EP3126552B1 - A system for industrial yarn production from composite polyethylene naphthalate material - Google Patents

A system for industrial yarn production from composite polyethylene naphthalate material Download PDF

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Publication number
EP3126552B1
EP3126552B1 EP15724103.5A EP15724103A EP3126552B1 EP 3126552 B1 EP3126552 B1 EP 3126552B1 EP 15724103 A EP15724103 A EP 15724103A EP 3126552 B1 EP3126552 B1 EP 3126552B1
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EP
European Patent Office
Prior art keywords
polyethylene naphthalate
primary
mixture
yarn production
raw
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.)
Not-in-force
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EP15724103.5A
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German (de)
French (fr)
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EP3126552A1 (en
Inventor
Emine Guven
Ozlem TURKARSLAN
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.)
Kordsa Teknik Tekstil AS
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Kordsa Teknik Tekstil AS
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Publication of EP3126552A1 publication Critical patent/EP3126552A1/en
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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D13/00—Complete machines for producing artificial threads
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
    • 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
    • D01F6/92—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 polyesters

Definitions

  • the present invention relates a system for industrial polyester yarn production, in which the mechanical properties of the yarn (tenacity, modulus, dimensional stability) are improved with additive, in order to be used in industrial fabric production.
  • Liquid Crystal Polymers which can be used as reinforcing phase in different polymeric materials, are high performance resins with a unique structure comprising long, hard, rod like high oriented molecules. Rod-like molecules orient themselves in the flow direction during injection or extrusion molding.
  • LCP The parts molded in LCP exhibit very high dimensional stability even if they are heated up to 200-250°C. Melting temperature of some LCP classes can reach up to 300°C. LCP can generally be used as an additive in many fields depending on its properties. Electronic and electrical components, fuel and gas barrier structures and sensors can be given as example for these fields.
  • the objective of the present invention is to provide a system for liquid crystal polymer added industrial polyester yarn production.
  • Another objective of the present invention is to provide a system for industrial yarn production wherein polyethylene naphthalate is used as polymer.
  • a further objective of the present invention is to provide a system for industrial yarn production with improved tensile strength and elastic modulus.
  • Figure 1 is the schematic view of the inventive system for yarn production.
  • the inventive system for composite polyethylene naphthalate industrial yarn production system (1) essentially comprises
  • the raw mixture forming unit (1) present in the inventive system (1) comprises
  • PEN:LCP ratio of the mixture prepared in the raw particle loading unit (21) is 60:40 by weight.
  • the raw material which is prepared in this ratio and solidified in cooling unit (23) melted and blended in the twin screw extruder (22) is become as particles.
  • Primary mixture forming unit (3) comprises
  • the raw mixture particles prepared in raw mixture forming unit (2) are sent to the primary molten forming unit (3), and the polymer particles diluted with pure PEN are produced here.
  • the PEN:LCP raw mixture is mixed with PEN till the LCP ratio becomes 1-3% by weight in the particle loading and diluting unit (31). At the said process is preferably carried out at 260-300°C.
  • the molecular weight of the blended polymer particles that are obtained are increased at the outlet of the primary mixture forming unit (3), and their internal viscosity (IV) is increased above 1 dL/g at 240-250°C with solid state polymerization, which takes 12-24 hours.
  • IV internal viscosity
  • the purpose here is to increase molecular weight to obtain a polymer suitable for yarn drawing by decreasing the degradation and chain movement during extrusion. %Crystallinity increase is above 100% with solid state polymerization.
  • the particles obtained at primary mixture forming unit (3) with increased IV via solid state polymerization are dried in vacuum furnace for at least 24 hours at 120-140°C, and loaded to the primary particle loading unit (4) under nitrogen atmosphere at 120 °C.
  • the humidity value of the blended and solid state polymerized particles should be under 60 ppm before loading to the extruder (32).
  • the primary polymer mixture coming out of the primary mixture forming unit (3) is transferred to the primary particle loading unit (4), and dried here at 100-120 °C and sent to the extruder (5) which is heated to 290-320 °C.
  • PEN-LCP polymer mixture comprising 1-3% LCP by weight is become filaments via spinneret at the exit of the extruder (5).
  • the length/diameter ratio of the spinneret used at the extruder exit (5) is 2-5, the hole diameter is 1mm.
  • the jet velocity of the material from the extruder (5) is 6-7 m/min, the residence time of the material in the extruder is 11-12 minutes.
  • the throughput here is adjusted as 6-7 g/min.
  • the PEN-LCP filament coming out of the extruder (5) is transferred to the cooling unit (6) preferably treated with cooling water.
  • the length of the cooling unit is 70cm and its temperature is 80-95°C.
  • the distance between the extruder (5) and the cooling unit (6) is adjusted as maximum 10cm.
  • the yarn coming out of the cooling unit (6) first comes to the primary roller (71) and it is sent to the secondary roller (72) from here.
  • the temperature of the primary roller (71) is between 100-140°C
  • the temperature of the secondary roller (72) is between 140-160°C. Cold drawing process is applied on the yarn between these rollers (7).
  • the yarn coming out of the secondary roller (72) is transferred to the first hot chamber (81) and heated with hot air to 200-250°C here and then transferred to the tertiary roller (73).
  • the temperature of the tertiary roller (73) may vary between 200-250°C. Therefore, hot drawing is performed between the secondary roller (72) and the tertiary roller (73).
  • the yarn coming out of the tertiary roller (73) enters into the second hot chamber (82) at temperature of 120-180°C. It comes to the quaternary roller (74) which is the last roller without heating, at room temperature; here it is relaxed in ratio of 1-2% and sent to the winding unit (9) in order to be wound.
  • the ratio of the primary roller (71) speed to the extruder (5) exiting speed is between4-6.
  • the ratio of the tertiary roller (73) speed to the primary roller (71) speed may vary between 5-6,5.
  • the conversion ratio is in range of 80-90% when the monofilament yarn which is produced with the inventive system is twisted as 2 layers with 50 twists.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)

Description

    Field of the Invention
  • The present invention relates a system for industrial polyester yarn production, in which the mechanical properties of the yarn (tenacity, modulus, dimensional stability) are improved with additive, in order to be used in industrial fabric production.
    • Background of the Invention
  • Improved mechanical properties and a strong structure are required in conveyor band chafer, membrane and coating fabrics. For such embodiments, processes should be improved without increasing the cost that much, and the resultant fiber should provide high modulus and better dimensional stability compared to the reference. For this reason, studies have been carried out to produce self-reinforced composite PEN yarns.
  • Liquid Crystal Polymers (LCP), which can be used as reinforcing phase in different polymeric materials, are high performance resins with a unique structure comprising long, hard, rod like high oriented molecules. Rod-like molecules orient themselves in the flow direction during injection or extrusion molding.
  • The parts molded in LCP exhibit very high dimensional stability even if they are heated up to 200-250°C. Melting temperature of some LCP classes can reach up to 300°C. LCP can generally be used as an additive in many fields depending on its properties. Electronic and electrical components, fuel and gas barrier structures and sensors can be given as example for these fields.
    • Summary of the Invention
  • The objective of the present invention is to provide a system for liquid crystal polymer added industrial polyester yarn production.
  • Another objective of the present invention is to provide a system for industrial yarn production wherein polyethylene naphthalate is used as polymer.
  • A further objective of the present invention is to provide a system for industrial yarn production with improved tensile strength and elastic modulus.
    • Detailed Description of the Invention
  • A system for industrial yarn production with LCP added polyethylene naphthalate developed to fulfill the objectives of the present invention is illustrated in the accompanying figure, wherein
  • Figure 1 is the schematic view of the inventive system for yarn production.
  • The components shown in Figure 1 are each given with reference numerals as follows:
    1. 1. System for industrial yarn production
    2. 2. Raw mixture forming unit
      • 21. Raw particle loading unit
      • 22. Raw molten extruder
      • 23. Raw molten cooling unit
    3. 3. Primary mixture forming unit
      • 31. Particle loading and diluting unit
      • 32. Primary molten extruder
      • 33. Primary molten cooling unit
    4. 4. Primary particle loading unit
    5. 5. Extruder
    6. 6. Cooling unit
    7. 7. Roller
      • 71. Primary roller
      • 72. Secondary roller
      • 73. Tertiary roller
      • 74. Quaternary roller
    8. 8. Hot chamber
      • 81. First hot chamber
      • 82. Second hot chamber
    9. 9. Winding unit
  • The inventive system for composite polyethylene naphthalate industrial yarn production system (1) essentially comprises
    • at least one raw mixture forming unit (2) wherein the raw polymer particles are prepared,
    • at least one primary mixture forming unit (3) wherein the primary polymer mixture is obtained diluting the raw polymer mixture with the main polymer,
    • at least one primary particle loading unit (4) wherein the polymer particles forming the primary mixture are filled and heated,
    • at least one extruder (5) wherein the primary polymer mixture obtained in primary particle loading unit (4) is melted and spun as filaments with the help of the spinneret located at the exit,
    • at least one cooling unit (6) wherein the material coming from the extruder (5) is cooled,
    • at least one roller (7) wherein the material is drawn and oriented,
    • at least one hot chamber (8) wherein the material is annealed,
    • at least one winding unit (9) wherein the material is drawn via the rollers (7) by cooling and heating is wound as yarn.
  • The raw mixture forming unit (1) present in the inventive system (1) comprises
    • at least one raw particle loading unit (21) wherein polyethylene naphthalate (PEN) and liquid crystal polymer (LCP) are mixed,
    • at least one raw molten extruder (22) wherein the raw molten mixture is extruded,
    • at least one raw molten cooling unit (23) wherein the material going out of the raw molten extruder (22) is cooled.
  • In the preferred embodiment of the inventive system (1), PEN:LCP ratio of the mixture prepared in the raw particle loading unit (21) is 60:40 by weight. The raw material which is prepared in this ratio and solidified in cooling unit (23) melted and blended in the twin screw extruder (22) is become as particles.
  • Primary mixture forming unit (3) comprises
    • at least one particle loading and diluting unit (31) wherein the polymer particles coming from the raw mixture forming unit (2) are melted and diluted with PEN,
    • at least one primary molten extruder (32) wherein the primary raw molten mixture is extruded,
    • at least one primary molten cooling unit (33) wherein the material going out of the main molten extruder (32) is cooled.
  • The raw mixture particles prepared in raw mixture forming unit (2) are sent to the primary molten forming unit (3), and the polymer particles diluted with pure PEN are produced here. The PEN:LCP raw mixture is mixed with PEN till the LCP ratio becomes 1-3% by weight in the particle loading and diluting unit (31). At the said process is preferably carried out at 260-300°C.
  • In one embodiment of the invention, the molecular weight of the blended polymer particles that are obtained are increased at the outlet of the primary mixture forming unit (3), and their internal viscosity (IV) is increased above 1 dL/g at 240-250°C with solid state polymerization, which takes 12-24 hours. The purpose here is to increase molecular weight to obtain a polymer suitable for yarn drawing by decreasing the degradation and chain movement during extrusion. %Crystallinity increase is above 100% with solid state polymerization.
  • In one embodiment of the invention, the particles obtained at primary mixture forming unit (3) with increased IV via solid state polymerization are dried in vacuum furnace for at least 24 hours at 120-140°C, and loaded to the primary particle loading unit (4) under nitrogen atmosphere at 120 °C. In order to prevent hydrolytic degradation, the humidity value of the blended and solid state polymerized particles should be under 60 ppm before loading to the extruder (32).
  • The primary polymer mixture coming out of the primary mixture forming unit (3) is transferred to the primary particle loading unit (4), and dried here at 100-120 °C and sent to the extruder (5) which is heated to 290-320 °C. PEN-LCP polymer mixture comprising 1-3% LCP by weight is become filaments via spinneret at the exit of the extruder (5). In the preferred embodiment of the invention, the length/diameter ratio of the spinneret used at the extruder exit (5) is 2-5, the hole diameter is 1mm. The jet velocity of the material from the extruder (5) is 6-7 m/min, the residence time of the material in the extruder is 11-12 minutes. The throughput here is adjusted as 6-7 g/min.
  • The PEN-LCP filament coming out of the extruder (5) is transferred to the cooling unit (6) preferably treated with cooling water. In one embodiment of the invention, the length of the cooling unit is 70cm and its temperature is 80-95°C. In the same embodiment of the invention, the distance between the extruder (5) and the cooling unit (6) is adjusted as maximum 10cm. The yarn coming out of the cooling unit (6) first comes to the primary roller (71) and it is sent to the secondary roller (72) from here. In the preferred embodiment of the invention the temperature of the primary roller (71) is between 100-140°C, and the temperature of the secondary roller (72) is between 140-160°C. Cold drawing process is applied on the yarn between these rollers (7).
  • The yarn coming out of the secondary roller (72) is transferred to the first hot chamber (81) and heated with hot air to 200-250°C here and then transferred to the tertiary roller (73). The temperature of the tertiary roller (73) may vary between 200-250°C. Therefore, hot drawing is performed between the secondary roller (72) and the tertiary roller (73).
  • The yarn coming out of the tertiary roller (73) enters into the second hot chamber (82) at temperature of 120-180°C. It comes to the quaternary roller (74) which is the last roller without heating, at room temperature; here it is relaxed in ratio of 1-2% and sent to the winding unit (9) in order to be wound.
  • In the preferred embodiment of the invention, the ratio of the primary roller (71) speed to the extruder (5) exiting speed is between4-6. The ratio of the tertiary roller (73) speed to the primary roller (71) speed may vary between 5-6,5.
  • When the tenacity and elastic modulus of LCP added PEN yarn in ratio of 1-3% obtained using the inventive system (1) and the yarn manufactured from pure PEN material with the total draw ratio of 6 are compared; the tenacity of the composite yarn produced in the inventive system has increased by 40-45%, and its elastic modulus has increased by 5-10%. When the total draw ratio is more than 6 the tenacity increase is between 25-30%, the elastic modulus improves by 2-5%. When the dimensional stability is considered, the dimensional stability of the 1-3% LCP added PEN yarn is 15-25% better than the pure PEN yarn in 6 drawing ratio.
  • The conversion ratio is in range of 80-90% when the monofilament yarn which is produced with the inventive system is twisted as 2 layers with 50 twists.

Claims (16)

  1. A system for industrial yarn production from composite polyethylene naphthalate material comprising
    - at least one raw mixture forming unit (2) wherein the raw polymer particles are prepared,
    - at least one primary mixture forming unit (3) wherein the primary polymer mixture is obtained and become particles by using raw polymer particles,
    - at least one primary particle loading unit (4) wherein the polymer particles forming the primary mixture are filled and heated,
    - at least one extruder (5) wherein the primary polymer mixture obtained in primary particle loading unit (4) are melted and become filaments with the help of the spinneret located at the exit,
    - at least one cooling unit (6) wherein the material coming from the extruder (5) is cooled,
    - at least one roller (7) wherein the material is drawn and oriented,
    - at least one hot chamber (8) wherein the material is annealed,
    - at least one winding unit (9) wherein the material is drawn via the rollers (7) by cooling and heating is wound as yarn, and characterized in that
    - polyethylene naphthalate (PEN) and the liquid crystal polymer (LCP) are mixed in ratio of 60:40 respectively in raw mixture forming unit (2),
    - The LCP ratio in the mixture is decreased to 1-3% by weight by diluting the raw mixture with PEN in primary mixture forming unit (3).
  2. A system (1) for industrial yarn production from composite polyethylene naphthalate material according to claim 1, characterized by raw mixture forming unit (2) which has at least one raw particle loading unit (21) wherein polyethylene naphthalate (PEN) and the liquid crystal polymer (LCP) is mixed by loading in ratio of 60:40 by weight respectively, at least one raw molten extruder (22) wherein raw mixture is melted and extruded;
    at least one raw molten cooling unit (23) wherein the material coming out of the raw molten extruder (22) is cooled.
  3. A system (1) for industrial yarn production from composite polyethylene naphthalate material according to any one of the preceding claims, characterized by primary mixture forming unit (3) which has at least one particle loading and diluting unit (31) wherein the polymer particles coming from the raw mixture forming unit (2) are melted and diluted with PEN such that the LCP ratio will be 1-3% by weight; at least one primary molten extruder (32) wherein the primary raw molten mixture is extruded, at least one primary molten cooling unit (33) wherein the material going out of the main molten extruder (32) is cooled.
  4. A system (1) for industrial yarn production from composite polyethylene naphthalate material according to any one of the preceding claims, characterized by particle loading and diluting unit (31) wherein PEN is added until the LCP ratio in the mixture is 1-3% by weight the raw PEN-LCP mixture is extruded at 260-300°C.
  5. A system (1) for industrial yarn production from composite polyethylene naphthalate material according to any one of the preceding claims, characterized by primary particle loading unit (4) wherein the particles obtained at primary mixture forming unit (3) outlet are loaded at nitrogen atmosphere at 120°C after being dried in vacuum furnace for at least 24 hours at 120-140°C.
  6. A system (1) for industrial yarn production from composite polyethylene naphthalate material according to any one of the preceding claims, characterized by extruder (5) wherein the primary polymer mixture is become filament, and which has a spinneret with length/diameter ratio of 2-5 and the hole diameter is 1mm.
  7. A system (1) for industrial yarn production from composite polyethylene naphthalate material according to any one of the preceding claims, characterized by extruder (5) wherein the jet velocity of the polymer mixture as filament is 6-7 m/min.
  8. A system (1) for industrial yarn production from composite polyethylene naphthalate material according to any one of the preceding claims, characterized by extruder (5) wherein the throughput of the polymer mixture as filament is adjusted as 6-7 g/min.
  9. A system (1) for industrial yarn production from composite polyethylene naphthalate material according to any one of the preceding claims, characterized by cooling unit (6) wherein the filament coming out of the extruder (5) is cooled with cooling water at 80-95°C.
  10. A system (1) for industrial yarn production from composite polyethylene naphthalate material according to any one of the preceding claims, characterized by primary roller (71) to which the filament coming out of the cooling unit (6) is transferred, at temperature of 100-140°C.
  11. A system (1) for industrial yarn production from composite polyethylene naphthalate material according to any one of the preceding claims, characterized by the secondary roller (72) at temperature of 140-160°C to which the filament coming out of the primary roller (71) is transferred and wherein cold drawing is applied on the filament.
  12. A system (1) for industrial yarn production from composite polyethylene naphthalate material according to any one of the preceding claims, characterized by first hot chamber (81) to which the filament coming out of the secondary roller (72) is transferred and in which it is used with hot air at temperature of 200-250°C.
  13. A system (1) for industrial yarn production from composite polyethylene naphthalate material according to any one of the preceding claims, characterized by the tertiary roller (73) at temperature of 200-250°C to which the filament coming out of the first hot chamber (81) is transferred and wherein hot drawing is applied on the filament.
  14. A system (1) for industrial yarn production from composite polyethylene naphthalate material according to any one of the preceding claims, characterized by second hot chamber (82) at temperature of 120-180°C to which the filament coming out of the tertiary roller (73) is transferred.
  15. A system (1) for industrial yarn production from composite polyethylene naphthalate material according to any one of the preceding claims, characterized by the quaternary roller (74) without heating to which the filament coming out of the second hot chamber (82) is transferred and wherein hot drawing is applied on the filament.
  16. A system (1) for industrial yarn production from composite polyethylene naphthalate material according to any one of the preceding claims, characterized by winding unit (9) wherein the filament coming out of the quaternary roller (74) is wound as yarn by relaxing 1-2%.
EP15724103.5A 2014-04-01 2015-03-25 A system for industrial yarn production from composite polyethylene naphthalate material Not-in-force EP3126552B1 (en)

Applications Claiming Priority (2)

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TR201403779 2014-04-01
PCT/TR2015/000117 WO2015152844A1 (en) 2014-04-01 2015-03-25 A system for industrial yarn production from composite polyethylene naphthalate material

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EP3126552A1 EP3126552A1 (en) 2017-02-08
EP3126552B1 true EP3126552B1 (en) 2018-03-21

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US (1) US20170114477A1 (en)
EP (1) EP3126552B1 (en)
KR (1) KR20160137641A (en)
CN (1) CN106574402B (en)
BR (1) BR112016023020A2 (en)
LU (1) LU92889B1 (en)
RU (1) RU2647386C1 (en)
WO (1) WO2015152844A1 (en)

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KR20220048879A (en) 2020-10-13 2022-04-20 서무경 Mono filament process apparatus using liquid crystal polymer

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WO2015152844A1 (en) 2015-10-08
BR112016023020A2 (en) 2017-10-10
LU92889B1 (en) 2016-03-30
US20170114477A1 (en) 2017-04-27
RU2647386C1 (en) 2018-03-15
KR20160137641A (en) 2016-11-30
CN106574402B (en) 2018-10-23
EP3126552A1 (en) 2017-02-08

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