US20080014440A1 - Polyoxadiazole composite fibers - Google Patents

Polyoxadiazole composite fibers Download PDF

Info

Publication number
US20080014440A1
US20080014440A1 US11/486,243 US48624306A US2008014440A1 US 20080014440 A1 US20080014440 A1 US 20080014440A1 US 48624306 A US48624306 A US 48624306A US 2008014440 A1 US2008014440 A1 US 2008014440A1
Authority
US
United States
Prior art keywords
composite fiber
polymer
polyoxadiazole
fiber
flexible chain
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.)
Abandoned
Application number
US11/486,243
Inventor
Kiu-Seung Lee
Jon David Hartzler
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.)
EIDP Inc
Original Assignee
Individual
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
Application filed by Individual filed Critical Individual
Priority to US11/486,243 priority Critical patent/US20080014440A1/en
Assigned to E. I. DU PONT DE NEMOURS AND COMPANY reassignment E. I. DU PONT DE NEMOURS AND COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LEE, KIU-SEUNG, HARTZLER, JON DAVID
Priority to MX2009000354A priority patent/MX2009000354A/en
Priority to JP2009519446A priority patent/JP2009542935A/en
Priority to CA002655858A priority patent/CA2655858A1/en
Priority to BRPI0713241-7A priority patent/BRPI0713241A2/en
Priority to KR1020097001306A priority patent/KR20090031431A/en
Priority to EP07796527A priority patent/EP2041340A2/en
Priority to CN2007800265937A priority patent/CN101490320B/en
Priority to PCT/US2007/014973 priority patent/WO2008008185A2/en
Publication of US20080014440A1 publication Critical patent/US20080014440A1/en
Abandoned legal-status Critical Current

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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core

Definitions

  • the present invention is directed to preparation of a polyoxadiazole composite fiber and articles produced therefrom.
  • a need is present for a composite fiber comprising polyoxadiazole which exhibits dyeability and improved UV stability.
  • the present invention is directed to a composite fiber comprising a polyoxadiazole polymer and a flexible chain non-polyoxadiazole polymer.
  • the present invention relates to composite fibers of a polyoxadiazole and a flexible chain polymer and the preparation thereof.
  • fiber is used herein interchangeably with “filament”, and means a relatively flexible, macroscopically homogeneous body having a high ratio of length to width across its cross-sectional area perpendicular to its length.
  • the fiber cross section can be any shape, but is often somewhat circular.
  • Fiber spun onto a bobbin in a package is referred to as continuous fiber. Fiber can be cut into short lengths called staple fiber. Fiber can be cut into even smaller lengths called floc. Multifilament yarns can be combined to form cords. Yarn can be intertwined and/or twisted.
  • spin refers to the extrusion of a polymer solution through a spinneret.
  • Polyoxadiazole useful in this invention include any polyoxadiazole polymer which has suitable properties to allow it to be solution spun into a fiber from a solvent in which the second polymer can similarly be spun into a fiber can be used to produce composite fibers of this invention.
  • the polyoxadiazole polymers are 1,3,4-polyoxadiazole polymers or copolymers. More preferably, the polyoxadiazole polymers including copolymers include but are not limited to polyoxadiazoles comprising the repeat units:
  • the second polymer can be any polymer selected from known flexible chain polymers which include copolymers, but preferred polymers are those that form isotropic solutions in mineral acids, including chlorosulfonic acid and fluorosulfonic acid, particularly sulfuric acid.
  • a highly preferred polymer for use in the isotropic solution is polyvinylpyrrolidione (PVP).
  • PVP polyvinylpyrrolidione
  • suitable polymers include aliphatic polyamides (e.g., 6-nylon, 6,6-nylon, and 6,12-nylon), polyaniline, polyether ketone ketone (PEKK), aromatic polyamides (MPD-I, MPD-I/T), and copolymers of PVP, such as PVP/VA (Vinyl Acetate).
  • Polyoxadiazole polymers and flexible chain polymers can be combined in any ratio that allows the solution to be spun into a fiber.
  • any ratio of polyoxadiazole polymer to flexible chain polymer can be spun into a fiber.
  • One in the art will typically use the rule of mixtures to determine the ratio of the polymers that will produce a fiber with desired properties.
  • each polymer will be present by weight in the amount of at least 2 percent in order to produce a measureable change in properties of the resulting composite fiber.
  • Composite fibers of this invention can be spun by the process of continuously combining an isotropic polymer solution of a polyoxadiazole polymer and an isotropic solution of a second polymer to form a combined polymer solution; passing the combined polymer solution through at least one static mixer to form a spin dope; and extruding the spin dope through a spinneret to form a composite fiber.
  • the process can further include passing the composite fiber through an air gap; contacting the composite dope fiber with a quench solution to form a coagulated composite fiber; contacting the coagulated composite fiber with a wash solution; contacting the washed composite fiber with a neutralization solution to form a neutralized and washed composite fiber; drying the neutralized and washed composite fiber; and winding up the dried composite fiber.
  • the dried composite fiber can be wound onto a bobbin on a windup device.
  • the polyoxadiazole composite fibers exhibit improved dyeability over fibers of polyoxadiazole polymers alone.
  • the composite fibers can be solution dyed using both basic or acidic dyes.
  • Basic dyes or cationic dyes
  • Cationic dyes such as Basacryl Red GL (Basic Red 29 by Color Index) are frequently used for this purpose because of the depth of the color it generates.
  • Dyes are usually soluble in most of organic solvent and in aqueous medium, but dyeability was tested in aqueous medium.
  • Slight acidity pH of 4-6 is required to achieve level dyeing with basic dyes.
  • polyoxadiazole composite fibers typically improved over fibers of polyoxadiazole alone.
  • Polyoxadiazole fibers alone when exposed to a Xenon lamp for 20 hours typically do not exhibit measureable tenacity.
  • Composite fibers of polyoxadiazoles having at least 2 percent by weight of the second polymer when exposed to UV radiation using a Xenon lamp for 20 hours can retain measureable tenacity.
  • polyoxadiazole composite fibers contain a sufficient amount of the second polymer to retain greater than 20 percent of their tenacity after 20 hours of exposure to a Xenon lamp.
  • polyoxadiazole composite fibers contain a sufficient amount of the second polymer to retain greater than 35 percent of their tenacity after 20 hours of exposure to a Xenon lamp. Most preferably, polyoxadiazole composite fibers contain a sufficient amount of the second polymer to retain greater than 50 percent of their tenacity after 20 hours of exposure to a Xenon lamp.
  • Each polymer solution and/or the combined stream can contain additives such as anti-oxidants, lubricants, ultra-violet screening agents, colorants and the like which are commonly incorporated.
  • a polyoxadiazole copolymer was prepared by mixing 86.885 grams (0.668 moles) solid hydrazine sulfate, 88.74 grams (0.534 moles) of solid terephthalic acid, and 22.18 grams (0.133 moles) of solid isophthalic acid were mixed and blended together in a mixer for 30 min. To this blended mixture of solids was added a first addition of 30% Oleum, 534 grams Oleum (2.001 moles of SO3) at 25 degrees Celsius.
  • the mixture was mechanically stirred at 25 degrees Celsius for 15 minutes to dissolve the solids and form a solution.
  • the solution was then heated to 120 degrees Celsius with mechanical stirring until a constant torque (constant viscosity) was observed on the mixer (60 minutes).
  • the fiber sample prepared the same way except that low molecular weight PVP (K-30 with a weight average molecular weight of about 60,000) instead of K-90, was also dyed deep with Basacryl Red GL (a basic dye).
  • low molecular weight PVP K-30 with a weight average molecular weight of about 60,000
  • Basacryl Red GL a basic dye

Abstract

The present invention is directed to preparation of a polyoxadiazole composite fiber and a flexible chain polymer which is not a polyoxadiazole polymer and articles produced therefrom.

Description

    BACKGROUND OF THE INVENTION
  • The present invention is directed to preparation of a polyoxadiazole composite fiber and articles produced therefrom.
  • A need is present for a composite fiber comprising polyoxadiazole which exhibits dyeability and improved UV stability.
    • SUMMARY OF THE INVENTION
  • The present invention is directed to a composite fiber comprising a polyoxadiazole polymer and a flexible chain non-polyoxadiazole polymer.
    • DETAILED DESCRIPTION OF THE INVENTION
  • The present invention relates to composite fibers of a polyoxadiazole and a flexible chain polymer and the preparation thereof.
  • For purposes herein, the term “fiber” is used herein interchangeably with “filament”, and means a relatively flexible, macroscopically homogeneous body having a high ratio of length to width across its cross-sectional area perpendicular to its length. The fiber cross section can be any shape, but is often somewhat circular. Fiber spun onto a bobbin in a package is referred to as continuous fiber. Fiber can be cut into short lengths called staple fiber. Fiber can be cut into even smaller lengths called floc. Multifilament yarns can be combined to form cords. Yarn can be intertwined and/or twisted.
  • The term spin as used herein refers to the extrusion of a polymer solution through a spinneret.
  • Polyoxadiazole useful in this invention include any polyoxadiazole polymer which has suitable properties to allow it to be solution spun into a fiber from a solvent in which the second polymer can similarly be spun into a fiber can be used to produce composite fibers of this invention. Preferably, the polyoxadiazole polymers are 1,3,4-polyoxadiazole polymers or copolymers. More preferably, the polyoxadiazole polymers including copolymers include but are not limited to polyoxadiazoles comprising the repeat units:
  • Figure US20080014440A1-20080117-C00001
  • Processes for the production of polyoxadiazole polymers are well known in the art. Examples of processes for the production of polyoxadiazole (POD) polymers can be found in the Journal of Polymer Science: Part A, 3, 45-54 (1965), Journal of Polymer Science: Part A-1, 6, 3357-3370, (1968), Advanced Materials, 9(8), 601-613, (1997) and U.S. patent application Ser. No. 11/415,026. It is preferred to have a polyoxadiazole polymer of high inherent viscosity such as those produced by the method disclosed in U.S. patent application Ser. No. 11/415,026.
  • The second polymer can be any polymer selected from known flexible chain polymers which include copolymers, but preferred polymers are those that form isotropic solutions in mineral acids, including chlorosulfonic acid and fluorosulfonic acid, particularly sulfuric acid. A highly preferred polymer for use in the isotropic solution is polyvinylpyrrolidione (PVP). Examples of suitable polymers include aliphatic polyamides (e.g., 6-nylon, 6,6-nylon, and 6,12-nylon), polyaniline, polyether ketone ketone (PEKK), aromatic polyamides (MPD-I, MPD-I/T), and copolymers of PVP, such as PVP/VA (Vinyl Acetate).
  • Polyoxadiazole polymers and flexible chain polymers can be combined in any ratio that allows the solution to be spun into a fiber. Typically, any ratio of polyoxadiazole polymer to flexible chain polymer can be spun into a fiber. One in the art will typically use the rule of mixtures to determine the ratio of the polymers that will produce a fiber with desired properties. Typically, each polymer will be present by weight in the amount of at least 2 percent in order to produce a measureable change in properties of the resulting composite fiber.
  • Composite fibers of this invention can be spun by the process of continuously combining an isotropic polymer solution of a polyoxadiazole polymer and an isotropic solution of a second polymer to form a combined polymer solution; passing the combined polymer solution through at least one static mixer to form a spin dope; and extruding the spin dope through a spinneret to form a composite fiber. Additionally, the process can further include passing the composite fiber through an air gap; contacting the composite dope fiber with a quench solution to form a coagulated composite fiber; contacting the coagulated composite fiber with a wash solution; contacting the washed composite fiber with a neutralization solution to form a neutralized and washed composite fiber; drying the neutralized and washed composite fiber; and winding up the dried composite fiber. The dried composite fiber can be wound onto a bobbin on a windup device. Extrusion processes suitable for use in making composite fibers within the scope of the present invention are disclosed in U.S. Pat. Nos. 4,340,559, 4,298,565 and 4,965,033.
  • The polyoxadiazole composite fibers exhibit improved dyeability over fibers of polyoxadiazole polymers alone. The composite fibers can be solution dyed using both basic or acidic dyes. Basic dyes (or cationic dyes) are used to check the dyeability of the composite fibers. Cationic dyes such as Basacryl Red GL (Basic Red 29 by Color Index) are frequently used for this purpose because of the depth of the color it generates. Dyes are usually soluble in most of organic solvent and in aqueous medium, but dyeability was tested in aqueous medium. Slight acidity (pH of 4-6) is required to achieve level dyeing with basic dyes.
  • Without being bound to any theory it is believed that improved dyeability of the composite fiber is due to a diffusive channel created by chain mobility of the flexible chain polymer.
  • The UV stability of polyoxadiazole composite fibers is typically improved over fibers of polyoxadiazole alone. Polyoxadiazole fibers alone when exposed to a Xenon lamp for 20 hours typically do not exhibit measureable tenacity. Composite fibers of polyoxadiazoles having at least 2 percent by weight of the second polymer when exposed to UV radiation using a Xenon lamp for 20 hours can retain measureable tenacity. Preferably, polyoxadiazole composite fibers contain a sufficient amount of the second polymer to retain greater than 20 percent of their tenacity after 20 hours of exposure to a Xenon lamp. More preferably, polyoxadiazole composite fibers contain a sufficient amount of the second polymer to retain greater than 35 percent of their tenacity after 20 hours of exposure to a Xenon lamp. Most preferably, polyoxadiazole composite fibers contain a sufficient amount of the second polymer to retain greater than 50 percent of their tenacity after 20 hours of exposure to a Xenon lamp.
  • Each polymer solution and/or the combined stream can contain additives such as anti-oxidants, lubricants, ultra-violet screening agents, colorants and the like which are commonly incorporated.
  • All percentages are by weight unless otherwise indicated.
    • EXAMPLE 1
  • A polyoxadiazole copolymer was prepared by mixing 86.885 grams (0.668 moles) solid hydrazine sulfate, 88.74 grams (0.534 moles) of solid terephthalic acid, and 22.18 grams (0.133 moles) of solid isophthalic acid were mixed and blended together in a mixer for 30 min. To this blended mixture of solids was added a first addition of 30% Oleum, 534 grams Oleum (2.001 moles of SO3) at 25 degrees Celsius.
  • The mixture was mechanically stirred at 25 degrees Celsius for 15 minutes to dissolve the solids and form a solution. The solution was then heated to 120 degrees Celsius with mechanical stirring until a constant torque (constant viscosity) was observed on the mixer (60 minutes).
  • To this solution was added a second addition of 30% Oleum, 611 grams oleum (2.290 moles of SO3) at 130 degrees Celsius. The temperature was maintained at 130 degrees Celsius for 2 hours until the viscosity of the solution reached a plateau. The solution was then cooled to room temperature.
  • A small sample was removed from the cooled solution and added to water at 0 degrees Celsius to precipitate the polymer. The polymer was washed with water until a neutral pH was reached. The polymer was dried under vacuum and an inherent viscosity of 2.60. The solution was diluted to 5.0% solid by adding 581 grams of concentrated sulfuric acid.
  • To the rest of polymer solution prepared above, 5.06 grams of K-90 polyvinylpyrrolidone powder with a weight average molecular weight of about 90,000 was added at room temperature and stirred until all added solid was dissolved. The solution showed some shear opalescence and silky appearance. This solution was spun into fiber by air-gap spinning into coagulation bath of 7% sulfuric acid solution at room temperature followed by washing and neutralized in sodium bicarbonate. The resulting fiber was dried overnight in 120 C oven. Dyeability of the fiber was tested in 0.5% Basacryl Red GL (a basic dye) solution in acidic pH=4-5. The fiber was dyed deep, while the fiber prepared without added PVP was not dyed.
    • EXAMPLE 2
  • The fiber sample prepared the same way except that low molecular weight PVP (K-30 with a weight average molecular weight of about 60,000) instead of K-90, was also dyed deep with Basacryl Red GL (a basic dye).

Claims (14)

1. A composite fiber comprising:
at least one polyoxadiazole polymer; and
at least one flexible chain polymer, wherein, the flexible chain polymer is not a polyoxadiazole polymer.
2. The composite fiber of claim 1, wherein:
the polyoxadiazole polymer comprises a repeat unit selected from the list consisting of
Figure US20080014440A1-20080117-C00002
3. The composite fiber of claim 2, wherein:
the polyoxadiazole polymer comprises at least two repeat units selected from the list consisting of
Figure US20080014440A1-20080117-C00003
4. The composite fiber of claim 1, wherein:
the flexible chain polymer is selected from the list consisting of 6-nylon, 6,6-nylon, 6,12-nylon, polyaniline, polyether ketone ketone (PEKK), aromatic polyamides, polyvinylpyrrolidione (PVP), and copolymers of polyvinypyrrolidione (PVP).
5. The composite fiber of claim 4, wherein:
the flexible chain polymer is polyvinylpyrrolidione or a copolymer of polyvinylpyrrolidione.
6. The composite fiber of claim 1, wherein:
the polyoxadiazole polymer is a copolymer.
7. The composite fiber of claim 6, wherein:
the polyoxadiazole copolymer comprises at least two aromatic ring systems selected from the list consisting of:
Figure US20080014440A1-20080117-C00004
8. The composite fiber of claim 1, wherein:
the composite fiber retains at least 15 percent of its tenacity after exposure to a Xenon lamp for 20 hours.
9. The composite fiber of claim 1, wherein:
the composite fiber is dyeable.
10. The composite fiber of claim 1, wherein:
the flexible chain polymer is present in an amount between about 2 and 98 percent by weight.
11. The composite fiber of claim 10, wherein:
the flexible chain polymer is present in an amount between about 5 and 98 percent by weight.
12. The composite fiber of claim 10, wherein:
the composite fiber retains at least 15 percent of its tenacity after exposure to a Xenon lamp for 20 hours.
13. The composite fiber of claim 10, wherein:
the composite fiber retains at least 35 percent of its tenacity after exposure to a Xenon lamp for 20 hours.
14. An article containing the composite fiber of claim 1.
US11/486,243 2006-07-13 2006-07-13 Polyoxadiazole composite fibers Abandoned US20080014440A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US11/486,243 US20080014440A1 (en) 2006-07-13 2006-07-13 Polyoxadiazole composite fibers
PCT/US2007/014973 WO2008008185A2 (en) 2006-07-13 2007-06-27 Polyoxadiazole composite fibers
BRPI0713241-7A BRPI0713241A2 (en) 2006-07-13 2007-06-27 composite fiber and article
JP2009519446A JP2009542935A (en) 2006-07-13 2007-06-27 Polyoxadiazole composite fiber
CA002655858A CA2655858A1 (en) 2006-07-13 2007-06-27 Polyoxadiazole composite fibers
MX2009000354A MX2009000354A (en) 2006-07-13 2007-06-27 Polyoxadiazole composite fibers.
KR1020097001306A KR20090031431A (en) 2006-07-13 2007-06-27 Polyoxadiazole composite fibers
EP07796527A EP2041340A2 (en) 2006-07-13 2007-06-27 Polyoxadiazole composite fibers
CN2007800265937A CN101490320B (en) 2006-07-13 2007-06-27 Polyoxadiazole composite fibers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US11/486,243 US20080014440A1 (en) 2006-07-13 2006-07-13 Polyoxadiazole composite fibers

Publications (1)

Publication Number Publication Date
US20080014440A1 true US20080014440A1 (en) 2008-01-17

Family

ID=38779507

Family Applications (1)

Application Number Title Priority Date Filing Date
US11/486,243 Abandoned US20080014440A1 (en) 2006-07-13 2006-07-13 Polyoxadiazole composite fibers

Country Status (9)

Country Link
US (1) US20080014440A1 (en)
EP (1) EP2041340A2 (en)
JP (1) JP2009542935A (en)
KR (1) KR20090031431A (en)
CN (1) CN101490320B (en)
BR (1) BRPI0713241A2 (en)
CA (1) CA2655858A1 (en)
MX (1) MX2009000354A (en)
WO (1) WO2008008185A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090306265A1 (en) * 2008-06-10 2009-12-10 Gkss-Forschungszentrum Geesthacht Gmbh Production of composites made of polyoxadiazole polymers

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7528217B2 (en) 2006-10-06 2009-05-05 E.I. Du Pont De Nemours And Company Polymers and fibers formed therefrom
EP2861789B1 (en) * 2012-06-15 2020-09-09 DuPont Safety & Construction, Inc. Flame resistant spun staple yarns made from blends of fibers derived from sulfonated naphthalene polyoxadiazole polymers

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
UST969008I4 (en) * 1977-01-25 1978-04-04 Imperial Chemical Industries Limited Production of oriented fibrillar products
US4091159A (en) * 1975-10-13 1978-05-23 Imperial Chemical Industries Limited Bonded structures
US5057600A (en) * 1987-10-09 1991-10-15 The Dow Chemical Company Process for forming an article comprising poly(etheretherketone) (PEEK) type polymers
US5922830A (en) * 1996-03-29 1999-07-13 Toray Industries, Inc. Highly hygroscopic polyamide fiber, and production and application thereof
US6790528B2 (en) * 2000-08-18 2004-09-14 Transmit Gesellschaft Fuer Technologietransfer Mbh Production of polymer fibres having nanoscale morphologies

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4839776B1 (en) * 1970-10-08 1973-11-27
JPS4929298B1 (en) * 1970-12-16 1974-08-02
JPS518414B2 (en) * 1971-11-04 1976-03-16
US4054633A (en) * 1976-05-13 1977-10-18 Monsanto Company Process for continuously preparing shaped articles of aromatic oxadiazole or aromatic oxadiazole/N-alkylhydrazide polymers from monomer solutions
US4132757A (en) * 1977-12-27 1979-01-02 Monsanto Company Twist efficiency of oxadiazole/hydrazide yarn
DD279509A1 (en) * 1989-01-16 1990-06-06 Schwarza Chemiefaser METHOD FOR STABILIZING NITROGEN-CONTAINING POLYMERS

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4091159A (en) * 1975-10-13 1978-05-23 Imperial Chemical Industries Limited Bonded structures
UST969008I4 (en) * 1977-01-25 1978-04-04 Imperial Chemical Industries Limited Production of oriented fibrillar products
US5057600A (en) * 1987-10-09 1991-10-15 The Dow Chemical Company Process for forming an article comprising poly(etheretherketone) (PEEK) type polymers
US5922830A (en) * 1996-03-29 1999-07-13 Toray Industries, Inc. Highly hygroscopic polyamide fiber, and production and application thereof
US6790528B2 (en) * 2000-08-18 2004-09-14 Transmit Gesellschaft Fuer Technologietransfer Mbh Production of polymer fibres having nanoscale morphologies

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090306265A1 (en) * 2008-06-10 2009-12-10 Gkss-Forschungszentrum Geesthacht Gmbh Production of composites made of polyoxadiazole polymers
EP2133385A2 (en) 2008-06-10 2009-12-16 Gkss-Forschungszentrum Geesthacht Gmbh Production of composites from polyoxadiazol polymers.
DE102008027499A1 (en) 2008-06-10 2009-12-17 Gkss-Forschungszentrum Geesthacht Gmbh Production of composites from polyoxadiazole polymers

Also Published As

Publication number Publication date
EP2041340A2 (en) 2009-04-01
CN101490320A (en) 2009-07-22
WO2008008185A2 (en) 2008-01-17
BRPI0713241A2 (en) 2012-04-17
WO2008008185A3 (en) 2008-05-02
KR20090031431A (en) 2009-03-25
CA2655858A1 (en) 2008-01-17
MX2009000354A (en) 2009-01-27
JP2009542935A (en) 2009-12-03
CN101490320B (en) 2011-11-23

Similar Documents

Publication Publication Date Title
KR101386825B1 (en) Polymers and fibers formed therefrom
CA2796362C (en) Meta-type wholly aromatic polyamide fiber
KR102170294B1 (en) High strength copolymerized aramid fiber and method of manufacturing the same
US10233288B2 (en) Highly functional polyamide polymer, spinning dope composition containing same, and molded product thereof
RU2756466C2 (en) Process for the production of fiber from polyesterketonketone
US20080014440A1 (en) Polyoxadiazole composite fibers
JP2971338B2 (en) Easily dyeable meta-type aromatic polyamide fiber
EP2862964B1 (en) Para-type wholly aromatic copolyamide drawn fiber and production method therefor
JP2020117831A (en) Easily-dyeable meta-type wholly aromatic polyamide fiber, and method for producing the same
JP2018154945A (en) Easily-dyeable meta-type wholly aromatic polyamide fiber having excellent flame retardancy and method for producing the same
JP2744702B2 (en) Sulfonated poly (p-phenylene terephthalamide) fiber for textiles
KR101684874B1 (en) Polyketone Fiber with Improved Wearing Property and Method for Preparing the Same
JP7239382B2 (en) Easy-dyeable meta-type wholly aromatic polyamide fiber and method for producing the same
JPH03279412A (en) Method for spinning polyvinyl alcohol-based fiber
JP2005146474A (en) Polyvinyl alcohol bicomponent fiber and method for producing the same
JP2017008423A (en) Co-polyparaphenylene 3,4'-oxydiphenylene terephthalamide stretched fiber and method for producing the same
JP2015042792A (en) Rope

Legal Events

Date Code Title Description
AS Assignment

Owner name: E. I. DU PONT DE NEMOURS AND COMPANY, DELAWARE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:LEE, KIU-SEUNG;HARTZLER, JON DAVID;REEL/FRAME:018258/0941;SIGNING DATES FROM 20060824 TO 20060907

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION