WO1992001108A1 - Procede d'amelioration de la resistance hydrolytique de fibre aramide - Google Patents

Procede d'amelioration de la resistance hydrolytique de fibre aramide Download PDF

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Publication number
WO1992001108A1
WO1992001108A1 PCT/US1991/004771 US9104771W WO9201108A1 WO 1992001108 A1 WO1992001108 A1 WO 1992001108A1 US 9104771 W US9104771 W US 9104771W WO 9201108 A1 WO9201108 A1 WO 9201108A1
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WO
WIPO (PCT)
Prior art keywords
fiber
aramid fiber
hydrolytic resistance
coating
accordance
Prior art date
Application number
PCT/US1991/004771
Other languages
English (en)
Inventor
Charles H. Stephenson
Hung Han Yang
Original Assignee
E.I. Du Pont De Nemours And Company
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 E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Publication of WO1992001108A1 publication Critical patent/WO1992001108A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D06M2101/36—Aromatic polyamides

Definitions

  • the present invention provides a process for improving the hydrolytic resistance of aramid fiber by coating such fiber with an aqueous fluoropolymer dispersion.
  • the invention also contemplates poly(p- phenyleneterephthalamide) aramid fiber having improved hydrolytic resistance.
  • Trask, United States Patent, 4,232,087 discloses a method of coating "Nomex" aramid fibers with a dispersion comprised of polytetrafluoro- ethylene particles in the presence of water and a water soluble chromium complex of a long chain fluorochemical to improve the air permeability, acid resistance, water repellency, and oil repellency of the fibers.
  • Sasaki et al.. United States Patent, 4,337,155 discloses preparing an emulsion of a fluorine-containing polymeric resin and then coating the emulsion onto wholly aromatic polyamide fiber material to improve the air permeability, and acid resistance of the material.
  • compositions may then be applied as a water dispersion to provide oil and water '• *" repellent properties to films, fibers, yarns, fabrics, and other articles.
  • the present invention relates to treating aramid fiber with a dispersion of fluoropolymer in water, in order to improve the hydrolytic resistance of such fiber.
  • the invention provides a process of uniformly coating aramid fiber with an aqueous dispersion comprising a polymer of ethylenically unsaturated monomers, a major proportion by weight of which is at least one fluorinated alkyl methacrylate polymer of the monomer,
  • the polymer is a copolymer derived from about 75% by weight of the afore ⁇ mentioned fluorinated methacrylate monomer and about 25% by weight of a non-fluorine containing monomer such as 2- ethylhexylmethacrylate.
  • the fiber is then dried while the coating is cured to its surface, preferably by heating the fiber for 15 to 60 minutes at a temperature in the range of 1303 to 1703C.
  • poly(p-phenylene terephthalamide) aramid fiber is uniformly coated with a dispersion of fluoropolymer in water such that the amount of fluorocarbon containing coating is in the range of 0.25 to 2% based on total weight of the coated fiber.
  • the poly(p-phenylene terephthalamide) aramid fiber thus prepared exhibits an improvement in hydrolytic resistance by greater than 20% compared to an uncoated poly(p-phenylene terephthalamide) aramid fiber.
  • the present invention provides a process for improving the hydrolytic resistance of aramid fiber, particularly poly(p-phenylene terephthalamide) aramid fiber.
  • the process includes uniformly coating the aramid fiber with a dispersion of fluoropolymer in water, and then drying the fiber while curing the coating to its surface.
  • fluoropolymer dispersions employed in the practice of the invention are disclosed in the afore ⁇ mentioned Fasick et al. U.S. Patent 3,378,609. They are based on the fluorinated methacrylate monomer,
  • a preferred fluoropolymer of the invention is a copolymer of about 75% by weight of the fluorinated methacrylate monomer
  • the fluorinated methacrylate monomer is made by reacting methacrylic acid with a mixture of alcohols,
  • the fluoropolymer dispersion may optionally contain other polymers, such as for example a copolymer containing a small amount of a crosslinking agent.
  • the fluoropolymer dispersion is then applied to the aramid fiber when the fiber is either wet or dry. Any conventional coating method for example, immersing or spraying, can be used, but it is important that the dispersion is of a suitable viscosity to be uniformly applied to the fiber.
  • the dispersion can be diluted with water, if needed. A person having ordinary skill in the art will be able to identify which dispersions have suitable viscosities.
  • wet, never-dried poly(p-phenylene terephthalamide) aramid fiber which is produced according to spinning processes described in Blades, United States Patent, 3,767,756 and Yang, United States Patent, 4,340,559 is immersed in a coating bath containing the fluoropolymer dispersion at room temperature.
  • the coating bath is diluted to contain 1% by weight of the preferred fluoropolymer dispersion, a copolymer of about 75% by weight of the fluorinated methacrylate monomer,
  • CH 2 C(CH 3 )C0 2 CH 2 CH 2 C n F 2 n+l wherein n varies from 6 to 14, and about 25% by weight of
  • the fiber is dried while the fluorocarbon containing coating is cured to its surface by techniques known in the art.
  • curing is performed by heating the fiber for 15 to 60 minutes at a temperature in the range of 1303 to 1703C. Longer heating periods are required with lower temperatures, and vice-versa. At 1503C, for example, a drying time of 30-60 minutes is needed.
  • the aramid fiber is uniformly coated with the fluoropolymer dispersion such that the amount of fluorocarbon containing coating is in the range of 0.25 to 2% based on the total weight of the coated fiber.
  • the cured fluorocarbon containing coating improves the hydrolytic resistance of the aramid fiber by greater than 20% compared to an uncoated fiber. Testing Procedures Tensile Properties
  • Tenacity is reported as breaking strength divided by linear density. Modulus is reported as the slope of the initial stress/strain curve converted to the same units as tenacity. Elongation is the percent increase in length at break. Both tenacity and modulus are first computed in g/denier units which, when multiplied by 0.8838, yield dN/tex units. Each reported measurement is the average of 5 breaks.
  • Tensile properties for yarns are measured at 243C and 55% relative humidity after conditioning under test conditions for a minimum of 14 hours. Before testing, each yarn is twisted to a 1.1 twist multiplier (for example, nominal 1500 denier yarn is twisted about 0.8 turns/cm) . Each twisted specimen has a test length of 25.4 cm and is elongated 50% per minute (based on the original unstretched length) using a typical recording stress/strain device.
  • the twist multiplier (TM) of yarn is defined as:
  • a finish-free wet, never-dried poly(p-phenylene terephthalamide) aramid yarn was produced according to spinning processes described in Blades, United States Patent, 3,767,756 and Yang, United States Patent, 4,340,559.
  • the aramid fiber was then tested for its hydrolytic resistance.
  • the test yarn had a linear density of 1462 denier at 1.5 dpf (denier per filament). It gave tensile properties of 21.4 gpd (grams per denier) tenacity, 3.5% elongation at break, and 542 gpd initial modulus.
  • a 5 m long skein of the yarn was tested for hydrolytic resistance by immersing the yarn in a 10% NaOH solution at 953C for 20 hours.
  • test yarn skein was then thoroughly washed with water at room temperature and left to dry in air at zero tension.
  • the hydrolyzed yarn gave a retained tenacity of 4.2 gpd, which was a 19.6% retention of its original tenacity.
  • the alkaline hydrolysis was extended to 100 hours, the hydrolyzed yarn was too weak to be tested for its tensile properties.
  • This example illustrates the improved hydrolytic resistance of poly(p-phenylene terephthalamide) aramid yarn after such yarn is coated with a dispersion of fluoro-polymer in water.
  • the fluoropolymer dispersion is formed as an aqueous dispersion in water of two components, A and B.
  • Component A is a polymer formed by the polymerization of
  • CH 2 C(CH 3 )C0 2 CH 2 CH 2 C n F 2n+1 wherein n varies from 6 to 14 with an average of 8, together with about 0.25% each of N-methylolacrylamide and
  • Component B is a terpolymer of100 parts 2-ethylhexylmethacrylate with 2 parts
  • N-methylolacrylamide and 0.5 parts ethylene dimethacrylate about 8 parts of A is used with about 6 parts of B to produce an emulsion having 14% solids.
  • the fluoropolymer dispersion was added to a coating bath which was then diluted with water until the bath contained 1% of said fluoropolymer dispersion.
  • a 5 m long skein of the finish-free yarn used as a COMPARATIVE EXAMPLE was then immersed in the bath containing 1% fluoropolymer dispersion at room temperature for 40 hours.
  • the yarn was uniformly coated with the fluoropolymer dispersion such that the amount of fluoro ⁇ carbon containing coating was about 0.75% of the cured fiber.
  • the yarn was then dried while the coating was cured to its surface at 1503C at zero tension for half an hour.
  • Table I shows, the coated yarn was subjected to hydrolysis in a 10% NaOH solution at 953C for 20 hours.
  • the hydrolyzed yarn gave a retained tenacity of 15.2 gpd which was a 71.0% retention of its original tenacity.
  • the hydrolyzed yarn gave a retained tenacity of 7.9 gpd which was a 36.9% retention of its original tenacity.
  • This example illustrates similar improvements in the hydrolytic resistance of poly(p-phenylene terephthalamide) aramid yarn when the yarn is coated with a dispersion of fluoropolymer in water.
  • Table I the process of EXAMPLE I was carried out except that the time of immersing the yarn in the coating bath containing 1% of the fluoropolymer dispersion was decreased to 1 minute.
  • the yarn was uniformly coated with the fluoropolymer dispersion such that the amount of fluorocarbon containing coating was about 0.6% of the coated fiber.
  • the coated yarn was subjected to hydrolysis in a 10% NaOH solution at 953C for 20 hours.
  • the hydrolyzed yarn gave a retained tenacity of 14.7 gpd which was a 68.7% retention of its original tenacity.
  • the hydrolyzed yarn gave a retained tenacity of 6.8 gpd which was a 31.8% retention of its original tenacity.

Abstract

Procédé d'amélioration de la résistance hydrolytique d'une fibre aramide, notamment d'une fibre poly(p-phénylène téréphtalamide). Le procédé consiste à recouvrir une fibre aramide d'une dispersion de fluoropolymère aqueuse et à sécher la fibre tout en polymérisant le revêtement à sa surface.
PCT/US1991/004771 1990-07-11 1991-07-10 Procede d'amelioration de la resistance hydrolytique de fibre aramide WO1992001108A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US55112390A 1990-07-11 1990-07-11
US551,123 1990-07-11

Publications (1)

Publication Number Publication Date
WO1992001108A1 true WO1992001108A1 (fr) 1992-01-23

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PCT/US1991/004771 WO1992001108A1 (fr) 1990-07-11 1991-07-10 Procede d'amelioration de la resistance hydrolytique de fibre aramide

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AU (1) AU8327891A (fr)
WO (1) WO1992001108A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1396572A1 (fr) * 2002-09-06 2004-03-10 Teijin Twaron GmbH Procédé de fabrication d'un tissu d'aramide hydrofuge et son utilisation
US7153790B2 (en) * 2002-09-06 2006-12-26 Teijin Twaron Gmbh Penetration-resistant material and articles made of the same
CN101851859A (zh) * 2010-05-28 2010-10-06 浙江理工大学 一种抗水解聚乳酸纤维材料制备方法
US20130029151A1 (en) * 2011-03-18 2013-01-31 E. I. Du Pont De Nemours And Company Flame-resistant finish for inherently flame resistant polymer yarns and process for making same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1010539A (en) * 1961-05-03 1965-11-17 Du Pont Fluorine-containing polymer compositions
EP0032744A2 (fr) * 1980-01-22 1981-07-29 Teijin Limited Matériau de fibre de polyamide aromatique total résistant aux produits chimiques

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1010539A (en) * 1961-05-03 1965-11-17 Du Pont Fluorine-containing polymer compositions
EP0032744A2 (fr) * 1980-01-22 1981-07-29 Teijin Limited Matériau de fibre de polyamide aromatique total résistant aux produits chimiques

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Vol. 113, No. 16, 15 October 1990, Columbus, Ohio, US, Abstract No. 134087U, YONETANI MASAYUKI, "Manufacture of Para-Oriented Aramid Fibers with Low Moisture Adsorption", page 94; & JP,A,02 084 508, (ASAHI CHEMICAL INDUSTRY CO., LTD). *
PATENT ABSTRACTS OF JAPAN, Vol. 11, No. 332, (C-455), 29 October 1987; & JP,A,62 115 040, (ASAHI CHEM IND CO LTD.), 26 May 1987. *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1396572A1 (fr) * 2002-09-06 2004-03-10 Teijin Twaron GmbH Procédé de fabrication d'un tissu d'aramide hydrofuge et son utilisation
JP2004263360A (ja) * 2002-09-06 2004-09-24 Teijin Twaron Gmbh 疎水仕上げされたアラミド織物を製造するための方法およびその使用
US7132131B2 (en) * 2002-09-06 2006-11-07 Teijin Twaron Gmbh Method for producing a hydrophobically finished aramid fabric and use thereof
US7153790B2 (en) * 2002-09-06 2006-12-26 Teijin Twaron Gmbh Penetration-resistant material and articles made of the same
AU2003270135B2 (en) * 2002-09-06 2009-04-23 Teijin Aramid Gmbh Penetration-resistant material and articles made of the same
JP4614306B2 (ja) * 2002-09-06 2011-01-19 テイジン・アラミド・ゲーエムベーハー 疎水仕上げされたアラミド織物を製造するための方法およびその使用
CN101851859A (zh) * 2010-05-28 2010-10-06 浙江理工大学 一种抗水解聚乳酸纤维材料制备方法
US20130029151A1 (en) * 2011-03-18 2013-01-31 E. I. Du Pont De Nemours And Company Flame-resistant finish for inherently flame resistant polymer yarns and process for making same

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Publication number Publication date
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