[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2008055405A1 - Procédé de production de fibre de polyéthylène de masse moléculaire très élevée - Google Patents

Procédé de production de fibre de polyéthylène de masse moléculaire très élevée Download PDF

Info

Publication number
WO2008055405A1
WO2008055405A1 PCT/CN2007/002906 CN2007002906W WO2008055405A1 WO 2008055405 A1 WO2008055405 A1 WO 2008055405A1 CN 2007002906 W CN2007002906 W CN 2007002906W WO 2008055405 A1 WO2008055405 A1 WO 2008055405A1
Authority
WO
WIPO (PCT)
Prior art keywords
molecular weight
weight polyethylene
ultrahigh molecular
fiber
fibers according
Prior art date
Application number
PCT/CN2007/002906
Other languages
English (en)
Chinese (zh)
Inventor
Panpan Hu
Xiulan You
Zhaofeng Liu
Original Assignee
Panpan Hu
Xiulan You
Zhaofeng Liu
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 Panpan Hu, Xiulan You, Zhaofeng Liu filed Critical Panpan Hu
Priority to US12/299,205 priority Critical patent/US20100233480A1/en
Priority to DE602007008600T priority patent/DE602007008600D1/de
Priority to AT07816520T priority patent/ATE478178T1/de
Priority to EP07816520A priority patent/EP2080824B1/fr
Publication of WO2008055405A1 publication Critical patent/WO2008055405A1/fr

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 for preparing high molecular weight polyethylene fibers, in particular to a method for preparing ultrahigh molecular weight polyethylene fibers. Background technique
  • Ultra-high molecular weight polyethylene jelly spinning-super-stretching technology to prepare high-strength, high-modulus polyethylene fiber was patented by DSM in the Netherlands in 1979, and obtained British patent GB2042414 and GB2051667. Subsequently, Allied Company of the United States, Japan and the Netherlands jointly established Toyobo - DSM. Japan's Mitsui has achieved industrial production. In 1982, Allied Corporation of the United States obtained the US4413110 process patent for the production of ultra-high molecular weight polyethylene fibers. China Textile University has also obtained Chinese patents 89107905 and 97106768.
  • the main steps of ultra-high molecular weight polyethylene jelly spinning are: adding ultra-high molecular weight polyethylene into a suitable solvent and stirring to dissolve into a solution, the solution is extruded by a screw extruder, formed through a spinning hole, and then cooled, extracted, Dry and stretch over and finally obtain the finished fiber.
  • the preparation of ultra-high molecular weight polyethylene uniform solution, the process of extracting a large amount of the first solvent contained in the jelly fiber by the second solvent before the super-stretching of the jelly fiber is the key to obtain high-strength high-modulus fiber.
  • the molecular weight of polyethylene increases, its molecular size is large, and there are intertwined macromolecules.
  • the entanglement between macromolecules is beneficial to increase the stretchability of the fiber to obtain high orientation, so that the fiber reaches high strength and high modulus. the amount.
  • various viscoelastic effects caused by excessive and strong inter-molecular entanglement in the polymer make the dissolution much more complicated, which is disadvantageous for dissolution processing, and it is necessary to appropriately reduce inter-molecular entanglement.
  • the entanglement state can be changed by heat treatment, solvent treatment, and shear treatment.
  • the molecular weight difference between the polymer sample and the low molecular solvent is very different.
  • the polymer chain is very long and difficult to move.
  • the interaction between the polymer bonds is large and there is entanglement between the macromolecules.
  • the polymer does not diffuse into the solvent. If the polymer powder is easily agglomerated or forms a gel block due to incomplete penetration of the solvent by a conventional dissolution method, a uniform solution cannot be obtained.
  • the viscoelasticity caused by the inter-molecular entanglement of the ultrahigh molecular weight polyethylene produces a Weissenberg effect (crawling phenomenon) when stirred. As the molecular weight increases, the polymer concentration increases, and the agitation speed increases, the Weissenberg effect becomes more apparent, making it more difficult to make a uniform solution.
  • the European patent EP0255618 mentions the use of hydrotreated kerosene, followed by rectification to obtain a hydrocarbon mixture having a boiling point of 180 to 250 degrees Celsius free of naphthalene and biphenyl. Further, the ultrahigh molecular weight polyethylene and decalin were stirred at 135 ° C for several hours to obtain a polyethylene solution. The concentration of the polyethylene solution is not more than 50%.
  • Japanese Patent JP59232123 mentions that the ultrahigh molecular weight polyethylene and a small amount of solvent are mixed for several minutes and then heated, and the solvent is continuously added under stirring to finally obtain a solution.
  • Chinese Patent 97101010 proposes a pre-swelling kettle equipped with a new agitator baffle to pre-melt the powdered ultra-high molecular weight polymer to obtain a suspension solution, in order to avoid the phenomenon of climbing of high molecular weight polyethylene during dissolution and agitation.
  • the jelly fiber contains a large amount of the first solvent.
  • the solvent in the fiber must be extracted by the second solvent and then subjected to ultra-stretching to obtain high-strength high-modulus fibers.
  • the speed of the extraction process is related to the second solvent used and the extraction process. In addition, it is also related to the path of solvent diffusion.
  • the solvent of the outer layer of the fiber preferentially diffuses out of the jelly fiber during the extraction process. The longer the difference in the diffusion speed of the path, the more the existing method is
  • the jelly fiber of the round section of polyethylene has a thicker wall as seen from the cross section of the fiber. The greater the difference, the more the skin core structure is formed.
  • ultra-high molecular weight polyethylene jelly spinning has been industrially produced by preparing high-strength, high-modulus polyethylene fibers by ultra-stretching.
  • the polyethylene anti-spinning related patents EP0205960A EP0213208A US4413110, WO01/73173A EP1746187A1, etc. have been improved.
  • polyethylene fiber is widely used in anti-cutting gloves, body armor, bulletproof helmets, cables, etc. due to its excellent properties such as light weight, high strength, high modulus, UV, impact resistance and seawater corrosion resistance.
  • a composite with one or more substrates such as nitrile rubber, polyurethane, and epoxy resin.
  • the surface inertness of the polyethylene fibers results in poor interfacial adhesion between the fibers and the substrate, which has been highly valued by those skilled in the art.
  • USP 480136 provides a surface silylation grafting reaction of polyethylene fibers during the spinning process, and cross-linking treatment to improve the bonding performance of the fibers, but is not conducive to the subsequent super-stretching
  • the mechanical properties of the fiber are not ideal.
  • the adhesion properties of the surface of the polyethylene fiber by plasma, ozone, corona discharge or ultraviolet irradiation are proposed, but the process is It is cumbersome, high equipment investment, and the best process conditions for handling are difficult to master, and it is difficult to achieve industrialization.
  • CN163544 proposes a method for extracting a spun polyethylene gel fiber by using a composite extracting agent containing a polar polymer, thereby improving the surface bonding property of the fiber while maximally maintaining the original strength of the fiber, and is simple in operation. There is no need to add any equipment, but the process is effective in the relaxation state of the jelly fiber, and in the actual tensioning extraction process, the polar polymer is difficult to penetrate into the jelly fiber to bond the surface. The performance improvement effect is not obvious. Summary of the invention
  • the technical problem to be solved by the present invention is to overcome the technical defects of the existing ultrahigh molecular weight polyethylene fiber, solve the problem of obtaining a uniform raw material mixture, and removing the first solvent in the jelly fiber, and provide a simple and efficient operation.
  • a method for preparing a cost-effective high molecular weight polyethylene fiber The high molecular weight polyethylene fibers prepared by this method have high adhesion.
  • a method for preparing an ultrahigh molecular weight polyethylene fiber characterized in that a polyethylene powder having an ultrahigh relative molecular weight of 1 million to 6 million is added to a polar polymer, dispersed in a solvent, and formulated into a uniform mixed emulsion, and frozen
  • the mixed emulsion is quantitatively fed into the screw extruder while stirring to rapidly swell and dissolve to form a transparent and uniform spinning dope, which is extruded through a spinneret, cooled, solidified to form a spinning, and then passed through Extraction, drying, and ultra-stretching to obtain ultra-high molecular weight polyethylene fibers.
  • a polyethylene powder, a polar polymer and a solvent having an ultrahigh relative molecular weight of 1,000,000 million are injected into the unwinding apparatus in proportion to be unwrapped to form a uniform mixed emulsion.
  • the above homogeneous emulsion has a percentage concentration of 4% to 60%.
  • the above polar polymer is a polar polymer containing an ester group, a carbonyl group or an ether group.
  • the polar polymer containing an ester group, a carbonyl group or an ether group is an ethylene/ethylene acetate copolymer, a polyacrylate, a polyvinylpyrrolidone/ethylene acetate copolymer having a different K value, and a polyoxyethylene polymer.
  • the polar polymer is added in an amount of from 1 to 10% by weight based on the weight of the ultrahigh molecular weight of 1,000,000 million polyethylene powder. It is preferably 2-8%.
  • silicone oil or a derivative thereof may be added for unwinding. Or / and adding silicone oil or a derivative thereof during solidification; wherein the amount of the silicone oil or its derivative added is that the ultra-polymer halo polyethylene fiber contains 0.05-5 wt% of the silicone oil or its derivative.
  • one or more of an antioxidant, a stabilizer, a dye, and a flame retardant may be added.
  • the unwrapping device can provide a shear rate of at least 1000 seconds.
  • the unwinding apparatus may be 1000-5000 sec- 1 , more preferably 2000-4000 sec.
  • the unwinding apparatus may be one of a high speed disperser, a stirrer, a colloid mill, a homogenizer, a venturi, or a combination thereof.
  • the relative average molecular weight of the ultrahigh molecular weight polyethylene is preferably from 400 in case of 600 million. More preferably, it is 2 million to 5 million.
  • the solvent used is a solvent which is liquid at normal temperature, and may be a terpene hydrocarbon, a cyclic hydrocarbon, an aromatic hydrocarbon, a derivative of a terpene hydrocarbon, a derivative of a cyclic hydrocarbon, an aromatic hydrocarbon.
  • a solvent which is liquid at normal temperature, and may be a terpene hydrocarbon, a cyclic hydrocarbon, an aromatic hydrocarbon, a derivative of a terpene hydrocarbon, a derivative of a cyclic hydrocarbon, an aromatic hydrocarbon.
  • the nominal concentration of the ultrahigh molecular weight polyethylene and the solvent is from 1 to 50% by weight.
  • the screw extruder used in the invention is one of a single screw, a twin screw, a triple screw and a four screw extruder, and the screw extrusion temperature is above the dissolution temperature of the ultra high molecular weight polyethylene, such as a screw extruder.
  • the twin-screw extruder used can be rotated in the opposite direction or in the opposite direction, and the screw has an aspect ratio of 1:30-65.
  • the residence time of the homogeneous mixed emulsion in the twin-screw extruder is 10-60 minutes, preferably 20-40 minutes, the material temperature is 50-280 ° C, and the solution spinning temperature is controlled during extrusion. 140-280 °C. It is best at 200-260 °C.
  • the spinneret hole on the spinneret used in the screw extruder is a rectangular hole having an aspect ratio of 4-20, preferably 5-15.
  • the emulsion-like mixture may be directly fed to a screw extruder or fed to a screw extruder through a stirred storage tank.
  • the storage cylinders used are one or more.
  • the fiber has a stretching temperature of 80 to 130 ° C and a stretching ratio of 20 times or more, preferably 30 to 60 times.
  • the invention has the following advantages:
  • Ultra-high molecular weight polyethylene fiber impregnated PU or nitrile gloves which are soft, lightweight, corrosion-resistant, aging-resistant and oil-repellent, have become better cut-proof gloves on the market today.
  • the invention adopts high-shear unwinding ultrahigh molecular weight polyethylene and simultaneously adds a polar polymer containing an ester group, a carbonyl group and an ether group, and can be dispersed very uniformly in the ultrahigh molecular weight polyethylene to realize high adhesion polymerization.
  • the manufacture of vinyl fiber does not require any equipment and the process is simple.
  • Ultra-high molecular weight polyethylene and a proper amount of polar polymer mixed emulsion are rapidly swelled and completely dissolved in a twin-screw extruder, which is beneficial to reduce the degradation of the polymer and improve the bonding property of the fiber. Does not affect the mechanical properties of the fiber.
  • the ultrahigh molecular weight polyethylene fiber prepared by the invention has large fracture power and strong energy absorption ability, and the fracture extension is improved as much as possible under the premise of ensuring sufficient fracture strength, that is, the fracture strength has the best match with the fracture extension. Suitable for cut-resistant gloves.
  • the invention realizes rapid swelling and dissolution of the ultrahigh molecular weight polyethylene by moderately unwinding with high shear, and the fracture work can be made above 30030CN, mm/dtex under the premise of ensuring the breaking strength of the fiber is above 30CN/dtex.
  • the fiber for cut-proof gloves is generally used in a single layer. It is required to have good anti-cutting performance, and the gloves are required to be flat and the density is hooked. This puts high requirements on the uniformity of the fibers.
  • the ultra-high molecular weight polyethylene fiber has a CV value of 8-10%, and the present invention is effective in realizing rapid swelling, dissolution, and addition of a surfactant and a flat wire structure in the coagulation liquid.
  • the ultra-high molecular weight polyethylene fiber is controlled to have a fineness and strength CV value between 4 and 6%.
  • the ultra-high molecular weight polyethylene fiber is made into a flat structure, so that the specific surface area of the fiber is increased, which is favorable for uniform solidification, shortens the path of the solvent in the fiber to diffuse out of the jelly fiber, improves the extraction rate, and saves extraction.
  • the second solvent used reduces the cost and thus "improves the uniformity and strength of the fiber.
  • the invention is not only simple to operate, but also saves time and labor, saves cost, and dissolves more uniformly. Detailed ways
  • Ultra-high molecular weight polyethylene (relative average molecular mass 4.5 million) powder, and 90# solvent white oil were fed into the unwinding kettle at a weight ratio of 1:8 at room temperature, under nitrogen protection, at a shear rate of 2000 seconds. Under the action of shearing for 10 minutes, a uniform emulsion mixture was obtained, and a co-rotating twin-screw extruder with a diameter of 25 mm and an aspect ratio of 36 was fed. The temperature was controlled at 250 ° C, and the screw speed was adjusted to 35 rpm. minute. After the extrudate is filtered and the spinneret is sprayed out of the jelly filament, it is extracted and super-stretched 35 times to obtain ultrahigh molecular weight polyethylene.
  • Example 2
  • Ultra-high molecular weight polyethylene (relative average molecular mass 4.5 million) powder, and 90# solvent white oil were separately fed into the unwrapping kettle at a weight ratio of 1:8 at room temperature, and EVA28190 (ethylene-vinyl acetate copolymer, The content of vinyl acetate was 28%, the melt index was 190), the amount of addition was 4 wt% of polyethylene powder, and the shearing rate was 2000 sec under nitrogen protection for 10 minutes to obtain a uniform emulsion mixture.
  • Feeding a co-rotating twin-screw extruder with a diameter of 025 mm and a length to diameter ratio of 36 the temperature is controlled at 250 ° C, and the screw speed is adjusted to 35 rpm. The extrudate is filtered and the spinneret is sprayed out of the gel. After the silk, it was extracted and super-stretched 35 times to obtain a highly adhesive ultrahigh molecular weight polyethylene.
  • Ultra-high molecular weight polyethylene (relative average molecular mass 4.5 million) powder, and 90# solvent white oil were separately fed into the unwrapping kettle at a weight ratio of 1:8 at room temperature, and EVA28190 (ethylene-vinyl acetate copolymer, The content of vinyl acetate is 28%, the melt index is 190), the amount is 2wt% of polyethylene powder, and under nitrogen protection, it is sheared for 10 minutes under the action of shearing speed of 2000 seconds to obtain a uniform emulsion mixture.
  • a co-rotating twin-screw extruder having a diameter of ⁇ 25 ⁇ and a length to diameter ratio of 36 was fed, the temperature was controlled at 250 ° C, and the screw speed was adjusted to 35 rpm. After the extrudate is filtered and the spinneret is sprayed out of the jelly filament, it is extracted and super-stretched 35 times to obtain a highly adhesive ultrahigh molecular weight polyethylene.
  • Ultra-high molecular weight polyethylene (relative average molecular mass 4.5 million) powder, and 90# solvent white oil were fed into the unwrapped kettle at a weight ratio of 1:8 at room temperature, and EVA1030 (ethylene-vinyl acetate copolymer, The content of vinyl acetate is 10%, the melt index is 30), and the amount is 4wt% of polyethylene powder. Under nitrogen protection, it is sheared for 10 minutes under the action of shear rate of 2000 sec- 1 to obtain uniform emulsion mixture.
  • Example 5 The liquid was fed into a co-rotating twin-screw extruder having a diameter of ⁇ 25 ⁇ and a length to diameter ratio of 36, the temperature was controlled at 250 ° C, and the screw speed was adjusted to 35 rpm. After the extrudate is filtered and the spinneret is sprayed out of the jelly filament, it is extracted and super-stretched 35 times to obtain a highly adhesive ultrahigh molecular weight polyethylene.
  • Example 5 Example 5
  • Ultra-high molecular weight polyethylene (relative average molecular mass 4.5 million) powder, and 90# solvent white oil were transferred into the unwrapping kettle at a weight ratio of 1:8 at room temperature, and polyacrylate was added at the same time. 4wt% of the powder, under nitrogen protection, sheared for 10 minutes under the action of shearing speed of 2000 seconds, to obtain a uniform emulsion mixture, feeding the same direction twin screw extrusion with diameter ⁇ 25 ⁇ and length to diameter ratio of 36 The temperature is controlled at 250 ° C and the screw speed is adjusted to 35 rpm. After the extrudate is filtered and the spinneret is sprayed out of the jelly filament, it is extracted and super-stretched 35 times to obtain a highly adhesive ultrahigh molecular weight polyethylene. Example ⁇ .
  • Ultra-high molecular weight polyethylene (relative average molecular mass 4.5 million) powder, and 90# solvent white oil were respectively transferred into the unwrapping kettle at a weight ratio of 1:8 at room temperature, and polyoxyethylene was added at the same time. 4wt% of the powder, under nitrogen protection, sheared for 10 minutes under the action of shearing speed of 2000 seconds, to obtain a uniform emulsion mixture, feeding a co-rotating twin-screw extrusion with a diameter of 25 mm and a length to diameter ratio of 36. The temperature is controlled at 250 ° C and the screw speed is adjusted to 35 rpm. After the extrudate is filtered and the spinneret is sprayed out of the jelly filament, it is extracted and super-stretched 35 times to obtain a highly adhesive ultrahigh molecular weight polyethylene.
  • Ultra-high molecular weight polyethylene (relative average molecular mass 4.5 million), solvent white oil (70#), at room temperature, the above polyethylene and white oil are respectively injected into the unpacking kettle at a nominal concentration of 10% by weight, nitrogen protection
  • the lower shear was cut for 5 minutes and the shearing speed was 3000 seconds.
  • the uniform emulsion mixture was input into the storage tank and the mixture was quantitatively fed into the twin-screw extruder while stirring.
  • the extrudate is discharged from the nozzle through the filter tank to the metering pump, and then discharged into the water bath. After 3 ⁇ 4, extraction, drying, and ultra-stretching, the total stretching ratio is 40, and the obtained fiber strength reaches 30 cN/dtex, and the modulus is above 1000 cN/dtex.
  • Ultra-high molecular weight polyethylene (relative average molecular mass 5 million), solvent white oil (90#), at room temperature, the above polyethylene and white oil are respectively injected into the unpacking kettle at a nominal concentration of 5% by weight, nitrogen protection
  • the lower shearing was carried out for 5 minutes, and the shearing speed was 3000 sec -1 .
  • the uniform emulsion-like mixed liquid was input into the storage tank and fed to the twin-screw extruder while stirring.
  • the extrudate is ejected from the spinneret through the filter tank to the metering pump.
  • Ultra-high molecular weight polyethylene (relative average molecular mass 4.5 million), solvent white oil (90#), the above polyethylene and white oil were respectively injected into the unpacking kettle at a nominal concentration of 5% by weight at room temperature, adding 0.2% (Weight) Antioxidant, sheared under nitrogen for 5 minutes, shear rate 2000 sec -1 , and a uniform emulsion mixture was input into the storage tank and fed to the twin-screw extruder while stirring.
  • the extrudate is ejected from the filter tank through the filter tank to the metering pump, and then ejected from the nozzle hole after being treated in a water bath, and then subjected to extraction and drying, and the total stretching is 40, and the obtained fiber strength reaches 28 cN/dtex.
  • the amount is above 900 cN/dtex.
  • Ultra-high molecular weight polyethylene (relative average molecular mass 5 million), solvent white oil (90#), the above polyethylene and white oil were respectively injected into the unpacking kettle at a nominal concentration of 12% by weight under nitrogen protection.
  • the shearing was carried out for 10 minutes, and the shearing speed was 2000 seconds.
  • the uniform emulsion-like mixed liquid was input into the storage tank and fed to the twin-screw extruder while stirring.
  • the extrudate is discharged from the filter tank through the filter tank to the metering pump, and then discharged into the water bath, and then extracted, dried, and subjected to ultra-stretching.
  • the total stretching ratio is 40, and the obtained fiber strength reaches 35 cN/dtex.
  • the modulus is above 1050 cN/dtex.
  • Ultra-high molecular weight polyethylene (relative average molecular mass 4.5 million), solvent white oil (90#), white oil is injected into the unwrapping kettle at a nominal concentration of 10% by weight at room temperature.
  • concentration of 10% by weight was added to the unwrapped kettle by a screw propeller at a rate of 0.5 kg/min, and the shearing was added under nitrogen protection. The shear rate was 1000 seconds to obtain a uniform emulsion mixture.
  • the input tank was stirred and quantitatively fed.
  • Ultra-high molecular weight polyethylene (relative average molecular mass 4.5 million), solvent white oil (70#), the above polyethylene and white oil are respectively injected into the unpacking kettle at a nominal concentration of 10% by weight at room temperature, under nitrogen protection After shearing for 15 minutes and shearing speed for 1000 seconds, a uniform emulsion mixture was introduced into the storage tank, and fed to the twin-screw extruder while stirring.
  • the extrudate is ejected from the filter tank through the filter tank to the metering pump, and then ejected from the spinning hole after being treated in a water bath, and then subjected to extraction and drying, and the total stretching is 40, and the obtained fiber strength reaches 30 cN/dtex.
  • the amount is above 1000 cN/dtex.
  • Example 13 Ultrahigh molecular weight polyethylene (relative average molecular mass 4.5 million), solvent white oil (70#), the above polyethylene and white oil were respectively injected into the unpacking kettle at a nominal concentration of 10% by weight at room temperature. At the same time, adding 1% (by weight) epoxy modified silicone oil, shearing under nitrogen protection for 5 minutes, shearing speed of 3000 seconds - 1 , obtaining a uniform emulsion mixture into the storage tank, and feeding the twin-screw extrusion while stirring Out of the plane.
  • the extrudate is sprayed from the filter hole through the filter tank to the metering pump, and then sprayed into the water bath, and then subjected to extraction and drying, and the total stretching is 40, and the obtained fiber strength reaches 30 cN/dtex.
  • the amount is above 1000cN/dtex.
  • Ultra-high molecular weight polyethylene (relative average molecular mass 5 million), solvent white oil (90#), the above polyethylene and white oil were respectively injected into the unpacking kettle at a nominal concentration of 12% by weight under nitrogen protection. After shearing for 10 minutes and shearing rate of 2000 seconds, a uniform emulsion mixture was obtained and fed into the storage tank while being quantitatively fed into the twin-screw extruder.
  • Ultra-high molecular weight polyethylene (relative average molecular mass 4.5 million), solvent white oil (90#), the above polyethylene and white oil are respectively injected into the unwrapping kettle at a nominal concentration of 10% by weight at room temperature, ultrahigh molecular weight
  • the polyethylene was added into the unwrapped kettle at a nominal concentration of 10% by weight from a screw propeller at a rate of 0.5 kg/min.
  • the shearing speed was added under a nitrogen atmosphere and the shear rate was 1000 seconds to obtain a uniform emulsion mixture into the storage tank. Quantitatively fed to the twin-screw extruder while stirring.
  • the extrudate is sprayed from the filter hole through the filter box to the metering pump, and then added to a 2% by weight polyether-epoxy modified silicone oil water bath for treatment, extraction, drying, and ultra-stretching, pulling The total extension is 30, and the obtained fiber strength reaches 30 cN/dte X and the modulus is above 1000 cN/dtex.
  • the temperature is controlled at 240 ° C and the screw extruder speed is 30 rpm.
  • the extrudate is ejected from the filter box to the metering pump and is ejected from a spinneret having a rectangular orifice, the oblong hole having an aspect ratio of 8. Then, it is extracted into a water bath and then extracted, dried, super-stretched, and the total stretching ratio is 40, and the obtained fiber strength reaches 30 cN/dtex, and the modulus is above 1000 cN/dtex.
  • the screw extruder was rotated at 40 rpm at 250 °C.
  • the extrudate is ejected from the filter box to the metering pump and then ejected from a spinneret having a rectangular orifice having an aspect ratio of 12. Then, it is treated in a water bath, extracted, dried, and subjected to ultra-stretching.
  • the total stretching ratio is 40, and the obtained fiber strength reaches 30 cN/dtex, and the modulus is above 1000 cN/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)

Abstract

L'invention concerne un procédé de production de fibre de polyéthylène de masse moléculaire très élevée à section transversale plate et à forte cohésivité. Le procédé de l'invention consiste : à répartir une poudre de polyéthylène de masse moléculaire très élevée (UHMW-PE) dans un solvant de manière égale; à préparer une émulsion mélangée uniforme par démêlage à cisaillement élevé; à ajouter dans un même temps un polymère polaire comprenant des groupes polaires, par exemple un groupe carboxyle, un groupe carbonyle, un groupe éther, ou un groupe ester, etc.; à répartir de manière égale le polymère polaire avec la poudre de polyéthylène dans le solvant afin d'obtenir une émulsion mélangée uniforme; à former un filament de gel avec l'émulsion mélangée par un procédé de filage par gel; puis à extraire, à sécher et à étirer afin d'obtenir ladite fibre de UHMW-PE à section transversale plate, haute résistance et forte cohésivité. Les capacités de gonflage et de dissolution du UHMW-PE peuvent être accélérées en procédant à un démêlage correct, et le polymère polaire réparti de manière égale permet d'améliorer de manière significative l'adhérence de la fibre. Les opérations effectuées dans le procédé sont faciles à mettre en oeuvre, et des réductions en matière de temps, de travail et de coûts peuvent êtres réalisées. La section de la fibre est de forme rectangulaire plate et la paroi est mince et égale, de façon que le trajet pour le solvant dans la fibre diffusant vers l'extérieur le filament de gel puisse être significativement raccourci, et ainsi que l'efficacité d'extraction et l'uniformité de la fibre puissent être améliorées.
PCT/CN2007/002906 2006-11-08 2007-10-09 Procédé de production de fibre de polyéthylène de masse moléculaire très élevée WO2008055405A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US12/299,205 US20100233480A1 (en) 2006-11-08 2007-10-09 Process for producing fiber of ultra high molecular weight polyethylene
DE602007008600T DE602007008600D1 (de) 2006-11-08 2007-10-09 Verfahren zur herstellung von fasern aus polyethylen mit ultrahohem molekulargewicht
AT07816520T ATE478178T1 (de) 2006-11-08 2007-10-09 Verfahren zur herstellung von fasern aus polyethylen mit ultrahohem molekulargewicht
EP07816520A EP2080824B1 (fr) 2006-11-08 2007-10-09 Procédé de production de fibre de polyéthylène de masse moléculaire très élevée

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
CN200610118076.X 2006-11-08
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
CN200610147424.6 2006-12-18
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
CN200710040678.2 2007-05-15
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
CN200710043831.7 2007-07-16
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

Publications (1)

Publication Number Publication Date
WO2008055405A1 true WO2008055405A1 (fr) 2008-05-15

Family

ID=39364173

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2007/002906 WO2008055405A1 (fr) 2006-11-08 2007-10-09 Procédé de production de fibre de polyéthylène de masse moléculaire très élevée

Country Status (5)

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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US20120306109A1 (en) * 2009-11-26 2012-12-06 Ningbo Dacheng Advanced Material Co., Ltd. Method For Evenly Preparing Filament By Using High-Shearing Solution of Ultrahigh-Molecular-Weight Polyethylene
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
CN113668086A (zh) * 2021-08-24 2021-11-19 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

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9365953B2 (en) 2007-06-08 2016-06-14 Honeywell International Inc. Ultra-high strength UHMWPE fibers and products
US8747715B2 (en) 2007-06-08 2014-06-10 Honeywell International Inc Ultra-high strength UHMW PE fibers and products
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
TR201902872T4 (tr) 2011-12-14 2019-03-21 Dsm Ip Assets Bv Ultra-yüksek moleküler ağırlıklı polietilen multifilament iplik.
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
EP4234773A3 (fr) * 2014-12-02 2024-06-26 Braskem, S.A. Procédé et système continus pour la production d'au moins un fil polymère et fil polymère
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
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
CN114100187A (zh) * 2021-09-18 2022-03-01 江苏九九久科技有限公司 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

Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US480136A (en) 1892-08-02 Shutter-bower
US4115492A (en) 1975-10-03 1978-09-19 The Dow Chemical Company Process for preparing microporous polyethylene hollow fibers
GB2042414A (en) 1979-02-08 1980-09-24 Stamicarbon Dry-spinning polymer filaments
GB2051667A (en) 1979-06-27 1981-01-21 Stamicarbon Preparing polyethylene filaments
US4413110A (en) 1981-04-30 1983-11-01 Allied Corporation High tenacity, high modulus polyethylene and polypropylene fibers and intermediates therefore
JPS59232123A (ja) 1983-06-16 1984-12-26 Agency Of Ind Science & Technol 超高分子量ポリエチレン溶液の製造方法
CN85107352A (zh) 1985-02-15 1986-10-01 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
EP0205960A2 (fr) 1985-06-17 1986-12-30 AlliedSignal Inc. Fibre de polyoléfine à haute ténacité, à faible retrait, à module très élevé et à très bas fluage et ayant une bonne rétention de résistance à haute température ainsi que sa méthode de fabrication
EP0213208A1 (fr) 1985-02-15 1987-03-11 Toray Industries, Inc. Fil multifilament en polyethylene
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
JPS6353283B2 (fr) * 1984-11-19 1988-10-21 Ntn Toyo Bearing Co Ltd
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
US5294338A (en) 1990-11-28 1994-03-15 Mitsubishi Rayon Co., Ltd. Porous polyethylene hollow fiber membrane of large pore diameter, production process thereof, and hydrophilized porous polyethylene hollow fiber membranes
CN1160093A (zh) * 1997-01-02 1997-09-24 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
US5695702A (en) 1994-07-01 1997-12-09 Millipore Corporation Thermoplastic hollow fiber membrane module and method of manufacture
US5755913A (en) 1996-12-06 1998-05-26 Liaw; Der-Jang Adhesive-free adhesion between polymer surfaces
WO2001073173A1 (fr) 2000-03-27 2001-10-04 Honeywell International Inc. Filament a tenacite et module eleves
US6436319B1 (en) 1999-04-27 2002-08-20 Agency For Technology And Standards Method of preparing hollow fiber-type separation membrane from high density polyethylene
CN1693544A (zh) 2005-05-10 2005-11-09 东华大学 一种提高超高相对分子量聚乙烯表面粘结性能的方法
EP1746187A1 (fr) 2005-07-18 2007-01-24 DSM IP Assets B.V. Fil multifilament en polyéthylène

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5230854A (en) * 1991-12-09 1993-07-27 Allied-Signal Inc. Method for removal of spinning solvent from spun fiber
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
CN100410431C (zh) * 2002-12-10 2008-08-13 帝斯曼知识产权资产管理有限公司 制造和转化聚烯烃纤维的方法
JP4578483B2 (ja) * 2004-01-01 2010-11-10 ディーエスエム アイピー アセッツ ビー．ブイ． 高性能ポリエチレンマルチフィラメント糸の製造方法

Patent Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US480136A (en) 1892-08-02 Shutter-bower
US4115492A (en) 1975-10-03 1978-09-19 The Dow Chemical Company Process for preparing microporous polyethylene hollow fibers
GB2042414A (en) 1979-02-08 1980-09-24 Stamicarbon Dry-spinning polymer filaments
GB2051667A (en) 1979-06-27 1981-01-21 Stamicarbon Preparing polyethylene filaments
US4413110A (en) 1981-04-30 1983-11-01 Allied Corporation High tenacity, high modulus polyethylene and polypropylene fibers and intermediates therefore
JPS59232123A (ja) 1983-06-16 1984-12-26 Agency Of Ind Science & Technol 超高分子量ポリエチレン溶液の製造方法
JPS6353283B2 (fr) * 1984-11-19 1988-10-21 Ntn Toyo Bearing Co Ltd
CN85107352A (zh) 1985-02-15 1986-10-01 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
EP0213208A1 (fr) 1985-02-15 1987-03-11 Toray Industries, Inc. Fil multifilament en polyethylene
EP0213208B1 (fr) * 1985-02-15 1991-10-30 Toray Industries, Inc. Fil multifilament en polyethylene
EP0205960A2 (fr) 1985-06-17 1986-12-30 AlliedSignal Inc. Fibre de polyoléfine à haute ténacité, à faible retrait, à module très élevé et à très bas fluage et ayant une bonne rétention de résistance à haute température ainsi que sa méthode de fabrication
EP0255618A2 (fr) 1986-07-08 1988-02-10 Nippon Petrochemicals Co., Ltd. Solution de polyéthylène à masse moléculaire très haute
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
US5294338A (en) 1990-11-28 1994-03-15 Mitsubishi Rayon Co., Ltd. Porous polyethylene hollow fiber membrane of large pore diameter, production process thereof, and hydrophilized porous polyethylene hollow fiber membranes
US5695702A (en) 1994-07-01 1997-12-09 Millipore Corporation Thermoplastic hollow fiber membrane module and method of manufacture
US5755913A (en) 1996-12-06 1998-05-26 Liaw; Der-Jang Adhesive-free adhesion between polymer surfaces
CN1160093A (zh) * 1997-01-02 1997-09-24 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
US6436319B1 (en) 1999-04-27 2002-08-20 Agency For Technology And Standards Method of preparing hollow fiber-type separation membrane from high density polyethylene
WO2001073173A1 (fr) 2000-03-27 2001-10-04 Honeywell International Inc. Filament a tenacite et module eleves
CN1693544A (zh) 2005-05-10 2005-11-09 东华大学 一种提高超高相对分子量聚乙烯表面粘结性能的方法
EP1746187A1 (fr) 2005-07-18 2007-01-24 DSM IP Assets B.V. Fil multifilament en polyéthylène

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JIA G. ET AL.: "STUKING ON THE ADHESION OF UHMW-PE FIBER", CHINA SYNTHETIC FIBER INDUSTRY, no. 6, December 1995 (1995-12-01), pages 24 - 28, XP008100177 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120306109A1 (en) * 2009-11-26 2012-12-06 Ningbo Dacheng Advanced Material Co., Ltd. Method For Evenly Preparing Filament By Using High-Shearing Solution of Ultrahigh-Molecular-Weight Polyethylene
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
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
CN113668086A (zh) * 2021-08-24 2021-11-19 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

Also Published As

Publication number Publication date
EP2080824B1 (fr) 2010-08-18
DE602007008600D1 (de) 2010-09-30
US20100233480A1 (en) 2010-09-16
EP2080824A4 (fr) 2009-12-23
EP2080824A1 (fr) 2009-07-22
ATE478178T1 (de) 2010-09-15

Similar Documents

Publication Publication Date Title
WO2008055405A1 (fr) Procédé de production de fibre de polyéthylène de masse moléculaire très élevée
JP5742877B2 (ja) 高強度ポリエチレン繊維およびその製造方法
CN101235551A (zh) 一种高剪切超高分子量聚乙烯连续溶解纺丝新方法
CN101575743B (zh) 一种超高分子量聚乙烯纤维纺丝原液的制备方法
JP2005527698A5 (fr)
WO2010022596A1 (fr) Membrane poreuse à fibres creuses et sa préparation
CN109234850B (zh) 交联改性超高分子量聚乙烯纤维及其制备方法
JPH0116924B2 (fr)
CN106567274A (zh) 一种用对位芳纶纳米纤维制备芳纶纸的方法
CN101348944A (zh) 高粘接性超高分子量聚乙烯纤维的制造新方法
JP2017507216A5 (fr)
CN108277546A (zh) 一种防切割聚乙烯纤维的制备方法
JP7307873B2 (ja) 高性能な繊維および該繊維の製造に用いられる紡糸原液
WO2021255957A1 (fr) Procédé permettant de produire une fibre de polyamide 4
CN101307509A (zh) 一种超高分子量聚乙烯纤维纺丝新方法
CN1255460C (zh) 聚烯烃微多孔膜
CN107435171B (zh) 一种交联结构取向填充增强化纤的制备方法
JPS63265619A (ja) ポリエチレン延伸フィラメントおよび延伸フィルムの製造方法
KR101896476B1 (ko) 공용매를 이용한 고결정성 재생 셀룰로오스 섬유의 제조 방법
JP2007297763A (ja) 高強度ポリエチレン繊維およびその製造方法
Liu et al. Study of diffusion performance and preparation technology of the coloured PMIA fibre
JPH07238416A (ja) 高強度ポリエチレン繊維の製造方法
JPS60239509A (ja) 高強度高モジユラスポリオレフイン系繊維の製造方法
KR20110135333A (ko) 일종의 고강도고탄성률 폴리에틸렌 섬유의 생산방법
JPS6230024A (ja) 高分子量エチレンテレフタレ−ト系ポリエステル延伸物の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07816520

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2007816520

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE