2 % by weight of bis-2,2,6,6-tetra-
- the blend is melted in the extruder at a mass temperatureof 280 °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 3.2 cN/dtex and a tensile elongation of 122 %.
- a dry mixture consisting of 85 % by weight of a metallocene propylene homopolymer (melt index of 6.2 g/10 minutes at 230 °C/2.16 kg), 5 % of a propylene homopolymer having strain hardening behavior (melt index of 3,5 g/10 minutes at 230 °C/2.16 kg, strain hardening behaviour as usually defined in the literature), 10 % by weight of a Ziegler-Natta propylene homopolymer with high stereospecifity (melt index of 2,5 g/10 minutes at 230 °C/2.16 kg), and, the percentages in each case based on the sum of the propylene polymers, 0,35 % by weight of sodium-2,2'-methylenebis-(4,6-di-tert.-butylphenyl)phosphate, 0.25 % by weight of 2-t-butyl-4,6-diisopropylphenol, 0.2
- the blend is melted in the extruder at a mass temperature 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 3.0 cN/dtex and a tensile elongation of 137 %.
Landscapes
- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Nonwoven Fabrics (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01991772A EP1356142B1 (en) | 2000-12-07 | 2001-12-04 | Non-postdrawn polyolefin fibers with high tenacity |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00126834A EP1213375A1 (en) | 2000-12-07 | 2000-12-07 | Non-postdrawn polyolefin with high tenacity |
EP00126834 | 2000-12-07 | ||
PCT/EP2001/014155 WO2002046502A1 (en) | 2000-12-07 | 2001-12-04 | Non-postdrawn polyolefin fibers with high tenacity |
EP01991772A EP1356142B1 (en) | 2000-12-07 | 2001-12-04 | Non-postdrawn polyolefin fibers with high tenacity |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1356142A1 true EP1356142A1 (en) | 2003-10-29 |
EP1356142B1 EP1356142B1 (en) | 2006-04-19 |
Family
ID=8170598
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00126834A Withdrawn EP1213375A1 (en) | 2000-12-07 | 2000-12-07 | Non-postdrawn polyolefin with high tenacity |
EP01991772A Expired - Lifetime EP1356142B1 (en) | 2000-12-07 | 2001-12-04 | Non-postdrawn polyolefin fibers with high tenacity |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00126834A Withdrawn EP1213375A1 (en) | 2000-12-07 | 2000-12-07 | Non-postdrawn polyolefin with high tenacity |
Country Status (6)
Country | Link |
---|---|
EP (2) | EP1213375A1 (en) |
AT (1) | ATE323790T1 (en) |
AU (1) | AU2002231649A1 (en) |
DE (1) | DE60118978T2 (en) |
ES (1) | ES2260320T3 (en) |
WO (1) | WO2002046502A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2034056A1 (en) * | 2007-09-04 | 2009-03-11 | Total Petrochemicals Research Feluy | Metallocene polypropylene fibers and nonwovens with improved mechanical properties. |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6998081B2 (en) | 2001-12-21 | 2006-02-14 | Milliken & Company | Method of producing low-shrink polypropylene tape fibers |
US6887567B2 (en) * | 2002-11-02 | 2005-05-03 | Milliken & Company | Low-shrink polypropylene tape fibers comprising high amounts of nucleating agents |
US6759124B2 (en) | 2002-11-16 | 2004-07-06 | Milliken & Company | Thermoplastic monofilament fibers exhibiting low-shrink, high tenacity, and extremely high modulus levels |
US6863976B2 (en) | 2002-11-16 | 2005-03-08 | Milliken & Company | Polypropylene monofilament and tape fibers exhibiting certain creep-strain characteristics and corresponding crystalline configurations |
US7041368B2 (en) * | 2002-11-17 | 2006-05-09 | Milliken & Company | High speed spinning procedures for the manufacture of high denier polypropylene fibers and yarns |
CN1297697C (en) * | 2003-06-12 | 2007-01-31 | 中国石油化工股份有限公司 | Flameproof polyacrylonitrile fibre and method for preparing same |
US6849330B1 (en) | 2003-08-30 | 2005-02-01 | Milliken & Company | Thermoplastic fibers exhibiting durable high color strength characteristics |
CN101519810B (en) * | 2004-01-01 | 2011-04-06 | 帝斯曼知识产权资产管理有限公司 | Method for preparing high-performance polyethylene multifilament yarn |
BRPI0910444B1 (en) * | 2008-04-11 | 2018-11-27 | Dsm Ip Assets Bv | ultra high molecular weight polyethylene multifilament yarns and process for producing them |
BR112016010048B1 (en) * | 2013-12-09 | 2021-09-28 | Adeka Corporation | SUBSTRATE WITH IMPROVED COATING CAPACITY |
CN113227244A (en) * | 2018-12-27 | 2021-08-06 | 埃克森美孚化学专利公司 | Propylene-based spunbond fabrics with faster crystallization time |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5137973A (en) * | 1990-09-10 | 1992-08-11 | Allied-Signal Inc. | Polyolefins containing polyester nucleating agent and articles formed therefrom |
US5366786A (en) * | 1992-05-15 | 1994-11-22 | Kimberly-Clark Corporation | Garment of durable nonwoven fabric |
US6005034A (en) * | 1995-08-31 | 1999-12-21 | Chisso Corpoation | Propylene-ethylene copolymer composition and process for producing the same |
US6162887A (en) * | 1996-07-31 | 2000-12-19 | Japan Polyolefins Co., Ltd. | Highly crystalline polypropylene |
EP0878567B1 (en) * | 1997-05-14 | 2004-09-29 | Borealis GmbH | Polyolefin fibres and polyolefin yarns and textile materials thereof |
FI974175A (en) * | 1997-11-07 | 1999-05-08 | Borealis As | Process for producing polypropylene |
FI980342A0 (en) * | 1997-11-07 | 1998-02-13 | Borealis As | Polymerroer och -roerkopplingar |
-
2000
- 2000-12-07 EP EP00126834A patent/EP1213375A1/en not_active Withdrawn
-
2001
- 2001-12-04 ES ES01991772T patent/ES2260320T3/en not_active Expired - Lifetime
- 2001-12-04 EP EP01991772A patent/EP1356142B1/en not_active Expired - Lifetime
- 2001-12-04 AT AT01991772T patent/ATE323790T1/en not_active IP Right Cessation
- 2001-12-04 WO PCT/EP2001/014155 patent/WO2002046502A1/en active Search and Examination
- 2001-12-04 AU AU2002231649A patent/AU2002231649A1/en not_active Abandoned
- 2001-12-04 DE DE60118978T patent/DE60118978T2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO0246502A1 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2034056A1 (en) * | 2007-09-04 | 2009-03-11 | Total Petrochemicals Research Feluy | Metallocene polypropylene fibers and nonwovens with improved mechanical properties. |
WO2009030702A2 (en) * | 2007-09-04 | 2009-03-12 | Total Petrochemicals Research Feluy | Metallocene polypropylene fibers and nonwovens with improved mechanical properties. |
WO2009030702A3 (en) * | 2007-09-04 | 2009-06-04 | Total Petrochemicals Res Feluy | Metallocene polypropylene fibers and nonwovens with improved mechanical properties. |
Also Published As
Publication number | Publication date |
---|---|
EP1213375A1 (en) | 2002-06-12 |
ES2260320T3 (en) | 2006-11-01 |
DE60118978D1 (en) | 2006-05-24 |
DE60118978T2 (en) | 2007-03-15 |
AU2002231649A1 (en) | 2002-06-18 |
EP1356142B1 (en) | 2006-04-19 |
WO2002046502A1 (en) | 2002-06-13 |
ATE323790T1 (en) | 2006-05-15 |
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