EP1863956B1 - Process for removing phosphorous from a fiber or yarn - Google Patents

Process for removing phosphorous from a fiber or yarn Download PDF

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Publication number
EP1863956B1
EP1863956B1 EP06748888A EP06748888A EP1863956B1 EP 1863956 B1 EP1863956 B1 EP 1863956B1 EP 06748888 A EP06748888 A EP 06748888A EP 06748888 A EP06748888 A EP 06748888A EP 1863956 B1 EP1863956 B1 EP 1863956B1
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Prior art keywords
yarn
acid
washing
polymer
phosphorus
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German (de)
English (en)
French (fr)
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EP1863956A1 (en
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Steven R. Allen
Doetze Jakob Sikkema
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Magellan Systems International LLC
EIDP Inc
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EI Du Pont de Nemours and Co
Magellan Systems International LLC
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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
    • D01F13/00—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like
    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles

Definitions

  • the present invention generally relates to polymer fibers and processes for the preparation of such fibers. More particularly , the present invention relates to methods of removing polyphosphoric acid, inter alia, from filaments and spun yarns comprising polymers.
  • Many fibers are prepared from a solution of the polymer in a solvent (called the "polymer dope") by extruding or spinning the polymer dope through a die or spinneret to prepare or spin a dope filament.
  • the solvent is subsequently removed to provide the fiber or yarn.
  • the solvent utilized is a solvent acid, such as polyphosphoric acid (PPA).
  • PPA polyphosphoric acid
  • PPA removal is generally more difficult, in part due to its polymeric nature.
  • Incorporation of heteroatoms into the polymer may also act to inhibit removal of polyphosphoric acid from the fiber or yarn.
  • Existing processes for removal of polymeric PPA solvent from a polymeric material typically require long washing times or elevated leaching temperatures if a substantial amount of PPA is to be removed.
  • Sen et al. US 5,393,478 discloses a process for leaching polyphosphoric acid from the polybenzazole dope filament by contacting with a leaching fluid at a temperature of at least about 60°C.
  • Sen et al., US 5,525,638 discloses a process for washing polyphosphoric acid from the polybenzazole dope filament by using multiple washes, typically at about room temperature, slowly reducing phosphorous concentration from the spun fiber, allegedly to improve the physical properties of the resultant polymeric fiber.
  • the invention is directed to processes for removing phosphorus from a yarn spun from a polymer solution containing polyphosphoric acid, the yarn comprising at least about 1.5 percent by weight of the yarn of phosphorous, comprising contacting the yarn with a base and washing the yarn with an aqueous fluid, wherein the yarn is provided by heating a spun multifilament yarn comprising the polymer and polyphosphoric acid to at least 120 degrees Celsius for a time effective to hydrolyse polyphosphoric acid
  • Figure 1 is a schematic diagram of a polyarenezole fiber production process.
  • Filaments useful in the present invention can be made from polyareneazole polymer.
  • polyareneazole refers to polymers having either:
  • Y is an aromatic, heteroaromatic, aliphatic group, or nil; preferably an aromatic group; more preferably a six-membered aromatic group of carbon atoms. Still more preferably, the six-membered aromatic group of carbon atoms (Y) has para- oriented linkages with two substituted hydroxyl groups; even more preferably 2,5-dihydroxy-para-phenylene.
  • Ar and Ar 1 each represent any aromatic or heteroaromatic group.
  • the aromatic or heteroaromatic group can be a fused or non-fused polycyclic system, but is preferably a single six-membered ring.
  • the Ar or Ar 1 group is preferably heteroaromatic, wherein a nitrogen atom is substituted for one of the carbon atoms of the ring system or Ar or Ar 1 may contain only carbon ring atoms. Still more preferably, the Ar or Ar 1 group is heteroaromatic.
  • polybenzazole refers to polyareneazole polymer having repeating structure (a), (b1),or (b2) wherein the Ar or Ar 1 group is a single six-membered aromatic ring of carbon atoms.
  • polybenzazoles are a class of rigid rod polybenzazoles having the structure (b1) or (b2); more preferably rigid rod polybenzazoles having the structure (b1) or (b2) with a six-membered carbocyclic aromatic ring Ar 1 .
  • the polybenzazole is a polybenzimidazole, preferably it is poly(benzo[1,2-d:4,5-d']bisimidazole-2,6-diyl-1,4-phenylene.
  • the polybenzazole is a polybenzthiazole, preferably it is poly(benzo[1,2-d:4,5-d']bisthiazole-2,6-diyl-1,4-phenylene.
  • the polybenzazole is a polybenzoxazole, preferably it is poly(benzo[1,2-d:4,5-d']bisoxazole-2,6-diyl-1,4-phenylene.
  • polypyridazole refers to polyareneazole polymer having repeating structure (a), (b1),or (b2) wherein the Ar or Ar 1 group is a single six-membered aromatic ring of five carbon atoms and one nitrogen atom.
  • these polypyridazoles are a class of rigid rod polypyridazoles having the structure (b1) or (b2), more preferably rigid rod polypyridazoles having the structure (b1) or (b2) with a six-membered heterocyclic aromatic ring Ar 1 .
  • the number of repeating structures or units represented by structures is not critical.
  • each polymer chain has from 10 to 25,000 repeating units.
  • Filaments of the present invention are prepared from polybenzazole (PBZ) or polypyridazole polymers.
  • PBZ polybenzazole
  • fiber refers to a relatively flexible, macroscopically homogeneous body having a high ratio of length to width across its cross-sectional area perpendicular to its length.
  • the filament cross section may be any shape, but is typically circular.
  • “yarn” refers to a number of filaments laid, bundled, or assembled together with or without a degree of twist or interlacing, forming a continuous strand, which can be used, for example, in weaving, knitting, plaiting, or braiding, wherein fiber is as defined hereinabove.
  • fabric refers to any woven, knitted, or non-woven structure.
  • woven is meant any fabric weave, such as, plain weave, crowfoot weave, basket weave, satin weave, twill weave, and the like.
  • knitted is meant a structure produced by interlooping or intenneshing one or more ends, fibers or multifilament yarns.
  • non-woven is meant a network of fibers, including unidirectional fibers, felt, and the like.
  • coagulation bath refers to a medium provided to coagulate the dope filament.
  • the bath comprises a liquid, typically an alcohol, water, aqueous acid, or other aqueous liquid mixture.
  • the bath is water or aqueous phosphoric acid, but the liquid may be anything that provides water or other moiety that may assist in the hydrolysis of PPA.
  • the more preferred rigid rod polypyridazoles include, but are not limited to polypyridobisimidazole homopolymers and copolymers such as those described in U.S. Patent 5,674,969 (to Sikkema, et al. on Oct. 7 1997 ).
  • polypyridobisimidazole is homopolymer poly(1,4-(2,5-dihydroxy) phenylene-2,6-diimidazo[4,5-b:4' 5'-e]pyridinylene).
  • the polyareneazole polymers used in this invention may have properties associated with a rigid-rod structure, a semi-rigid-rod structure, or a flexible coil structure; preferably a rigid rod structure.
  • this class of rigid rod polymers has structure (b1) or (b2) it preferably has two azole groups fused to the aromatic group Ar 1 .
  • Suitable polyareneazoles useful in this invention include homopolymers and copolymers. Up to as much as 25 percent, by weight, of other polymeric material can be blended with the polyareneazole. Also copolymers may be used having as much as 25 percent or more of other polyareneazole monomers or other monomers substituted for a monomer of the majority polyareneazole. Suitable polyareneazole homopolymers and copolymers can be made by known procedures, such as those described in U.S. Patents 4,533,693 (to Wolfe et a l . on Aug. 6, 1985), 4,703,103 (to Wolfe et a l . on Oct.
  • Additives may also be incorporated in the polyareneazole in desired amounts, such as, for example, anti-oxidants, lubricants, ultra-violet screening agents, colorants and the like.
  • the present invention is directed to processes for removing polyphosphoric acid from a fiber, comprising the steps of heating a fiber comprising polymer and polyphosphoric acid to at least 120°C for a time effective to hydrolyze polyphosphoric acid; and in a separate step, removing hydrolyzed polyphosphoric acid from the fiber with a fluid having a temperature of 100°C or less.
  • the time effective to hydrolyze polyphosphoric acid is up to about 120 seconds.
  • the step of heating a fiber may include convective heating, radiant heating, radiation heating, RF heating, conductive heating, steam heating, or any combination thereof.
  • the polymer comprises a polyareneazole; more preferably wherein the polyareneazole is a polypyridazole.
  • the polyareneazole is a polypyridobisimidazole; more preferably poly(1,4-(2,5-dihydroxy) phenylene-2,6-diimidazo[4,5-b:4'5'-e]pyridinylene).
  • the polyareneazole is a polybenzazole, and more preferably a polybenzo bisoxazole.
  • removing hydrolyzed polyphosphoric acid includes washing the fiber with a base; more preferably, the fiber is washed with water prior to and after washing with the base.
  • the base must be selected to be strong enough to break a bond between the polymer and the phosphoric acid and typically includes sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium bicarbonate, or any combination thereof, preferably sodium hydroxide, potassium hydroxide, or any combination thereof.
  • removing hydrolyzed polyphosphoric acid includes washing the fiber with a base and subsequent washing with acid.
  • the steps of cooling the fiber to less than 60°C and removing hydrolyzed polyphosphoric acid from the fiber occur simultaneously.
  • the fluid used to remove hydrolyzed polyphosphoric acid has a temperature of about 60°C or less.
  • fiber comprising polymer and polyphosphoric acid is typically heated in an acidic medium having a pH less than 4.0 to a temperature above 120°C for a time effective to hydrolyze polyphosphoric acid.
  • the time effective to hydrolyze polyphosphoric acid is up to about 120 seconds.
  • the acidic medium comprises up to about 80% phosphoric acid by weight.
  • the acidic medium more typically has a pH less than 3.0, and preferably less than 2.0.
  • the acidic medium preferably comprises boiling phosphoric acid having a temperature less than 140°C.
  • the polymer remains substantially non-hydrolyzed after hydrolyzing the polyphosphoric acid.
  • the polymer “remains substantially non-hydrolyzed”, it is meant that the polymer inherent viscosity is not materially affected by the process.
  • the invention is directed to processes for removing phosphorus from a yarn spun from a polymer solution containing polyphosphoric acid, the yarn comprising at least about 1.5 percent by weight of the yarn of phosphorus, comprising contacting the yarn with a base and washing the yarn with an aqueous fluid.
  • the phosphorus content of the yarn prior to contacting the yarn with the base is typically in the range of from 2 to 20 percent based on yarn weight, more typically the phosphorus content is in the range of 4 to 15 percent based on yarn weight.
  • contacting the yarn with the base includes spraying, coating, flowing, drawing, dipping, or any combination thereof.
  • the base contacting the yarn includes sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium bicarbonate, or any combination thereof.
  • the aqueous fluid typically used in washing the yarn contains an acid, more typically a volatile acid.
  • volatile acids include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, or any combination thereof.
  • the volatile acid is acetic or propionic acid.
  • the polymer comprises a polyareneazole.
  • the polyareneazole is a polypyridazole; more preferably a polypyridobisimidazole.
  • the polyareneazole is poly(1,4-(2,5-dihydroxy) phenylene-2,6-diimidazo[4,5-b:4'5'-e]pyridinylene).
  • the polyareneazole is a polybenzazole, more typically a polybenzobisoxazole.
  • the yarn typically contains ⁇ 0.1 percent phosphorus based on yarn weight after washing with the aqueous fluid.
  • the yarn is provided by heating a spun multifilament yarn comprising the polymer and polyphosphoric acid to at least 120°C for a time effective to hydrolyze polyphosphoric acid, preferably up to about 600 seconds, more preferably up to about 120 seconds.
  • the base used in contacting the yarn is aqueous sodium hydroxide, or the aqueous washing fluid contains acetic acid, or both.
  • the duration of the contacting step with base is typically no more than 30 seconds, preferably 20 seconds or less.
  • the duration of the washing step with aqueous fluid is no more than 30 seconds, preferably 20 seconds or less.
  • the step of contacting the yarn with a base begins before the step of washing the yarn with an aqueous fluid.
  • the polymer is formed in acid solvent providing the dope solution 2.
  • the polymer is dissolved in the acid solvent after formation. Either is within the ambit of the invention.
  • the polymer is formed in acid solvent and provided for use in the invention.
  • the dope solution 2, comprising polymer and polyphosphoric acid typically contains a high enough concentration of polymer for the polymer to form an acceptable filament 6 after extrusion and coagulation.
  • the concentration of polymer in the dope 2 is preferably high enough to provide a liquid-crystalline dope.
  • the concentration of the polymer is preferably at least about 7 weight percent, more preferably at least about 10 weight percent and most preferably at least about 14 weight percent.
  • the maximum concentration is typically selected primarily by practical factors, such as polymer solubility and dope viscosity.
  • the concentration of polymer is preferably no more than 30 weight percent, and more preferably no more than about 20 weight percent.
  • the polymer dope solution 2 may contain additives such as anti-oxidants, lubricants, ultra-violet screening agents, colorants and the like which are commonly incorporated.
  • the polymer dope solution 2 is typically extruded or spun through a die or spinneret 4 to prepare or spin the dope filament.
  • the spinneret 4 preferably contains a plurality of holes. The number of holes in the spinneret and their arrangement is not critical to the invention, but it is desirable to maximize the number of holes for economic reasons.
  • the spinneret 4 can contain as many as 100 or 1000 or more holes, and they may be arranged in circles, grids, or in any other desired arrangement.
  • the spinneret 4 may be constructed out of any materials that will not be degraded by the dope solution 2.
  • Fibers may be spun from solution using any number of processes, however, wet spinning and "air-gap" spinning are the best known.
  • the general arrangement of the spinnerets and baths for these spinning processes is well known in the art, with the figures in U.S. Patent Nos. 3,227,793 , 3,414,645 , 3,767,756 , and 5,667,743 being illustrative of such spinning processes for high strength polymers.
  • air-gap the spinneret typically extrudes the fiber first into a gas, such as air.
  • dope solution 2 exiting the spinneret 4 enters a gap 8 (typically called an "air gap” although it need not contain air) between the spinneret 4 and a coagulation bath 10 for a very short duration of time.
  • the gap 8 may contain any fluid that does not induce coagulation or react adversely with the dope, such as air, nitrogen, argon, helium, or carbon dioxide.
  • the extruded dope 6 is drawn across the air gap 8, with or without stretching and immediately introduced into a liquid coagulation bath. Alternately, the fiber may be "wet-spun”.
  • the spinneret In wet spinning, the spinneret typically extrudes the fiber directly into the liquid of a coagulation bath and normally the spinneret is immersed or positioned beneath the surface of the coagulation bath. Either spinning process may be used to provide fibers for use in the processes of the invention. In some embodiments of the present invention, air-gap spinning is preferred.
  • the extruded dope 6 is "coagulated" in the coagulation bath 10 containing water or a mixture of water and phosphoric acid, which removes enough of the polyphosphoric acid to prevent substantial stretching of the extruded dope 6 during any subsequent processing. If multiple fibers are extruded simultaneously, they may be combined into a multifilament yarn before, during or after the coagulation step.
  • the term "coagulation” as used herein does not necessarily imply that the extruded dope 6 is a flowing liquid and changes into a solid phase.
  • the extruded dope 6 can be at a temperature low enough so that it is essentially non-flowing before entering the coagulation bath 10.
  • the coagulation bath 10 does ensure or complete the coagulation of the filament, i.e., the conversion of the polymer from a dope solution 2 to a substantially solid polymer filament 12.
  • the amount of solvent, i.e., polyphosphoric acid, removed during the coagulation step will depend on the residence time of the dope filament in the coagulation bath, the temperature of the bath 10, and the concentration of solvent therein.
  • the present invention is, in part, based on the discovery that long term fiber properties are better preserved if residual phosphorus levels are low. In part, this may be achieved by hydrolyzing PPA prior to its removal from the fiber in the belief that substantially hydrolyzed polyphosphoric acid may be effectively removed from the fiber to achieve low residual phosphorus.
  • PPA is substantially hydrolyzed under conditions whereby the fiber remains substantially non-hydrolyzed.
  • One manner of hydrolysis includes convective heating of the coagulated fiber for a short period of time.
  • the hydrolysis may be effected by heating the wet, as coagulated filament or yarn in a boiling water or aqueous acid solution.
  • the heat treatment provides PPA hydrolysis while adequately retaining the tensile strength of the product fiber.
  • the heat treatment step may occur in a separate cabinet 14, or as an initial process sequence followed by one or more subsequent washing steps in an existing washing cabinet 14.
  • the hydrolysis and removal are provided by (a) contacting the dope filament with a solution in bath or cabinet 14 thereby hydrolyzing PPA and then (b) contacting the filament with a neutralization solution in bath or cabinet 16 containing water and an effective amount of a base under conditions sufficient to neutralize sufficient quantities of the phosphoric acid, polyphosphoric acid, or any combination thereof in the filament.
  • hydrolyzed PPA may be removed from the filament or yarn 12 by washing in one or more washing steps to remove most of the residual acid solvent/and or hydrolyzed PPA from the filament or yarn 12.
  • the washing of the filament or yarn 12 may be carried out by treating the filament or yarn 12 with a base, or with multiple washings where the treatment of the filament or yarn with base is preceded and/or followed by washings with water.
  • the filament or yarn may also be treated subsequently with an acid to reduce the level of cations in the polymer. This sequence of washings may be carried out in a continuous process by running the filament through a series of baths and/or through one or more washing cabinets.
  • Figure 1 depicts one washing bath or cabinet 14.
  • Washing cabinets typically comprise an enclosed cabinet containing one or more rolls which the filament travels around a number of times, and across, prior to exiting the cabinet. As the filament or yarn 12 travels around the roll, it is sprayed with a washing fluid. The washing fluid is continuously collected in the bottom of the cabinet and drained therefrom.
  • the temperature of the washing fluid(s) impacts on the diffusion rates controlling the washing process, making the temperature selection a matter of practical importance. Preferably, temperatures between 20 and 90°Care used, depending on the residence time desired.
  • the washing fluid may be applied in vapor form (steam), but is more conveniently provided in liquid form.
  • a number of washing baths or cabinets are used.
  • the residence time of the filament or yarn 12 in any one washing bath or cabinet 14 will depend on the desired concentration of residual phosphorus in the filament or yarn 12, but preferably the residence time is the range of from about 1 second to less than about two minutes. In a continuous process, the duration of the entire washing process in the preferred multiple washing bath(s) and/or cabinet(s) is preferably no greater than about 10 minutes, more preferably more than about 5 seconds and no greater than about 160 seconds.
  • preferred bases for the removal of hydrolyzed PPA include NaOH; KOH; Na 2 CO 3 ; NaHCO 3 ; K 2 CO 3 ; KHCO 3 ; ammonia; or trialkylamines, preferably tributylamine; or mixtures thereof.
  • the base is water soluble.
  • Typical aqueous bases include NaOH, KOH, Na 2 CO 3 , NaHCO 3 K 2 CO 3 , and KHCO 3 or mixtures thereof; more typically NaOH.
  • the process may optionally include the step of contacting the filament with a washing solution containing water or acid or both to remove all or substantially all excess base or base cations otherwise bound or associated with the polymer fiber.
  • This washing solution can be applied in a washing bath or cabinet 18.
  • the fiber or yarn 12 may be dried in a dryer 20 to remove water and other liquids.
  • the temperature in the dryer is typically 80°C to 130°C.
  • the dryer residence time is typically 5 seconds to perhaps as much as 5 minutes at lower temperatures.
  • the dryer can be provided with a nitrogen or other non-reactive atmosphere.
  • the fiber may be optionally further processed in, for instance, a heat setting device 22. Further processing may be done in a nitrogen purged tube furnace 22 for increasing tenacity and/or relieving the mechanical strain of the molecules in the filaments.
  • the filament or yarn 12 is wound up into a package on a windup device 24. Rolls, pins, guides, and/or motorized devices 26 are suitably positioned to transport the filament or yarn through the process.
  • the phosphorus content of the dried filaments after removal of the hydrolyzed PPA is less than about 5,000 ppm (0.5 %) by weight, and more preferably, less than about 4,000 ppm(0.4%) by weight, and most preferably less than about 2,000 ppm (0.2 %) by weight.
  • Temperature All temperatures are measured in degrees Celsius (°C). Denier is determined according to ASTM D 1577 and is the linear density of a fiber as expressed as weight in grams of 9000 meters of fiber. Tenacity is determined according to ASTM D 885 and is the maximum or breaking stress of a fiber as expressed as grams per denier. Elemental Analysis : Elemental analysis of alkaline cation (M) and phosphorus (P) is determined according to the inductively coupled plasma (ICP) method as follows. A sample (1-2 grams), accurately weighed, is placed into a quartz vessel of a CEM Star 6 microwave system. Concentrated sulfuric acid (5 ml) is added and swirled to wet.
  • ICP inductively coupled plasma
  • a condenser is connected to the vessel and the sample is digested using the moderate char method. This method involves heating the sample to various temperatures up to 260°C to char the organic material. Aliquots of nitric acid are automatically added by the instrument at various stages of the digestion. The clear, liquid final digestate is cooled to room temperature and diluted to 50 ml with deionized water. The solution may be analyzed on a Perkin Elmer optima inductively coupled plasma device using the manufacturers' recommended conditions and settings. A total of twenty-six different elements may be analyzed at several different wavelengths per sample. A 1/10 dilution may be required for certain elements such as sodium and phosphorus. Calibration standards are from 1 to 10 ppm.
  • poly([dihydroxy]para-phenylene pyridobisimidazole) filaments (also referred to herein as "PIPD", shown below in one of its tautomeric forms) were spun from a polymer solution consisting of 18 weight percent of PIPD in polyphosphoric acid. The solution was extruded from a spinneret, drawn across an air gap and coagulated in water. Wet bobbins not processed within 6 hours were refrigerated until further processed.
  • Example A shows typical levels of P in fibers when no purposeful removal in undertaken.
  • Example B illustrates the difficulty of washing PPA from wet yarns using traditional washings with water.
  • Example C illustrates the acid level believed to be a preferred higher acid concentration limit when treating PIPD fibers. At levels above this in certain embodiments, the fibers may begin to disintegrate.
  • Example D illustrates the difficulty of washing PPA from wet yarns using traditional washings with boiling water.
  • Examples E-K show the benefits of currying out a heat treatment step to hydrolyze residual polyphosphoric acids combined with washing of the fiber or yarn.
  • This example illustrates the difficulty of washing PPA from wet yarns using traditional washings with water.
  • a solution of PIPD polymer and polyphosphoric acid having 81.6 wt % P 2 O 5 was spun into fibers using a 250 hole spinneret.
  • the wet as-coagulated yarn was allowed to air dry and was then analyzed for phosphorus.
  • the sample was found to contain a very high level of phosphorus (63400 ppm) along with 175 ppm sodium.
  • a sample of the wet, as-coagulated PIPD yarn was then soaked in fresh water at room temperature for 5 minutes.
  • the yarn sample was then rinsed for 20 seconds in fresh water, was allowed to air dry, and was then analyzed for phosphorus.
  • the sample was found to contain 58500 ppm phosphorus and 453 ppm sodium.
  • a sample of the wet, as coagulated PIPD yarn was then soaked for 5 minutes in gently boiling water at 100°C. This yarn sample was then rinsed for 20 seconds in fresh water at room temperature and then allowed to air dry. The sample was found to contain 55700 ppm phosphorus and 700 ppm sodium.
  • a solution of PIPD polymer and polyphosphoric acid having 82.5 wt % P 2 O 5 was spun into fibers using a 250 hole spinneret.
  • the wet as-coagulated yarn was gently boiled in water at 100°C for a period of 20 minutes. This yarn sample was then rinsed in fresh water for 10 seconds and allowed to air dry. The sample was found to contain 44500 ppm phosphorus and 1000 ppm sodium.
  • a solution of PIPD polymer and polyphosphoric acid having 81.9 wt % P 2 O 5 was spun into fibers using a 250 hole spinneret.
  • a sample of wet, as-coagulated PIPD yarn was treated in boiling 80% phosphoric acid (142°C) for 15 seconds, washed in 91°C water for 10 seconds, then in 60°C baths of 2% aqueous caustic, water, 2% aqueous acetic acid, and water for 10 seconds each. The sample was then allowed to air dry. This sample was found to exhibit stuck or fused filaments and had a residual phosphorus level of 7.44%.
  • a solution of PIPD polymer and polyphosphoric acid having about 82.1 wt % P 2 O 5 was spun into fibers using a 250 hole spinneret.
  • Samples of the wet as-coagulated yarn were then boiled in water for a variety of times as shown in Table 1.
  • the samples were then further washed at 60° C in successive baths of water, 2 wt % aqueous caustic, water, 2% aqueous acetic acid, and then water for 20 seconds in each bath. After drying, the samples were found to contain the phosphorus content as shown in the table. Table Sample Time, min.
  • a solution of PIPD polymer and polyphosphoric acid having 82.5 wt % P 2 O 5 was spun into fibers using a 250 hole spinneret.
  • Samples of wet, as-coagulated PIPD yarn were taken and first treated by high temperature, acidic hydrolysis conditions by employing boiling phosphoric acids of varying concentrations as shown in Table 2. Yarn samples were treated in hydrolyzing media for the times and temperatures shown. Washing of the samples was then done as shown in the Table 2.
  • the washing steps included a combination of the steps of a) washing in water; b) washing in 2% aqueous sodium hydroxide in water; c) washing in water, d) washing in 2% aqueous acetic acid in water; and washing in water.
  • a solution of PIPD polymer and polyphosphoric acid having 82.5 wt % P 2 O 5 was spun into fibers using a 250 hole spinneret.
  • a sample of wet, as-coagulated PIPD yarn was treated in atmospheric pressure steam (100°C) for 60 seconds followed by rinsing in 60°C water for 20 seconds. The sample was allowed to air dry and was found to contain 6.48 wt % P.
  • Another similarly treated sample that was not air-dried was further washed at 60°C in successive baths of 2 wt % aqueous sodium hydroxide, and then water for 20 seconds. After drying this sample was found to contain 2.1wt % phosphorus.
  • a solution of PIPD polymer and polyphosphoric acid having 82.5 wt % P 2 O 5 was spun into fibers using a 250 hole spinneret.
  • a sample of wet, as-coagulated PIPD yarn so spun was treated in saturated steam at about 4 bar (58 psig) and 148° C for 60 seconds followed by 20 second washes in the following baths at 60°C: water, 2 wt % aqueous caustic, water, 2% aqueous acetic acid, and then water. After drying, the sample was found to contain 0.33 wt % phosphorus.
  • a solution of PIPD polymer and polyphosphoric acid having 82.1 wt % P 2 O 5 was spun into fibers using a 100 hole spinneret.
  • the wet, as-coagulated PIPD yarns were strung up to pass through a one-foot long nitrogen-purged tube oven.
  • Table 3 shows the influence of tube oven temperature and residence time on the resulting levels of phosphorus in the samples following washing and drying. All samples were washed for 20 seconds each in 60°C baths of water, followed by 2% aqueous sodium hydroxide, water, 2% acetic acid in water, and water. Phosphorus levels under 1w% are obtained under many conditions using dry heat hydrolysis of wet, as coagulated yarn followed by the indicated washings.
  • a solution of PIPD polymer and polyphosphoric acid having 82.7 wt % P 2 O 5 was spun into fibers using a 250 hole spinneret.
  • a wet, as coagulated PIPD yarn was treated continuously in an oven, however, the residence times and the temperatures were as shown in Table 4. This time the yarn samples were only treated for 20 seconds in each of the following baths at 45-50°C, water, 2% aqueous sodium hydroxide, and water. Residual phosphorus and sodium values are given in Table 3 and illustrate the benefits of the high temperature hydrolysis treatment on reducing the level of residual phosphorus.
  • Table 4 Item Oven Temp Residence Time P Na (°C) (s) (micrograms/gram) I-1 140 30 21600 25600 I-2 160 30 16600 27300 I-3 180 30 11000 20900 I-4 200 30 5720 24200 I-5 220 30 3110 20500 I-6 240 30 3140 24500 I-7 - - 21200 39700 I-8 - - 21900 40000
  • the wet, as-quenched yarn as used above was analyzed for phosphorus and was found to contain 34600ppm. After drying this sample was found to contain 63900 ppm phosphorus. The difference in the percent weight of phosphorus between the yarn samples was due to the extra liquid in the wet yarn.
  • a solution of PIPD polymer and polyphosphoric acid having 82.1 wt % P 2 O 5 was spun into fibers using a 100 hole spinneret. Wet, as-coagulated PIPD yarn was strung up to pass through a one-foot long tube oven purged with atmospheric pressure steam. Table 5 shows the influence of temperature and residence time on the resulting levels of phosphorus in the samples following washing and drying. All samples were washed for 20 seconds each in 60°C baths of water, followed by 2 % aqueous sodium hydroxide, water, 2 % aqueous acetic acid, and water. Phosphorus levels under 1 wt % are again easily obtained under preferred conditions.
  • Table 5 Item Oven Temp (C) Residence Time (s) P Na (micrograms/gram) J-1 280 41 2500 697 J-2 250 41 6910 890 J-3 230 41 6550 833 J-4 230 30 3910 776 J-5 230 20 3490 714 J-6 230 10 22400 793 J-7 200 10 24800 928 J-8 200 20 3870 819 J-9 200 30 6040 1180 J-10 180 30 7440 613 J-11 180 20 9880 391
  • PIPD filaments were spun from a polymer solution consisting of 18 weight percent of PIPD in polyphosphoric acid (82.1 wt % P 2 0 5 ). The solution was extruded from a spinneret having approximately 250 holes, drawn across an air gap and coagulated in water. The wet yarns were processed at 61 meters/min (200 ft/min) on the pair of heated rolls operating at measured surface temperatures of 201-221°C and wound up on bobbins. The yarns that had been processed on hot rolls were observed to be very stiff and have excessive fusing of individual filaments. In addition, undesirable fiber residue was observed on the hot rolls. Additional processing details and results are shown in Table 6.
  • the yarns on the bobbins were then washed and neutralized by immersing the bobbins for five minutes each in five consecutive baths that were at room temperature.
  • the baths were, in order, water; 2% sodium hydroxide in water; water; 2% acetic acid in water; and water.
  • the yarns on the bobbins were then allowed to air-dry and a sample of yarn was taken and the residual phosphorus content was found to be very variable, ranging from about 0.77 weight percent to about 3.42 weight percent phosphorus.
  • Table 6 Item Roll Temp Tension Yarn Phosphorus °C Denier (wt%) K-1 202 250 503 3.42 K-2 201 250 465 1.77 K-3 221 250 458 0.77

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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)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
EP06748888A 2005-03-28 2006-03-27 Process for removing phosphorous from a fiber or yarn Expired - Lifetime EP1863956B1 (en)

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US66574105P 2005-03-28 2005-03-28
PCT/US2006/011513 WO2006105225A1 (en) 2005-03-28 2006-03-27 Process for removing phosphorous from a fiber or yarn

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Families Citing this family (25)

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WO2006105076A2 (en) 2005-03-28 2006-10-05 E.I. Du Pont De Nemours And Company Processes for preparing monomer complexes
WO2006105080A1 (en) 2005-03-28 2006-10-05 E.I. Du Pont De Nemours And Company Processes for increasing polymer inherent viscosity
US7906613B2 (en) 2005-03-28 2011-03-15 Magellan Systems International, Llc Process for removing cations from polyareneazole fiber
ATE417951T1 (de) 2005-03-28 2009-01-15 Du Pont Verfahren zur herstellung von polyarenazolgarn
US7977453B2 (en) 2005-03-28 2011-07-12 E. I. Du Pont De Nemours And Company Processes for hydrolyzing polyphosphoric acid in shaped articles
US7968030B2 (en) 2005-03-28 2011-06-28 E.I. Du Pont De Nemours And Company Hot surface hydrolysis of polyphosphoric acid in spun yarns
US7754846B2 (en) 2005-03-28 2010-07-13 E. I. Du Pont De Nemours And Company Thermal processes for increasing polyareneazole inherent viscosities
DE602006004037D1 (de) 2005-03-28 2009-01-15 Du Pont Verfahren zur herstellung von polyarenazolen mit höher inhärenter viskosität unter verwendung von metallpulvern
US7683157B2 (en) 2005-03-28 2010-03-23 E.I. Du Pont De Nemours And Company Process for the production of polyarenazole polymer
CN101203547A (zh) 2005-03-28 2008-06-18 纳幕尔杜邦公司 高特性粘度聚合物和由其制成的纤维
KR101327632B1 (ko) 2005-03-28 2013-11-12 마젤란 시스템즈 인터내셔날, 엘엘시 폴리아렌아졸 필라멘트 중 폴리인산의 가수분해 방법
KR101327612B1 (ko) 2005-03-28 2013-11-12 마젤란 시스템즈 인터내셔날, 엘엘시 방사된 멀티필라멘트사 중의 폴리인산의 무-융합 가수분해
US7906615B2 (en) 2005-03-28 2011-03-15 Magellan Systems International, Llc Process for hydrolyzing polyphosphoric acid in a spun yarn
US7888457B2 (en) 2005-04-01 2011-02-15 E. I. Du Pont De Nemours And Company Process for removing phosphorous from a fiber or yarn
WO2013105949A1 (en) * 2012-01-11 2013-07-18 E. I. Du Pont De Nemours And Company Process for preparing yarn derived from aramid copolymer fiber having low residual sulfur
BR112014016856A8 (pt) * 2012-01-11 2017-07-04 Du Pont método de remoção de enxofre de uma fibra feita de um polímero
RU2014132856A (ru) * 2012-01-11 2016-03-10 Е.И.Дюпон Де Немур Энд Компани Способ удаления серы из волокна с применением водного раствора кислоты
WO2013105938A1 (en) * 2012-01-11 2013-07-18 E. I. Du Pont De Nemours And Company Method for removing sulfur from fiber using monovalent salt ion exchange
BR112014017066A2 (pt) * 2012-01-11 2018-05-22 Du Pont processo para produzir um fio
WO2013105950A1 (en) * 2012-01-11 2013-07-18 E. I. Du Pont De Nemours And Company Method for removing sulfur from fiber using halide acid ion exchange
RU2014132710A (ru) 2012-01-11 2016-03-10 Е.И.Дюпон Де Немур Энд Компани Способ получения пряжи на основе арамидного сополимера с применением промывки кислотой
WO2013105955A1 (en) * 2012-01-11 2013-07-18 E. I. Du Pont De Nemours And Company Process for preparing aramid copolymer yarn using a halide acid wash
US9469922B2 (en) 2012-01-11 2016-10-18 E I Du Pont De Nemours And Company Method for removing sulfur from fiber using a weak base
EP2844787A1 (en) * 2012-05-03 2015-03-11 E. I. Du Pont de Nemours and Company Process for obtaining low residual aramid materials
US11959196B2 (en) * 2015-07-06 2024-04-16 Pbi Performance Products, Inc. Phosphonated PBI fiber

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100306676B1 (ko) 1993-04-28 2001-11-30 샬크비즈크 피이터 코르넬리스; 페트귄터 피리도비스이미다졸성분의강성막대형중합체
US5393478A (en) * 1993-08-20 1995-02-28 The Dow Chemical Company Process for coagulation and washing of polybenzazole fibers
EP0783603B1 (en) 1994-09-30 1999-12-08 Toyobo Co., Ltd. Process for the preparation of polybenzazole filaments and fibres
US5525638A (en) * 1994-09-30 1996-06-11 The Dow Chemical Company Process for the preparation of polybenzazole filaments and fibers
JP3651621B2 (ja) * 1995-09-05 2005-05-25 東洋紡績株式会社 ポリベンザゾール繊維の製造方法
US5772942A (en) * 1995-09-05 1998-06-30 Toyo Boseki Kabushiki Kaisha Processes for producing polybenzazole fibers
JP3661802B2 (ja) * 1995-09-13 2005-06-22 東洋紡績株式会社 ポリベンザゾール繊維の製造方法
JPH10110329A (ja) * 1996-10-01 1998-04-28 Toyobo Co Ltd ポリベンザゾール繊維およびその製造方法
CN1665886A (zh) * 2002-06-26 2005-09-07 东洋纺织株式会社 高耐久性聚吲哚组合物、纤维以及薄膜
US7189346B2 (en) * 2004-07-22 2007-03-13 E. I. Du Pont De Nemours And Company Polybenzazole fibers and processes for their preparation
US7906615B2 (en) * 2005-03-28 2011-03-15 Magellan Systems International, Llc Process for hydrolyzing polyphosphoric acid in a spun yarn

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ATE495287T1 (de) 2011-01-15
DE602006019564D1 (de) 2011-02-24
WO2006105225A1 (en) 2006-10-05
CN101218384A (zh) 2008-07-09
EP1863956A1 (en) 2007-12-12
KR20080034829A (ko) 2008-04-22
KR101337734B1 (ko) 2013-12-06
CN101218384B (zh) 2010-12-08
JP2008534804A (ja) 2008-08-28

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