US3642706A - Process for spinning wholly aromatic polyamide filaments - Google Patents

Process for spinning wholly aromatic polyamide filaments Download PDF

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US3642706A
US3642706A US16265A US3642706DA US3642706A US 3642706 A US3642706 A US 3642706A US 16265 A US16265 A US 16265A US 3642706D A US3642706D A US 3642706DA US 3642706 A US3642706 A US 3642706A
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filaments
spinning
polymer
solution
bath
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Herbert S Morgan Jr
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Monsanto Co
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Monsanto Co
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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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols

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  • the spinning of large numbers of filaments from a given spinnerette is highly desirable, as is also the spinning of filaments with large individual deniers.
  • the present invention one is able to spin wholly aromatic polyamide solutions into dense attenuated filaments of unusually high crystallinity, orientation and thermal stability at high rates of production.
  • a process for the preparation of improved filaments and the like from wholly aromatic polyamides, especially from those polyamides having a pronounced tendency toward preorientation and random crystallization, is provided.
  • a solution of such polyamide is extruded from a spinnerette or other type of extrusion nozzle into a spin bath also called a coagulating bath.
  • the point of extrusion is disposed a short distance of about A; to 1 /2 inches above the liquid level in the bath.
  • the resulting filaments are withdrawn from the coagulating bath and then washed and dried. Thereafter, the filaments are hot drawn. Improvements result from incorporating in the solution prior to extrusion a small but effective amount of a wax.
  • the wax preferably has a melting point above 25 C. and is obtained by the reaction of a saturated fatty acid having about 8-28 carbon atoms with a hexahydric alcohol in an amount of about 0.1% to 5.0% based on the weight of the polyamide in solution.
  • Typical of polymers useful in carrying out the process of this invention are those wholly aromatic polyamides, having recurring structural units as follows:
  • Ar and Ar are divalent unsaturated carbocyclic ring radicals.
  • the polyamides may be generally described as having no aliphatic linkages or segments in their regularly recurring structural units.
  • unsaturated carbocyclic ring radicals as used herein refers to any resonance-stabilized ring system whether benzene-aromatic or hetero-aromatic.
  • benzene-aromatic refers to single, multiple or fused ring residues, such as phenylene, biphenylene and naphthalene and also applies to aromatic ring systems which have been modified by internal aromatic amide block units.
  • Ar and Ar may be the same or different and may be substituted or unsubstituted.
  • the substituents may be nitro, halogen, lower alkyl groups and the like.
  • either one or both of the Ar groups may contain optionally linkages other than carbon-to-carbon, such as u C; -O; CH2; iNH-; SOaetc.
  • Two preferred wholly aromatic polymers are poly[N,N'-m-phenylene bis(m-benzamide) naphthalene-2,6-dicarboxamide] and poly[N,N m phenylene bis (m-benzamide) ]terephthalamide.
  • solvents suitable for preparing the polymers and spinning solutions of this invention include N-methyl-Z-pyrrolidone, hexamethyl phosphoric triamide, trifluoroacetic acid and the like. Mixtures of solvents are also contemplated. Concentrated sulfuric acid and dimethyl sulfoxide may also be used for redissolving polymers which have been isolated and purified, as for example, when interfacial techniques are used to prepare the polymers. Preferably, the same solvent is used for both polymer preparation and spinning.
  • the hydrogen halide formed during the polymerization should be neutralized or removed from the polymer solution prior to spinning in order to prevent its harmful effect on the resulting product and corrosive effect on the spinning equipment used.
  • Neutralization may be conveniently accomplished, by adding an alkali or alkaline earth metal base to the polymer solution.
  • bases include lithium carbonate, lithium hydroxide, calcium, hydroxide, calcium carbonate, calcium acetate and magnesium carbonate.
  • the polymers are dissolved in the solvent, preferably a lower dialkyl amide, containing an amount of salt and water proportional to the amount of hydrogen halide formed during the polymerization.
  • the salt contributes to the polymer solubilization and varies in amount with the chemical structure and molecular weight of the polymer, but generally ranges from about 1% to about 8% based on solution weight.
  • the polymer spinning solutions may also be prepared by dissolving a washed isolated polymer, such as one prepared by the interfacial technique, in a solvent containing from about 1% to about 8% of an alkali or alkaline earth metal chloride or bromide at a temperature of about 60-90 C.
  • Suitable salts are lithium chloride, lithium bromide, calcium chloride, zinc chloride and the like. Of these, calcium chloride and lithium chloride are preferred. Although it is not essential, the addition of up to about 4% water to these spinning solutions will im- 0 prove their stability.
  • esters of hexahydric alcohols and the anhydro derivatives thereof such as sorbitol, mannitol, dulcitol, sorbitan, mannitan, sorbide, mannide and the like.
  • the fatty cadi portion of the ester is advantageously derived from the long-chain fatty acids including lauric, myristic, palmitic, stearic, oleic, ricinoleic, and the like.
  • the esters may be either predominantly mono-, di-, tri-esters, or mixtures thereof and should have a melting point about about 25 C.
  • esters examples include sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, sorbitan monolaurate, sorbitol tetrastearate, mannitan monopalmitate, mannide monooleate, sorbide dipalmitate, sorbide distearate, sorbide monomyristate, and sorbide monostearate.
  • alkoxylated derivates of these esters can be employed such as polyoxyethylene (20 ethylene oxide units) sorbitan monopalmitate, polyoxyethylene (40 ethylene oxide units) sorbitan monostearate, polyoxyethylene (20 ethylene oxide units) monooleate, polyoxyethylene (20 ethylene oxide units) sorbitol oleate, polyoxyethylene (20 ethylene oxide units) sorbitol palmitate.
  • these additives with similar additives such as ethoxylated castor oil, glycerol monostearate, glycerol monopalmitate,
  • polyoxyethylene glycerol monostearate can be employed.
  • the concentration of the additive used may be in the range of from about 0.1% to about 5% and preferably from about 0.1% to about 1% by weight based on the weight of polymer in the solution. Obviously, the optimum amount of additive is dependent on the spinning conditions employed such as rate of spinning, dope temperature, spin bath concentration and temperature, fiber denier and number of filaments and polymer variables such as composition, molecular weight and concentration.
  • the additives may be dissolved in a small amount of the solvent used as the polymerization solvent and added to the polymer solution at an elevated temerature. In a preferred mode of operation, the additives may be incorporated immediately following completion of the polymerization step and prior to the neutralization step.
  • the presence of the wax additives in the spinning solution is thought to prevent the polymer solution from coagulating too rapidly in the spin bath.
  • the wax additives reduce the rate of coagulation by controlling the rate of diffusion of water and solvent into and from the coagulating filaments, which are maintained in a substantially amorphous state.
  • the major portion of the residual salt in the spining solution is thus removed by the coagulation bath.
  • Extruded streams of solutions of wholly aromatic polyamides containing no wax additives are believed to coagulate rapidly at the surface in the vicinity of the extrusion nozzle resulting in an undesirable skin-core effect in the filaments.
  • the rapidly coagulated skin reduces the diffusity of Water into the filaments and inhibits the removal of salt and solvent therefrom.
  • the differing rates of coagulation between the skin and core are believed responsible for preorientation and random crystallization.
  • filaments emerging from the bath have a high degree of orientation, some random crystallization and retention of considerable amounts of salts. These factors are responsible for poor fiber structure and void formation, both of which reduce the maximum orientation stretch obtainable.
  • spin orientation refers to orientation resulting from the shear effect produced by the flow of a viscous solution through a spinneret orifice.
  • pre-orientation refers to the combined effect of spin orientation plus the added orientation produced by the drag of the spin bath liquid on freshly coagulated filaments.
  • preorientation refers to those cases in which random crystallization predominantly occurs in the spin bath and spin orientation in those cases in which orientation in the spin bath is a dominant factor and random crystallization is a negligible factor.
  • the filaments coming from the spin bath are weak, delustered and brittle and cannot be processed satisfactorily.
  • the filaments may be strong but the maximum orientation stretch is considerably reduced, thereby resulting in a lower productivity and physical strength.
  • the use of the wax additives in accordance with the present invention results in a pronounced reduction in random crystallization and a reduction in pre-orientation. Furthermore, the additives often improve the stability of the polymers from having a tendency to develop gel formation on standing and heating. Thus, the spinnability of spinning solutions containing the additive is enhanced.
  • Numeral 1 denotes a spinning solution supply tank.
  • a wholly aromatic polyamide is prepared and dissolved in a suitable solvent.
  • the resulting polymer solution is the feed material supplied to tank 1.
  • the percent of polymer in the solution is conveniently from about to about 30.
  • the solution contains about 6 to about 18 percent polymer.
  • the solubility of the aromatic polyamides varies inter alia with the structure of the polymer and with regard to the solvent used.
  • the polymers should have an inherent viscosity of from about 0.6 to 3.0 or higher, and preferably about 1.2 as measured at 30 C. as a 0.5% solution in N,N-dimethylacetamide containing 5% lithium chloride.
  • the polymer solution is moved from tank 1 by means of pump 2 and is conveyed through an in-line filter 3 to an extrusion head or spinnerette assembly 4.
  • the solution containing a sufficiently high concentration of polymer can be extruded at temperatures of from about 40 C. to about 120 C., and preferably from about 6090 C.
  • the polymer concentration can be increased or decreased within the preferred limits of 6 to 18 percent in order to provide a suitable viscosity for spinning. Additionally, the viscosity at a given concentration can be adjusted by heating or cooling the polymer-containing spinning solution.
  • the spinning solution is forced through a suitable number of holes provided in a spinnerette 5. As shown the extrusion face of the spinnerett is disposed just above the liquid level of the spin bath, although it may very well be submerged in the spin bath.
  • the polymer streams emerging from the spinnerette pass around guide 6 and move through the spin bath composition 7.
  • Spin baths, suitable for use in the present invention for converting the extruded viscous polymer solutions into strand-like objects may be comprised of water or a mixture of water and a lower alkylamide solvent.
  • the spin bath composition may vary over a wide range, depending on the composition of the polymer and solvent being used in the spinning solution, as well as on other factors.
  • a spin bath consisting of about 35-45% N,N-dimethylacetamide in water is preferred.
  • a spin bath of from about 020%, preferably 010% of N,N-dimethylacetamide in water is desirable.
  • the solvent used in making up the spin bath should be the same as that used for dissolving the polymer.
  • Other solvents, useful as coagulation baths, when mixed with water, include ethylene glycol, polyethylene glycol, dimethylsulfoxide and the like.
  • the solution In order to maintain an essentially constant environment for coagulation in the bath, the solution should be circulated and maintained at the optimum concentration by the continuous addition of water while maintaining a constant volume of liquid bath coagulation media.
  • the temperature of the spin bath may be from about -l0 C. to about 50 C., and preferably from about C. to 25 C. during coagulation.
  • void-free filaments emerging from the spin bath have a low birefringence, or orientation, and low salt content which permits their conversion by further processing into useful filaments.
  • the filaments After coagulation the filaments are washed, stretched, dried and stretched again.
  • the filaments are conveyed by a set of drums 8 under spray heads provided with a shower of washing liquid, preferably hot water. From these drums the filaments are moved through a wash bath 9 by means of a second set of drums 10 also provided with spray heads.
  • the filaments may be stretched from about one to four times their length in bath 9 containing hot water having a temperature of about 50 C.
  • the amount of washing depends on the salt concentrations present in the polymer solutions, the total denier of the threadline, and other factors.
  • the washed, drawn filaments are next passed through an optional aqueous finish bath 11 containing conventional yarn lubricants and/or antistatic agents.
  • a third set of drums 12 are used to pull the filaments through the bath. Drums 12 are heated so that drying of the filaments is accomplished. The temperature of these drying rolls are preferably maintained from about 100-160 C.
  • the filament bundle may be heated even higher by passing over a heated draw pin 13 as shown or through a heated enclosure such as an oven, furnace or hot block slot where the filaments are continuously conditioned at about 300-500 C., and preferably about 400-450 C.
  • the filaments are then drawn from one to four times over a heated surface such as that of a hot metal shoe 14 at about 300-450 C.
  • a fourth set of drums 15 is shown as providing the traction sufficient to draw the bundle of filaments.
  • the filaments may be heat relaxed prior to being collected in package form 16.
  • Example I Polymeric [N,N-m-phenylene bis(rn-benzamide)] terephthalamide was prepared. 209 parts of N,N-m-phenylene bis-(m-aminobenzamide) was charged to a reactor along with 57 parts of powdered calcium carbonate. The reactor was closed and swept with nitrogen gas. 1300 parts of dry N,N-dimethylacetamide was then added to the reactor, and the previously added aromatic diamine dissolved with stirring. A coolant bath at -20 C. was placed around the reactor. After 1 /2 hours 122 parts of terephthaloyl chloride was added with rapid stirring. The diacid chloride was rinsed into the reactor with 60 parts of dimethylacetamide.
  • the temperature of the reaction mixture was raised to 35 C.
  • a solution composed of 200 parts of dimethylacetamide and 11 parts water was added and stirred.
  • the resulting solution was degassed and cooled to room temperature.
  • the polymer had an inherent viscosity of 2.29.
  • the solution contained 15.5% polymer.
  • This polymer solution at 70 C. was spun into a spin bath to produce filaments.
  • the spin bath composition was 55% water by volume and 45% dimethylacetamide and had a temperature of 25 C.
  • the spinneret face was below the spin bath surface.
  • the calculated jet stretch accomplished between the spinneret and the first set of rolls was only 0.22.
  • the filaments were stretched 1.21 X.
  • the threadline was hot drawn 2.75 X.
  • the maximum total draw was 0.73.
  • the filament denier was 8.5 and the fila ments had a tenacity of 2.4 grams per denier and an elongation of 13.9 percent.
  • Example II A polymer solution was prepared as described in Exam ple I; and sorbitan monopalmitate was added in an amount of 0.25% based on the weight of the polymer. Spinning conditions were the same as in the first example. The total stretch was 1.85. Filaments having an individual denier of 3.0 were prepared. The tenacity thereof was 5.1 grams per denier and the elongation was 15.2 percent. Again it is seen that greater work is required to break the filaments spun in the presence of the wax additive employed as compared to the filaments prepared without the presence of the additive.
  • Example III A polymer solution was prepared as described in Example I; and sorbitan monopalmitate was added in an amount of 0.50% based on the weight of the polymer. Spinning conditions were the same as in the first example. The total draw was 1.89. Filaments having an individual denier of 3.3 were prepared. The tenacity thereof was 5.8 grams per denier and the elongation was 12.1%. Again it is seen that greater work is required to break the filaments spun in the presence of the wax additive as compared to the filaments prepared without the additive.
  • Example IV With polymer and solution preparation being identical to that described in Example I, 1% by weight polyoxyethylene sorbitol oleate (about ethylene oxide units per mol) was added to the spinning solution instead of sorbitan monopalmitate. Spinning and aftertreating conditions identical to that of Example I were used to pro prise filaments. The optimum jet stretch was 1.0x. While being washed with water at 60 C. the filaments were stretched 2.0x. After the application of the lubricant and drying of the filaments, the threadline was drawn 1.65 X. The maximum total draw was 3.3x. The filament denier was 3.6 with a tenacity of 3.9 grams per denier and an elongation of 17.8. Again it is seen that greater work is required to break the filaments spun in the presence of the wax additive employed as compared to the filaments prepared without the presence of the additive.
  • Example V A polyamide hydrazide from p-aminobenzhydrazide and terephthaloyl chloride was prepared.
  • a stirred reaction vessel was charged with 57 parts of p-aminobenzhydrazide to which 1300 parts of dimethylacetamide had been added.
  • the hydrazide dissolved rapidly and completely.
  • the temperature of the vessel was reduced to 10 C. whereupon 76 parts of solid terephthaloyl chloride was added thereto.
  • 66 parts of calcium acetate monohydrate, 13 parts of water and 304 parts of dimethylacetamide were added to the vessel.
  • the solution was heated to 70 C. and divided into two parts to provide material for wet spinning filaments.
  • Example VI Polymeric N,N'-m-phenylene bis(m-benzamidc)terephthalamide was prepared as described in Example I.
  • the polymer had an inherent viscosity of 2.4-3. This polymer was dissolved in dimethylacetamide to provide 13% polymer solids. To this solution was added 0.5 sorbitan monopalmitate based on the weight of the polymer.
  • the spinning solution at 110 C. was pumped through a hundred hole spinnerette immersed in a spin bath having a temperature of 20 C. and being composed of water and 45% dimethylacetamide. The diameter of the spinnerette holes was 3 mils.
  • the coagulated filaments had an immersion length in the bath of 42 inches.
  • the calculated jet stretch was 0.53
  • the freshly spun filaments were Washed with hot water and stretched while wet 2.52
  • the filaments were then coated with a lubricant, dried and hot stretched at 300 C. 1.36
  • the total draw was 1.8.
  • the filament denier was 3.0 and the filaments had a tenacity of 5.1 grams per denier and an elongation of 15.2%.
  • Example VII A polyamide hydrazide from p-aminobenzhydrazide and terephthaloyl chloride with an inherent viscosity of 1.4 was prepared as described in Example V.
  • the polymer was polymerized in dimethyl acetamide to provide 6% polymer solids.
  • To this solution was added 1.0% sorbitan monopalmitate based on the weight of the polymer.
  • the solution was divided into two equal parts. The first part was used in a conventional wet spinning procedure wherein the spinnerette is 2 inches below the level of the spin bath. The second part was used in a wet spinning procedure wherein the extrusion surface of the spinnerette is disposed /2" above the level of the spin bath.
  • the first part was extruded through a fifteen hole spinnerette with the diameter of the holes being 6 mils.
  • the spin bath had a temperature of 20 C. and a concentration of 99% water and 1% dimethylacetamide.
  • the coagulated filaments had an immersion length of 31 inches.
  • the calculated jet stretch was 0.47X.
  • the freshly spun filaments were washed with hot water C.) and stretched while wet 1.31X.
  • the filaments were then coated with a lubricant, dried and hot stretched over a 12 inch hot shoe at 350 C. 1.29X.
  • the total draw was 0.79.
  • the filament denier was 11 and the filaments had a tenacity of 8.5 grams per denier and an elongation of 2.2%.
  • the second part was extruded through the same fifteen hole spinnerette.
  • the extruded streams after passing through the one-half inch air gap moved 31 inches through a spin bath having a temperature of 20 C. and a concentration of 99% water and 1% dimethylacetamide.
  • the calculated jet stretch was 0.43X.
  • the freshly spun filaments were washed with hot water (85 C.) and stretched while wet 1.44
  • the filaments were then coated with a lubricant, dried and hot stretched over a 12 inch hot shoe at 350 C. 1.4l
  • the total draw was 0.87.
  • the individual filament denier was 10.0 and the filaments had a tenacity of 19.3 grams per denier and an elongation of 4.3. It is readily apparent that when the spinnerette is disposed outside the spin bath one obtains filaments requiring considerable more work to break.
  • Example VIII To the polymer solution described in Example VI a blend consisting of 60% by weight sorbitan monopalmitate and 40% by weight castor oil ethoxylated with 20 moles of ethylene oxide in an amount to provide 1% additives by weight based on the polymer.
  • the resulting spinning solution at 65 C. was extruded through a fifteen 7 mil hole spinneret.
  • the extruded streams after passing through a one-half inch air gap moved 25 inches through a spin bath having a temperature of 25 C. and a concentration of 99% water and 1% dimethylacetamide.
  • the calculated jet stretch was 2.17
  • the freshly spun filaments were Washed with ethylene glycol at 135 C. and stretched 2.7x.
  • the filaments were Washed and dried and hot stretched 1.05 X at 370 C.
  • the individual filament denier was 6.4 and the filaments had a tenacity of 6.6 grams per denier and an elongation of 20%..
  • the total stretch was 6.2x.
  • Example IX To the polymer solution described in Example VI a blend consisting of 60% by weight sorbitan monopalmitate and 40% by weight castor oil ethoxylated with 200 moles of ethylene oxide in an amount to provide 0.5% additives by weight based on the polymer.
  • the resulting spinning solution at 65 C. was extruded through a thirty mil hole spinnerette.
  • the extruded streams after passing through a one-half inch air gap moved 25 inches through a spin bath having a temperature of 23 C. and a concentration of 99% water and 1% dimethylacetamide.
  • the calculated jet stretch was 1.67
  • the freshly spun filaments were washed with ethylene glycol at 135 C. and stretched 274x.
  • the filaments were washed and dried and hot stretched 1.47 at 370 C.
  • the individual filament denier was 4.6 and the filaments had a tenacity of 5.6 grams per denier and an elongation of 34%.
  • the total stretch was 6.7x.
  • a composition of matter comprising (a) a fiber-forming wholly aromatic polyamide and (b) about 0.1 to 5.0% based on the weight of the polymer of a wax having a melting point above 25 C. and obtained by the reaction of a saturated fatty acid having at least about 8 carbon atoms with a hexahydric alcohol.
  • composition of matter consisting of '(a) polymeric fiber-forming N,N-m-phenylene bis(mbenzamide) terephthalamide; and
  • composition of matter consisting of (a) polymeric fiber-forming N,N-m-phenylene bis(mbenzamide) terephthalamide; and
  • composition of matter consisting of (a) a polyamide hydrazide prepared from p-aminobenzhydrazide and terephthaloyl halide; and
  • polyamide is polymeric N,N'-m-phenylene bis(m-benzamide) terephthalamide.
  • polyamide is thepolyamide hydrazide prepared from p-aminobenzhydrazide and terephthaloyl halide.

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3867499A (en) * 1971-02-16 1975-02-18 Monsanto Co Process for wet-spinning fibers derived from acrylic polymers
US3869429A (en) * 1971-08-17 1975-03-04 Du Pont High strength polyamide fibers and films
US3869430A (en) * 1971-08-17 1975-03-04 Du Pont High modulus, high tenacity poly(p-phenylene terephthalamide) fiber
US3985934A (en) * 1974-07-26 1976-10-12 The Upjohn Company Polyimide fiber having a serrated surface and a process of producing same
US3991037A (en) * 1973-03-17 1976-11-09 Hoechst Aktiengesellschaft Process for preparing filaments, fibers and sheets of aromatic polyamides
US4029835A (en) * 1975-01-16 1977-06-14 Mitsubishi Rayon Co., Ltd. Heat resistant sheet
US4081430A (en) * 1975-10-20 1978-03-28 Mitsubishi Rayon Co., Ltd. Aromatic polyamide crystalline complex and the method for producing the same
US4115503A (en) * 1973-08-22 1978-09-19 Monsanto Company Novel process for the preparation of fiber of arylene oxadiazole/arylene N-alkylhydrazide copolymer
US4132757A (en) * 1977-12-27 1979-01-02 Monsanto Company Twist efficiency of oxadiazole/hydrazide yarn
US4224271A (en) * 1975-11-25 1980-09-23 Tse Woon W Process for biconstituent polymer compositions
US4263245A (en) * 1979-04-23 1981-04-21 Celanese Corporation Process for producing high-strength, ultralow denier polybenzimidazole (PBI) filaments
US4702876A (en) * 1984-07-11 1987-10-27 Akzo N.V. Variable-aperture process for the manufacture of filaments from aromatic polyamides
US4842796A (en) * 1985-12-11 1989-06-27 Teijin Limited Process for producing high strength polymetaphenylene isophthalamide fiber
US5643518A (en) * 1995-03-29 1997-07-01 Industrial Technology Research Institute Process for preparing fibers of soluble wholly aromatic polyamides
US5667743A (en) * 1996-05-21 1997-09-16 E. I. Du Pont De Nemours And Company Wet spinning process for aramid polymer containing salts
CN117966294A (zh) * 2024-03-29 2024-05-03 江苏新视界先进功能纤维创新中心有限公司 一种纤维及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL39187A (en) * 1971-04-28 1976-02-29 Du Pont Polyamide fibers and films and their preparation
KR102486322B1 (ko) 2017-03-09 2023-01-06 어드밴식스 레진즈 앤드 케미컬즈 엘엘씨 폴리아미드의 겔 방적을 위한 조성물 및 방법

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3867499A (en) * 1971-02-16 1975-02-18 Monsanto Co Process for wet-spinning fibers derived from acrylic polymers
US3869429A (en) * 1971-08-17 1975-03-04 Du Pont High strength polyamide fibers and films
US3869430A (en) * 1971-08-17 1975-03-04 Du Pont High modulus, high tenacity poly(p-phenylene terephthalamide) fiber
US3991037A (en) * 1973-03-17 1976-11-09 Hoechst Aktiengesellschaft Process for preparing filaments, fibers and sheets of aromatic polyamides
US4115503A (en) * 1973-08-22 1978-09-19 Monsanto Company Novel process for the preparation of fiber of arylene oxadiazole/arylene N-alkylhydrazide copolymer
US3985934A (en) * 1974-07-26 1976-10-12 The Upjohn Company Polyimide fiber having a serrated surface and a process of producing same
US4029835A (en) * 1975-01-16 1977-06-14 Mitsubishi Rayon Co., Ltd. Heat resistant sheet
US4081430A (en) * 1975-10-20 1978-03-28 Mitsubishi Rayon Co., Ltd. Aromatic polyamide crystalline complex and the method for producing the same
US4224271A (en) * 1975-11-25 1980-09-23 Tse Woon W Process for biconstituent polymer compositions
US4132757A (en) * 1977-12-27 1979-01-02 Monsanto Company Twist efficiency of oxadiazole/hydrazide yarn
US4263245A (en) * 1979-04-23 1981-04-21 Celanese Corporation Process for producing high-strength, ultralow denier polybenzimidazole (PBI) filaments
US4702876A (en) * 1984-07-11 1987-10-27 Akzo N.V. Variable-aperture process for the manufacture of filaments from aromatic polyamides
US4842796A (en) * 1985-12-11 1989-06-27 Teijin Limited Process for producing high strength polymetaphenylene isophthalamide fiber
US5643518A (en) * 1995-03-29 1997-07-01 Industrial Technology Research Institute Process for preparing fibers of soluble wholly aromatic polyamides
US5667743A (en) * 1996-05-21 1997-09-16 E. I. Du Pont De Nemours And Company Wet spinning process for aramid polymer containing salts
CN117966294A (zh) * 2024-03-29 2024-05-03 江苏新视界先进功能纤维创新中心有限公司 一种纤维及其制备方法

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CA925636A (en) 1973-05-01
DE2109906A1 (de) 1971-09-30
GB1298314A (en) 1972-11-29
FR2084082A5 (show.php) 1971-12-17

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