EP0310171A2 - Melt-spinning process - Google Patents

Melt-spinning process Download PDF

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Publication number
EP0310171A2
EP0310171A2 EP88202039A EP88202039A EP0310171A2 EP 0310171 A2 EP0310171 A2 EP 0310171A2 EP 88202039 A EP88202039 A EP 88202039A EP 88202039 A EP88202039 A EP 88202039A EP 0310171 A2 EP0310171 A2 EP 0310171A2
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EP
European Patent Office
Prior art keywords
melt
fibres
polymer
ethylene
temperature
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.)
Granted
Application number
EP88202039A
Other languages
German (de)
French (fr)
Other versions
EP0310171B1 (en
EP0310171A3 (en
Inventor
Johan Maria Beyen
Ebel Klei
Houston Slade Brown
Paul Aldred Westbrook
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.)
Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Priority claimed from GB878722967A external-priority patent/GB8722967D0/en
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Priority to AT88202039T priority Critical patent/ATE97962T1/en
Publication of EP0310171A2 publication Critical patent/EP0310171A2/en
Publication of EP0310171A3 publication Critical patent/EP0310171A3/en
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Publication of EP0310171B1 publication Critical patent/EP0310171B1/en
Anticipated expiration legal-status Critical
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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
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • 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
    • D01F6/96—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers

Definitions

  • the invention relates to a process for producing thermoplastic polymer fibres by melt spinning, and to tyres comprising fibres thus spun.
  • melt-spun thermoplastic fibres can be applied in the manufacture of car tyres and today large tonnage quantities are consumed in that market.
  • Large volume polymers for this application are polyamides and polyesters, whereas polypropylene fibres can be employed as well.
  • per tyre a fairly large quantity of fibre has to be used relative to the amount of elastomer. This is due to balance of properties of the aforesaid polymers which balance is mainly governed by the combination of tensile strength, flex-modulus and adhesion to rubber.
  • thermoplastic fibres such as polyaramide (available under the trademarks KEVLAR or TWARON) or gel-spun high mol. weight polyethylene might be better suited in this respect, however, they are far too expensive to find their way in the tyre manufacturing industry.
  • thermoplastic polymers viz. alternating copolymers of an olefinically unsaturated hydrocarbon and carbon monoxide, has a very promising potential for solving the problem of reducing the relative weight of fibre to be employed for tyre manufacturing.
  • melt-spun fibres made of the aforesaid alternating copolymer type show an improved balance of combined tensile strength, flex modulus and adhesion to rubber, provided the melt-spinning and stretching of the fibre is implemented at certain critical temperature conditions.
  • the present invention is concerned with a process for the production of thermoplastic polymer fibres, characterized in that an alternating copolymer of carbon monoxide and an olefinically unsaturated compound, this polymer having an average molecular weight of at least 2000, is melt-spun at a temperature of at least (T+20) K, and the fibre is subsequently stretched at a temperature of at most (T-10) K, in which T is the crystalline melting point of the polymer.
  • the stretching is effected at a stretching ratio of at least 3:1, more preferably at least 7:1, and at most 15:1.
  • Preferred stretching temperatures are those of at least 40 K below the crystalline melting point of the polymer and preferred melt-spinning temperatures are those of at least 40 K above the crystalline melting point of the polymer.
  • alternating copolymer refers to those copolymers in which the CO-units in the macromolecules are in alternating arrangement in respect of the units derived from the olefin.
  • each CO-unit is positioned next to a single unit of olefin, e.g. ethylene.
  • the copolymer can be a true copolymer of carbon monoxide and one particular olefin, preferably ethylene or they can be copolymers of carbon monoxide and more than one olefin, e.g. ethylene and propylene.
  • ethylene is preferably employed as the major olefin.
  • the relevant alternating copolymers are known per se, for example from EP-A-121965, EP-A-213671, EP-A-229408 and US-A-3914391, likewise, their methods of preparation by catalytic copolymerization are known from these references.
  • Suitable polymerization catalysts are based upon palladium/phosphine systems. Use of other known ethylene/CO copolymers which do not display an alternating structure and which are produced using free radical catalysts, is not contemplated in this invention.
  • the copolymers have a molecular weight between 1000 and 500,000.
  • the copolymers should have an average molecular weight of at least 5000, more preferably at least 8000. Especially good results are obtained with those of molecular weight from 10,000 to 50,000.
  • polyketone polymers will depend in part on the molecular weight of the polymer, whether the polymer is a copolymer or a terpolymer and the relative proportion of the second hydrocarbon present in the case of terpolymers.
  • Typical melting points for such polymers are from about 175 °C to about 300 °C, more typically from 180°C to 280 °C.
  • Useful polymers for the novel fibres have limiting viscosity numbers (LVN) as measured by the method wherein the polymer is dissolved in metacresol at 60°C; using a standard capillary viscosity measuring device such as a Cannon-Ubbelohde viscometer, in the range of 0.5 to 10 LVN and more preferably 0.8 to 4 LVN and most preferably 0.8 to 2.5 LVN.
  • LDN viscosity numbers
  • the fibres produced with the process of this invention have a markedly improved ITS.IM product as compared with fibres produced from polyamides, polyester or polypropylene.
  • ITS represents the factor of improvement of tensile strength
  • IM represents the factor of improvement of modulus.
  • the comparison is made whilst employing identical stretching ratios to typical fibre grades of the various thermoplastics. The improvement is recorded relative to the same property determined with non-stretched, conventional compression moulded test specimina.
  • thermoplastic polymers to be employed in the process of this invention are copolymers of ethylene and carbon monoxide, and terpolymers of ethylene, propylene and carbon monoxide, preferably those in which the ethylene to propylene molar ratio in the polymer chains is at least 3:1.
  • terpolymers are terpolymers of ethylene and carbon monoxide with butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, styrene, methyl acrylate, methylmethacrylate, vinylacetate, undecenoic acid, undecenol, 6-chlorohexene, N-vinyl-­pyrrolidon and diethylester of vinyl-phosphonic acid, provided the molar ratio of ethylene to other unsaturated monomer in the polymer macromolecules is at least 3:1, preferably at least 8:1.
  • the fibres according to the invention are very suitable too for the preparation of polymer mats.
  • Such mats especially spun-bonded non-woven mats, may be used, for example, as the reinforcing layer in rolled roofing membranes prepared from modified bitumen.
  • roofing membranes are superior to known polyester-­reinforced roofings because the fibres show higher mechanical strength and better adhesion to the bitumen.
  • Another useful application of these mats, particularly when woven into a fabric or mesh lies in the preparation of a so-called geotextile, that is a permeable synthetic membrane specifically designed to be used as a construction material in civil engineering situations such as roads, drains, riverbanks, coastlines, embankments and so on. It appears that geotextiles made from the fibres according to the invention, suitably including a UV-stabiliser, have the required tensile strength, E-modulus, water permeability and soil tightness.
  • Nominal tensile strength and flex modulus were determined with conventional compression moulded test specimina and fibres were melt-spun and stretched at a 6:1 ratio.
  • the stretch temperature for the alternating copolymer was 480 K and the melt-spinning temperature was 560 K.
  • Adhesion of the fibres to styrene-butadiene elastomer was determined by testing methods current in the tyre manufacturing industry. The results are represented on a relative scale: + means fair to good, ++ stands for very good and +++ is excellent.
  • Copolymer of carbon monoxide, ethylene and propylene of the same batch as used in example 1, is melt-spun at a range of temperatures from 515 to 560 K, via a multi-hole spinneret, quenched with forced air at a temperature of 30 ⁇ 0.5 °C, and stretched 5 to 10-fold.
  • the multi-filaments thus obtained are lightly twisted to yarns, after which 2 or 3 yarns are twined to a cord. These cords are woven to fabrics, which are dipped in adhesive.
  • the fabrics are post-stretched and annealed, thus obtaining fabric cords, presenting attractive adhesion, tensile and flex properties rendering them suitable for use as tyre cords.

Abstract

A process for producing thermoplastic polymer fibres by melt-spinning, characterized in that an alternating copolymer of an olefinically unsaturated compound and carbon monoxide, having a molecular weight of at least 2000, is melt-spun at a temperature of at least (T+20) K and the fibre is subsequently stretched at a temperature of at most (T-10) K, in which T is the crystalline melting point of the polymer. The fibres thus spun are suitable as tyre reinforcements.

Description

  • The invention relates to a process for producing thermoplastic polymer fibres by melt spinning, and to tyres comprising fibres thus spun.
  • Melt-spun thermoplastic fibres can be applied in the manufacture of car tyres and today large tonnage quantities are consumed in that market. Large volume polymers for this application are polyamides and polyesters, whereas polypropylene fibres can be employed as well. However, per tyre a fairly large quantity of fibre has to be used relative to the amount of elastomer. This is due to balance of properties of the aforesaid polymers which balance is mainly governed by the combination of tensile strength, flex-modulus and adhesion to rubber. In view thereof it is not possible to reduce the amount of fibre per tyre without paying the penalty of adversily affecting the quality of the tyre, thus making the tyre unsuitable for most of the market applications. Other thermoplastic fibres such as polyaramide (available under the trademarks KEVLAR or TWARON) or gel-spun high mol. weight polyethylene might be better suited in this respect, however, they are far too expensive to find their way in the tyre manufacturing industry.
  • The Applicants have found that another type of thermoplastic polymers, viz. alternating copolymers of an olefinically unsaturated hydrocarbon and carbon monoxide, has a very promising potential for solving the problem of reducing the relative weight of fibre to be employed for tyre manufacturing.
  • Compared with polyamides, polyesters or poly­propylene, melt-spun fibres made of the aforesaid alternating copolymer type show an improved balance of combined tensile strength, flex modulus and adhesion to rubber, provided the melt-spinning and stretching of the fibre is implemented at certain critical temperature conditions.
  • The present invention is concerned with a process for the production of thermoplastic polymer fibres, characterized in that an alternating copolymer of carbon monoxide and an olefinically unsaturated compound, this polymer having an average molecular weight of at least 2000, is melt-spun at a temperature of at least (T+20) K, and the fibre is subsequently stretched at a temperature of at most (T-10) K, in which T is the crystalline melting point of the polymer.
  • Preferably, the stretching is effected at a stretching ratio of at least 3:1, more preferably at least 7:1, and at most 15:1. Preferred stretching temperatures are those of at least 40 K below the crystalline melting point of the polymer and preferred melt-spinning temperatures are those of at least 40 K above the crystalline melting point of the polymer.
  • The term "fibre" wherever used in this speci­fication includes mono- and multifilaments in addition to fibres. The term "alternating" copolymer refers to those copolymers in which the CO-units in the macromolecules are in alternating arrangement in respect of the units derived from the olefin. Thus, in the macromolecular chains, each CO-unit is positioned next to a single unit of olefin, e.g. ethylene. The copolymer can be a true copolymer of carbon monoxide and one particular olefin, preferably ethylene or they can be copolymers of carbon monoxide and more than one olefin, e.g. ethylene and propylene. In the latter case ethylene is preferably employed as the major olefin. The relevant alternating copolymers are known per se, for example from EP-A-121965, EP-A-213671, EP-A-229408 and US-A-3914391, likewise, their methods of preparation by catalytic copolymerization are known from these references. Suitable polymerization catalysts are based upon palladium/phosphine systems. Use of other known ethylene/CO copolymers which do not display an alternating structure and which are produced using free radical catalysts, is not contemplated in this invention.
  • Usually the copolymers have a molecular weight between 1000 and 500,000.
  • Preferably the copolymers should have an average molecular weight of at least 5000, more preferably at least 8000. Especially good results are obtained with those of molecular weight from 10,000 to 50,000.
  • The physical properties of the "polyketone" polymers will depend in part on the molecular weight of the polymer, whether the polymer is a copolymer or a terpolymer and the relative proportion of the second hydrocarbon present in the case of terpolymers.
  • Typical melting points for such polymers are from about 175 °C to about 300 °C, more typically from 180°C to 280 °C.
  • Useful polymers for the novel fibres have limiting viscosity numbers (LVN) as measured by the method wherein the polymer is dissolved in metacresol at 60°C; using a standard capillary viscosity measuring device such as a Cannon-Ubbelohde viscometer, in the range of 0.5 to 10 LVN and more preferably 0.8 to 4 LVN and most preferably 0.8 to 2.5 LVN.
  • Melt-spinning and stretching of the fibre can be carried out with equipment that is currently available on the market.
  • The fibres produced with the process of this invention have a markedly improved ITS.IM product as compared with fibres produced from polyamides, polyester or polypropylene. In this product ITS represents the factor of improvement of tensile strength and IM represents the factor of improvement of modulus. The comparison is made whilst employing identical stretching ratios to typical fibre grades of the various thermoplastics. The improvement is recorded relative to the same property determined with non-stretched, conventional compression moulded test specimina.
  • Particularly suitable thermoplastic polymers to be employed in the process of this invention are copolymers of ethylene and carbon monoxide, and terpolymers of ethylene, propylene and carbon monoxide, preferably those in which the ethylene to propylene molar ratio in the polymer chains is at least 3:1. Other suitable terpolymers are terpolymers of ethylene and carbon monoxide with butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, styrene, methyl acrylate, methylmethacrylate, vinylacetate, undecenoic acid, undecenol, 6-chlorohexene, N-vinyl-­pyrrolidon and diethylester of vinyl-phosphonic acid, provided the molar ratio of ethylene to other unsaturated monomer in the polymer macromolecules is at least 3:1, preferably at least 8:1.
  • The fibres according to the invention are very suitable too for the preparation of polymer mats. Such mats, especially spun-bonded non-woven mats, may be used, for example, as the reinforcing layer in rolled roofing membranes prepared from modified bitumen. Such roofing membranes are superior to known polyester-­reinforced roofings because the fibres show higher mechanical strength and better adhesion to the bitumen. Another useful application of these mats, particularly when woven into a fabric or mesh, lies in the preparation of a so-called geotextile, that is a permeable synthetic membrane specifically designed to be used as a construction material in civil engineering situations such as roads, drains, riverbanks, coastlines, embankments and so on. It appears that geotextiles made from the fibres according to the invention, suitably including a UV-stabiliser, have the required tensile strength, E-modulus, water permeability and soil tightness.
    • Example 1
  • Comparative tests were carried out with melt-­spinning of current commercial fibre grades of Nylon-6 (N-6), polypropylene (PP) and with a fibre grade of an alternating copolymer of carbon monoxide, ethylene, and, based upon ethylene, 8 mol% of propylene ethylene (CE). The polyamide had a molecular weight of from 10,000 to 25,000, the polypropylene grade had a melt index of 20 dg/min and the copolymer had a molecular weight of 10,000 to 25,000 and a crystalline melting point of 493 K.
  • Nominal tensile strength and flex modulus were determined with conventional compression moulded test specimina and fibres were melt-spun and stretched at a 6:1 ratio. The stretch temperature for the alternating copolymer was 480 K and the melt-spinning temperature was 560 K.
  • The table below lists the testing results. Table
    Tensile Strength, MPa Flex modulus, GPa Product ITS.IM Adhesion
    nominal stretched nominal stretched
    N-6x 30 950 1 5.7 180.5 ++
    PPx 35 700 1.5 9.2 122.4 +
    CE 50 1400 1.4 15.1 302.4 +++
    x for comparison
  • Adhesion of the fibres to styrene-butadiene elastomer was determined by testing methods current in the tyre manufacturing industry. The results are represented on a relative scale: + means fair to good, ++ stands for very good and +++ is excellent.
    • Example 2
  • Copolymer of carbon monoxide, ethylene and propylene of the same batch as used in example 1, is melt-spun at a range of temperatures from 515 to 560 K, via a multi-hole spinneret, quenched with forced air at a temperature of 30 ± 0.5 °C, and stretched 5 to 10-fold. The multi-filaments thus obtained are lightly twisted to yarns, after which 2 or 3 yarns are twined to a cord. These cords are woven to fabrics, which are dipped in adhesive. The fabrics are post-stretched and annealed, thus obtaining fabric cords, presenting attractive adhesion, tensile and flex properties rendering them suitable for use as tyre cords.

Claims (10)

1. A process for producing thermoplastic polymer fibres by melt-spinning, characterized in that an alternating copolymer of an olefinically unsaturated compound and carbon monoxide, having a molecular weight of at least 2000, is melt-spun at a temperature of at least (T+20) K and the fibre is subsequently stretched at a temperature of at most (T-10) K, in which T is the crystalline melting point of the polymer.
2. A process as claimed in claim 1, in which the melt-spinning temperature is at least (T+40) K.
3. A process as claimed in claim 1 or 2, in which the stretching temperature is at most (T-25) K.
4. A process as claimed in any of claims 1 to 3, in which the stretching ratio is at least 3:1.
5. A process as claimed in claim 4, in which the stretching ratio is at least 7:1.
6. A process as claimed in any of claims 1 to 5, in which the molecular weight of the polymer is at least 5000.
7. A process as claimed in claim 6 in which the molecular weight of the polymer is at least 8000.
8. A process as claimed in any of claims 1 to 7, in which the copolymer is an ethylene/CO copolymer.
9. A process as claimed in any of claims 1 to 7, in which the copolymer is an ethylene/propylene/CO terpolymer comprising at most 25% mol of propylene in respect of ethylene.
10. A tyre comprising fibres characterized in that they have been produced with a process as claimed in any of claims 1 to 9.
EP88202039A 1987-09-30 1988-09-15 Melt-spinning process Revoked EP0310171B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88202039T ATE97962T1 (en) 1987-09-30 1988-09-15 MELT SPINNING PROCESS.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB878722967A GB8722967D0 (en) 1987-09-30 1987-09-30 Melt-spinning process
GB8722967 1987-09-30
US17502488A 1988-03-30 1988-03-30
US175024 1988-03-30

Publications (3)

Publication Number Publication Date
EP0310171A2 true EP0310171A2 (en) 1989-04-05
EP0310171A3 EP0310171A3 (en) 1990-01-10
EP0310171B1 EP0310171B1 (en) 1993-12-01

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Application Number Title Priority Date Filing Date
EP88202039A Revoked EP0310171B1 (en) 1987-09-30 1988-09-15 Melt-spinning process

Country Status (8)

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EP (1) EP0310171B1 (en)
JP (1) JP2763779B2 (en)
KR (1) KR960000787B1 (en)
CN (1) CN1014155B (en)
AU (1) AU604972B2 (en)
BR (1) BR8805005A (en)
DE (1) DE3885996T2 (en)
ES (1) ES2047022T3 (en)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0360358A2 (en) * 1988-09-22 1990-03-28 Shell Internationale Researchmaatschappij B.V. Process for the preparation of thermoplastic fibres
WO1990014453A1 (en) * 1989-05-19 1990-11-29 Stamicarbon B.V. Elongated object made of a copolymer of carbon monoxide and an olefinically unsaturated monomer, and method for the production thereof
EP0456306A1 (en) * 1990-05-09 1991-11-13 Akzo Nobel N.V. Process for making polyketone fibres
US5494998A (en) * 1994-11-14 1996-02-27 Akzo Nobel N.V. Polymerization of carbon monoxide and ethylene using catalyst containing non-coordinating, non-acidic anion
US5565546A (en) * 1995-05-05 1996-10-15 Akzo Nobel Nv Copolymer of carbon monoxide and ethylene containing ketal structures
US5597389A (en) * 1993-02-19 1997-01-28 Shell Oil Company Dyeing of polyketone fiber
WO1997017524A2 (en) * 1995-11-08 1997-05-15 Shell Internationale Research Maatschappij B.V. Deformable well screen and method for its installation
WO1999041437A1 (en) * 1998-02-12 1999-08-19 Akzo Nobel N.V. Process for preparing polyketone fibres
WO2000009788A1 (en) * 1998-08-11 2000-02-24 Acordis Industrial Fibers B.V. Fibres melt-spun from a thermoplastic alternating copolymer and a process for preparing such fibres
EP1111103A1 (en) * 1999-12-20 2001-06-27 Acordis Industrial Fibers BV Dipped cord made of melt spun filament yarns of an alternating copolymer and a process for manufacturing said cord
US6818728B2 (en) 2001-02-27 2004-11-16 Asahi Kasei Kabushiki Kaisha Polyketone fiber and process for producing the same
WO2012146612A1 (en) 2011-04-28 2012-11-01 Compagnie Generale Des Etablissements Michelin Aramid/polyketone composite textile cord
DE202017002839U1 (en) 2017-05-30 2018-08-31 Perlon Nextrusion Monofil GmbH Polyketone fibers, their preparation and use
WO2019122619A1 (en) 2017-12-22 2019-06-27 Compagnie Generale Des Etablissements Michelin Pneumatic tyre comprising an improved bracing ply
WO2019122620A1 (en) 2017-12-22 2019-06-27 Compagnie Generale Des Etablissements Michelin Tyre comprising an improved hooping ply
WO2019122621A1 (en) 2017-12-22 2019-06-27 Compagnie Generale Des Etablissements Michelin Method for producing a threadlike reinforcement element

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3652116B2 (en) * 1998-05-28 2005-05-25 横浜ゴム株式会社 Pneumatic radial tire
JP2007283896A (en) 2006-04-17 2007-11-01 Bridgestone Corp Pneumatic tire
JP2008273264A (en) * 2007-04-25 2008-11-13 Bridgestone Corp Run flat tire
CN108237899B (en) 2016-12-27 2020-02-21 比亚迪股份有限公司 Drive shaft locking device, power drive system and vehicle
EP4174624A4 (en) * 2021-08-26 2024-01-17 Elasto Lc Input device for computer

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076911A (en) * 1975-11-05 1978-02-28 Union Oil Company Of California Ethylene-carbon monoxide copolymers
GB1506565A (en) * 1974-03-05 1978-04-05 Nat Res Dev Production of polyethylene filaments
EP0121965A2 (en) * 1983-04-06 1984-10-17 Shell Internationale Researchmaatschappij B.V. Process for the preparation of polyketones
EP0213671A1 (en) * 1985-08-29 1987-03-11 Shell Internationale Researchmaatschappij B.V. New polymers of carbon monoxide and ethene
EP0228733A1 (en) * 1985-12-23 1987-07-15 Shell Internationale Researchmaatschappij B.V. Process for the working-up of ethylene/carbon monoxide copolymers

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57191322A (en) * 1981-05-11 1982-11-25 Toray Ind Inc Aromatic polyether ketone fiber and its preparation
US4747988A (en) * 1985-05-10 1988-05-31 Hoechst Celanese Corporation Process of making an aromatic polyetherketone fiber product

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1506565A (en) * 1974-03-05 1978-04-05 Nat Res Dev Production of polyethylene filaments
US4076911A (en) * 1975-11-05 1978-02-28 Union Oil Company Of California Ethylene-carbon monoxide copolymers
EP0121965A2 (en) * 1983-04-06 1984-10-17 Shell Internationale Researchmaatschappij B.V. Process for the preparation of polyketones
EP0213671A1 (en) * 1985-08-29 1987-03-11 Shell Internationale Researchmaatschappij B.V. New polymers of carbon monoxide and ethene
EP0228733A1 (en) * 1985-12-23 1987-07-15 Shell Internationale Researchmaatschappij B.V. Process for the working-up of ethylene/carbon monoxide copolymers

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
A. Ziabicki, "Fundamentals of Fibre Formation", John Wiley & Sons, London, 1976, pages 4 to 6 *
A. Ziabicki, "Fundamentals of Fibre Formation", John Wiley & Sons, London, 1976, pages 427 to 429 *
Béla von Falkai, "Synthesefasern", verlag Chemie, Weinheim, 1981, pages 14, 163, 165, 173, 174 and 191 to 193 *
C.M. Blow et al., "Rubber Technology and Manufacture", 2nd Edition, Butterworth scientific for the plastics and rubber Institute 1982, page 537 *
Encyclopedia of Polymer Science and Engineering; 2nd edition, Vol.6: Fibers; J. Wiley & Sons, New York, 1986, pages 648, 649 *
J. Smook et al., "Is High-Modulus Polyamide-6 Feasible?", Enka b.v. Research Institute, Arnhem, NL *
J.M. Preston "Fibre Science", the Textile Institute, Manchester, 1949, pages 69 to 73 *

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0360358A2 (en) * 1988-09-22 1990-03-28 Shell Internationale Researchmaatschappij B.V. Process for the preparation of thermoplastic fibres
EP0360358B1 (en) * 1988-09-22 1992-12-23 Shell Internationale Researchmaatschappij B.V. Process for the preparation of thermoplastic fibres
WO1990014453A1 (en) * 1989-05-19 1990-11-29 Stamicarbon B.V. Elongated object made of a copolymer of carbon monoxide and an olefinically unsaturated monomer, and method for the production thereof
US5281692A (en) * 1989-05-19 1994-01-25 Dsm N.V. Elongated object made of a copolymer of carbon monoxide and an olefinically unsaturated monomer
US5403531A (en) * 1989-05-19 1995-04-04 Dsm N.V. Elongated object made of a copolymer of carbon monoxide and an olefinically unsaturated monomer, and method for the production thereof
EP0456306A1 (en) * 1990-05-09 1991-11-13 Akzo Nobel N.V. Process for making polyketone fibres
US5597389A (en) * 1993-02-19 1997-01-28 Shell Oil Company Dyeing of polyketone fiber
US5494998A (en) * 1994-11-14 1996-02-27 Akzo Nobel N.V. Polymerization of carbon monoxide and ethylene using catalyst containing non-coordinating, non-acidic anion
US5506338A (en) * 1994-11-14 1996-04-09 Akzo Nobel Nv Polymerization of carbon monoxide and ethylene using catalyst containging non-coordinating, non-acidic anion
US5523385A (en) * 1994-11-14 1996-06-04 Akzo Nobel N. V. Polymerization of carbon monoxide and ethylene using catalyst containing non-coordinating, non-acidic anion
US5565546A (en) * 1995-05-05 1996-10-15 Akzo Nobel Nv Copolymer of carbon monoxide and ethylene containing ketal structures
WO1997017524A3 (en) * 1995-11-08 1997-06-19 Shell Int Research Deformable well screen and method for its installation
WO1997017524A2 (en) * 1995-11-08 1997-05-15 Shell Internationale Research Maatschappij B.V. Deformable well screen and method for its installation
WO1999041437A1 (en) * 1998-02-12 1999-08-19 Akzo Nobel N.V. Process for preparing polyketone fibres
US6495075B1 (en) 1998-02-12 2002-12-17 Acordis Industrial Fibers Bv Process for preparing polyketone fibres
WO2000009788A1 (en) * 1998-08-11 2000-02-24 Acordis Industrial Fibers B.V. Fibres melt-spun from a thermoplastic alternating copolymer and a process for preparing such fibres
EP1111103A1 (en) * 1999-12-20 2001-06-27 Acordis Industrial Fibers BV Dipped cord made of melt spun filament yarns of an alternating copolymer and a process for manufacturing said cord
US6881478B2 (en) 2001-02-27 2005-04-19 Asahi Kasei Kabushiki Kaisha Polyketone fiber and process for producing the same
US6818728B2 (en) 2001-02-27 2004-11-16 Asahi Kasei Kabushiki Kaisha Polyketone fiber and process for producing the same
WO2012146612A1 (en) 2011-04-28 2012-11-01 Compagnie Generale Des Etablissements Michelin Aramid/polyketone composite textile cord
DE202017002839U1 (en) 2017-05-30 2018-08-31 Perlon Nextrusion Monofil GmbH Polyketone fibers, their preparation and use
WO2018219494A1 (en) 2017-05-30 2018-12-06 Perlon Gmbh Polyketone fibers, production and use thereof
WO2018219495A1 (en) 2017-05-30 2018-12-06 Perlon Gmbh Bristle made of a plastic filament, brush comprising bristles of this kind, and method for producing bristles of this kind
WO2019122619A1 (en) 2017-12-22 2019-06-27 Compagnie Generale Des Etablissements Michelin Pneumatic tyre comprising an improved bracing ply
WO2019122620A1 (en) 2017-12-22 2019-06-27 Compagnie Generale Des Etablissements Michelin Tyre comprising an improved hooping ply
WO2019122621A1 (en) 2017-12-22 2019-06-27 Compagnie Generale Des Etablissements Michelin Method for producing a threadlike reinforcement element

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JPH01124617A (en) 1989-05-17
CN1034767A (en) 1989-08-16
DE3885996T2 (en) 1994-04-07
KR960000787B1 (en) 1996-01-12
BR8805005A (en) 1989-05-02
ES2047022T3 (en) 1994-02-16
DE3885996D1 (en) 1994-01-13
EP0310171B1 (en) 1993-12-01
KR890005313A (en) 1989-05-13
EP0310171A3 (en) 1990-01-10
AU604972B2 (en) 1991-01-03
JP2763779B2 (en) 1998-06-11
CN1014155B (en) 1991-10-02
AU2290888A (en) 1989-04-06

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