EP0310171B1 - Melt-spinning process - Google Patents

Melt-spinning process Download PDF

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Publication number
EP0310171B1
EP0310171B1 EP88202039A EP88202039A EP0310171B1 EP 0310171 B1 EP0310171 B1 EP 0310171B1 EP 88202039 A EP88202039 A EP 88202039A EP 88202039 A EP88202039 A EP 88202039A EP 0310171 B1 EP0310171 B1 EP 0310171B1
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EP
European Patent Office
Prior art keywords
melt
copolymer
ethylene
polymer
fibres
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.)
Revoked
Application number
EP88202039A
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German (de)
French (fr)
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EP0310171A3 (en
EP0310171A2 (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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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)°C ((T+20) K), and the fibre is subsequently stretched at a temperature of at most (T-10)°C ((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 25 °C (25 K), more preferably at least 40 °C (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. 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.
  • 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 207 °C (480 K) and the melt-spinning temperature was 287 °C (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 242 to 287 °C (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.

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)°C ((T+20) K), and the fibre is subsequently stretched at a temperature of at most (T-10)°C ((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 25 °C (25 K), more preferably at least 40 °C (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.
  • In EP-A-213671, reference has been made to the processing of the copolymers by known techniques into films and fibres.
  • 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 220 °C (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 207 °C (480 K) and the melt-spinning temperature was 287 °C (560 K).
  • The table below lists the testing results.
    Figure imgb0001
  • 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 242 to 287 °C (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 an alternating copolymer of an olefinically unsaturated compound and carbon monoxide, having a molecular weight of at least 2000, characterized in that the copolymer is melt-spun at a temperature of at least (T+20) °C ((T+20) K) and the fibre is subsequently stretched at a temperature of at most (T-10) °C ((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) °C ((T+40) K).
  3. A process as claimed in claim 1 or 2, in which the stretching temperature is at most (T-25) °C ((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 1993-12-29

Publications (3)

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

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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 (1)

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Publication number Priority date Publication date Assignee Title
US5901789A (en) * 1995-11-08 1999-05-11 Shell Oil Company Deformable well screen

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GB8822349D0 (en) * 1988-09-22 1988-10-26 Shell Int Research Process for preparation of thermoplastic fibres
NL8901253A (en) * 1989-05-19 1990-12-17 Stamicarbon POLYMERIC FILAMENTS, TAPES AND FILMS WITH HIGH MODULUS, HIGH STRENGTH AND HIGH MELTING TEMPERATURE AND A METHOD FOR THE PRODUCTION THEREOF.
US5194210A (en) * 1990-05-09 1993-03-16 Akzo Nv Process for making polyketone fibers
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
US5565546A (en) * 1995-05-05 1996-10-15 Akzo Nobel Nv Copolymer of carbon monoxide and ethylene containing ketal structures
DE69914584T2 (en) * 1998-02-12 2005-01-05 Acordis Industrial Fibers Bv METHOD FOR PRODUCING POLYETHONE FIBERS
JP3652116B2 (en) * 1998-05-28 2005-05-25 横浜ゴム株式会社 Pneumatic radial tire
EP1123428A1 (en) * 1998-08-11 2001-08-16 Acordis Industrial Fibers BV 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
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
FR2974583B1 (en) 2011-04-28 2013-06-14 Michelin Soc Tech ARAMIDE-POLYCETONE COMPOSITE TEXTILE CABLE
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
DE202017002839U1 (en) 2017-05-30 2018-08-31 Perlon Nextrusion Monofil GmbH Polyketone fibers, their preparation and use
EP3727826B1 (en) 2017-12-22 2023-07-12 Compagnie Generale Des Etablissements Michelin Method for producing a threadlike reinforcement element
JP7365342B2 (en) 2017-12-22 2023-10-19 コンパニー ゼネラール デ エタブリッスマン ミシュラン Tires with improved hooping plies
WO2019122619A1 (en) 2017-12-22 2019-06-27 Compagnie Generale Des Etablissements Michelin Pneumatic tyre comprising an improved bracing ply
EP4174624A4 (en) * 2021-08-26 2024-01-17 Elasto Lc Input device for computer

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EP0228733A1 (en) * 1985-12-23 1987-07-15 Shell Internationale Researchmaatschappij B.V. Process for the working-up of ethylene/carbon monoxide copolymers

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5901789A (en) * 1995-11-08 1999-05-11 Shell Oil Company Deformable well screen
US6012522A (en) * 1995-11-08 2000-01-11 Shell Oil Company Deformable well screen

Also Published As

Publication number Publication date
EP0310171A3 (en) 1990-01-10
KR960000787B1 (en) 1996-01-12
ES2047022T3 (en) 1994-02-16
JP2763779B2 (en) 1998-06-11
CN1034767A (en) 1989-08-16
AU2290888A (en) 1989-04-06
EP0310171A2 (en) 1989-04-05
DE3885996T2 (en) 1994-04-07
AU604972B2 (en) 1991-01-03
BR8805005A (en) 1989-05-02
DE3885996D1 (en) 1994-01-13
KR890005313A (en) 1989-05-13
JPH01124617A (en) 1989-05-17
CN1014155B (en) 1991-10-02

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