[go: up one dir, main page]

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

Info

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
Authority
EP
European Patent Office
Prior art keywords
uhmwpe
fiber
fiber according
solvent
emulsion mixture
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
Application number
EP07816520A
Other languages
English (en)
French (fr)
Other versions
EP2080824A4 (de
EP2080824A1 (de
Inventor
Panpan Hu
Xiulan You
Zhaofeng Liu
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.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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
Application filed by Individual filed Critical Individual
Publication of EP2080824A1 publication Critical patent/EP2080824A1/de
Publication of EP2080824A4 publication Critical patent/EP2080824A4/de
Application granted granted Critical
Publication of EP2080824B1 publication Critical patent/EP2080824B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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.

Landscapes

  • 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)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
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

Publications (3)

Publication Number Publication Date
EP2080824A1 EP2080824A1 (de) 2009-07-22
EP2080824A4 EP2080824A4 (de) 2009-12-23
EP2080824B1 true EP2080824B1 (de) 2010-08-18

Family

ID=39364173

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07816520A Not-in-force EP2080824B1 (de) 2006-11-08 2007-10-09 Verfahren zur herstellung von fasern aus polyethylen mit ultrahohem molekulargewicht

Country Status (5)

Country Link
US (1) US20100233480A1 (de)
EP (1) EP2080824B1 (de)
AT (1) ATE478178T1 (de)
DE (1) DE602007008600D1 (de)
WO (1) WO2008055405A1 (de)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8747715B2 (en) 2007-06-08 2014-06-10 Honeywell International Inc Ultra-high strength UHMW PE fibers and products
US9365953B2 (en) 2007-06-08 2016-06-14 Honeywell International Inc. Ultra-high strength UHMWPE fibers and products
CN101724921B (zh) * 2009-11-26 2012-11-21 宁波大成新材料股份有限公司 超高分子量聚乙烯高剪切溶液均匀制备纺丝方法
US8131483B2 (en) * 2010-05-07 2012-03-06 Testing Machines, Inc. Yarn entanglement strength tester
CN101956238B (zh) 2010-08-24 2012-05-30 北京同益中特种纤维技术开发有限公司 一种超高分子量聚乙烯纤维纺丝溶液的制备方法
CN102534838B (zh) * 2010-12-07 2014-09-03 北京同益中特种纤维技术开发有限公司 一种超高分子量聚乙烯纤维纺丝原液及其制备方法
EP3795727B1 (de) 2011-12-14 2022-11-23 DSM IP Assets B.V. Paneel aus polyethylen-multifilamentgarnen mit ultrahohem molekulargewicht
CN102580159A (zh) * 2012-03-13 2012-07-18 中国矿业大学 一种自增强超高分子量聚乙烯髋关节臼的制备工艺
CN103590130A (zh) * 2013-10-11 2014-02-19 杭州翔盛高强纤维材料股份有限公司 一种改善超高分子量聚乙烯纤维纺丝液流动性的方法
US11124895B2 (en) * 2013-10-29 2021-09-21 Braskem America, Inc. System and method for measuring out a polymer and first solvent mixture, device, system and method for extracting a solvent from at least one polymer strand, system and method for mechanically pre-recovering at least one liquid from at least one polymer strand, and a continuous system and method for the production of at least one polymer strand
US20150164158A1 (en) * 2013-12-13 2015-06-18 Honeywell International Inc. Protective overglove for glove-box gloves
CN104790050B (zh) * 2014-03-28 2019-05-21 上海斯瑞科技有限公司 一种超高分子量聚乙烯纤维的制备方法及水洗装置
EP4234772A3 (de) * 2014-12-02 2024-06-26 Braskem, S.A. Kontinuierliches verfahren und system zur herstellung von wenigstens einem polymergarn und polymergarn
CN104846446B (zh) * 2015-05-22 2018-10-02 江苏神鹤科技发展有限公司 交联的超高分子量聚乙烯纤维及其干式制备方法
CN109666976B (zh) * 2017-10-16 2021-04-06 中国石油化工股份有限公司 提高超高分子量聚乙烯纤维产品性能的方法
CN109306061A (zh) * 2018-06-06 2019-02-05 深圳大学 超高分子量聚乙烯纺丝溶液的制备方法和超高分子量聚乙烯纤维
CN109161978B (zh) * 2018-09-03 2021-06-11 中国科学院宁波材料技术与工程研究所 一种高粘结、高强超高分子量聚乙烯纤维的制备方法及其产品
CN112111802B (zh) * 2019-06-20 2022-06-10 李乾坤 一种超高强度超高分子量聚乙烯纤维及其制造方法
CN112778598B (zh) * 2019-11-08 2023-02-28 中国石油化工股份有限公司 一种聚烯烃组合物及其制备方法和应用
CN112281237B (zh) * 2020-11-03 2022-09-27 北京复维新材科技有限公司 一种高模量抗蠕变超高分子量聚乙烯纤维及其制备方法
CN112725918A (zh) * 2020-12-23 2021-04-30 中国纺织科学研究院有限公司 聚乙烯纤维的制备方法及纤维
CN113668086B (zh) * 2021-08-24 2022-08-16 盐城工学院 高界面粘附性超高分子量聚乙烯纤维及其制备方法
CN114100187B (zh) * 2021-09-18 2024-11-26 九州星际科技有限公司 一种萃取槽
CN115054735B (zh) * 2022-07-05 2023-02-10 首都医科大学附属北京口腔医院 多孔复合支架及其制备方法与应用、epl修饰支架及其制备方法与应用
CN115262015B (zh) * 2022-07-28 2023-06-16 中国水产科学研究院东海水产研究所 一种持久高效抗菌纤维的制备方法

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US480136A (en) 1892-08-02 Shutter-bower
US4020230A (en) 1975-10-03 1977-04-26 The Dow Chemical Company Microporous polyethylene hollow fibers and process of preparing them
NL177759B (nl) 1979-06-27 1985-06-17 Stamicarbon Werkwijze ter vervaardiging van een polyetheendraad, en de aldus verkregen polyetheendraad.
NL177840C (nl) 1979-02-08 1989-10-16 Stamicarbon Werkwijze voor het vervaardigen van een polyetheendraad.
US4413110A (en) * 1981-04-30 1983-11-01 Allied Corporation High tenacity, high modulus polyethylene and polypropylene fibers and intermediates therefore
JPH0246053B2 (ja) 1983-06-16 1990-10-12 Kogyo Gijutsu Incho Chokobunshiryohoriechirenyoekinoseizohoho
JPS61124621A (ja) * 1984-11-19 1986-06-12 Ntn Toyo Bearing Co Ltd 超高分子量ポリエチレン繊維の製造方法
CN1004364B (zh) 1985-02-15 1989-05-31 斯塔米卡本公司(Dsm附属公司) 连续制备均匀的高分子聚合物溶液的方法
DE3682241D1 (de) 1985-02-15 1991-12-05 Toray Industries Polyaethylen-multifilament-garn.
EP0205960B1 (de) 1985-06-17 1990-10-24 AlliedSignal Inc. Polyolefinfaser mit hoher Festigkeit, niedrigem Schrumpfen, ultrahohem Modul, sehr niedrigem Kriechen und mit guter Festigkeitserhaltung bei hoher Temperatur sowie Verfahren zu deren Herstellung
JPS6315838A (ja) 1986-07-08 1988-01-22 Nippon Petrochem Co Ltd 超高分子量ポリエチレン溶液
US5039549A (en) 1989-10-17 1991-08-13 Allied-Signal Inc. Treatment of ultrahigh molecular weight polyolefin to improve adhesion to a resin
CN1056544A (zh) * 1990-05-14 1991-11-27 中国纺织大学 高强、高模聚乙烯纤维的制备方法
EP0513390B1 (de) 1990-11-28 1996-02-14 Mitsubishi Rayon Co., Ltd. Poröse hohlfasermembran aus polyethylen und ihre herstellung
US5230854A (en) * 1991-12-09 1993-07-27 Allied-Signal Inc. Method for removal of spinning solvent from spun fiber
US5695702A (en) 1994-07-01 1997-12-09 Millipore Corporation Thermoplastic hollow fiber membrane module and method of manufacture
JPH08245799A (ja) * 1995-03-08 1996-09-24 Tonen Chem Corp ポリオレフィン溶液の製造方法
US6054086A (en) * 1995-03-24 2000-04-25 Nippon Petrochemicals Co., Ltd. Process of making high-strength yarns
US5755913A (en) 1996-12-06 1998-05-26 Liaw; Der-Jang Adhesive-free adhesion between polymer surfaces
CN1060543C (zh) * 1997-01-02 2001-01-10 中国纺织科学研究院 超高分子量聚乙烯纤维连续制备方法和设备
KR100302209B1 (ko) 1999-04-27 2001-09-22 주덕영 순환연신법에 의한 고밀도 폴리에틸렌 중공사 분리막의 제조방법 및 그 장치
US6448359B1 (en) 2000-03-27 2002-09-10 Honeywell International Inc. High tenacity, high modulus filament
JP4444118B2 (ja) * 2002-12-10 2010-03-31 ディーエスエム アイピー アセッツ ビー．ブイ． ポリオレフィン繊維の製造方法および転化方法
WO2005066400A1 (en) * 2004-01-01 2005-07-21 Dsm Ip Assets B.V. Process for making high-performance polyethylene multifilament yarn
CN100395386C (zh) 2005-05-10 2008-06-18 东华大学 一种提高超高相对分子量聚乙烯纤维表面粘结性能的方法
EP1746187A1 (de) 2005-07-18 2007-01-24 DSM IP Assets B.V. Polyethylen-Multifilamentgarn

Also Published As

Publication number Publication date
EP2080824A4 (de) 2009-12-23
US20100233480A1 (en) 2010-09-16
ATE478178T1 (de) 2010-09-15
DE602007008600D1 (de) 2010-09-30
EP2080824A1 (de) 2009-07-22
WO2008055405A1 (fr) 2008-05-15

Similar Documents

Publication Publication Date Title
EP2080824B1 (de) Verfahren zur herstellung von fasern aus polyethylen mit ultrahohem molekulargewicht
JP6023700B2 (ja) 超高強度ｕｈｍｗｐｅ繊維および製品
US9296875B2 (en) Method for preparing spinning solution of ultra-high molecular weight polyethylene fiber
CN1128835C (zh) 聚烯烃微多孔膜及其制造方法
CN101235551A (zh) 一种高剪切超高分子量聚乙烯连续溶解纺丝新方法
CN101342465B (zh) 一种中空纤维多孔膜及其制备方法
KR101683089B1 (ko) 젤라틴화된 사전-배향된 필라멘트 및 이의 제조 방법 그리고 초고분자량 폴리에틸렌 섬유 및 이의 제조 방법
EP2063004B1 (de) Polyethylenfaser und herstellungsverfahren dafür
EP2563955B1 (de) Verfahren und produkt von hoher stärke aus uhmw-pe-fasern
CN1294608A (zh) 聚烯烃微多孔膜及其制造方法
EP2639346A1 (de) Verfahren zur herstellung von polyethylenfasern mit ultrahohem molekulargewicht
CN101348944A (zh) 高粘接性超高分子量聚乙烯纤维的制造新方法
CN101575743B (zh) 一种超高分子量聚乙烯纤维纺丝原液的制备方法
CN102850573B (zh) 一种湿法制备聚烯烃微孔膜的方法
CN109400942A (zh) 一种复合微多孔膜及其制备方法
JPH0240763B2 (de)
CN101608344A (zh) 一种超高分子量聚乙烯连续溶解纺丝新方法
CN101307509A (zh) 一种超高分子量聚乙烯纤维纺丝新方法
JPS648083B2 (de)
EP3011087B1 (de) Polyolefinfasern mit kleinem durchmesser
CN113802216A (zh) 含有植物精油的聚丁二酸丁二醇酯复合纤维及其制备方法
JPH0379173B2 (de)
KR20110135333A (ko) 일종의 고강도고탄성률 폴리에틸렌 섬유의 생산방법
CN85107352A (zh) 连续制备均匀的高分子聚合物溶液的方法
KR101684874B1 (ko) 마모성이 개선된 폴리케톤 섬유 및 그 제조방법

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090223

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

A4 Supplementary search report drawn up and despatched

Effective date: 20091125

17Q First examination report despatched

Effective date: 20100219

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

DAX Request for extension of the european patent (deleted)
RIC1 Information provided on ipc code assigned before grant

Ipc: D01D 1/02 20060101ALI20100412BHEP

Ipc: D01F 6/46 20060101AFI20100412BHEP

Ipc: D01D 5/06 20060101ALI20100412BHEP

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REF Corresponds to:

Ref document number: 602007008600

Country of ref document: DE

Date of ref document: 20100930

Kind code of ref document: P

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20100818

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100818

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100818

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100818

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20100917

Year of fee payment: 4

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101220

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100818

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101118

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100818

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100818

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101218

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20100920

Year of fee payment: 4

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100818

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100818

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101119

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100818

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100818

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101031

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100818

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100818

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100818

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20110519

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602007008600

Country of ref document: DE

Effective date: 20110519

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101009

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100818

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101009

BERE Be: lapsed

Owner name: HU, PANPAN

Effective date: 20111031

Owner name: LIU, ZHAOFENG

Effective date: 20111031

Owner name: YOU, XIULAN

Effective date: 20111031

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20120501

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20111009

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120501

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111031

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111031

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111009

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110219

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101009

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100818

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20121010

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20131018

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20131022

Year of fee payment: 7

Ref country code: IT

Payment date: 20131031

Year of fee payment: 7

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602007008600

Country of ref document: DE

Effective date: 20140501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140501

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20150630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141031

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141009

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20160202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141010