EP2080824B1 - Verfahren zur herstellung von fasern aus polyethylen mit ultrahohem molekulargewicht - Google Patents

Verfahren zur herstellung von fasern aus polyethylen mit ultrahohem molekulargewicht Download PDF

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Publication number
EP2080824B1
EP2080824B1 EP07816520A EP07816520A EP2080824B1 EP 2080824 B1 EP2080824 B1 EP 2080824B1 EP 07816520 A EP07816520 A EP 07816520A EP 07816520 A EP07816520 A EP 07816520A EP 2080824 B1 EP2080824 B1 EP 2080824B1
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European Patent Office
Prior art keywords
uhmwpe
fiber
fiber according
solvent
emulsion mixture
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EP07816520A
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French (fr)
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EP2080824A1 (de
EP2080824A4 (de
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Panpan Hu
Xiulan You
Zhaofeng Liu
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Priority claimed from CN200610118076XA external-priority patent/CN101235551B/zh
Priority claimed from CNA2006101474246A external-priority patent/CN101205637A/zh
Priority claimed from CNA2007100406782A external-priority patent/CN101307509A/zh
Priority claimed from CNA2007100438317A external-priority patent/CN101348944A/zh
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Publication of EP2080824A1 publication Critical patent/EP2080824A1/de
Publication of EP2080824A4 publication Critical patent/EP2080824A4/de
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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
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • 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
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • 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
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/298—Physical dimension

Definitions

  • the invention relates to a method of preparing fiber of High Molecular Weight Polyethylene (HMWPE), specifically, a method of preparing fiber of Ultra High Molecular Weight Polyethylene (UHMWPE).
  • HMWPE High Molecular Weight Polyethylene
  • UHMWPE Ultra High Molecular Weight Polyethylene
  • a method of preparing a high strength, high modulus polyethylene (PE) fiber from UH MWPE gel via drawing or stretching technology is disclosed in UK Patent Nos. GB2042414 and GB2051667 , assigned to DSM Company, Netherlands in 1979. After that, this technology was industrialized by Allied Company from the U.S., Toyobo-DSM Company, a joint venture by Japan and Netherlands, as well as Mitsui Company from Japan. In 1982, Allied Company obtained US Patent No. 4413110 , which covers a process ofpreparing UHMWPE fiber. Donghua University in China also obtained Chinese Patent Nos. 89107905 and 97106768 in this area.
  • UHMWPE Ultra High Density Polyethylene
  • a suitable solvent to prepare a solution by stirring
  • the solution is extruded by an extruder and spun through a spinnerette, followed by cooling, extraction, drying, and stretching, to form the desired fiber product.
  • key steps include the preparation of a homogeneous UHMWPE solution, and the extraction with a second solvent to remove the large amount of a first solvent contained in gel fiber prior to stretching of the gel fiber.
  • the entanglement among the macromolecules is beneficial to increase the draw ratio and can result in highly oriented fiber with higher strength and modulus.
  • the viscoelastic effect due to the entanglement among the macromolecules of polymer makes the dissolving process much more complicated, and is not beneficial to the dissolving and shaping process. Therefore, the entanglement among the macromolecules should be controlled.
  • the state of such entanglement can be controlled by heat treatment, solvent treatment and cutting.
  • the molecular weight for polymer and low molecule solvent is quite different. Polymer has a long molecule chain and it is difficult for the polymer to move. Due to the strong intra-molecular interactions and entanglement among the polymer molecules, the polymer does not diffuse into a solvent when the polymer and low molecule solvent are just mixed. If the conventional dissolution method is used to prepare the solution, the polymer powder tends to be aggregated, or form a gel solid due to incomplete permeation of the solvent, and a homogeneous solution cannot be obtained. Furthermore, the Weissenberg Effect (climbing effect) will appear due to the viscoelastic effect caused by entanglement between macromolecules of polyethylene when stirring.
  • EP 0255618 discloses that a hydrocarbon mixture free of naphthalin and diphenyl, with boiling point around 180-250°C, is obtained after a rectification separation from hydrogenated coal oil. Such hydrocarbon mixture is further mixed with UHMWPE and decahydronaphthalene at 135°C, agitated for several hours to form a PE solution. The concentration of the PE solution is no greater than 50%.
  • Japanese Patent No. 59232123 describes a process to mix UHMWPE with small amount of a solvent for several minutes, followed by heating, then more solvent is added gradually with stirring to form a solution containing UHMWPE.
  • a fractional coal oil is catalytically hydrogenated to provide a solvent.
  • the solvent is further added with an anti-oxidant and PE, and the resulting mixture is agitated for 3 hours at 140°C to form a 10%(w/w) UHMWPE solution.
  • Chinese Patent No. 970106768 discloses that an alkane hydrocarbon solvent can be used to swell PE under certain conditions, and to prepare a suspension solution containing UHMWPE.
  • Cipheral Patent No. 97101010 describes that a pre-swelling pan equipped with an new mixer baffle is used to swell UHMWPE to form a suspension solution so as to avoid the Weissenberg Effect of UHMWPE during dissolving and stirring.
  • Chinese Patent No. 20041009607615 titled “A Method For Continuous Mixing and Preparation of UHMWPE Solution,” discloses the use of a static mixer with a screw having a small Length/Diameter ratio to allow continuous preparation of UHMWPE solution.
  • DSM company provides a method of preparing a homogeneous solution of polymer, comprising: feeding a fine polymer powder and a solvent into an extruder, where a suspension and a solution is formed within the extruder, with an operation temperature above the melting point of the polymer and at a mechanical cutting rate of about 30-2000S -1 .
  • this method can damage the molecule chain of UHMWPE and result in a decrease of its molecular weight.
  • the fiber with high strength and high modulus can be obtained only after large amount of the first solvent contained in the gel fiber is extracted with a second solvent and the stretching of the gel fiber is performed.
  • the extraction speed depends on the second solvent used, the extraction process, as well as the diffusion path of the solvent.
  • the solvent in the outer surface of the fiber will first diffuse from the gel fiber.
  • the longer the diffusion distance the bigger the difference in diffusion speeds.
  • the cross section of a PE gel fiber is round and has a thicker wall. The bigger the difference, the easier to form a skin-core structure, which is not a homogeneous structure and which has a negative influence on the stretching process so as to affect the mechanical properties of the fiber product.
  • PE gel fiber includes EP 0205960A , EP 0213208A1 , US Patent No. 4413110 , WO 01/73173A1 , and EP 1746187A1 , which made some modifications on spinning technology.
  • UHMWPE gel spinning process it is critical to obtain a homogeneous polymer solution and a stable drawing of gel fiber. As a pre-condition for the formation of fiber with stable properties, it is important to have a good solution and a stable drawing operation.
  • PE fiber has the advantages of light weight, flexible, high strength and high modulus, UV-proof, anti-impact, and anti-corrosion to seawater, it can be used for cutting-proof gloves, bullet-proof jacket or helmet, cable etc.
  • base materials such as acrylonitrile butadiene rubber, polyurethane and epoxy resin, can be combined with the PE fiber. Due to the inertia surface of the PE fiber, the interface adhesion between the fiber and the base material is poor, which has brought great attention of those skilled in this field.
  • US Patent No. 480136 discloses that during spinning, thermal initiated surface silanization grafting reaction occurs on PE fiber, with a further cross-linking process, and results in the improvement of the adhesive property of the PE fiber.
  • the process has a negative influence on the subsequent drawing process, and the mechanical properties of the fiber is not satisfying.
  • US 5039549 , US 5755913 and ZL 03115300.3 describe that plasma, ozone, corona arc or UV radiation can be used to improve the adhesive property on PE fiber surface.
  • these processes are complicated and involve expensive equipment, and the process parameters are difficult to control. Therefore, the processes are difficult to be industrialized.
  • Jiang Shen et al. proposes to use strong oxidizing agents, such as chromic acid, kali permanganate, to etch the surface of the PE fiber (see, UHMWPE Fiber Adhesive Property Study, Reinforced Glass/Complex Material, 2004(3):47 ). Because this method requires the merging of the PE fiber in a strong oxidation environment for a long time, while the fiber infiltrating property may be improved, the mechanical properties of the fiber is decreased. In addition, such processes are also complicated, with a strict requirement on the equipment, and also have the pollution problem from the waste liquid.
  • strong oxidizing agents such as chromic acid, kali permanganate
  • CN 163544 proposes to use a composite extracting agent containing polar polymer compound to treat the spinned PE gel fiber to improve the adhesive property on the fiber surface while maximally maintaining the original strength of the fiber. This process is relatively simple, without requiring any additional equipment. Although this process is efficient for loose gel fiber, in practical production with tension extraction, it is difficult for polar polymer compound to diffuse into gel fiber, and therefore, the improvement made on the adhesive property is not apparent.
  • the present invention is to solve the existing technical problems in UHMWPE fiber production, and specifically to solve the problem in the preparation of homogeneous solution containing raw material, and in the removal of the first solvent from the gel fiber.
  • One objective of the present invention is to provide a simple, efficient and low cost method to prepare the HMWPE fiber.
  • the HMWPE fiber prepared by this method has high adhesive property.
  • the method of preparing UHMWPE fiber comprises: mixing PE powder having a relative average molecule weight (MW) of 1 million to 6 million with polar polymer in a solvent, to form an emulsion mixture; the mixture being fed into an extruder with agitation, where the mixture swells and dissolves rapidly to form a transparent and homogeneous solution; and the solution being extruded through an spinnerette to spin into a gel filament, followed by cooling, extraction, drying and stretching (or drawing) to produce the desired UHMWPE fiber, and wherein
  • MW relative average molecule weight
  • the PE powder having a relative MW of 1 million to 6 million is mixed with polar polymer and solvent in an appropriate ratio, and the resulting mixture is fed into an untwisting equipment to untwist, and thereby forming a uniform emulsion mixture.
  • the concentration of the above-mentioned uniform emulsion mixture is about 4% to 60% (wt).
  • the polar polymer mentioned above includes polar polymer containing ester group, carbonyl group or ether group.
  • the polar polymer containing ester group, carbonyl group or ether group refers to ethylene/vinyl acetate co-polymer, polyacrylates, polyethylene pyrrolidone /vinyl acetate co-polymer with different K value, polyoxyethylene polymer, or mixtures thereof.
  • the added weight% for the polar polymer relative to the UHMWPE powder with relative MW of 1 million to 6 million is about 1-10%, preferably about 2-8%.
  • silicone oil or its derivative can be used for untwisting. Additionally, silicone oil or its derivative can also be used during the cooling (solidifying) process. Silicone oil or its derivative may comprise about 0.05-5 wt% of the UHMWPE fiber.
  • one or more antioxidant, stabilizer, coloring agent, fire retardant can be added.
  • the untwisting equipment may provide a cutting speed of at least 1000S -1 , preferably 1000-5000 S -1 , and more preferably 2000-4000S -1 .
  • the untwisting equipment mentioned above can be high-speed dispersion machine, agitator (intensive mixing vessel), colloid mill, homogenizer, venturi, or any combinations thereof.
  • the preferred relative average MW for UHMWPE is 4 million to 6 million, and more preferably 2 million to 5 million.
  • the solvent used is liquid under room temperature, and it may be alkane (or paraffin) or its derivative, cycloalkane (or cycloparaffin) or its derivative, aromatic hydrocarbon or its derivative, or mixtures thereof.
  • the nominal concentration for the UHMWPE and the solvent is 1-50 wt%.
  • the extruder used in the present invention includes single screw, double-screw, triple-screw or four-screw extruder, where the extruding temperature is above the melting point of the UHMWPE, for example, 80-250°C as the working temperature for the extruder.
  • the double-screw extruder can rotate in same direction or reverse direction, and the screw's length/diameter ratio is 1:30-65.
  • the uniform emulsion mixture stays in the double-screw extruder for 10-60 minutes (residence time), and preferably 20-40 minutes; with a material temperature inside the extruder at 50-280°C, and the extruding temperature for gel spinning at 140-280°C, preferably at 200-260°C.
  • the spinnerette of the extruder has a rectangle shape, with a Length/Width ratio of 4-20, preferably 5-15.
  • the emulsion mixture can be fed into the extruder directly, or via a storage vessel with an agitator (e.g., mixing vessel).
  • the vessel can be one set or more than two sets.
  • the drawing temperature for fiber is 80-130°C, at a draw ratio of more than 20/1, preferably 30/1-60/1.
  • the present invention has the following advantages:
  • UHMWPE Relative Average Molecule Weight 4.5M powder and #90 solvent white oil with a weight ratio of 1:8, were fed into an untwisting pan at room temperature, and underwent cutting for 1 0minutes at a speed of 2000S -1 under N 2 protection, to form a homogeneous emulsion mixture.
  • the extruded material was filtered, and spun into a gel filament through a spinnerette, then extracted and stretched at a stretch ratio of 35, to provide UHMWPE.
  • the extruded material was filtered, and spun into a gel filament through a spinnerette, then extracted and stretched at a draw ratio of 35, to produce UHMWPE with high adhesive properties.
  • the extruded material was filtered, and spun into a gel filament through a spinnerette, then extracted and stretched at a draw ratio of 35, to produce UHMWPE with high adhesive properties.
  • UHMWPE Relative Average Molecule Weight 4.5M powder
  • the extruded material was filtered, and spun into a gel filament through a spinnerette, then extracted and stretched at a draw ratio of 35, to produce UHMWPE with high adhesive properties.
  • UHMWPE (Relative Average Molecule Weight 4.5M) powder and #90 solvent white oil with weight ratio of 1:8 were fed into an untwisting pan at room temperature, and further added polyacrylate with an amount of 2 % by weight of the UHMWPE powder, and underwent cutting for 10 minutes under N 2 protection at a speed of 2000S -1 , to produce a homogeneous emulsion mixture.
  • the extruded material was filtered, and spun into a gel filament through a spinnerette, then extracted and stretched at a draw ratio of 35, to produce UHMWPE with high adhesive properties.
  • UHMWPE (Relative Average Molecule Weight 4.5M) powder and #90 solvent white oil with weight ratio of 1:8 were fed into an untwisting pan at room temperature, and further added polyoxyethylene with an amount of 4 % by weight of the UHMWPE powder, and underwent cutting for 10 minutes under N 2 protection at a speed of 2000S -1 , to form a homogeneous emulsion mixture.
  • the extruded material was filtered, and spun into a gel filament through a spinnerette, then extracted and stretched at a draw ratio of 35, to produce UHMWPE with high adhesive properties.
  • the following procedure is used to measure the adhesive strength of the UHMWPE fiber:
  • the UHMWPE fiber is passed through a capsule with small hole, the height of the capsule being about 7mm.
  • An epoxy resin and a solidifying agent are mixed at a ratio of 4:1, and charged into the capsule, and allow for solidifying for 48 hours.
  • UHMWPE (Relative Average Molecule Weight 4.5M) powder and #90 solvent white oil with a nominal concentration of 10% (wt) were fed into an untwisting pan at room temperature, and underwent cutting for 5 minutes under N 2 protection at a speed of 3000S -1 , to form a homogeneous emulsion mixture.
  • the extruded material passed through a filter tank and a metering pump to get a measurement, and spun into a gel filament through a spinnerette, passed through a water bath, followed by extraction, drying and stretching at a draw ratio of 40, to produce UHMWPE fiber with Rupture Strength (i.e., Tenacity) of 30cN/dtex and Young's Modulus of over 1000cN/dtex.
  • Rupture Strength i.e., Tenacity
  • UHMWPE (Relative Average Molecule Weight 5 M) powder and #90 solvent white oil with a nominal concentration of 5% (wt) were fed into an untwisting pan at room temperature, and underwent cutting for 5 minutes under N 2 protection at a speed of 3000S -1 , to form a homogeneous emulsion mixture.
  • the extruded material was passed through a filter tank and a metering pump to get a measurement, and spun into a gel filament through a spinnerette, passed through a water bath, followed by extraction, drying and stretching at a draw ratio of 40, to produce UHMWPE fiber with Rupture Strength of 28cN/dtex and Young's Modulus of over 900cN/dtex.
  • UHMWPE (Relative Average Molecule Weight 4.5 M) powder and #90 solvent white oil with a nominal concentration of 5% (wt) were fed into an untwisting pan at room temperature, and further added 0.2% (wt) of an anti-oxidant, and underwent cutting for 5 minutes under N 2 protection at a speed of 2000S -1 , to form a homogeneous emulsion mixture.
  • the extruded material was passed through a filter tank and a metering pump to get a measurement, and spun into a gel filament through a spinnerette, passed through a water bath, followed by extraction, drying and stretching at a draw ratio of 40, to produce UHMWPE fiber with Rupture Strength of 28cN/dtex and Young's Modulus of over 900cN/dtex.
  • UHMWPE Relative Average Molecule Weight 5 M powder and #90 solvent white oil with a nominal concentration of 12% (wt) were fed into an untwisting pan at room temperature, and underwent cutting for 10 minutes under N 2 protection at a speed of 2000S -1 , to form a homogeneous emulsion mixture.
  • the extruded material was passed through a filter tank and a metering pump to get a measurement, and spun into a gel filament through a spinnerette, passed through a water bath, followed by extraction, drying and stretching at a draw ratio of 40, to produce UHMWPE fiber with Rupture Strength of 35cN/dtex and Young's Modulus of over 1050cN/dtex.
  • UHMWPE (Relative Average Molecule Weight 4.5 M) powder and #90 solvent white oil with a nominal concentration of 10% (wt) were fed into an untwisting pan at room temperature via a spiral propeller at a speed of 0.5kg/min, and underwent cutting under N 2 protection at a speed of 1000S -1 , to form a homogeneous emulsion mixture.
  • the extruded material was passed through a filter tank and a metering pump to get a measurement, and spun into a gel filament through a spinnerette, passed through a water bath containing 2% polyether-epoxy modified silicone oil, followed by extraction, drying and stretching at a draw ratio of 40, to produce UHMWPE fiber with Rupture Strength of 30cN/dtex and Young's Modulus of over 1000cN/dtex.
  • UHMWPE Relative Average Molecule Weight 4.5 M powder and #70 solvent white oil with a nominal concentration of 12% (wt) were fed into an untwisting pan at room temperature, and underwent cutting for 15 minutes under N 2 protection at a speed of 1 000S -1 . to form a homogeneous emulsion mixture.
  • the extruded material was passed through a filter tank and a metering pump to get a measurement, and spun into a gel filament through a spinnerette, passed through a water bath, followed by extraction, drying and stretching at a draw ratio of 40, to produce UHMWPE fiber with Rupture Strength of 30cN/dtex and Young's Modulus of over 1000cN/dtex.
  • UHMWPE Relative Average Molecule Weight 4.5 M powder and #70 solvent white oil with a nominal concentration of 10% (wt) were fed into an untwisting pan at room temperature, and further added 1% (wt) of epoxy modified silicone oil, and underwent cutting for 5 minutes under N 2 protection at a speed of 3000S -1 , to form a homogeneous emulsion mixture.
  • the extruded material was passed through a filter tank and a metering pump to get a measurement, and spun into a gel filament through a spinnerette, passed through a water bath, followed by extraction, drying and stretching at a draw ratio of 40, to produce UHMWPE fiber with Rupture Strength of 30cN/dtex and Young's Modulus of over 1000cN/dtex.
  • UHMWPE Relative Average Molecule Weight 5 M powder and #90 solvent white oil with a nominal concentration of 12% (wt) were fed into an untwisting pan at room temperature, and underwent cutting for 10 minutes under N 2 protection at a speed of 2000S -1 , to form a homogeneous emulsion mixture.
  • the extruded material was passed through a filter tank and a metering pump to get a measurement, and spun into a gel filament through a spinnerette, passed through a water bath containing 1.5wt% of epoxy modified silicone oil, followed by extraction, drying and stretching at a draw ratio of 40, to produce UHMWPE fiber with Rupture Strength of 35cN/dtcx and Young's Modulus of over 1050cN/dtex.
  • UHMWPE (Relative Average Molecule Weight 4.5 M) powder and #90 solvent white oil with a nominal concentration of 10% (wt) were fed into an untwisting pan at room temperature via a spiral propeller at a speed of 0.5kg/min, and underwent cutting under N 2 protection at a speed of 1000S -1 , to form a homogeneous emulsion mixture.
  • the extruded material was passed through a filter tank and a metering pump to get a measurement, and spun into a gel filament through a spinnerette, passed through a water bath containing 2% polyether-epoxy modified silicone oil, followed by extraction, drying and stretching at a draw ratio of 30, to produce UHMWPE fiber with Rupture Strength of 30cN/dtex and Young's Modulus of over 1000cN/dtex.
  • the extruded material was passed through a filter tank and a metering pump to get a measurement, and spun into a gel filament through a spinnerette comprising apertures having a rectangular shape with a Length/Width ratio of 8, passed through a water bath, followed by extraction, drying and stretching at a draw ratio of 40, to produce UHMWPE fiber with Rupture Strength of 30cN/dtex and Young's Modulus of over 1000cN/dtex.
  • the extruded material was passed through a filter tank and a metering pump to get a measurement, and spun into a gel filament through a spinnerette comprising apertures having a rectangular shape with a Length/Width ratio of 12, passed through a water bath, followed by extraction, drying and stretching at a draw ratio of 40, to produce UHMWPE fiber with Rupture Strength of30cN/dtex and Young's Modulus of over 1000cN/dtex.

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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)
  • Artificial Filaments (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)

Claims (14)

  1. Verfahren zur Herstellung von UHMWPE-Faser, welches dadurch gekennzeichnet ist, dass UHMWPE-Pulver mit einem relativen durchschnittlichen Molekulargewicht von 1 Million bis 6 Millionen zu einem polaren Polymer zugegeben und in einem Lösungsmittel dispergiert wird, um eine homogene Emulsionsmischung zu bilden, die für das Gel-Spinning-Verfahren langsam und unter Rührbewegungen in einen Extruder überführt wird, in welchem die Mischung aufquillt, sich auflöst und eine transparente und homogene Lösung entsteht; die Lösung wird dann durch eine Spinndüse extrudiert, um so ein Gelfilament zu spinnen, wobei die Spinndüse Öffnungen umfasst, welche eine rechteckige Form aufweisen; im Anschluss folgen die Schritte Abkühlung, Verfestigung, Extraktion, Trocknung und Streckung, um die UHMWPE-Faser zu bilden, wobei:
    - während der Herstellung der homogenen Emulsionsmischung das UHMWPE-Pulver mit einem relativen Molekulargewicht von 1 Million bis 6 Millionen, das polare Polymer und das Lösungsmittel in einem geeigneten Verhältnis gemischt werden und in eine aufdrehende Vorrichtung zum Aufdrehen überführt werden, um die homogene Emulsionsmischung zu bilden;
    - die Menge an polarem Polymer in Bezug auf das UHMWPE-Pulver im Bereich von 1-10 Gewichtsprozent liegt, und
    - die aufdrehende Vorrichtung eine Schnittgeschwindigkeit von mindestens 1000S-1 besitzt.
  2. Verfahren zur Herstellung von UHMWPE-Faser nach Anspruch 1 oder Anspruch 2, wobei die Konzentration der homogenen Emulsionsmischung im Bereich von 4 % bis 60 % liegt.
  3. Verfahren zur Herstellung von UHMWPE-Faser nach Anspruch 1, wobei das polare Polymer:
    • ein polares Polymer ist, welches eine Estergruppe, eine Carbonylgruppe oder eine Ethergruppe umfasst;
    • eine Estergruppe, eine Carbonylgruppe oder eine Ethergruppe umfasst, die ausgewählt ist unter Ethylen-/Vinyl-Acetat-Copolymer, Polyacrylaten, Polyethylen-Pyrrolidon-/Vinyl-Acetat-Copolymer, Polyoxyethylenpolymer und Mischungen daraus.
  4. Verfahren zur Herstellung von UHMWPE-Faser nach Anspruch 1, wobei die Menge an polarem Polymer bezogen auf UHMWPE-Pulver im Bereich von 2-8 Gewichtsprozent liegt.
  5. Verfahren zur Herstellung von UHMWPE-Faser nach Anspruch 1, wobei während des Verfahrens zum Aufdrehen, Silikonöl oder eines seiner Derivate für den Aufdrehvorgang zugesetzt wird; und/oder während des Verfestigungsvorgangs Silikonöl oder eines seiner Derivate zugesetzt wird, wobei das Silikonöl oder eines seiner Derivate einen Anteil von 0,05-5 Gewichtsprozent der UHMWPE-Faser aufweist, wobei vorzugsweise ein Zusatz oder mehrere dieser Zusätze, ausgewählt unter einem Antioxidans, einem Stabilisierungsmittel, einem Farbstoff und einem Brandschutzmittel, während des Aufdreh-Verfahrens zugesetzt wird/werden.
  6. Verfahren zur Herstellung von UHMWPE-Faser nach Anspruch 1, wobei die aufdrehende Vorrichtung eine Schnittgeschwindigkeit von 1000 bis 5000S-1 aufweist; vorzugsweise stellt die aufdrehende Vorrichtung eine Schnittgeschwindigkeit von 2000 bis 4000S-1 bereit.
  7. Verfahren zur Herstellung von UHMWPE-Faser nach Anspruch 1, wobei die aufdrehende Vorrichtung ausgewählt ist unter Hochgeschwindigkeits-Dispersionsvorrichtungen, Mixern, Kolloidmühlen, Homogenisatoren, Venturi-Düse sowie Kombinationen aus diesen Vorrichtungen.
  8. Verfahren zur Herstellung von UHMWPE-Faser nach Anspruch 1, welches dadurch gekennzeichnet ist, dass das UHMWPE ein relatives durchschnittliches Molekulargewicht von 4 Millionen bis 6 Millionen aufweist, vorzugsweise ein relatives durchschnittliches Molekulargewicht von etwa 2 Millionen bis 5 Millionen besitzt.
  9. Verfahren zur Herstellung von UHMWPE-Faser nach Anspruch 1, wobei das Lösungsmittel, welches zur Bildung einer homogenen Emulsionsmischung verwendet wird, bei Raumtemperatur in flüssiger Form vorliegt und ausgewählt ist unter Alkanhydrocarbon oder seinen Derivaten, Cycloalkanhydrocarbon oder seinen Derivaten, aromatischem Hydrocarbon oder seinen Derivaten und Mischungen daraus.
  10. Verfahren zur Herstellung von UHMWPE-Faser nach Anspruch 1, wobei während der Herstellung der homogenen Emulsionsmischung die nominelle Konzentration des UHMWPE-Pulvers in dem Lösungsmittel etwa im Bereich von 1-50 Gewichtsprozent liegt.
  11. Verfahren zur Herstellung von UHMWPE-Faser nach Anspruch 1, wobei der Extruder ausgewählt ist unter einem Einzelschnecken-Extruder, einem Doppelschnecken-Extruder, einem Dreischnecken-Extruder und einem Vierschnecken-Extruder und die Betriebstemperatur für den Extruder bei 80-250 °C liegt; vorzugsweise kann der Doppelschnecken-Extruder in die gleiche Richtung oder in die umgekehrte Richtung drehen und das Verhältnis von Länge/Durchmesser des Schneckengangs beträgt 1:30 -65; bevorzugter liegt die Verweilzeit der homogenen Emulsionsmischung in dem Doppelschnecken-Extruder bei 10-60 Minuten, vorzugsweise 20-40 Minuten; die Materialtemperatur beträgt 50-280 °C und die Temperatur des extrudierten Gelfilaments liegt bei 140-280 °C, vorzugsweise bei 200-260 °C, bevorzugter beläuft sich die Verweilzeit der homogenen Emulsionsmischung in dem Doppelschnecken-Extruder auf 20-40 Minuten und die Temperatur des extrudierten Gelfilaments beträgt 200-260 °C.
  12. Verfahren zur Herstellung von UHMWPE-Faser nach Anspruch 1, wobei die Spinndüse des Extruders Öffnungen umfasst, die eine rechteckige Form aufweisen und ein Verhältnis von Länge/Breite von 4:20, vorzugsweise ein Verhältnis von Länge/Breite von 5:15 besitzen.
  13. Verfahren zur Herstellung von UHMWPE-Faser nach Anspruch 1, wobei die Emulsionsmischung direkt in den Extruder überführt werden kann oder diesem über ein Aufnahmegefäß, welches mit einem Rührwerk ausgestattet ist, zugeführt wird.
  14. Verfahren zur Herstellung von UHMWPE-Faser nach Anspruch 1, wobei der Streckvorgang bei einer Temperatur von 80-130 °C und einem Zugverhältnis von mindestens 20/1 ausgerührt wird, vorzugsweise beträgt das Zugverhältnis beim Streckvorgang 30/1 bis 60/1.
EP07816520A 2006-11-08 2007-10-09 Verfahren zur herstellung von fasern aus polyethylen mit ultrahohem molekulargewicht Not-in-force EP2080824B1 (de)

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CN200610118076XA CN101235551B (zh) 2006-11-08 2006-11-08 一种高剪切超高分子量聚乙烯连续溶解纺丝新方法
CNA2006101474246A CN101205637A (zh) 2006-12-18 2006-12-18 高强高模超高分子量聚乙烯扁平纤维制备方法
CNA2007100406782A CN101307509A (zh) 2007-05-15 2007-05-15 一种超高分子量聚乙烯纤维纺丝新方法
CNA2007100438317A CN101348944A (zh) 2007-07-16 2007-07-16 高粘接性超高分子量聚乙烯纤维的制造新方法
PCT/CN2007/002906 WO2008055405A1 (fr) 2006-11-08 2007-10-09 Procédé de production de fibre de polyéthylène de masse moléculaire très élevée

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WO2008055405A1 (fr) 2008-05-15
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