EP0064167B1 - Process for producing high tenacity, high modulus crystalline thermoplastic article and novel product fibers - Google Patents

Process for producing high tenacity, high modulus crystalline thermoplastic article and novel product fibers Download PDF

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Publication number
EP0064167B1
EP0064167B1 EP82102964A EP82102964A EP0064167B1 EP 0064167 B1 EP0064167 B1 EP 0064167B1 EP 82102964 A EP82102964 A EP 82102964A EP 82102964 A EP82102964 A EP 82102964A EP 0064167 B1 EP0064167 B1 EP 0064167B1
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Prior art keywords
fiber
solvent
temperature
gel
denier
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German (de)
English (en)
French (fr)
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EP0064167A1 (en
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Sheldon Kavesh
Dusan Ciril Prevorsek
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Allied Corp
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Allied Corp
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Priority claimed from US06/359,019 external-priority patent/US4413110A/en
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    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene

Definitions

  • the present invention relates to crystalline thermoplastic articles such as fibers or films having high tenacity, modulus and toughness values and a process for their production which includes a gel intermediate.
  • GB ⁇ A ⁇ 2,042,414 of Smith and Lemstra describes a process in which a dilute solution of ultrahigh molecular weight polyethylene (UHMWPE) is spun into a quench bath where a gel fiber (still dilute in UHMWPE) is formed.
  • UHMWPE ultrahigh molecular weight polyethylene
  • the wet gel (98% solvent in the Examples) was hot-stretched and simultaneously dried of the solvent (see page 1, line 102-page 2, line 1).
  • Decalin is used in the Examples.
  • the product UHMWPE fiber of GB-A-2,042,414 is described as having, at maximum stretch ratio, a tenacity of 3.02 GPa and a modulus of 90.2 GPa.
  • An article by the named inventors in J. Mat. Sci., vol. 15, pp. 505-514 (1980) describes the same process and essentially the same example (compare Table 1 at page 509 of the article to Table 1 at page 3 of GB-A-2,042,414) and indicates (on page 510 and in Figure 10) that the peak melting temperature (by DSC at 10°C/minute heating rate) reached asymtotically a value of 145.5°C at a draw ratio of 31.7.
  • the product polypropylene fibers of GB-A-2,042,414 had weight average molecular weights of 1,500,000 and 3,000,000 and tensile strengths of 1.56 GPa and 1 GPa. No moduli or melting temperatures are reported.
  • the moduli obtainable exceeded 80 GPa when the filament entering the drawing step exceeded 90% solvent (open circles), exceeded 70 GPa when the filament entering the drawing step was 6% solvent (closed circles) and remained under 45 GPa when the filament entering the drawing step has been extracted with methanol (see conclusions at page 4, lines 1-7).
  • the substantially dry (6% solvent) filaments could be hot stretched to fibers of lesser modulus than filaments containing over 90% solvent.
  • Kalb and Pennings in Polymer, vol. 21, pp. 3 ⁇ 4 (1980) describe a process in which a 5% UHMWPE solution in paraffin oil was spun through a conical die (into air), extracted with hexane, dried under vacuum (to form a porous gel fiber) and drawn in a tube with a temperature gradient of 1-0°C to 148°C.
  • the success of the process is described as being based upon a high microporosity of the fiber to be drawn (0.55 cm 3 free volume/cm 3 porous fiber or 55% porosity). Maximum properties obtained were 3.0 GPa tensile strength, 106 GPa modulus and 6.4% elongation at break.
  • the present invention includes a continuous process for producing a high strength, high modulus fiber or film which comprises the steps: -
  • the present invention also includes a continuous polyethylene fiber of weight average molecular weight at least 500,000 and having a tenacity of at least 20 g/denier (1.7 GPa) and a tensile modulus at least 500 g/denier (43 GPa), characterized by having a creep value no more than 5% (when measured at 10% of breaking load for 50 days at 23°C), a porosity less than 10% and a main melting temperature of at least 147°C (measured by DSC at 10°C/minute heating rate).
  • the present invention also includes a continuous polypropylene fiber of weight average molecular weight at least 750,000 and having a tenacity of at least 8 g/denier (0.6 GPa), characterized by having a tensile modulus of at least 160 g/denier (13.7 GPa) and a main melting temperature of at least 168°C (measured by DSC at 10°C/minute heating rate).
  • the present invention also includes a continuous polyolefin gel fiber comprising between 4 and 20 weight % solid polyethylene of weight average molecular weight at least 500,000 or solid polypropylene of weight average molecular weight at least 750,000, and between 80 and 96 weight % of a swelling solvent miscible with high boiling hydrocarbon and having an atmospheric boiling point less than 50°C.
  • marine ropes and cables such as the mooring lines used to secure supertankers to loading stations and the cables used to secure deep sea drilling platforms to underwater anchorage, are presently constructed of materials such as nylon, polyester, aramids and steel which are subject to hydrolytic or corrosive attack by sea water.
  • mooring lines and cables are constructed with significant safety factors and are replaced frequently. The greatly increased weight and the need for frequent replacement create substantial operational and economic burdens.
  • the fibers and films of this invention are of high strength, extraordinarily high modulus and great toughness. They are dimensionally and hydrolytically stable and resistant to creep under sustained loads.
  • the fibers and films of the invention prepared according to the present process possess these properties in a heretofore unattained combination, and are therefore quite novel and useful materials.
  • Fibers and films of this invention include reinforcements in thermoplastics, thermosetting resins, elastomers and concrete for uses such as pressure vessels, hoses, power transmission belts, sports and automotive equipment, and building construction.
  • the strongest fibers of the present invention are of higher melting point, higher tenacity and much higher modulus. Additionally, they are more uniform, and less porous than the prior art fibers.
  • the process of the present invention has the advantage of greater controllability and reliability in that the steps of drying and stretching may be separate and each step may be carried out under optimal conditions.
  • Smith & Lemstra in Polymer Bulletin, vol. 1, pp. 733-36 (1979) indicate that drawing temperature, below 143°C, had no effect on the relationships between either tenacity or modulus and stretch ratio.
  • the properties of the fibers of the present invention may be controlled in part by varying stretch temperature with other factors held constant.
  • the process of the present invention has the advantage that the intermediate gel fibers which are spun are of uniform concentration and this concentration is the same as the polymer solution as prepared.
  • the advantages of this uniformity are illustrated by the fact that the fibers of the present invention may be stretched in a continuous operation to prepare packages of indefinite length.
  • the intermediate xerogel fibers of the present invention preferably contain less than 10 volume % porosity compared to 23-65% porosity in the dry gel fibers described by Smook et a/. and Kalb and Pennings.
  • the crystallizable polymer used in the present invention may be a polyolefin such as polyethylene, polypropylene or poly(methylpentene-1) or may be another polymer such as poly(oxymethylene) or poly(vinylidene fluoride).
  • suitable polymers have molecular weights (by intrinsic viscosity) in the range of one to ten million. This corresponds to a weight average chain length of 3.6x 10 4 to 3.6x10 5 monomer units or 7x 10 4 to 7.1x10 5 carbons.
  • Other polyolefins and poly(haloolefins) should have similar backbone carbon chain lengths.
  • the total chain length should preferably be in the same general range, i.e. 7x10 4 to 71 X 10 4 atoms, with some adjustment possible due to the differences in bond angles between C-C-C and C-0-C.
  • the weight average molecular weight of polyethylene used is at least 500,000 (6 IV), preferably at least 1,000,000 (10 IV), and more preferably between 2,000,000 (16 IV) and 8,000,000 (42 IV).
  • the weight average molecular weight of polypropylene used is at least 750,000 (5 IV), preferably at least 1,000,000 (6 IV), more preferably at least 1,500,000 (9 IV) and most preferably between 2,000,000 (11 IV) and 8,000,000 (33 IV).
  • the IV numbers represent intrinsic viscosity of the polymer in decalin at 135°C.
  • the first solvent should be non-volatile under the processing conditions. This is necessary in order to maintain essentially constant the concentration of solvent upstream and through the aperture (die) and to prevent non-uniformity in liquid content of the gel fiber or film containing first solvent.
  • the vapor pressure of the first solvent should be no more than 20 kPa (one-fifth of an atmosphere) at 175°C, or at the first temperature.
  • Preferred first solvents for hydrocarbon polymers are aliphatic and aromatic hydrocarbons of the desired non-volatility and solubility for the polymer.
  • the polymer may be present in the first solvent at a first concentration which is selected from a relatively narrow range, e.g.
  • the concentration should not vary adjacent the die or otherwise prior to cooling to the second temperature.
  • the concentration should also remain reasonably constant over time (i.e. length of the fiber or film).
  • the first temperature is chosen to achieve complete dissolution of the polymer in the first solvent.
  • the first temperature is the minimum temperature at any point between where the solution is formed and the die face, and must be greater than the gelation temperature for the polymer in the solvent at the first concentration.
  • the gelation temperature is approximaely 100-130°C; therefore, a preferred first temperature can be between 180°C and 250°C, more preferably 200-240. While temperatures may vary above the first temperature at various points upstream of the die face, excessive temperatures causitive of polymer degradation should be avoided.
  • a first temperature is chosen whereat the solubility of the polymer exceeds the first concentration, and is typically at least 100% greater.
  • the second temperature is chosen whereas the solubility of the polymer is much less than the first concentration.
  • the rate at which the extruded polymer solution stream is cooled from the first temperature to the second temperature should be at least 50°C per minute.
  • the gel fiber formed upon cooling to the second temperature consists of a continuous polymeric network highly swollen with solvent.
  • the gel usually has regions of high and low polymer density on a microscopic level but is generally free of large (greater than 500 nm) regions void of solid polymer.
  • both gels will be gel fibers
  • the xerogel will be an xerogel fiber
  • the final product will be a fiber.
  • the diameter of the aperture is not critical, with representative apertures being between 0.25 mm and 5 mm in diameter (or other major axis).
  • the length of the aperture in the flow direction should normally be at least 10 times the diameter of the aperture (or other similar major axis), preferably at least 15 times and more preferably at least 20 times the diameter (or other similar major axis).
  • both gels will be gel films
  • the xerogel will be a xerogel film
  • the final product will be a film.
  • the width and height of the aperture are not critical, with representative apertures being between 2.5 mm and 2 m in width (corresponding to film width), between 0.25 mm and 5 mm in height (corresponding to film thickness).
  • the depth of the aperture (in the flow direction) should normally be at least 10 times the height of the aperture, preferably at least 15 times the height and more preferably at least 20 times the height.
  • the extraction with second solvent is conducted in a manner that replaces the first solvent in the gel with second solvent without significant changes in gel structure. Some swelling or shrinkage of the gel may occur, but preferably no substantial dissolution, coagulation or precipitation of the polymer occurs.
  • suitable second solvents include hydrocarbons, chlorinated hydrocarbons, chlorofluorinated hydrocarbons and others, such as pentane, hexane, heptane, toluene, methylene chloride, carbon tetrachloride, trichlorotrifluoroethane (TCTFE), diethyl ether and dioxane.
  • hydrocarbons chlorinated hydrocarbons, chlorofluorinated hydrocarbons and others, such as pentane, hexane, heptane, toluene, methylene chloride, carbon tetrachloride, trichlorotrifluoroethane (TCTFE), diethyl ether and dioxane.
  • the most preferred second solvents are methylene chloride (B.P. 39.8°C) and TCFE (B.P. 47.5°C).
  • Preferred second solvents are the non-flammable volatile solvents having an atmospheric boiling point below 80°C, more preferably below 70°C and most preferably below 50°C. Conditions of extraction should remove the first solvent to less than 1% of the total solvent in the gel.
  • a preferred combination of conditions is a first temperature between 150°C and 250°C, a second temperature between -40°C and 40°C and a cooling rate between the first temperature and the second temperature of at least 50°C/minute.
  • the first solvent be a hydrocarbon, when the polymer is a polyolefin such as ultrahigh molecular weight polyethylene.
  • the first solvent should be substantially non-volatile, one measure of which is that its vapor pressure at the first temperature should be less than one-fifth atmosphere (20 kPa), and more preferably less than 2 kPa.
  • the primary desired difference relates to volatility as discussed above. It is also preferred that the polymers be less soluble in the second solvent at 40°C than in the first solvent at 150°C.
  • the gel containing second solvent is formed, it is then dried under conditions where the second solvent is removed leaving the solid network of polymer substantially intact.
  • the resultant material is called herein a "xerogel” meaning a solid matrix corresponding to the solid matrix of a wet gel, with the liquid replaced by gas (e.g. by an inert gas such as nitrogen or by air).
  • gas e.g. by an inert gas such as nitrogen or by air.
  • xerogel is not intended to delineate any particular type of surface area, porosity or pore size.
  • the dried xerogel fibers of the present invention preferably contain less than ten volume percent pores compared to approximately 55 volume percent pores in the Kalb and Pennings dried gel fibers and approximately 23-65 volume percent pores in the Smook et a/. dried gel fibers.
  • the dried xerogel fibers of the present invention show a surface area (by the B.E.T. technique) of less than 1 m 2 /g as compared to 28.8 m 2 /g in a fiber prepared by the prior art method (see Comparative Example 1 and Example 2, below).
  • the xerogel fibers of the present invention are also novel compared to dry, unstretched fibers of GB-A-2,051,667 and DE-A-3004699 and related articles by Smith and Lemstra. This difference is evidenced by the deleterious effect of stretching below 75°C or above 135°C upon the Smith and Lemstra unstretched fibers. In comparison, stretching of the present xerogel fibers at room temperature and above 135°C has beneficial rather than deleterious effects (see, for example, Examples 540-542, below).
  • Stretching may be performed upon the gel fiber after cooling to the second temperature or during or after extraction.
  • stretching of the xerogel fiber may be conducted, or a combination of gel stretch and xerogel stretch may be performed.
  • the stretching may be conducted in a single stage or it may be conducted in two or more stages.
  • the first stage stretching may be conducted at room temperatures or at an elevated temperature.
  • the stretching is conducted in two or more stages with the last of the stages performed at a temperature between 120°C and 160°C.
  • Most preferably the stretching is conducted in at least two stages with the last of the stages performed at a temperature between 135°C and 150°C.
  • the Examples, and especially Examples 3-99 and 111-486 illustrate how the stretch ratios can be related to obtaining particular fiber properties.
  • the product polyethylene fibers produced by the present process represent novel articles in that they include fibers with a unique combination of properties: a modulus at least 500 g/denier (preferably at least 1000 g/denier, more preferably at least 1600 g/denier and most preferably at least 2000 g/denier), a tenacity at least 20 g/denier (preferably at least 30 g/denier and more preferably at least 40 g/denier), a main melting temperature of at least 147°C (preferably at least 149°C), measured at 10°C/minute heating rate by differential scanning calorimetry, a porosity of no more than 10% (preferably no more than 6%) and a creep value no more than 5% (preferably no more than 3%) when measured a 10% of breaking load for 50 days at 23°C.
  • a modulus at least 500 g/denier preferably at least 1000 g/denier, more preferably at least 1600 g/denier and most preferably at least 2000 g/denier
  • the fiber has an elongation to break at most 7%.
  • the fibers have high toughness and uniformity. Furthermore, as indicated in Examples 3-99 and 111-489 below, trade-offs between various properties can be made in a controlled fashion with the present process.
  • novel polypropylene fibers of the present invention also include a unique combination of properties, previously unachieved for polypropylene fibers: a tenacity of at least 8 g/denier (preferably at least 11 g/denier and more preferably at least 13 g/denier), a tensile modulus at least 160 g/denier (preferably at least 200 g/denier), a main melting temperature at least 168°C (preferably at least 170°C) measured at 10°C/minute heating rate by differential scanning calorimetry and a porosity less than 10% (preferably no more than 5%).
  • the polypropylene fibers also have an elongation to break less than 20%.
  • novel class of fibers of the invention are polypropylene fibers possessing a modulus of at least 200 g/denier, preferably at least 220 g/denier.
  • the gel fibers containing first solvent, gel fibers containing second solvent and xerogel fibers of the present invention also represent novel articles of manufacture, distinguished from somewhat similar products described by Smook et al. and by Kalb and Pennings in having volume porosities of 10% or less compared to values of 23%-65% in the references.
  • the second gel fibers differ from the comparable prior art materials in having a solvent with an atmospheric boiling point less than 50°C.
  • the uniformity and cylindrical shape of the xerogel fibers improved progressively as the boiling point of the second solvent declined.
  • substantially higher tenacity fibers were produced under equivalent drying and stretching conditions by using trichlorotrifluoroethane (boiling point 47.5°C) as the second solvent compared to fibers produced by using hexane (boiling point 68.7°C) as second solvent.
  • the improvement in final fiber is then directly attributable to changes in the second solvent in the second gel fiber.
  • Preferred such second solvents are halogenated hydrocarbons of the proper boiling point such as methylene chloride (dichloromethane) and trichlorotrifluoroethane, with the latter being most preferred.
  • FIG 5 illustrates in schematic form a first embodiment of the present invention, wherein the stretching step F is conducted in two stages on the xerogel fiber subsequent to drying step E.
  • a first mixing vessel 10 is shown, which is fed with an ultra high molecular weight polymer 11 such as polyethylene of weight average molecular weight at least 500,000 and preferably at least 1,000,000, and to which is also fed a first, relatively non-volatile solvent 12 such as paraffin oil.
  • First mixing vessel 10 is equipped with an agitator 13. The residence time of polymer and first solvent in first mixing vessel 10 is sufficient to form a slurry containing some dissolved polymer and some relatively finely divided polymer particles, which slurry is removed in line 14 to an intensive mixing vessel 15.
  • Intensive mixing vessel 15 is equipped with helical agitator blades 16.
  • the residence time and agitator speed in intensive mixing vessel 15 is sufficient to convert the slurry into a solution.
  • the temperature in intensive mixing vessel 15, either because of external heating, heating of the slurry 14, heat generated by the intensive mixing, or a combination of the above is sufficiently high (e.g. 200°C) to permit the polymer to be completely dissolved in the solvent at the desired concentration (generally between 6 and 10 percent polymer, by weight of solution).
  • the solution is fed to an extrusion device 18, containing a barrel 19 within which is a screw 20 operated by motor 22 to deliver polymer solution at reasonably high pressure to a gear pump and housing 23 at a controlled flow rate.
  • a motor 24 is provided to drive gear pump 23 and extrude the polymer solution, still hot, through a spinnerette 25 comprising a plurality of apertures, which may be circular, X-shaped, or, oval-shaped, or in any of a variety of shapes having a relatively small major axis in the plane of the spinnerette when it is desired to form fibers, and having a rectangular or other shape with an extended major axis in the plane of the spinnerette when it is desired to form films.
  • the temperature of the solution in the mixing vessel 15, in the extrusion device 18 and at the spinnerette 25 should all equal or exceed a first temperature (e.g. 200°C) chosen to exceed the gellation temperature (approximately 100-130°C for polyethylene in paraffin oil).
  • the temperature may vary (e.g. 220°C, 210°C and 200°C) or may be constant (e.g. 220°C) from the mixing vessel 15 to extrusion device 18 to the spinnerette 25. At all points, however, the concentration of polymer in the solution should be substantially the same.
  • the number of apertures, and thus the number of fibers formed, is not critical, with convenient numbers of apertures being 16, 120, or 240.
  • the polymer solution stream passes through an air gap 27, optionally enclosed and filled with an inert gas such as nitrogen, and optionally provided with a flow of gas to facilitate cooling.
  • a plurality of gel fibers 28 containing first solvent pass through the air gap 27 and into a quench bath 30, so as to cool the fibers, both in the air gap 27 and in the quench bath 30, to a second temperature at which the solubility of the polymer in the first solvent is relatively low, such that most of the polymer precipitates as a gel material. While some stretching in the air gap 27 is permissible, it is preferably less than 2:1, and is more preferably much lower.
  • quench liquid in quench bath 30 be water. While the second solvent may be used as the quench fluid (and quench bath 30 may even be integral with solvent extraction device 37 described below), it has been found in limited testing that such a modification impairs fiber properties.
  • Rollers 31 and 32 in the quench bath 30 operate to feed the gel fiber through the quench bath, and preferably operate with little or no stretch. In the event that some stretching does occur across rollers 31 and 32, some first solvent exudes out of the fibers and can be collected as a top layer in quench bath 30.
  • the cool first gel fibers 33 pass to a solvent extraction device 37 where a second solvent, being of relatively low boiling such as trichlorotrifluoroethane, is fed in through line 38.
  • the solvent outflow in line 40 contains second solvent and essentially all of the first solvent brought in with the cool gel fibers 33, either dissolved or dispersed in the second solvent.
  • the second gel fibers 41 conducted out of the solvent extraction device 37 contain substantially only second solvent, and relatively little first solvent.
  • the second gel fibers 41 may have shrunken somewhat compared to the first gel fibers 33, but otherwise contain substantially the same polymer morphology.
  • the second solvent is evaporated from the second gel fibers 41 forming essentially unstretched xerogel fibers 47 which are taken up on spool 52.
  • the fibers are fed over driven feed roll 54 and idler roll 55 into a first heated tube 56, which may be rectangular, cylindrical or other convenient shape. Sufficient heat is applied to the tube 56 to cause the internal temperature to be between 120 and 140°C.
  • the fibers are stretched at a relatively high draw ratio (e.g. 10:1) so as to form partially stretched fibers 58 taken up by driven roll 61 and idler roll 62. From rolls 61 and 62, the fibers are taken through a second heated tube 63, heated so as to be at somewhat higher temperature, e.g.
  • the solution forming step A is conducted in mixers 13 and 15.
  • the extruding step B is conducted with device 18 and 23, and especially through spinnerette 25.
  • the cooling step C is conducted in airgap 27 and quench bath 30.
  • Extraction step D is conducted in solvent extraction device 37.
  • the drying step E is conducted in drying device 45.
  • the stretching step F is conducted in elements 52-72, and especially in heated tubes 56 and 63. It will be appreciated, however, that various other parts of the system may also perform some stretching, even at temperatures substantially below those of heated tubes 56 and 63. Thus, for example, some stretching (e.g. 2:1) may occur within quench bath 30, within solvent extraction device 37, within drying device 45 or between solvent extraction device 37 and drying device 45.
  • a second embodiment of the present invention is illustrated in schematic form by Figure 6.
  • the solution forming and extruding steps A and B of the second embodiment are substantially the same as those in the first embodiment illustrated in Figure 5.
  • polymer and first solvent are mixed in first mixing vessel 10 and conducted as a slurry in line 14 to intensive mixing device 15 operative to form a hot solution of polymer in first solvent.
  • Extrusion device 18 impells the solution under pressure through the gear pump and housing 23 and then through a plurality of apertures in spinnerette 27.
  • the hot stream 28 pass through air gap 27 and quench bath 30 so as to form cool first gel fibers 33.
  • the cool first gel fibers 33 are conducted over driven roll 54 and idler roll 55 through a heated tube 57 which, in general, is longer than the first heated tube 56 illustrated in Figure 5.
  • the length of heated tube 57 compensates, in general, for the higher velocity of fibers 33 in the second embodiment of Figure 6 compared to the velocity of xerogel fibers (47) between take-up spool 52 and heated tube 56 in the first embodiment of Figure 5.
  • the fibers 33 are drawn through heated tube 57 by driven take-up roll 59 and idler roll 60, so as to cause a relatively high stretch ratio (e.g. 10:1).
  • the once-stretched first gel fibers 35 are conducted into extraction device 37.
  • the first solvent is extracted out of the gel fibers by second solvent and the gel fibers 42 containing second solvent are conducted to a drying device 45. There the second solvent is evaporated from the gel fibers; and xerogel fibers 48, being once-stretched, are taken up on spool 52.
  • Fibers on spool 52 are then taken up by driven feed roll 61 and idler 62 and passed through a heated tube 63, operating at the relatively high temperature of between 130 and 160°C.
  • the fibers are taken up by driven take up roll 65 and idler roll 66 operating at a speed sufficient to impart a stretch in heated tube 63 as desired, e.g. 2.5:1.
  • the twice-stretched fibers 69 produced in the second embodiment are then taken up on spool 72.
  • the stretching step F has been divided into two parts, with the first part conducted in heated tube 57 performed on the first gel fibers 33 prior to extraction (D) and drying (E), and the second part conducted in heated tube 63, being conducted on xerogel fibers 48 subsequent to drying (E).
  • the third embodiment of the present invention is illustrated in Figure 7, with the solution forming step A, extrusion step B, and cooling step C being substantially identical to the first embodiment of Figure 5 and the second embodiment of Figure 6.
  • polymer and first solvent are mixed in first mixing vessel 10 and conducted as a slurry in line 14 to intensive mixing device 15 operative to form a hot solution of polymer in first solvent.
  • Extrusion device 18 impells the solution under pressure through the gear pump and housing 23 and then through a plurality of apertures in spinnerette 27.
  • the hot streams 28 pass through air gap 27 and quench bath 30 so as to form cool first gel fibers 33.
  • the cool first gel fibers 33 are conducted over driven roll 54 and idler roll 55 through a heated tube 57 which, in general, is longer than the first heated tube 56 illustrated in Figure 5.
  • the length of heated tube 57 compensates, in general, for the higher velocity of fibers 33 in the third embodiment of Figure 7 compared to the velocity of xerogel fibers 47 between takeup spool 52 and heated tube 56 in the first embodiment of Figure 5.
  • the first gel fibers 33 are now taken up by driven roll 61 and idler roll 62, operative to cause the stretch ratio in heated tube 57 to be as desired, e.g. 10:1.
  • heated tube 64 in the third embodiment of Figure 7 will, in general, be longer than heated tube 63 in either the second embodiment of Figure 6 or the first embodiment of Figure 5. While first solvent may exude from the fiber during stretching in heated tubes 57 and 64 (and be collected at the exit of each tube), the first solvent is sufficiently non-volatile so as not to evaporate to an appreciable extent in either of these heated tubes.
  • the twice-stretched first gel fibers 36 are then conducted through solvent extraction device 37, where the second, volatile solvent extracts the first solvent out of the fibers.
  • the second gel fibers, containing substantially only second solvent, are then dried in drying device 45, and the twice-stretched fibers 70 are then taken up on spool 72.
  • the process of the invention will be further illustrated by the examples below.
  • the first example illustrates the prior art techniques of Smook et. al. and the Kalb and Pennings articles.
  • a glass vessel equipped with a PTFE paddle stirrer was charged with 5.0 wt% linear polyethylene (sold as Hercules UHMW 1900, having 24 IV and approximately 4x 10 6 M.W.), 94.5 wt% paraffin oil (J. T. Baker, 345-355 Saybolt viscosity) and 0.5 wt% antioxidant (sold under the trademark lonol).
  • linear polyethylene sold as Hercules UHMW 1900, having 24 IV and approximately 4x 10 6 M.W.
  • paraffin oil J. T. Baker, 345-355 Saybolt viscosity
  • 0.5 wt% antioxidant sold under the trademark lonol
  • the vessel was sealed under nitrogen pressure and heated with stirring to 150°C. The vessel and its contents were maintained under slow agitation for 48 hours. At the end of this period the solution was cooled to room temperature. The cooled solution separated into two phases-A "mushy" liquid phase consisting of 0.43 wt% polyethylene and a rubbery gel phase consisting of 8.7 wt% polyethylene. The gel phase was collected, cut into pieces and fed into a 2.5 cm (one inch) Sterling extruder equipped with a 21/1 UD polyethylene-type screw. The extruder was operated at 10 RPM, 170°C and was equipped with a conical single hole spinning die of 1 cm inlet diameter, 1 mm exit diameter and 6 cm length.
  • the deformation and compression of the gel by the extruder screw caused exudation of paraffin oil from the gel.
  • This liquid backed up in the extruder barrel and was mostly discharged from the hopper end of the extruder.
  • a gel fiber of approximately 0.7 mm diameter was collected at the rate of 1.6 m/min.
  • the gel fiber consisted of 24-38 wt% polyethylene.
  • the solids content of the gel fiber varied substantially with time.
  • the paraffin oil was extracted from the extruded gel fiber using hexane and the fiber was dried under vacuum at 50°C.
  • the dried gel fiber had a density of 0.326 g/cm 3. Therefore, based on a density of 0.960 for the polyethylene constituent, the gel fiber consisted of 73.2 volume percent voids.
  • Measurement of pore volume using a mercury porosimeter showed a pore volume of 2.58 cm 3 /g.
  • a B.E.T. measurement of surface area gave a value of 28.8 m 2 /g.
  • the dried fiber was stretched in a nitrogen atmosphere within a hot tube of 1.5 meters length. Fiber feed speed was 2 cm/min. Tube temperature was 100°C at the inlet increasing to 150°C at the outlet.
  • the properties of the fiber prepared at 30/1 stretch ratio were as follows:
  • An oil jacketed double helical (Helicone@) mixer constructed by Atlantic Research Corporation was charged with 5.0 wt% linear polyethylene (Hercules UHMW 1900 having 17 IV and approximately 2.5x 10 6 M.W.) and 94.5 wt% paraffin oil (J. T. Baker, 345-355 Saybolt viscosity). The charge was heated with agitation at 20 rpm to 200°C under nitrogen pressure over a period of two hours. After reaching 200°C, agitation was maintained for an additional two hours.
  • the bottom discharge opening of the Helicone mixer was fitted with a single hole capillary spinning die of 2 mm diameter and 9.5 mm length.
  • the temperature of the spinning die was maintained at 200°C.
  • Nitrogen pressure applied to the mixer and rotation of the blades of the mixer were used to extrude the charge through the spinning die.
  • the extruded uniform solution filament was quenched to a gel state by passage through water bath located at a distance of 33 cm (13 inches) below the spinning die.
  • the gel filament was wound up continuously on a 15.2 cm (6 inch) diameter bobbin at the rate of 4.5 meters/min.
  • the bobbins of gel fiber were immersed in trichlorotrifluoroethane (fluorocarbon 113 or "TCTFE") to exchange this solvent for paraffin oil as the liquid constituent of the gel.
  • TCTFE trichlorotrifluoroethane
  • the gel fiber was unwound from a bobbin, and the fluorocarbon solvent evaporated at 22 ⁇ 50°C.
  • the dried fiber was of 970 ⁇ 100 denier.
  • the density of the fiber was determined to be 950 kg/m 3 by the density gradient method. Therefore, based on a density of 960 kg/m 3 for the polyethylene constituent, the dried fiber contained one volume percent voids.
  • a B.E.T. measurement of the surface area gave a value less than 1 m 2 /g.
  • the dried gel fiber was fed at 2 cm/min into a hot tube blanketed with nitrogen and maintained at 100°C at its inlet and 140°C at its outlet.
  • the fiber was stretched continuously 45/1 within the hot tube for a period of three hours without experiencing fiber breakage.
  • the properties of the stretched fiber were:
  • Figures 2 and 3 present response surface contours for tenacity calculated from the regression equation on two important planes.
  • fibers of these examples showed higher tenacities and/or modulus values than had been obtained by prior art methods.
  • all fibers prepared had tenacities less than 3.0 GPa (35 g/d) and moduli less than 100 GPa (1181 g/d).
  • fiber examples Nos. 21, 67, 70, 73, 82, 84 and 88 exceeded both of these levels and other fiber examples surpassed on one or the other property.
  • Example 71 showed 1.4% creep in 50 days at 23°C under the sustained load equal to 10% of the breaking load.
  • both the commercial nylon 6 tire cord and the surface grown polyethylene fiber showed 5% creep under similar test conditions.
  • the melting temperatures and the porosities of the fibers of Examples 64, 70 and 71 were determined. Melting temperatures were measured using a DuPont 990 differential scanning calorimeter. Samples were heated in an argon atmosphere at the rate of 10°C/min. Additionally, the melting temperature was determined for the starting polyethylene powder from which the fibers of Examples 64, 70 and 71 were prepared.
  • Porosities of the fibers were determined by measurements of their densities using the density gradient technique and comparison with the density of a compression molded plaque prepared from the same initial polyethylene powder. (The density of the compression molded plaque was 960 kg/m 3 ).
  • the particular level and combination of properties exhibited by the fiber of Examples 64, 70 and 71 i.e., tenacity at least 30 g/d, modulus in excess of 1000 g/d (86 GPa) and creep (at 23°C and 10% of breaking load) less than 3% in 50 days, main melting temperature of at least 147°C (by DSC at 10°C/min. heating rate) and porosity less than 10% appears not to have been attained heretofore.
  • Fiber samples were prepared as described in Example 2, but with the following variations.
  • the bottom discharge opening of the Helicone mixer was adapted to feed the polymer solution first to a gear pump and thence to a single hole conical spinning die.
  • the cross-section of the spinning die tapered uniformly at a 7.5° angle from an entrance diameter of 10 mm to an exit diameter of 1 mm.
  • the gear pump speed was set to deliver 5.84 cm'/min. of polymer solution to the die.
  • the extruded solution filament was quenched to a gel state by passage through a water bath located at a distance of 20 cm below the spinning die.
  • the gel filament was wound up continuously on bobbins at the rate of 7.3 meters/min.
  • the bobbins of gel fiber were immersed in several different solvents at room temperature to exchange with the paraffin oil as the liquid constituent of the gel.
  • the solvents and their boiling points were:
  • the solvent exchanged gel fibers were air dried at room temperature. Drying of the gel fibers was accompanied in each case by substantial shrinkage of transverse dimensions. Surprisingly, it was observed that the shape and surface texture of the xerogel fibers departed progressively from a smooth cylindrical form in approximate proportion to the boiling point of the second solvent. Thus, the fiber from which diethyl ether had been dried was substantially cylindrical whereas the fiber from which toluene had been dried was "C" shaped in cross-section.
  • the xerogel fibers prepared using TCTFE and n-hexane as second solvents were further compared by stretching each at 130°C, incrementally increasing stretch ratio until fiber breakage occurred.
  • the tensile properties of the resulting fibers were determined as shown in Table III.
  • the xerogel fiber prepared using TCTFE as the second solvent could be stretched continuously to a stretch ratio of 49/1, whereas the xerogel fiber prepared using n-hexane could be stretched continuously only to a stretch ratio of 33/1.
  • the stretched fiber prepared using TCTFE second solvent was of 39.8 g/d tenacity and of 1580 g/d modulus. This compares to 32.0 g/d tenacity and 1140 g/d modulus obtained using n-hexane as the second solvent.
  • Fiber properties were as follows:
  • a series of xerogel fiber samples was prepared as in Example 2 but using a gear pump to control melt flow rate. Variations were introduced in the following material and process parameters:
  • Each of the xerogel fiber samples prepared was stretched in a hot tube of 1.5 meter length blanketed with nitrogen and maintained at 100°C at the fiber inlet and 140°C at the fiber outlet. Fiber feed speed into the hot tube was 4 cm/min. (Under these conditions the actual fiber temperature was within 1°C of the tube temperature at distances beyond 15 cm from the inlet). Each sample was stretched continuously at a series of increasing stretch ratios. The independent variables for these experiments are summarized below:
  • the take-up velocity varied from 90-1621 cm/min, the xerogel fiber denier from 98-1613, the stretch ratio from 5-174, the tenacity from 9 ⁇ 45 g/denier, the tensile modulus from 218-1700 g/denier and the elongation from 2.5-29.4%.
  • High fiber tenacity was favored by increasing polymer IV, increasing gel concentration, increasing spinning temperature, decreasing die diameter, decreasing distance to quench, decreasing xerogel fiber diameter, increasing stretch ratio and 0° die angle (straight capillary).
  • Fiber modulus was correlated with tenacity as follows:
  • the densities and porosities of several of the xerogel and stretched fibers were determined.
  • polymer solutions were prepared as in Example 2.
  • the solutions were spun through a 16 hole spinning die using a gear pump to control solution flow rate.
  • the apertures of the spinning die were straight capillaries of length-to-diameter ratio of 25/1. Each capillary was preceded by a conical entry region of 60° included angle.
  • the multi-filament solution yarns were quenched to a gel state by passing through a water bath located at a short distance below the spinning die.
  • the gel yarns were wound up on perforated dye tubes.
  • the wound tubes of gel yarn were extracted with TCTFE in a large Sohxlet apparatus to exchange this solvent for paraffin oil as the liquid constituent of the gel.
  • the gel fiber was unwound from the tubes and the TCTFE solvent was evaporated at room temperature.
  • the dried xerogel yarns were stretched by passing the yarn over a slow speed feed godet and idler roll through a hot tube blanketed with nitrogen, onto a second godet and idler roll driven at a higher speed.
  • the stretched yarn was collected on a winder.
  • Example 487-495 the diameter of each hole of the 16 filament spinning die was 0.040 inch (one millimeter) the spinning temperature was 220°C, the stretch temperature (in the hot tube) was 140°C and the feed roll speed during stretching was 4 cm/min.
  • the polymer IV was 17.5 and the gel concentration was 7 weight %.
  • the polymer IV was 22.6.
  • the gel concentration was 9 weight % in Example 491, 8 weight % in Examples 492-493 and 6 weight % in Examples 494 and 495.
  • the distance from the die face to the quench bath was 3 inches (7.52 cm) in Examples 487, 488, 494 and 495 and 6 inches (15.2 cm) in Examples 490-493.
  • the other spinning conditions and the properties of the final yarns were as follows.
  • the wound gel yarns still containing the paraffin oil were stretched by passing the yarn over a slow speed feed godet and idler roll through a hot tube blanketed with nitrogen onto a second godet and idler roll driven at high speed. It was noted that some stretching of the yarn (approximately 2/1) occurred as it departed the feed godet and before it entered the hot tube.
  • the overall stretch ratio i.e., the ratio of the surface speeds of the godets is given below.
  • the stretching caused essentially no evaporation of the paraffin oil (the vapor pressure of the paraffin oil is 0.001 atmospheres at 149°C). However, half of the paraffin oil content of the gel yarns was exuded during stretching.
  • the stretched gel yarns were extracted with TCTFE in a Sohxlet apparatus, then unwound and dried at room temperature.
  • the spinning temperatures was 220°C
  • the gel concentration was 6 weight %
  • the distance from the spinning die to the water quench was 3 inches (7.6 cm).
  • Example 496 and 499-501 the diameter of each hole of the spinning die was 0.040 inches (0.1 cm). In Examples 497 and 498 the hole diameters were 0.030 inches (0.075 cm). In Examples 496 and 494-501 the polymer IV was 17.5. In Examples 497 and 498 the polymer IV was 22.6.
  • the other spinning conditions and properties of the final yarns were as follows: Examples 502-533
  • the gel yarn was prepared from a 6 weight % solution of 22.6 IV polyethylene as in Example 2.
  • the yarn was spun using a 16 holexO.030 inch (0.075 cm) die.
  • Spinning temperature was 220°C.
  • Spin rate was 1 cm 3 /min-fil.
  • Distance from the die face to the quench bath was 3 inches (7.6 cm).
  • Take-up speed was 308 cm/min.
  • Nine rolls of 16 filament gel yarn was prepared.
  • the remainder of the first stage stretched gel yarn was restretched at 1 m/min feed speed.
  • Other second stage stretching conditions and physical properties of the stretched yarns are given below.
  • the density of the fiber of Example 515 was determined to be 980 kglm 3. The density of the fiber was therefore higher than the density of a compression molded plaque and the porosity was essentially zero.
  • the first stage three of the rolls of 16 filament gel yarn described in Example 502 were combined and stretched together to prepare a 48 filament stretched gel yarn.
  • the first stage stretching conditions were: stretch temperature 120°C, feed speed 35 cm/min, stretch ratio 12/1.
  • the first stage stretched gel yarn was extracted with TCTFE in a Soxhlet apparatus, rewound and air dried at room temperature, then subjected to a second stage of stretching in the dry state at a feed speed of 1 m/min.
  • Other second stage stretching conditions and physical properties of the stretched yarn are given below.
  • Example 502 the gel yarn described in Example 502 was extracted with TCTFE, dried, then stretched in two stages.
  • first stage three of the rolls of 16 filament yarn were combined and stretched together to prepare a 48 filament stretched xerogel yarn.
  • the first stage stretching conditions were: stretch temperature 120°C, feed speed 35 cm/min., stretch ratio 10/1.
  • the properties of the first stage stretched xerogel yarn are given as Example 523 below.
  • second stretch stage the feed speed was 1 m/min.
  • Other second stage stretching conditions and physical properties of the stretched yarns are given below.
  • the density of the fiber of Example 529 was determined to be 940 Kg/m 3.
  • the porosity of the fiber was therefore 2%.
  • Example 6 A 6 weight % solution of 22.6 IV polyethylene yarn was prepared as in Example 2. A 16 filament yarn was spun and wound as in Example 502.
  • the unstretched gel yarn prepared as in Example 534 was led continuously from a first godet which set the spinning take-up speed to a second godet operating at a surface speed of 616 cm/min.
  • the as-spun gel fiber was stretched 2/1 at room temperature in-line with spinning. The once stretched gel fiber was wound on tubes.
  • the 16 filament gel yarns prepared in Examples 534 and 535 were stretched twice at elevated temperature. In the first of such operations the gel yarns were fed at 35 cm/min to a hot tube blanketed with nitrogen and maintained at 120°C. In the second stage of elevated temperature stretching the gel yarns were fed at 1 m/min and were stretched at 150°C. Other stretching conditions and yarn properties are given below.
  • the following Examples illustrate the preparation of novel polyethylene yarns of modulus exceeding 1600 g/d and in some cases of modulus exceeding 2000 g/d. Such polyethylene fibers and yarns were heretofore unknown.
  • all yarns were made from a 22.6 IV polyethylene, 6 weight % solution prepared as in Example 2 and spun as in Example 502. All yarns were stretched in two stages. The first stage stretch was at a temperature of 120°C. The second stage stretch was at a temperature of 150°C. Several 16 filament yarn ends may have been combined during stretching. Stretching conditions and yarn properties are given below.
  • the yarns of Examples 548 and 550 were characterized by differential scanning calorimetry at 10°C/min. and density measurement. The results, displayed below, indicate two distinct peaks at the melting points indicated, quite unlike the broad single peak at 145.5°C or less reported by Smith and Lemstra in J. Mat. Sci., vol 15, 505 (1980).
  • fibers were made from an 18 IV polypropylene, 6 weight % solution in paraffin oil prepared as in Example 2.
  • the fibers were spun with a single hole conical die of 0.040" (0.1 cm) exit diameter and 7.5% angle. Solution temperature was 220°C. A melt pump was used to control solution flow rate at 2.92 cm 3 /min. Distance from the die face to the water quench was 3 inches (7.6 cm).
  • the gel fibers were one stage wet stretched at 25 cm/min feed roll speed into a 1.5 m hot tube blanketed with nitrogen. The stretched fibers were extracted in TCTFE and air dried. Other spinning and stretching conditions as well as fiber properties are given below.
  • the fiber of Example 556 was determined by differential scanning calorimetry at 10°C/min to have a first melting temperature of 170-171°C with higher order melting temperatures of 173°C, 179°C and 185°C. This compares with the 166°C melting point of the initial polymer. The moduli of these fibers substantially exceed the highest previously reported values.
  • Example 557 and 558 the yarns were spun with a 16 holexO.040 inch (1 mm) capillary die.
  • the solution temperature was 223°C, and the spinning rate was 2.5 cm 3 /min-filament.
  • the distance from the die face to the water quench bath was 3 inches (7.6 cm).
  • Take-up speed was 430 cm/min.
  • the gel yarns were "wet-wet" stretched in two stages. The first stage stretching was at 140°C at a feed speed of 35 cm/min.
  • the second stage stretching was at a temperature of 169°C, a feed speed of 100 cm/min and a stretch ratio of 1.25/1.
  • Other stretching conditions as well as fiber properties are given below.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
EP82102964A 1981-04-30 1982-04-07 Process for producing high tenacity, high modulus crystalline thermoplastic article and novel product fibers Expired EP0064167B1 (en)

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US06/359,019 US4413110A (en) 1981-04-30 1982-03-19 High tenacity, high modulus polyethylene and polypropylene fibers and intermediates therefore
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6723267B2 (en) 1998-10-28 2004-04-20 Dsm N.V. Process of making highly oriented polyolefin fiber
WO2008131925A1 (en) * 2007-05-01 2008-11-06 Dsm Ip Assets B.V. Uhmwpe fiber and process for producing thereof
CN101775666B (zh) * 2010-01-22 2011-07-27 东华大学 一种高强高模聚乙烯纤维的制备方法
US8188206B2 (en) 2008-02-26 2012-05-29 Shandong Icd High Performance Fibres Co., Ltd. 10-50 G/D high strength polyethylene fiber and preparation method thereof

Families Citing this family (77)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU549453B2 (en) * 1981-04-30 1986-01-30 Allied Corporation High tenacity, high modulus, cyrstalline thermoplastic fibres
US4543286A (en) * 1982-03-19 1985-09-24 Allied Corporation Composite containing coated extended chain polyolefin fibers
US4501856A (en) † 1982-03-19 1985-02-26 Allied Corporation Composite containing polyolefin fiber and polyolefin polymer matrix
US4584347A (en) * 1982-09-30 1986-04-22 Allied Corporation Modified polyolefin fiber
US4599267A (en) * 1982-09-30 1986-07-08 Allied Corporation High strength and modulus polyvinyl alcohol fibers and method of their preparation
US4455273A (en) * 1982-09-30 1984-06-19 Allied Corporation Producing modified high performance polyolefin fiber
DE3363610D1 (en) * 1982-12-28 1986-06-26 Mitsui Petrochemical Ind Process for producing stretched articles of ultrahigh-molecular-weight polyethylene
JPS59187614A (ja) * 1983-04-07 1984-10-24 Mitsui Petrochem Ind Ltd 超高分子量ポリエチレン延伸物の製造法
DE3480796D1 (de) * 1983-02-18 1990-01-25 Allied Signal Inc Verfestigung von polyaethylenfasernetzwerken.
US5135804A (en) * 1983-02-18 1992-08-04 Allied-Signal Inc. Network of polyethylene fibers
JPS59216912A (ja) * 1983-05-20 1984-12-07 Toyobo Co Ltd 高強度・高弾性率ポリエチレン繊維の製造方法
JPS59227420A (ja) * 1983-06-10 1984-12-20 Mitsui Petrochem Ind Ltd 超高分子量ポリオレフイン二軸延伸フイルム及びその製造方法
EP0139141B1 (en) * 1983-08-15 1991-05-08 Toyo Boseki Kabushiki Kaisha Production of stretched polymeric material having high strength and high modulus
JPS6045630A (ja) * 1983-08-23 1985-03-12 東洋紡績株式会社 ゲルフアイバ−の延伸方法
JPS6052613A (ja) * 1983-08-30 1985-03-25 Toyobo Co Ltd 高強力、高弾性率ポリエチレン繊維
JPS59216913A (ja) * 1983-10-22 1984-12-07 Toyobo Co Ltd 高強度・高弾性率ポリエチレン繊維
JPS59216914A (ja) * 1983-10-22 1984-12-07 Toyobo Co Ltd 超高強力ポリエチレン繊維の製造方法
NL8304263A (nl) * 1983-12-10 1985-07-01 Stamicarbon Werkwijze voor het bereiden van polyacrylonitrilfilamenten met hoge treksterkte en modulus.
JPS60138507A (ja) * 1983-12-27 1985-07-23 Toyobo Co Ltd ポリエチレン抗張力線
JPS60164421A (ja) * 1984-02-07 1985-08-27 東洋紡績株式会社 新規な釣糸
JPS60173114A (ja) * 1984-02-16 1985-09-06 Toyobo Co Ltd ゲル状成形体の処理方法
JPS60189420A (ja) * 1984-03-09 1985-09-26 Mitsui Petrochem Ind Ltd 超高分子量ポリエチレンの延伸物の製造方法
JPS60190330A (ja) * 1984-03-12 1985-09-27 Mitsui Petrochem Ind Ltd 超高分子量ポリエチレン延伸物の製造法
JPS60210425A (ja) * 1984-04-04 1985-10-22 Mitsui Petrochem Ind Ltd ポリエチレン延伸物の製造方法
JPS60242035A (ja) * 1984-04-27 1985-12-02 Toa Nenryo Kogyo Kk ポリエチレン微多孔膜の製造方法
JPS60239509A (ja) * 1984-05-04 1985-11-28 Toray Ind Inc 高強度高モジユラスポリオレフイン系繊維の製造方法
JPH062841B2 (ja) * 1984-05-31 1994-01-12 三菱化成株式会社 多孔化透過性ポリエチレンフイルム
JPS6147809A (ja) * 1984-08-06 1986-03-08 Toray Ind Inc 高強度高モジユラスポリオレフイン系繊維の製造方法
NL8402964A (nl) * 1984-09-28 1986-04-16 Stamicarbon Werkwijze voor het bereiden van polyalkeenfilms met hoge treksterkte en hoge modulus.
DE3577110D1 (de) * 1984-09-28 1990-05-17 Stamicarbon Verfahren zur kontinuierlichen herstellung von homogenen loesungen von hochmolekularen polymeren.
NL8402963A (nl) * 1984-09-28 1986-04-16 Stamicarbon Werkwijze voor het bereiden van dunne films van hoogmolekulaire polyalkenen.
US4663101A (en) * 1985-01-11 1987-05-05 Allied Corporation Shaped polyethylene articles of intermediate molecular weight and high modulus
US4623574A (en) * 1985-01-14 1986-11-18 Allied Corporation Ballistic-resistant composite article
JPH06102847B2 (ja) * 1985-05-31 1994-12-14 三井石油化学工業株式会社 プラスチツクワイヤ−及びその製造方法
WO1986004936A1 (en) * 1985-02-15 1986-08-28 Toray Industries, Inc. Polyethylene multifilament yarn
NL8500477A (nl) * 1985-02-20 1986-09-16 Stamicarbon Werkwijze voor het bereiden van polyolefine gelvoorwerpen, alsmede voor het hieruit bereiden van voorwerpen met hoge treksterkte en modulus.
EP0193318B1 (en) * 1985-02-25 1990-12-19 Tonen Corporation Microporous membrane of ultra-high molecular weight alpha-olefin polymer
JPS61215708A (ja) * 1985-03-19 1986-09-25 Toray Ind Inc マルチフイラメントヤ−ンの製造方法
JPH06102846B2 (ja) * 1985-05-01 1994-12-14 三井石油化学工業株式会社 超高分子量ポリエチレン延伸物の製造方法
EP0205960B1 (en) * 1985-06-17 1990-10-24 AlliedSignal Inc. Very low creep, ultra high moduls, low shrink, high tenacity polyolefin fiber having good strength retention at high temperatures and method to produce such fiber
JPS623728A (ja) * 1985-07-01 1987-01-09 旭化成株式会社 釣糸
US5032338A (en) * 1985-08-19 1991-07-16 Allied-Signal Inc. Method to prepare high strength ultrahigh molecular weight polyolefin articles by dissolving particles and shaping the solution
EP0212133B2 (en) * 1985-08-19 1999-09-22 AlliedSignal Inc. Method to prepare high strength ultrahigh molecular weight polyolefin articles by dissolving particles and shaping the solution
NL8502298A (nl) * 1985-08-21 1987-03-16 Stamicarbon Werkwijze voor het vervaardigen van polyethyleenvoorwerpen met hoge treksterkte en modulus.
ES2023813B3 (es) 1985-11-07 1992-02-16 Akzo Nv Elemento reforzador de material sintetico para uso en hormigon reforzado, mas particularmente hormigon pretensado, hormigon reforzado provisto de tales elementos de refuerzo y proceso para fabricar elementos de refuerzo, y hormigon reforzado y pretensado.
CA1279167C (en) * 1985-11-30 1991-01-22 Mitsui Chemicals, Incorporated Molecularly oriented, silane-crosslinked ultra-high- molecular-weight polyethylene molded article and process for preparation thereof
JPS62141110A (ja) * 1985-12-11 1987-06-24 Canon Inc ゲル繊維の製造方法
JPS62184110A (ja) * 1986-02-06 1987-08-12 Toray Ind Inc 新規なポリエチレンフイラメント
JPS63175111A (ja) * 1987-01-09 1988-07-19 Toyobo Co Ltd 架橋された高強力，高弾性率ポリエチレン繊維
JPS63273651A (ja) * 1987-04-30 1988-11-10 Toa Nenryo Kogyo Kk 超高分子量ポリエチレン微多孔膜の製造方法
JPS63288264A (ja) * 1987-05-18 1988-11-25 三井化学株式会社 フイラメント等の処理槽
JPH02251545A (ja) * 1988-12-23 1990-10-09 Nitto Denko Corp 超高分子量ポリエチレン多孔質フィルムおよびその製造法
DE3923139A1 (de) * 1989-07-13 1991-01-17 Akzo Gmbh Verfahren zur herstellung von polyaethylenfaeden durch schnellspinnen von ultra-hochmolekularem polyaethylen
JPH06104736B2 (ja) * 1989-08-03 1994-12-21 東燃株式会社 ポリオレフィン微多孔膜
GB9027601D0 (en) * 1990-12-20 1991-02-13 Thermalite Limited Fibre-reinforced materials
JP3070694B2 (ja) * 1991-06-11 2000-07-31 三井化学株式会社 超高分子量ポリプロピレン延伸成形体およびその製造方法
US5230854A (en) * 1991-12-09 1993-07-27 Allied-Signal Inc. Method for removal of spinning solvent from spun fiber
US5213745A (en) * 1991-12-09 1993-05-25 Allied-Signal Inc. Method for removal of spinning solvent from spun fiber
WO1993012276A1 (en) * 1991-12-09 1993-06-24 Allied-Signal Inc. Method for removal of spinning solvent from spun fiber
NL1010413C1 (nl) * 1998-10-28 2000-05-01 Dsm Nv Hooggeoriënteerde polyolefinevezel.
US6448359B1 (en) * 2000-03-27 2002-09-10 Honeywell International Inc. High tenacity, high modulus filament
NL1016356C2 (nl) * 2000-10-09 2002-04-10 Dsm Nv Oven voor het op verhoogde temperatuur verstrekken van vezels.
ES2375278T3 (es) * 2004-01-01 2012-02-28 Dsm Ip Assets B.V. Procedimiento para producir hilo multifilamento de polietileno de alto rendimiento.
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
BRPI0702310A2 (pt) * 2007-05-24 2009-01-13 Braskem Sa processo para a preparaÇço de fios polimÉricos a partir de homopolÍmeros ou copolÍmeros de ultra alto peso molecular, fios polimÉricos, artigos polimÉricos moldados, e, uso de fios polimÉricos
CN101122051B (zh) * 2007-09-24 2010-04-14 湖南中泰特种装备有限责任公司 低纤度、高强高模聚乙烯纤维的制备方法
JP2010540792A (ja) * 2007-10-05 2010-12-24 ディーエスエム アイピー アセッツ ビー．ブイ． 低クリープ、高強度ｕｈｍｗｐｅ繊維およびその製造方法
KR101522051B1 (ko) * 2007-10-05 2015-05-20 디에스엠 아이피 어셋츠 비.브이. Ｕｈｍｗｐｅ 섬유 및 이의 제조 방법
KR100959867B1 (ko) * 2008-03-24 2010-05-27 김용건 초고강도 폴리에틸렌 섬유의 제조방법 및 이로부터 제조된초고강도 폴리에틸렌 섬유
DK2294254T3 (da) * 2008-06-20 2013-03-11 Dsm Ip Assets Bv Polyethylengarn med ultrahøj molekylvægt
KR101715420B1 (ko) 2009-04-20 2017-03-10 바데이 인코포레이티드 큰 필라멘트당 데니어 고성능 얀을 갖는 개선된 방탄 복합체
US8895138B2 (en) 2009-11-17 2014-11-25 E I Du Pont De Nemours And Company Impact resistant composite article
US20110113534A1 (en) 2009-11-17 2011-05-19 E.I.Du Pont De Nemours And Company Impact Resistant Composite Article
CN102002769B (zh) 2010-11-08 2012-12-12 宁波大成新材料股份有限公司 超高分子量聚乙烯纤维制备方法
KR20150096412A (ko) * 2012-12-20 2015-08-24 디에스엠 아이피 어셋츠 비.브이. 폴리올레핀 얀 및 제조 방법
EP3564415A1 (en) * 2013-10-29 2019-11-06 Braskem S.A. System and method of dosing a polymer mixture with a first solvent
CN104862791B (zh) * 2015-05-19 2017-06-23 上海化工研究院有限公司 一种用于超高分子量聚乙烯干法纺丝生产均质加料装置

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE562603A (ko) * 1956-12-08
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.
AU549453B2 (en) * 1981-04-30 1986-01-30 Allied Corporation High tenacity, high modulus, cyrstalline thermoplastic fibres

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Journal of Materials Science, 15, (1980), pages 505-514 *
POLYMER BULLETIN, vol.1, 1979, Springer Verlag, Berlin (DE) B. KALB et al.: "Spinning of high molecular weight polyethylene solution and subsequent drawing in a temperature gradient", pages 871-876 *
POLYMER BULLETIN, vol.2, 1980, Springer Verlag, Berlin (DE) J. SMOOK et al.: "Influence of spinning/hot drawing conditions on the tensile strenght of porous high molecular weight polyethylene", pages 775-783 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6723267B2 (en) 1998-10-28 2004-04-20 Dsm N.V. Process of making highly oriented polyolefin fiber
WO2008131925A1 (en) * 2007-05-01 2008-11-06 Dsm Ip Assets B.V. Uhmwpe fiber and process for producing thereof
US8188206B2 (en) 2008-02-26 2012-05-29 Shandong Icd High Performance Fibres Co., Ltd. 10-50 G/D high strength polyethylene fiber and preparation method thereof
CN101775666B (zh) * 2010-01-22 2011-07-27 东华大学 一种高强高模聚乙烯纤维的制备方法

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ES513190A0 (es) 1983-06-16
ES8306775A1 (es) 1983-06-16
AU549453B2 (en) 1986-01-30
AU581702B2 (en) 1989-03-02
CA1174818A (en) 1984-09-25
AU8225482A (en) 1982-11-04
JP2582985B2 (ja) 1997-02-19
DE3267521D1 (en) 1986-01-02
AU5024285A (en) 1986-06-12
JPS585228A (ja) 1983-01-12
KR830010224A (ko) 1983-12-26
EP0064167A1 (en) 1982-11-10
KR860000202B1 (ko) 1986-03-03
JPH05106107A (ja) 1993-04-27

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