EP1349972B1 - Melanges d'azeotrope avec du perfluorobutylethylene - Google Patents

Melanges d'azeotrope avec du perfluorobutylethylene Download PDF

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Publication number
EP1349972B1
EP1349972B1 EP00984514A EP00984514A EP1349972B1 EP 1349972 B1 EP1349972 B1 EP 1349972B1 EP 00984514 A EP00984514 A EP 00984514A EP 00984514 A EP00984514 A EP 00984514A EP 1349972 B1 EP1349972 B1 EP 1349972B1
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Prior art keywords
spin
azeotropic
composition
pressure
azeotrope
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Expired - Lifetime
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EP00984514A
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German (de)
English (en)
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EP1349972A1 (fr
Inventor
Hyunkook Shin
Chien-Ping Chai Kao
Thomas A. J. Schweiger
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EIDP Inc
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EI Du Pont de Nemours and Co
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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
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/32—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising halogenated hydrocarbons as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5036—Azeotropic mixtures containing halogenated solvents
    • C11D7/504—Azeotropic mixtures containing halogenated solvents all solvents being halogenated hydrocarbons
    • C11D7/5054—Mixtures of (hydro)chlorofluorocarbons and (hydro) fluorocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5036—Azeotropic mixtures containing halogenated solvents
    • C11D7/5068—Mixtures of halogenated and non-halogenated solvents
    • C11D7/5072—Mixtures of only hydrocarbons
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/11—Flash-spinning
    • 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
    • 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

  • This invention is directed to azeotropic and azeotropic-like mixtures useful for flash spinning processes and other applications.
  • U.S. Patent No. 3,081,519 to Blades et al. assigned to E.I. du Pont de Nemours and Company, Wilmington, DE (hereafter DuPont) discloses a process for making flash-spun plexifilamentary film-fibril strands from a fiber-forming polymer in a liquid spin agent that is not a solvent for the polymer below the liquid's normal boiling point.
  • DuPont discloses a process for making flash-spun plexifilamentary film-fibril strands from a fiber-forming polymer in a liquid spin agent that is not a solvent for the polymer below the liquid's normal boiling point.
  • the flash-spinning process requires a spin agent that: (1) is a non-solvent to the polymer below the spin agent's normal boiling point; (2) forms a solution with the polymer at high pressure; (3) forms a desired two-phase dispersion with the polymer when the solution pressure is reduced slightly in a letdown chamber; and (4) flash vaporizes when released from the letdown chamber into a zone of substantially lower pressure through a spin orifice.
  • Spunbonded products made from polyethylene plexifilamentary film-fibril strands have been produced by flash spinning a spin fluid comprised of polyethylene in a trichlorofluoromethane spin agent.
  • trichlorofluoromethane is considered to be a stratospheric ozone depletion chemical, and therefore, there is a need for alternative spin agents for use in the flash-spinning process.
  • Flashspun products have typically been made from polyethylene. However, it is known that other polymers have higher melting points than does polyethylene and, as such, can provide a flashspun product usable at higher temperatures when compared to product made from polyethylene. Moreover, certain solvents can not dissolve polyethylene but can dissolve other polymers; therefore motivation exists to find solvents that are particularly suited to other polymers and yet satisfy the need for non-flammability and low tendency to deplete the ozone as measured by their global warming potential (GWP).
  • the 100 year GWP can be rated on a scale from 1 for carbon dioxide to greater than 4000 for some perfluorocarbons.
  • Azeotropic mixtures containing perfluroalkylethylenes have been used for cleaning and drying agents as disclosed in U.S. Patent 5,302,212 to Desbiendras, et al.
  • Azeotropic mixtures have been used as spin agents in flash spinning processes as described in U.S. Patent 6,153,134 issued November 20, 2000 and assigned to DuPont.
  • Spin agents containing perfluorobutylethylene for use in flash spinning are described in related, pending International Patent Application PCT/US00/22729, also assigned to DuPont.
  • Binary azeotropic or azeotrope-like compositions of substantially constant-boiling mixtures can be characterized, depending upon the conditions chosen, in a number of ways. For example, it is well known by those skilled in the art, that, at different pressures the composition of a given azeotrope or azeotrope-like composition will vary at least to some degree, as will the boiling point temperature. Thus, an azeotropic or azeotrope-like composition of two compounds represents a unique type of relationship but with a variable composition that depends on temperature and/or pressure. Therefore, compositional ranges, rather than fixed compositions, are often used to define azeotropes and azeotrope-like compositions.
  • the present invention relates to binary azeotropic and azeotrope-like compositions containing 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluoro-1-hexene, also referred to herein as perfluorobutylethylene or PFBE.
  • the azeotropic and azeotrope-like compositions of the invention are useful as spin agents for flash-spinning of fiber-forming polymers, and also as cleaning agents, blowing agents for making foams, or working fluids for electrical parts.
  • the terms azeotrope or azeotropic will be understood to include the term azeotrope-like.
  • the azeotropic and azeotrope-like compositions of the present invention are binary mixtures that contain perfluorobutylethylene and a second component where the second component is trans-1,2-dichloroethylene.
  • an azeotropic composition may be defined in terms of the unique relationship that exists among components or in terms of the exact amounts of each component of the composition characterized by a fixed boiling point at a specific pressure.
  • An azeotrope or azeotrope-like composition of two compounds can be characterized by defining compositions characterized by a boiling point at a given pressure, thus providing identifying characteristics without unduly limiting the scope of the invention by a specific numerical composition, which is limited by and is only as accurate as the analytical equipment available.
  • Relative volatility is the ratio of the volatility of component 1 to the volatility of component 2.
  • the ratio of the mole fraction of a component in vapor to that in liquid is the volatility of the component.
  • a method known as the PTx method can be used. In this procedure, the total absolute pressure in a cell of known volume is measured at a constant temperature for various compositions of the two compounds.
  • Use of the PTx Method is described in detail in "Phase Equilibrium in Process Design", Wiley-Interscience Publisher, 1970, written by Harold R. Null, on pages 124 to 126; hereby incorporated by reference.
  • NRTL Non-Random, Two-Liquid
  • the NRTL equation can sufficiently predict the relative volatilities of the perfluorobutylethylene-containing compositions of the present invention and can therefore predict the behavior of these mixtures in multi-stage separation equipment such as distillation columns.
  • Perfluorobutylethylene has been found to form binary azeotropic compositions with trans-1,2-dichloroethylene.
  • the azeotropic compositions comprise 30.7 mole % PFBE and 69.3 mole % trans-DCE at 35.3°C and 11.9 pounds per square inch absolute (psia)(82 kPa). From these data it has been calculated that PFBE forms binary azeotropic and azeotrope-like mixtures having a range of compositions for the pressure ranges shown in Table 1. This range may occur elsewhere in the specification in rounded-off form. Table 1.
  • the azeotropic or azeotrope-like compositions of the invention are useful as spin agents for flash spinning of fiber-forming polymers. It has been a goal in flash spinning processes to find spin agents that have low flammability and low GWP.
  • the spin agents of the subject invention have GWP of less than 20. They also have very low flammability.
  • Fiber-forming synthetic polymers that can be flash-spun using the azeotropic or azeotrope-like compositions of the invention as spin agents include polyolefins such as polypropylene and poly(4-methyl pentene-1), and blends thereof.
  • Other fiber-forming synthetic polymers that can be flash spun using certain of the azeotropic compositions described above as the spin agent include partially fluorinated hydrocarbon polymers in which between 10% and 70% of the total number of hydrogen atoms in the hydrocarbon polymer are replaced by fluorine atoms.
  • the partially fluorinated hydrocarbon polymers are comprised of at least 80% by weight of polymerized monomer units selected from ethylene, tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride and vinyl fluoride.
  • a particularly preferred partially fluorinated hydrocarbon polymer is comprised of 40% to 70% by weight of polymerized monomer units of tetrafluoroethylene and 30% to 60% by weight of polymerized monomer units of ethylene, such as a copolymer comprised of substantially alternating units of ethylene and tetrafluoroethylene with the chemical structure -(CH 2 CH 2 )-(CF 2 CF 2 )-.
  • ethylene/tetrafluoroethylene copolymers are disclosed, for example, in U.S. Patents 3,624,250 to Carlson (assigned to DuPont), 3,870,689 to Modena et al., and 4,677,175 to Ihara et al.
  • Ethylene/tetrafluoroethylene copolymer resin is commercially available from DuPont under the tradename TEFZEL®, which is a registered trademark of DuPont.
  • TEFZEL® fluoropolymer resins have melting points between 235° and 280°C.
  • Another partially fluorinated hydrocarbon polymer that may be flash-spun using certain of the azeotropic compositions described above as the spin agent is a copolymer of alternating monomer units of ethylene and chlorotrifluoroethylene, such as HALAR® fluoropolymer resin obtained from Ausimont.
  • each plexifilamentary strand was tensioned by hanging a 40-gram load to it for three minutes to remove bends and waviness.
  • Tenacity and elongation of the flash-spun strand were determined with an Instron tensile-testing machine. The strands were conditioned and tested at 70°F (21°C) and 65% relative humidity. The strands were twisted to 10 turns per inch (2.54 cm) and mounted in the jaws of the Instron Tester. A two-inch (5.08 cm) gauge length was used with an initial elongation rate of 4 inches (20.3 cm) per minute. The tenacity at break is recorded in grams per denier (gpd). The elongation at break is recorded as a percentage of the two-inch gauge length of the sample. Modulus corresponds to the slope of the stress/strain curve and is expressed in units of gpd.
  • the apparatus used in Example 3 - 5 is the spinning apparatus described in U.S. Patent 5,147,586 to Shin et al.
  • the apparatus consists of two high-pressure cylindrical chambers, each equipped with a piston which is adapted to apply pressure to the contents of the chamber.
  • the cylinders have an inside diameter of 1.0 inch (2.54 cm) and each has an internal capacity of 50 cubic centimeters.
  • the cylinders are connected to each other at one end through a 3/32 inch (0.23 cm) diameter channel and a mixing chamber containing a series of fine mesh screens that act as a static mixer. Mixing is accomplished by forcing the contents of the vessel back and forth between the two cylinders through the static mixer.
  • a spinneret assembly with a quick-acting means for opening the orifice is attached to the channel through a tee.
  • the spinneret assembly consisted of a lead hole of 0.25 inch (0.63 cm) diameter and about 2.0 inch (5.08 cm) length with a 60 degree entrance angle to the orifice, and a spinneret orifice with a length and a diameter each measuring 30 mils (0.762 mm).
  • the pistons are driven by high-pressure water supplied by a hydraulic system.
  • the pressure of the spin fluid was reduced to a desired spinning pressure just prior to spinning. This was accomplished by opening a valve between the spin cell and a much larger tank of high-pressure water ("the accumulator") held at the desired spinning pressure.
  • the spinneret orifice is opened as rapidly as possible after the opening of the valve between the spin cell and the accumulator. This generally takes about one second. This is intended to simulate the letdown chamber effect that is used in larger scale spinning operations.
  • the resultant flash-spun product was collected in a stainless steel open mesh screen basket. The pressure recorded just before the spinneret using a computer during spinning is entered as the spin pressure.
  • pressures may be expressed as psig (pounds per square inch gage) which is approximately 15 psi less than psia (pound per square inch absolute).
  • the unit psi is considered the same as psia.
  • 1 psi 6.9 kPa.
  • Example 1 and Reference Example 2 demonstrate the existence of azeotropic or azeotrope-like compositions between the binary pairs consisting essentially of PFBE and trans-1,2-dichloroethylene (trans-DCE) (Example 1 of the invention); and PFBE and cis-1,2-dichloroethylene (cis-DCE) (Reference Example 2).
  • trans-DCE trans-1,2-dichloroethylene
  • cis-DCE PFBE and cis-1,2-dichloroethylene
  • Reference Example 2 To determine the relative volatility of each binary pair, the PTx Method was used. In this procedure, for each binary pair, the total absolute pressure in a sample cell having a volume of 85 ml or 950 ml was measured at constant temperature for various binary compositions. These measurements were then reduced to equilibrium vapor and liquid compositions using the NRTL equation. The vapor pressure measured versus the composition in the PTx sample cell for these binary systems are shown in Figs. 1 and 2. The experimental data points are shown in each
  • Fig. 1 illustrates graphically the formation of an azeotropic composition of trans-DCE and PFBE at 35.3°C, as indicated by a mixture of about 69.3 mole % trans-DCE and 30.7 mole % PFBE having the highest pressure over the range of compositions at this temperature. Based upon these findings, it has been calculated that an azeotropic or azeotrope-like composition of 69.5 mole % trans-DCE and 30.5 mole % PFBE is formed at 130°C and 139.7 psia (963 kPa).
  • the present invention provides an azeotropic or azeotrope-like composition of from about 30.5 to about 30.7 mole % trans-DCE and from about 69.5 to about 69.3 mole % PFBE, said composition having a boiling point of from about 130°C at about 139.7 psia (963 kPa) to about 35°C at about 11.9 psia (82 kPa).
  • Fig. 2 illustrates graphically the formation of an azeotropic composition of cis-DCE and PFBE at 60°C, as indicated by a mixture of 57 mole % cis-DCE and 43 mole % PFBE having the highest pressure over the range of compositions at this temperature. Based upon these findings, it has been calculated that an azeotropic or azeotrope-like composition of 54.4 mole % cis-DCE and 45.6 mole % PFBE is formed at 140°C and 140.7 psia (970 kPa).
  • cis-1,2-dichloroethylene Under conditions generally used in flash-spinning processes on a large scale, some portion of the trans-1,2-dichloroethylene can isomerize to form cis-1,2-dichloroethylene.
  • the amount of cis-1,2-dichloroethylene present in the spin fluid under a steady state condition can vary from less than 5% to greater than 50%, depending on the amount of stabilizers added to the spin fluid, operating temperature, and the rate of make-up spin agent added to the system.
  • trans-1,2-dichloroethylene is used herein as part of the azeotropic spin agent, it is understood to include both trans- and cis-1,2-dichloroethylene, and the corresponding azeotropic composition will lie somewhere between the azeotropic compositions of trans-1,2-dichloroethylene/PFBE and cis-1,2-dichloroethylene/PFBE.
  • azeotropic spin agents were prepared using azeotropic spin agents, as described above, and having the polymer concentrations as identified in Table 2.
  • Zonyl® perfluorobutylethylene obtained from DuPont, was a common ingredient used to prepare the azeotropic spin agents.
  • the other ingredients for making the azeotropic spin agents were obtained as follows:
  • Polypropylene (experimental grade 89-6, obtained from Montell) having a melt flow rate of 1.4 g/10 min (measured according to ASTM D1238 at 190 °C and 2.16 kg load) and a melting point of 165 °C was used in Example 3.
  • Tefzel® fluoropolymer (grade HT 2127, obtained from DuPont) was used in Example 4.
  • Tefzel® HT 2127 fluoropolymer is a copolymer of substantially alternating monomer units of ethylene and tetrafluoroethylene with a melt flow rate of 7 g/10 min (measured according to ASTM D3159) and a melting point of about 240 °C.
  • Halar® fluoropolymer resin (grade 901, obtained from Ausimont), comprising a copolymer of ethylene and chlorotrifluoroethylene, was used in Example 5.
  • Halar® 901 fluoropolymer resin has a melting point of 240 °C and a melt index of about 1 g/10 min.
  • the spin agent was the azeotrope composition identified in Example 1.
  • the spin fluids were flash-spun using the method described above and spin conditions given in Table 2 to obtain well-fibrillated plexifilaments having the properties shown in Table 2.
  • the weight percent polymer in Table 2 is reported as the weight percent based on the total weight of the spin fluid, whereas the compositions of the spin agent are reported as weight percent based on the total weight of the spin agent.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Claims (7)

  1. Composition azéotrope de 31 à 30 pour-cent en moles de perfluorobutyléthylène et de 69 à 70 pour-cent en moles de trans-1,2-dichloroéthylène, la composition possédant un point d'ébullition de 35°C à 11,9 psia (82 kPa) à 130°C à 139,7 psia (963 kPa).
  2. Fluide de filage constitué essentiellement (a) de 5 à 30% en poids d'un polymère formant une fibre synthétique, (b) d'un agent de filage choisi parmi la composition azéotrope suivant la revendication 1.
  3. Fluide de filage (a) de 5 à 30% en poids d'un polymère formant une fibre synthétique choisi dans le groupe constitué de polyoléfines et d'hydrocarbures partiellement fluorés et (b) d'un agent de filage choisi parmi la composition azéotrope suivant la revendication 1.
  4. Fluide de filage suivant la revendication 3, dans lequel le polymère formant une fibre synthétique est une polyoléfine choisie dans le groupe constitué de polypropylène et de polyméthylpentène.
  5. Fluide de filage suivant la revendication 3, dans lequel l'hydrocarbure partiellement fluoré est choisi dans le groupe constitué d'un copolymère d'éthylène et de tétrafluoroéthylène et d'un copolymère d'éthylène et de chlorotrifluoroéthylène.
  6. Procédé pour la préparation de torons de film-fibrilles plexifilamentaires qui comprend les étapes:
    (A) de génération d'un fluide de filage constitué essentiellement (1) de 5 à 30% en poids d'un polymère formant une fibre synthétique choisi dans le groupe constitué de polyoléfines et d'hydrocarbures partiellement fluorés et (2) d'un agent de filage qui est une composition azéotrope de perfluorobutyléthylène et de trans-1,2-dichloroéthylène,
    (B) de filage éclair du fluide de filage à une pression qui est supérieure à la pression autogène du fluide de filage dans une région à pression inférieure pour former des torons de film-fibrilles plexifilamentaires du polymère formant une fibre synthétique.
  7. Procédé suivant la revendication 6, dans lequel la polyoléfine est choisie dans le groupe constitué de polypropylène et de polyméthylpentène et dans lequel l'hydrocarbure partiellement fluoré est choisi dans le groupe constitué d'un copolymère d'éthylène et de tétrafluoroéthylène et d'un copolymère d'éthylène et de chlorotrifluoroéthylène.
EP00984514A 2000-12-22 2000-12-22 Melanges d'azeotrope avec du perfluorobutylethylene Expired - Lifetime EP1349972B1 (fr)

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PCT/US2000/035311 WO2002052072A1 (fr) 2000-12-22 2000-12-22 Melanges d'azeotrope avec du perfluorobutylethylene

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EP1349972B1 true EP1349972B1 (fr) 2007-01-24

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US7504060B2 (en) 2003-10-16 2009-03-17 Kimberly-Clark Worldwide, Inc. Method and apparatus for the production of nonwoven web materials
US7153448B2 (en) 2004-05-26 2006-12-26 E.I. Du Pont De Nemours And Company 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone compositions comprising a hydrofluorocarbon and uses thereof
US7264745B2 (en) * 2005-04-26 2007-09-04 E.I. Du Pont De Nemours And Company Heat transfer and refrigerant compositions comprising 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and a hydrofluorocarbon
US8318038B2 (en) 2007-02-06 2012-11-27 Solvay Fluor Gmbh Nonflammable compositions comprising fluorinated compounds and use of these compositions
PL3461805T3 (pl) * 2007-04-27 2023-02-27 The Chemours Company Fc, Llc Azeotropowe i podobne do azeotropowych kompozycje Z-1,1,1,4,4,4-heksafluoro-2-butenu
US11261543B2 (en) * 2015-06-11 2022-03-01 Dupont Safety & Construction, Inc. Flash spinning process
CN116005282A (zh) * 2023-03-07 2023-04-25 东华大学 一种均一连续的微纳米纤维超临界纺丝方法

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JP2004525879A (ja) 2004-08-26
JP4974442B2 (ja) 2012-07-11
DE60033199T2 (de) 2007-11-15
WO2002052072A1 (fr) 2002-07-04
EP1349972A1 (fr) 2003-10-08
DE60033199D1 (de) 2007-03-15

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