EP0144793A2 - Fibre en polyacrylonitrile à haute ténacité et haut module, et procédé de fabrication - Google Patents

Fibre en polyacrylonitrile à haute ténacité et haut module, et procédé de fabrication Download PDF

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Publication number
EP0144793A2
EP0144793A2 EP84113512A EP84113512A EP0144793A2 EP 0144793 A2 EP0144793 A2 EP 0144793A2 EP 84113512 A EP84113512 A EP 84113512A EP 84113512 A EP84113512 A EP 84113512A EP 0144793 A2 EP0144793 A2 EP 0144793A2
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Prior art keywords
solvent
temperature
gel
fiber
fibers
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English (en)
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EP0144793A3 (en
EP0144793B1 (fr
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Young D. Kwon
Sheldon Kavesh
Dusan C. Prevorsek
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Honeywell International Inc
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Allied Corp
AlliedSignal Inc
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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
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
    • 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
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide

Definitions

  • the present invention relates to a process for preparing polyacrylonitrile (PAN) fibers and fibers as produced, and especially to such a process and fiber product employing PAN of ultrahigh molecular weight.
  • PAN polyacrylonitrile
  • PAN has been spun conventionally using either wet spinning (e.g., 9.5% PAN in sodium thiocyanate-water (50:50) spun into 10% sodium thiocyanate in water at -2°C for coagulation) or dry spinning (e.g. 30% PAN in diethylformamide spun at 130°C).
  • Typical properties of the resultant fibers are 2.4-3.7 g/denier tenacity and 42-53 g/denier tensile molecules. See Table 1 on page 155 of S.S. Chari et al., Fibre Science and Technology, Vol. 15, pp. 153-60 (1981).
  • U.S. Patent 4,413,110 of Kavesh and Prevorsek June 1, 1983).
  • the present invention includes a gel-spinning process employing a polyacrylonitrile of very high molecular weight. Unlike wet-spinning (coagulation) processes, in gel spinning, the spun solution is cooled to below the gelling temperature before extraction of the spinning solvent.
  • the present invention includes process comprising the steps:
  • the present invention also includes a polyacrylonitrile fiber of weight average molecular weight at least about 500,000 and having a tenacity of at least about 5 g/denier and a secant modulus of at least about 100 g/denier.
  • a polyacrylonitrile fiber of weight average molecular weight at least about 500,000 and having a tenacity of at least about 5 g/denier and a secant modulus of at least about 100 g/denier are useful in tire cord and in the preparation of carbon fibers, especially for composites.
  • the process and fibers of the present invention employ a linear ultrahigh molecular weight polyacrylonitrile (PAN) described more fully below that enables the preparation of PAN fibers (and films) of heretofore unobtained properties by extrusion of dilute solutions of concentration lower than used in Wet Spinning or Dry Spinning.
  • PAN linear ultrahigh molecular weight polyacrylonitrile
  • the preferred solvents of the present invention do not phase-separate from PAN on cooling to form a non-PAN coating or occluded phase, but rather form a dispersed fairly homogeneous gel.
  • the PAN polymer used is substantially linear and of weight average molecular weight at least about 500,000, preferably at least about 750,000, more preferably between about 1,000,000 and about 4,000,000 and most preferably between about 1,500,000 and about 2,500,000.
  • Such substantially linear ultrahigh molecular weight PAN can be prepared by the procedures illustrated in Preparations A and B immediately proceeding Example 1, below. While ultrahigh molecular weight PAN is known (see U.S. patent 4,254,250 Col. 5, Table I), its prior use was in preparing water treatment polymers.
  • the first solvent should be substantailly 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 80 kPa (four-fifths of an atmosphere) at 130°C, or at the first temperature.
  • Suitable first solvents for PAN include dimethylsulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), gamma-butyrolactone and ethylene carbonate. Other homologs and analogs of these solvents (e.g., propylene carbonate) may also be used. Less preferred are aqueous solutions of salts such as concentrated aqueous sodium thiocyanate. DMSO is most preferred.
  • the polymer may be present in the first solvent at a first concentration which is selected from a relatively narrow range, e.g. about 2 to about 15 weight percent, preferably about 4 to about 10 weight percent more preferably about 5 to about 8 weight percent; however, once chosen, the concentration should not vary significantly adjacent the die or otherwise prior to cooling to the second temperature.
  • the concentration at any one point 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 approximately 25-100°C; therefore, a preferred first temperature can be about 130°C to about 200°C, more preferably about 140-180°C. While temperatures may vary above the first temperature at various points upstream of the die face, excessive temperatures causative 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 20% greater.
  • the second temperature is chosen whereat the first solvent-polymer system behaves as a gel, i.e., has a yield point and reasonable dimensional stability for subsequent handling. Cooling of the extruded polymer solution from the first temperature to the second temperature should be accomplished at a rate sufficiently rapid to form a gel fiber which is of substantially the same polymer concentration as existed in the polymer solution. Preferably the rate at which the extruded polymer solution is cooled from the first temperature to the second temperature should be at least 50°C per minute.
  • a preferred means of cooling to the second temperature involves the use of a quench bath.
  • the quench bath will preferably comprise a mixture of the first solvent with water.
  • the water concentration of the quench bath may range from about 0 to about 95%.
  • the quench bath may also comprise a liquid which is relatively immiscible with the first solvent. Suitable liquids include soybean oil, silicon oil, etc. Quenching temperatures that may be employed range from about 0°C to about 50°C with a temperature near room temperature being preferred.
  • both gels will be gel fibers
  • the xerogel will be a xerogel fiber
  • the thermoplastic article 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 thermoplastic article 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 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 a second more volatile solvent.
  • a suitable second solvent is water.
  • Preferred second solvents are the volatile solvents having an atmospheric boiling point of 100°C or lower. Conditions of extraction should remove the first solvent to less than 1% solvent by weight of polymer in the gel after extraction.
  • first solvents such as DMSO or DMF
  • a preferred combination of conditions is a first temperature between 130°C and 250°C, a second temperature between 0°C and 50°C and a cooling rate of at least 50°C/minute.
  • 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 four-fifths atmosphere (80 kPa).
  • the primary desired difference relates to volatility as discussed above.
  • the fibrous structure 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.
  • 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 first stage 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 temperature 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 100°C and 250°C.
  • Most preferably the stretching is conducted in at least two stages with the last of the stages performed at a temperature between 130°C and 230°C.
  • Such temperatures may be achieved with heated tubes as in the Figures, or with other heating means such as heating blocks or steam jets.
  • the product PAN fibers produced by the present process represent novel articles in that they include fibers with a unique combination of properties: a molecular weight of at least about 500,000, a (secant) modulus at least about 100 g/denier and a tenacity at least about 5 g/denier.
  • the molecular weight is preferably at least about 750,000, more preferably between about 1,000,000 and about 4,000,000 and most preferably between about 1,500,000 and about 2,500,000.
  • the tenacity is preferably at least about 7 g/denier.
  • the secant modulus is preferably at least about 100 g/denier, more preferably at least about 125 g/denier.
  • the fiber has an elongation to break at most 7%.
  • FIG 1 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 PAN of weight average molecular weight at least 500,000 and frequently at least 750,000, and to which is also fed a first, relatively non-volatile solvent 12 such as DMSO.
  • 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. 150°C) to permit the polymer to be completely dissolved in the solvent at the desired concentration (generally between 5 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 aperatures, 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. 150°C) chosen to exceed the gellation temperature (approximately 0-100°C for PAN in DMSO).
  • the temperature may vary (e.g. 140°C, 160°C) or may be constant (e.g. 150°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 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 containing any of a variety of liquids, so as to cool the fibers, both in the air gap 27 and in the quench bath 30, to a second temperature such that the polymer- solvent system forms a gel.
  • the quench liquid in quench batch 30 be a mixture of first solvent (DMSO) and water. While some stretching in the air gap 27 and in the quench medium is permissible, it is preferably less than about 10:1. Rollers 31 and 32 in the quench bath 30 operate to feed the fiber through the quench bath, and preferably operate with little or no stretch.
  • the cool first gel fibers 33 pass (preferably with some room temperature stretching) to a solvent extraction device 37 where a second solvent, being of relatively low boiling temperature such as water, is fed 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 fibrous structure 41 conducted out of the solvent extraction device 37 contains substantially only second solvent, and relatively little first solvent.
  • the fibrous structure 41 may have shrunken somewhat compared to the first gel fibers 33.
  • the second solvent is evaporated from the fibrous structure 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 fiber temperature to be between 100-200°C.
  • the fibers are stretched at a relatively high draw ratio (e.g. 4:1) 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. 1.5:1 to 5:1) may occur within quench bath 30, between the quench bath 30 and the solvent extraction device 37, 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 2.
  • 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 1.
  • 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 first gel fibers 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 heated tube 57 which, in general, is longer than the first heated tube 56 illustrated in 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 fibrous structures 42 containing second solvent are conducted to a drying device 45. There the second solvent is evaporated from the fibrous structures; 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 150 and 270°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. 1.8:1.
  • 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 per- formed 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 3, with the solution forming step A, extrusion step B, and cooling step C being substantially identical to the first embodiment of Figure 1 and the second embodiment of Figure 2.
  • 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 first gel fibers 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 take-up spool 52 and heated tube 56 in the first embodiment of Figure 1.
  • 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. 5:1.
  • heated tube 64 in the third embodiment of Figure 3 will, in general, be longer than heated tube 63 in either the second embodiment of Figure 2 or the first embodiment of Figure 1. 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 fiber 36 is then conducted through solvent extraction device 37, where the second, volatile solvent extracts the first solvent out of the fibers.
  • the fibrous structures 43, 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 present polyacrylonitrile fibers may be used as such in tire cord and other applications.
  • they may be carbonized or graphitized, in the manner conventionally employed for polyacrylonitrile fibers (see Kirk-Othmer, Encyclopedia of Chemical Technology, vol. 4, pp. 625-26 (1978); British Patent 1,110,791 (April 24, 1968)) and the above-cited Chari et al article) to produce carbon fibers of superior properties.
  • the reactor consisted of a 1-liter, 3-neck, roundbottom flask with indented wall. It was fitted with a stirrer, a condenser, and a stopper. The flask is placed in a constant temperature bath at 35°C. It was evacuated and filled with oxygen-free nitrogen four times using a Firestone valve. The system was blanketed with nitrogen throughout the polymerization period.
  • the intrinsic viscosity was found to be 5.67 dL/g when measured in N,N-dimethylformamide at 35°C. On the basis described in Preparation A, this corresponds to an estimated molecular weight of 5.5x10 5 .
  • a 500 ml 3-neck flash equipped with a stirrer, a condenser and a stopper was flushed well and blanketed with nitrogen.
  • the polymer formed was obtained by filtration and then washed four times with water until the filtrate was free of chloride.
  • the polyacrylonitrile was collected by filtration and dried in air at room temperature. Its intrinsic viscosity was found to be 13.65 dL/g when measured in N,N-dimethylformamide at 35°C. This was calculated to have an estimated molecular weight of 1.63x10 using the equation given in Preparation A.
  • the modulus values reported in Example 1-4 represent secant modulus (the slope of a chord on the stress-strain curve drawn between the origin and the breaking point). Such secant modulus values are normally lower than the initial modulus, in some cases by a factor of 2. Selected fibers were also evaluate for initial modulus, and both values are given in Table 1 at the end of the Examples.
  • the extruded uniform solution filament was quenched to a gel state by passage through a bath comprising 50 weight percent water and 50 weight percent dimethyl sulfoxide, said bath being located 1 cm below the spinning die.
  • the gel filament was wound up continuously on a 6.5 cm diameter, 20.4 cm long bobbin at the rate of 599 cm/min.
  • the gel fiber was then kept in a stirred water bath having a temperature of 22°C for 18 hours in order to extract the dimethyl sulfoxide from the fiber. Thereafter, the fiber was dried at a temperature of 25°C. Drying of the fiber was accomplished by leaving in air at room temperature.
  • the dried fiber was then drawn via a two stage drawing process.
  • First stage drawing was accomplished by feeding the fiber at a speed of 118 cm/min into a hot tube, five-eighths inch (14 mm) inside diameter, and 6 feet (180 cm) in length, blanketed with nitrogen.
  • the temperature at the entrance of the hot tube was 135°C with the exit temperature of the hot tube being 150°C.
  • the fiber was drawn at a ratio of 4.07/1 within the tube.
  • Second stage drawing of the once stretched fiber was accomplished by drawing the fiber in the same tube wherein the fiber was fed into the tube at a speed of 215 cm/min, with the tube entrance temperature being 146°C, the tube exit temperature being 160°C, and the drawing ratio being 2.11/1.
  • the properties of the twice stretched fiber was as follows:
  • Example 1 was repeated with 6% PAN in DMSO and the extrusion rate lowered from 2.03 to 1.97 cm 3 /min and the take-up speed raised from 599 cm/min to 605 cm/min (so as to produce a die-draw of 1.4:1 instead of 1.35:1).
  • Six sets of fibers were prepared using various first stretch conditions (tube temperature, draw ratio, draw duration) as follows:
  • Fiber properties were measured (4 replications) on such once-drawn fibers, and are indicated below, with average values indicated, followed by maximum values in parentheses:
  • Example 1 was repeated, now mixing the PAN to 6.0% concentration in gamma-butyrolactone for four hours at 145°C.
  • Spinning was at 145°C, at 2.17 mL/min into water-methanol (50:50). Take-up speed was 617 cm/min (1.3:1 die-draw).
  • the fibers were extracted at 22°C for 18 hours in stirred methanol.
  • the fibers were twice drawn as follows:
  • Example 1 was repeated using 6.0% PAN in dimethyl formamide, mixed at 145°C for four hours. Spinning through the 0.030 inch (0.78 mm) diameter die was at 133°C at 1.96 mL/min with take-up at 519 cm/min (1.20:1 die-draw). Extraction was in water for 17 hours with stirring and then 4 hours without stirring. Two stage drawing was as follows:
  • Fiber properties were determined (one replication for the three once-drawn fibers, four replications for the six twice-drawn fibers) as follows:

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
EP84113512A 1983-12-05 1984-11-09 Fibre en polyacrylonitrile à haute ténacité et haut module, et procédé de fabrication Expired EP0144793B1 (fr)

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US55798483A 1983-12-05 1983-12-05
US557984 1983-12-05

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EP0144793A2 true EP0144793A2 (fr) 1985-06-19
EP0144793A3 EP0144793A3 (en) 1985-09-11
EP0144793B1 EP0144793B1 (fr) 1988-10-12

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2184057A (en) * 1985-12-11 1987-06-17 Canon Kk Process for producing gel fiber
US5510072A (en) * 1993-06-21 1996-04-23 Shell Oil Company Process for the manufacture of elastic articles from poly(monovinylaromatic/conjugated diene) block copolymers and elastic articles obtainable therewith
DE102009019120A1 (de) * 2009-04-29 2010-11-04 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Formkörper aus Polyacrylnitril und Verfahren zu deren Herstellung
CN109440214A (zh) * 2018-11-09 2019-03-08 中国科学院山西煤炭化学研究所 一种碳纤维前驱体纤维的制备方法及碳纤维前驱体纤维的应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6228407A (ja) * 1985-07-25 1987-02-06 Kuraray Co Ltd 高強度高弾性率繊維の製造方法
JPS62299510A (ja) * 1986-06-19 1987-12-26 Japan Exlan Co Ltd 高物性アクリル繊維及びその製造法
CN112899807B (zh) * 2021-01-21 2022-04-15 中国科学院山西煤炭化学研究所 高强、高模、高韧性聚丙烯腈纤维及其制备方法

Citations (4)

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Publication number Priority date Publication date Assignee Title
GB1100497A (en) * 1965-02-01 1968-01-24 Tno Production of fibres from thermosensitive polymers
FR2405275A1 (fr) * 1977-10-07 1979-05-04 Mobil Oil Pellicules d'acrylonitrile polymere et leur procede de preparation
EP0044534A2 (fr) * 1980-07-23 1982-01-27 Hoechst Aktiengesellschaft Filaments et fibres à haut module, en polyacrylonitrile, et leur procédé de fabrication
US4344908A (en) * 1979-02-08 1982-08-17 Stamicarbon, B.V. Process for making polymer filaments which have a high tensile strength and a high modulus

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GB2184057A (en) * 1985-12-11 1987-06-17 Canon Kk Process for producing gel fiber
GB2184057B (en) * 1985-12-11 1990-01-10 Canon Kk Process for producing gel fiber
US5510072A (en) * 1993-06-21 1996-04-23 Shell Oil Company Process for the manufacture of elastic articles from poly(monovinylaromatic/conjugated diene) block copolymers and elastic articles obtainable therewith
DE102009019120A1 (de) * 2009-04-29 2010-11-04 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Formkörper aus Polyacrylnitril und Verfahren zu deren Herstellung
CN109440214A (zh) * 2018-11-09 2019-03-08 中国科学院山西煤炭化学研究所 一种碳纤维前驱体纤维的制备方法及碳纤维前驱体纤维的应用
CN109440214B (zh) * 2018-11-09 2021-07-30 中国科学院山西煤炭化学研究所 一种碳纤维前驱体纤维的制备方法及碳纤维前驱体纤维的应用

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EP0144793A3 (en) 1985-09-11
JPS60139809A (ja) 1985-07-24
CA1234662A (fr) 1988-04-05
EP0144793B1 (fr) 1988-10-12
DE3474573D1 (en) 1988-11-17
JPH064923B2 (ja) 1994-01-19

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