EP0472834A2 - Anisotrope Spinnlösung mit reduzierter Viskosität - Google Patents

Anisotrope Spinnlösung mit reduzierter Viskosität Download PDF

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Publication number
EP0472834A2
EP0472834A2 EP91109761A EP91109761A EP0472834A2 EP 0472834 A2 EP0472834 A2 EP 0472834A2 EP 91109761 A EP91109761 A EP 91109761A EP 91109761 A EP91109761 A EP 91109761A EP 0472834 A2 EP0472834 A2 EP 0472834A2
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EP
European Patent Office
Prior art keywords
viscosity
poly
polymer
solution
reciprocal
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Withdrawn
Application number
EP91109761A
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English (en)
French (fr)
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EP0472834A3 (en
Inventor
William Cheng Uy
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
EI Du Pont de Nemours and Co
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Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0472834A2 publication Critical patent/EP0472834A2/de
Publication of EP0472834A3 publication Critical patent/EP0472834A3/en
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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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles

Definitions

  • Poly-p-phenylenebenzobisthiazole, poly-p-phenylenebenzobisoxazole and poly-2,5-benzoxazole are commonly prepared in polyphosphoric acid (PPA).
  • PPA polyphosphoric acid
  • Liquid crystalline solutions of poly-p-phenylenebisthiazole in solvents such as polyphosphoric acid, methanesulfonic acid and chlorosulfonic acid are taught in U.S. 4,225,700 to be useful in the preparation of high modulus, high strength materials having excellent thermal stability.
  • solvents such as polyphosphoric acid, methanesulfonic acid and chlorosulfonic acid
  • the Figure is a curve of dope viscosity as a function of concentration at 170°C at a shear rate of 0.1 reciprocal second for a solution of poly-p-phenylenebenzobisthiazole in polyphosphoric acid.
  • This invention provides an improved process for spinning a polymer selected from poly-p-phenylenebenzobisthiazole, poly-p-phenylenebenzobisoxazole or poly-2,5-benzoxazole directly from the polyphosphoric acid solution in which it was prepared, comprising adding to the polymer solution an amount of a solvent selected from methanesulfonic or chlorosulfonic acids sufficient to reduce the viscosity to less than about 50,000 poises at 170°C and 0.1 reciprocal second shear rate, spinning the solution through a spinneret and coagulating the extrudate to form fiber.
  • a solvent selected from methanesulfonic or chlorosulfonic acids
  • the viscosity of solutions of poly-p-phenylenebenzobisthiazole, poly-p-phenylenebenzobisoxazole or poly-2,5-benzoxazole in their polyphosphoric acid (PPA) polymerization medium is reduced by addition of methanesulfonic acid (MSA) or chlorosulfonic acid to yield spin dopes that can be readily extruded to form fiber.
  • MSA methanesulfonic acid
  • chlorosulfonic acid chlorosulfonic acid
  • the polymers under consideration and their preparation are well-known in the art.
  • the polymer intrinsic viscosities (I.V.) range from about 10 to 25 with poly-p-2,5-benzoxazole generally exhibiting viscosity levels at the upper end of this range.
  • the polymer concentrations in PPA as produced can vary from 5 to 15 wt.% but is generally at least 10%.
  • the spin dope viscosity of the as-produced solution of the polymer in the polymerization medium at any particular temperature and shear rate will depend on the polymer, its molecular weight and its concentration in the polymerization medium. For this reason, the amount of MSA to be added will necessarily vary.
  • a spin-dope viscosity of less than 50,000 poises and preferably less than 30,000 poises at 170°C and 0.1 reciprocal second shear rate is used.
  • the MSA or chlorosulfonic acid is added to reduce the viscosity to a readily spinnable level. It is expected that the final mixed solvent of the spin dope will contain from 20 to 60 wt. % MSA. Amounts of MSA in excess of 60 wt. % are not preferred because the polymer content will be too low for economic operation. One should also avoid the possibility of converting from an optically anisotropic to an isotropic spin-dope.
  • the figure is a plot of viscosity versus concentration of a solution of poly-p-phenylenebenzobisthiazole in polyphosphoric acid at 170°C and at a shear rate of 0.1 reciprocal second.
  • the viscosity of the solution rises as the concentration is increased to about 4% (the isotropic range) and then drops precipitously beyond that point as the concentration increases further.
  • the addition of MSA or chlorosulfonic acid in essence reduces the viscosity by lowering the curve.
  • the spinnable dope containing the mixture of solvents may be spun by procedures well known in the art as shown by Japanese Patent Application Disclosure Tokukai 61-28015 (1986) and U.S. Patent No. 4,533,693.
  • the spin dope is extruded through a spinneret into a coagulating bath from which the fibers are withdrawn.
  • the extruded dope is first passed through an air gap prior to entry into the coagulating bath which may be an aqueous solution or water itself.
  • Example 1 49 lbs. of the same 15% 100,000-poise dope as in Example 1 was mixed with 27.8 lbs of MSA in a 10-gallon Atlantic Mixer. The mixture was mixed under vacuum at 40 rpm for 3 hours. The resulting dope of 10.6% concentration was extruded at 110°C through a 290-hole spinneret through an air-gap and into a water quench bath. The resulting yarns were washed with fresh water until most of the acid solvents were extracted. The as-spun wet yarns were then heat-treated on the run (30 meters/min.) under 1.0 gpd tension at 670°C for 9 seconds.
  • the as-spun yarns had filament strengths ranging from 13.6 to 15.0 gpd and moduli of from 380 to 449 gpd.
  • the heat-treated yarns had filament strengths of about 20 gpd and moduli between about 1,800 and 2,000 gpd.
  • Example 2 46 lbs. of a 15% dope as in Example 1 was mixed with 26.0 lbs of MSA in a 10-gallon Atlantic Mixer. The mixing and processing conditions of Example 2 were used.
  • the as-spun yarns had filament strengths of from 13.1 to 14.8 gpd and moduli of from 286 to 411 gpd.
  • the heat-treated yarns had filament strengths of from 19.3 to 21.9 gpd and moduli between about 1,800 and 2,000 gpd.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
EP19910109761 1990-06-15 1991-06-14 Anisotropic spin dopes of reduced viscosity Withdrawn EP0472834A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US53843790A 1990-06-15 1990-06-15
US538437 1990-06-15

Publications (2)

Publication Number Publication Date
EP0472834A2 true EP0472834A2 (de) 1992-03-04
EP0472834A3 EP0472834A3 (en) 1992-10-14

Family

ID=24146934

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910109761 Withdrawn EP0472834A3 (en) 1990-06-15 1991-06-14 Anisotropic spin dopes of reduced viscosity

Country Status (3)

Country Link
EP (1) EP0472834A3 (de)
JP (1) JPH04241111A (de)
CA (1) CA2044407A1 (de)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994012705A1 (en) * 1992-12-03 1994-06-09 The Dow Chemical Company Rapid heat-treatment method for polybenzazole fiber
WO1994012701A1 (en) * 1992-12-03 1994-06-09 The Dow Chemical Company Polybenzazole fibers with ultra-high physical properties and method for making them
WO1994012700A1 (en) * 1992-12-03 1994-06-09 The Dow Chemical Company Low denier polybenzazole fibers and the preparation thereof
WO1994012703A1 (en) * 1992-12-03 1994-06-09 The Dow Chemical Company Method for spinning a polybenzazole fiber
WO1994012702A1 (en) * 1992-12-03 1994-06-09 The Dow Chemical Company Method for rapid spinning of a polybenzazole fiber
WO1994012704A1 (en) * 1992-12-03 1994-06-09 The Dow Chemical Company Method for rapid drying of a polybenzazole fiber
US5367042A (en) * 1992-08-27 1994-11-22 The Dow Chemical Company Process for fabricating oriented polybenzazole films
EP0834608A2 (de) * 1996-10-01 1998-04-08 Toyo Boseki Kabushiki Kaisha Polybenzazolfaser und Verfahren zu ihrer Herstellung
CN1040347C (zh) * 1992-12-03 1998-10-21 东洋纺织株式会社 聚吲哚纤维的快速干燥法
EP2576437A1 (de) * 2010-06-01 2013-04-10 Innophos, Inc. Polyphosphorsäure-zusammensetzungen mit verminderter viskosität

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4225700A (en) * 1979-04-23 1980-09-30 Sri International Thermally stable rod-like polybenzobisthiazole polymers
US4606875A (en) * 1983-04-11 1986-08-19 Celanese Corporation Process for preparing shaped articles of rigid rod heterocyclic liquid crystalline polymers
WO1987000844A1 (en) * 1985-08-05 1987-02-12 Commtech International A process for the production of a liquid crystalline extended chain polymer composition
EP0264271A2 (de) * 1986-10-15 1988-04-20 E.I. Du Pont De Nemours And Company Spinnlösung und daraus hergestellte Artikel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4225700A (en) * 1979-04-23 1980-09-30 Sri International Thermally stable rod-like polybenzobisthiazole polymers
US4606875A (en) * 1983-04-11 1986-08-19 Celanese Corporation Process for preparing shaped articles of rigid rod heterocyclic liquid crystalline polymers
WO1987000844A1 (en) * 1985-08-05 1987-02-12 Commtech International A process for the production of a liquid crystalline extended chain polymer composition
EP0264271A2 (de) * 1986-10-15 1988-04-20 E.I. Du Pont De Nemours And Company Spinnlösung und daraus hergestellte Artikel

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5367042A (en) * 1992-08-27 1994-11-22 The Dow Chemical Company Process for fabricating oriented polybenzazole films
WO1994012703A1 (en) * 1992-12-03 1994-06-09 The Dow Chemical Company Method for spinning a polybenzazole fiber
WO1994012700A1 (en) * 1992-12-03 1994-06-09 The Dow Chemical Company Low denier polybenzazole fibers and the preparation thereof
WO1994012705A1 (en) * 1992-12-03 1994-06-09 The Dow Chemical Company Rapid heat-treatment method for polybenzazole fiber
WO1994012702A1 (en) * 1992-12-03 1994-06-09 The Dow Chemical Company Method for rapid spinning of a polybenzazole fiber
WO1994012704A1 (en) * 1992-12-03 1994-06-09 The Dow Chemical Company Method for rapid drying of a polybenzazole fiber
WO1994012701A1 (en) * 1992-12-03 1994-06-09 The Dow Chemical Company Polybenzazole fibers with ultra-high physical properties and method for making them
CN1040347C (zh) * 1992-12-03 1998-10-21 东洋纺织株式会社 聚吲哚纤维的快速干燥法
EP0834608A2 (de) * 1996-10-01 1998-04-08 Toyo Boseki Kabushiki Kaisha Polybenzazolfaser und Verfahren zu ihrer Herstellung
EP0834608A3 (de) * 1996-10-01 1999-02-03 Toyo Boseki Kabushiki Kaisha Polybenzazolfaser und Verfahren zu ihrer Herstellung
US5993963A (en) * 1996-10-01 1999-11-30 Toyo Boseki Kabushiki Kaisha Polybenzazole fiber and method for production thereof
EP2576437A1 (de) * 2010-06-01 2013-04-10 Innophos, Inc. Polyphosphorsäure-zusammensetzungen mit verminderter viskosität
EP2576437A4 (de) * 2010-06-01 2015-04-08 Innophos Inc Polyphosphorsäure-zusammensetzungen mit verminderter viskosität

Also Published As

Publication number Publication date
CA2044407A1 (en) 1991-12-16
JPH04241111A (ja) 1992-08-28
EP0472834A3 (en) 1992-10-14

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