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EP2167710B1 - Fibre de polytétrafluoroéthylène thermiquement stable et procédé pour sa fabrication - Google Patents

Fibre de polytétrafluoroéthylène thermiquement stable et procédé pour sa fabrication Download PDF

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Publication number
EP2167710B1
EP2167710B1 EP08780812A EP08780812A EP2167710B1 EP 2167710 B1 EP2167710 B1 EP 2167710B1 EP 08780812 A EP08780812 A EP 08780812A EP 08780812 A EP08780812 A EP 08780812A EP 2167710 B1 EP2167710 B1 EP 2167710B1
Authority
EP
European Patent Office
Prior art keywords
fiber
fluoropolymer
rotational speed
sintering
polytetrafluoroethylene
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.)
Active
Application number
EP08780812A
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German (de)
English (en)
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EP2167710A1 (fr
EP2167710A4 (fr
Inventor
Mike Donckers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Fluorofibers America Inc
Original Assignee
Toray Fluorofibers America Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US11/763,249 external-priority patent/US7498079B1/en
Application filed by Toray Fluorofibers America Inc filed Critical Toray Fluorofibers America Inc
Publication of EP2167710A1 publication Critical patent/EP2167710A1/fr
Publication of EP2167710A4 publication Critical patent/EP2167710A4/fr
Application granted granted Critical
Publication of EP2167710B1 publication Critical patent/EP2167710B1/fr
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Classifications

    • 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
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • 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
    • D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
    • D01F6/12—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polymers of fluorinated hydrocarbons
    • 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
    • D01F6/48—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 polymers of halogenated 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
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions

Definitions

  • the present invention relates to a thermally stable fluoropolymer fiber and method of making same, and in particular to a thermally stable, dispersion spun polytetrafluoroethylene (“PTFE”) fiber prepared by heat setting the fiber subsequent to drawing.
  • PTFE thermally stable, dispersion spun polytetrafluoroethylene
  • Dispersion spun or wet PTFE yarns are typically produced by forming a spin mix containing an aqueous dispersion of poly(tetrafluoroethylene) particles and a solution of a cellulosic ether matrix polymer.
  • the spin mix is then extruded at relatively low pressure (e.g., less than 150 pounds per square inch) through an orifice into a coagulation solution usually containing sulfuric acid to coagulate the matrix polymer and form an intermediate fiber structure.
  • the intermediate fiber structure once washed free of acid and salts, is passed over a series of heated rolls to dry the fiber structure and sinter the PTFE particles into a continuous PTFE filament yarn.
  • the dried and sintered yarn is often drawn by accelerating the yarn speed over the last pair of heated rolls by passing the yarn onto a series of draw rolls having a rotational speed greater than the rotational speed of the heated rolls.
  • the yarn is drawn or stretched over the last pair of heated rolls since it is being retrieved by the drawing rolls faster than it is being supplied by the heated rolls.
  • the amount the yarn is drawn is referred to as the draw length or draw ratio.
  • Typical draw ratios for a dispersion spun PTFE yarn range between 6.7 and 7.4, (i.e., the yarn is drawn to a length that is between 6.7 and 7.4 times greater than its pre-drawn length). After drawing, the yarn is wound into packages.
  • drawing PTFE yarn increases the tenacity of the yarn, it has the undesired effect of decreasing the yarn's thermal stability and elongation prior to break of the yarn. Accordingly, what is needed is a method of making a dispersion spun PTFE yarn that allows for increased productivity while maintaining or increasing yarn thermal stability and elongation prior to break of the yarn.
  • the primary benefit of maintaining or increasing yarn thermal stability in a dispersion spun PTFE yarn is centered in the hot gas filtration market. Because filter media made from PTFE yarn are exposed to and in continuous service in applications where air temperatures are regularly at or above 260 degrees Celsius, it is necessary to heat treat the PTFE yarn prior to putting it into service. When this step is accomplished standard yarns produced by dispersion spinning PTFE homopolymer shrink 20% or more. While the resulting shrunken PTFE yarn filter media performs well, it requires users to buy greater amounts of PTFE yarn to cover the loss of filter surface area caused by the shrinking.
  • the present invention is based on the discovery that by modifying the draw scenario for a dispersion spun PTFE fiber yarn, the long established understanding that increasing the total draw of a PTFE yarn decreases yarn elongation prior to yarn break can be inverted while simultaneously increasing the yarn's thermal stability, (i.e., decreasing the amount the yarn shrinks at elevated temperatures.).
  • the fiber is drawn and the PTFE molecules aligned and held above the Tg of the PTFE molecules for a period of time. It is believed that by maintaining the drawn fiber at or above the Tg while the fiber is held at length relaxes the internal stresses within the fiber created by drawing.
  • the present invention is directed to a dispersion spun fluoropolymer fiber that exhibits improved elongation prior to fiber break and increased thermally stability.
  • dispersion spun it is meant that the fiber is prepared by forming a dispersion of insoluble fluoropolymer particles, such as PTFE and polymers generally known as fluorinated olefinic polymers, and mixing the dispersion with a solution of a soluble matrix polymer to produce a spin mix. This spin mix is then coagulated into an intermediate fluoropolymer fiber structure by extruding the mixture into a coagulation solution in which the matrix polymer becomes insoluble.
  • insoluble fluoropolymer particles such as PTFE and polymers generally known as fluorinated olefinic polymers
  • One method which is commonly used to spin PTFE and related polymers includes spinning the polymer from a mixture of an aqueous dispersion of the polymer particles and viscose, where cellulose xanthate is the soluble form of the matrix polymer, as taught for example in U.S. Pat. Nos. 3,655,853 ; 3,114,672 and 2,772,444 .
  • the fluoropolymer fiber of the present invention is prepared using a more environmentally friendly method than those methods utilizing viscose.
  • One such method is described in U.S. Pat. Nos. 5,820,984 ; 5,762,846 , and 5,723,081 , which patents are incorporated herein in their entireties by reference.
  • this method employs a cellulosic ether polymer such as methylcellulose, hydroxyethylcellulose, methylhydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, ethylcellulose or carboxymethylcellulose as the soluble matrix polymer, in place of viscose.
  • a cellulosic ether polymer such as methylcellulose, hydroxyethylcellulose, methylhydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, ethylcellulose or carboxymethylcellulose
  • the intermediate fluoropolymer fiber structure is sintered and partially dried by heating the fiber and passing it over a series of sintering rolls operating at a temperature greater than the Tg of the PTFE molecules of the fiber. Sintering the structure coalesces and entangles the fluoropolymer particles, forming a continuous fluoropolymer filament fiber.
  • the partially dried continuous fluoropolymer filament fiber is passed directly from the series of sintering rolls to a series of drawing rolls operating at ambient temperature.
  • the continuous fluoropolymer filament fiber cools slightly, preferably about 30 degrees Fahrenheit, but remains in a transitional state.
  • the continuous fluoropolymer filament fiber is drawn or elongated by passing the fiber directly from the series of drawing rolls to a series of heat setting rolls rotating at a speed greater than the series of sintering and drawing rolls.
  • the continuous fluoropolymer filament fiber is accelerated and stretched between the next to last drawing roll and the first heat setting roll and slid across the last drawing roll resulting in the fiber undergoing drawing.
  • the series of heating rolls operate at a rotational speed that is approximately six times the rotational speed of the series of drawing rolls. This results in the fiber having a total draw ratio ranging from 6.7 to 7.4.
  • the continuous fluoropolymer filament fiber is further dried and heat set or stabilized by passing the fiber over the series of heat setting rolls.
  • the heat setting rolls operate at a temperature that is greater than the series of drawing rolls and essentially the same as the sintering rolls.
  • the drawn continuous fluoropolymer filament fiber is heated and maintained at or near the temperature of the heat setting rolls for a period of time allowing the internal stresses created within the fiber by drawing to relax.
  • the continuous fluoropolymer filament is wound and stored.
  • the intermediate, cellulosic ether-based PTFE fiber structures were prepared in accordance with the method described in U.S. Pat. Nos. 5,820,984 ; 5,762,846 , and 5,723,081 and subsequently processed.
  • the fiber structures were processed in accordance with the prior art and a number of 400 denier 6.7 denier per filament PTFE yarns were prepared and examined for comparing to PTFE yarns made in accordance with the present invention.
  • the fiber structures were processed in accordance with the present invention and a number of 400 denier 6.7 denier per filament PTFE yarns were prepared and examined.
  • the fiber structures were processed in accordance with the present invention and a number of 1200 denier 6.7 denier per filament PTFE yarns were prepared and examined.
  • tensile strength and elongation prior to break a fiber section was pulled and force applied to the fiber using the instron tensile tester. Throughout the pull the amount of force applied to the fiber is measured. Tensile strength was determined by dividing the total pound force by the denier. The amount the fiber stretches prior to breaking is the elongation. For example, 6 inch lengths of fiber are pulled and tested. At break the fibers are 7.2 inches long. Thus, the amount of stretch is 1.2 inches. This amount is divided by the original length of 6 inches to provide the elongation prior to breaking of 0.20 or 20% elongation at break.
  • the intermediate PTFE fiber structure was prepared from a spin mix having a density of 1.275 grams per cubic centimeter. The fiber structure was then processed by heating it to a temperature about two times greater than the Tg of the PTFE molecules by passing it over a series of heated rolls. The resulting continuous PTFE filament yarn was passed directly to a series of drawing rolls operating at ambient temperature at rotating at a speed approximately six times greater than the rotational speed of the heated rolls.
  • Example 1 400 denier 6.7 denier per filament yarn production with altered draw scenario
  • the test comprised 2 different spin mix ratios. They were 1.275 grams per cubic centimeter and 1.291 grams per cubic centimeter. 1.275 grams per cubic centimeter is considered a standard spin mix ratio and is used commercially on Teflon® yarns within a defined range. All test conditions labeled "1" were run at this spin mix ratio. 1.291 grams per cubic centimeter is considered a "PTFE rich” spin mix ratio and is not presently used commercially on Teflon® yarns within a defined range. All test conditions labeled "2" were run at this spin mix ratio.
  • the test was performed with 3 different draw scenarios resulting in 6 sample sets.
  • the draw scenarios were denoted as A, B, and C, resulting in test condition 1A, 1B, 1C, 2A, 2B, and 2C.
  • the "A” samples represent a standard draw scenario, but with an increased total draw.
  • the "B” samples represent separating the total draw into 2 steps for instance drawing between a set of rolls, followed by heat setting on a second set of rolls, followed a second draw. This scenario had no merit.
  • the "C” sample represent a draw scenario in accordance the present invention.
  • Test 2 Production of a 1200 denier 6.7 denier per filament yarn with an early draw section and heat setting prior to winding.
  • Shrinkage of yarn at elevated temperatures was measured as follows: 200 millimeter lengths of yarn were measure and placed in a preheated, calibrated, hot air oven for 30 minutes and then measured. Percent shrink was then determined. A graphical representation of the results and test settings is shown at FIG. 4.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)

Claims (20)

  1. Fibre de polytétrafluoroéthylène présentant une rétraction inférieure à 15% lorsque soumise à une température de 300 degrés Celsius pendant 30 minutes, dans laquelle la fibre de polytétrafluoroéthylène est une fibre filée par dispersion.
  2. Fibre de polytétrafluoroéthylène selon la revendication 1, dans laquelle la fibre présente une rétraction inférieure à 9% lorsque soumise à une température de 300 degrés Celsius pendant 30 minutes.
  3. Fibre de polytétrafluoroéthylène selon la revendication 1, dans laquelle la fibre présente une rétraction inférieure à 5% lorsque soumise à une température de 300 degrés Celsius pendant 30 minutes.
  4. Fibre de polytétrafluoroéthylène selon l'une quelconque des revendications précédentes, présentant un allongement supérieur à environ 30% avant la rupture de la fibre de polytétrafluoroéthylène.
  5. Fibre de polytétrafluoroéthylène selon l'une quelconque des revendications précédentes, dans laquelle la fibre est comprise entre 385 deniers et 412 deniers.
  6. Fibre de polytétrafluoroéthylène selon l'une quelconque des revendications précédentes, fabriquée selon un procédé comprenant le frittage de la fibre de polytétrafluoroéthylène, puis l'étirage de la fibre de polytétrafluoroéthylène, et enfin le thermofixage de la fibre de polytétrafluoroéthylène.
  7. Fibre de polytétrafluoroéthylène selon la revendication 6, dans laquelle le procédé prévoit un rapport total d'étirage d'environ 7,4 pour la fibre de polytétrafluoroéthylène.
  8. Procédé de fabrication d'une fibre comprenant :
    • la production d'une fibre de fluoropolymère filée par dispersion suivie,
    • du frittage de la fibre de fluoropolymère,
    • de l'étirage de la fibre de fluoropolymère, et
    • du thermofixage de la fibre de fluoropolymère.
  9. Procédé selon la revendication 8, dans lequel le frittage du fluoropolymère est effectué en chauffant et en faisant passer la fibre de fluoropolymère sur une série de rouleaux de frittage fonctionnant à une première température et à une première vitesse de rotation.
  10. Procédé selon la revendication 9, dans lequel l'étirage de la fibre de fluoropolymère est effectué en faisant passer la fibre de fluoropolymère entre une série de rouleaux d'étirage fonctionnant à une seconde température et à une seconde vitesse de rotation, et entre une série de rouleaux de thermofixage fonctionnant à une troisième température et à une troisième vitesse de rotation.
  11. Procédé selon la revendication 10, dans lequel la première vitesse de rotation et la seconde vitesse de rotation sont sensiblement identiques.
  12. Procédé selon la revendication 10 ou la revendication 11, dans lequel la troisième vitesse de rotation est supérieure à la seconde vitesse de rotation.
  13. Procédé selon la revendication 12, dans lequel la troisième vitesse de rotation est au moins cinq fois supérieure à la seconde vitesse de rotation.
  14. Procédé selon l'une quelconque des revendications 10 à 13, dans lequel la vitesse de rotation des rouleaux de thermofixage est supérieure à la vitesse de rotation de la série de rouleaux de frittage et d'étirage.
  15. Procédé selon l'une quelconque des revendications 10 à 14, dans lequel la seconde température est inférieure à la première et à la troisième température.
  16. Procédé selon l'une quelconque des revendications 10 à 15, dans lequel la température des rouleaux de thermofixage est sensiblement identique à la température des rouleaux de frittage.
  17. Procédé selon l'une quelconque des revendications 8 à 16, comprenant en outre le refroidissement de la fibre de fluoropolymère après le frittage et avant l'étirage.
  18. Procédé selon l'une quelconque des revendications 8 à 17, dans lequel le thermofixage de la fibre de fluoropolymère est effectué en faisant passer la fibre de polytétrafluoroéthylène sur la série de rouleaux de thermofixage.
  19. Procédé de fabrication d'une fibre selon l'une quelconque des revendications 1 à 7, le procédé comprenant :
    • l'extrusion d'une fibre de fluoropolymère intermédiaire à partir d'un mélange de filage suivie,
    • du frittage de la fibre de fluoropolymère intermédiaire,
    • de l'étirage de la fibre de fluoropolymère intermédiaire, et
    • du thermofixage de la fibre de fluoropolymère intermédiaire.
  20. Procédé selon l'une quelconque des revendications 8 à 18, le procédé comprenant :
    • la formation d'un mélange de filage contenant une dispersion de particules de poly(tétrafluoroéthylène),
    • la formation d'une structure de fibre de fluoropolymère intermédiaire à partir du mélange de filage,
    • le frittage de la structure de fibre de fluoropolymère intermédiaire et la formation d'un fil continu de fluoropolymère,
    • l'étirage du fil continu de fluoropolymère, et
    • ensuite le thermofixage du fil continu de fluoropolymère.
EP08780812A 2007-06-14 2008-06-13 Fibre de polytétrafluoroéthylène thermiquement stable et procédé pour sa fabrication Active EP2167710B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US76324207A 2007-06-14 2007-06-14
US11/763,249 US7498079B1 (en) 2007-06-13 2007-06-14 Thermally stable polytetrafluoroethylene fiber and method of making same
PCT/US2008/066854 WO2008157307A1 (fr) 2007-06-14 2008-06-13 Fibre de polytétrafluoroéthylène thermiquement stable et procédé pour sa fabrication

Publications (3)

Publication Number Publication Date
EP2167710A1 EP2167710A1 (fr) 2010-03-31
EP2167710A4 EP2167710A4 (fr) 2011-01-05
EP2167710B1 true EP2167710B1 (fr) 2012-01-25

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EP08780812A Active EP2167710B1 (fr) 2007-06-14 2008-06-13 Fibre de polytétrafluoroéthylène thermiquement stable et procédé pour sa fabrication

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EP (1) EP2167710B1 (fr)
CN (1) CN101778968B (fr)
AT (1) ATE542933T1 (fr)
WO (1) WO2008157307A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102493007B (zh) * 2011-11-15 2014-01-29 厦门柏润氟材料科技有限公司 糊状聚四氟乙烯挤出纤维的微波烧结牵伸装置
WO2013159020A1 (fr) * 2012-04-19 2013-10-24 Toray Fluorofibers (America), Inc. Fibre de fluoropolymère filée par dispersion préparée à partir de polytétrafluoroéthylène non transformable à l'état fondu et de perfluoroalcoxy
US9422642B2 (en) * 2013-07-29 2016-08-23 Toray Fluorofibers (America), Inc. Wear polytetrafluoroethylene (PTFE) fiber and method of making same
EP2942426B1 (fr) * 2014-05-05 2019-04-17 Filmop International s.r.l. Fil poy
EP3670716A1 (fr) * 2018-12-17 2020-06-24 Evonik Operations GmbH Fluoropolymèrs étirés
CN110158166A (zh) * 2019-04-03 2019-08-23 苏州耐德新材料科技有限公司 一种氯碱离子交换膜用聚四氟乙烯单丝的制备工艺

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4064214A (en) * 1975-09-22 1977-12-20 E. I. Du Pont De Nemours And Company Process for making polytetrafluoroethylene yarn
JP2729837B2 (ja) * 1988-07-25 1998-03-18 旭化成工業株式会社 ポリテトラフルオロエチレン糸状物及びその製造法
DE69529746T2 (de) * 1994-06-30 2003-09-04 Daikin Industries, Ltd. Voluminöse langfaser und split-garn aus polytetrafluorethyten, verfahren zu ihreherstellung und herstellung von baumwollähnlichem material unter verwendung dieser faser und dieses garns und stoff für staubfilter
DE69531625T2 (de) * 1994-10-04 2004-06-24 Daikin Industries, Ltd. Polytetrafluorethylenfaser, baumwollartiges diese faser enthaltendes material und verfahren zu deren herstellung
US5723081A (en) * 1996-12-20 1998-03-03 E. I. Du Pont De Nemours And Company Dispersion spinning process for polytetrafluoroethylene and related polymers
US5762846A (en) * 1996-12-20 1998-06-09 E. I. Du Pont De Nemours And Company Dispersion spinning process for polytetrafluoroethylene and related polymers
AU2002237116A1 (en) * 2002-03-07 2003-09-16 Manegro Administracao E Participacoes Ltda. Expanded ptfe fiber

Also Published As

Publication number Publication date
EP2167710A1 (fr) 2010-03-31
ATE542933T1 (de) 2012-02-15
WO2008157307A1 (fr) 2008-12-24
CN101778968B (zh) 2012-09-05
EP2167710A4 (fr) 2011-01-05
CN101778968A (zh) 2010-07-14

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