EP0014803A1 - Procédé pour la fabrication de fibres de polymère d'acrylonitrile de structure creuse ou ouverte - Google Patents

Procédé pour la fabrication de fibres de polymère d'acrylonitrile de structure creuse ou ouverte Download PDF

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Publication number
EP0014803A1
EP0014803A1 EP79302908A EP79302908A EP0014803A1 EP 0014803 A1 EP0014803 A1 EP 0014803A1 EP 79302908 A EP79302908 A EP 79302908A EP 79302908 A EP79302908 A EP 79302908A EP 0014803 A1 EP0014803 A1 EP 0014803A1
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EP
European Patent Office
Prior art keywords
orifice
fiber
extrudate
counterbore
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP79302908A
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German (de)
English (en)
Inventor
Ronald E. Pfeiffer
Francesco Demaria
Relmond Harold Hamilton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wyeth Holdings LLC
Original Assignee
American Cyanamid Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US06/013,346 external-priority patent/US4261945A/en
Priority claimed from US06/013,353 external-priority patent/US4278415A/en
Priority claimed from US06/013,344 external-priority patent/US4316714A/en
Application filed by American Cyanamid Co filed Critical American Cyanamid Co
Publication of EP0014803A1 publication Critical patent/EP0014803A1/fr
Withdrawn legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • 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

  • This invention relates to a process for preparing an acrylonitrile polymer fiber of modified cross-sectional shape. More particularly, this invention relates to such a process wherein a single phase fusion melt of acrylonitrile polymer and water is extruded through a spinnerette the orifices of which are partially blocked by solid inserts.
  • this fusion melt is extruded through a spinnerette directly into a steam-pressurized solidification zone maintained under conditions which prevent sheath-core structure in the cross-section of the nascent filament and enable stretching to provide orientation of the polymer molecules to be accomplished while the extrudate remains within the solidification zone.
  • This proccss provides a rapidly solidified extrudate composition which upon exit from the spinnerette shows n tendency towards stickiness and high conformity to the shape of the spinnerette orifices through which it is spun.
  • Fibers having hollow or open cross-sectional shape are desirable for a number of reasons. Because of their structure such fibers have a higher extent of surface area than do conventional shaped fibers. This high surface area consists of both external surface area and internal surface area of hollow and open structural modifications. This high surface area permits increased adsorption of water, dyes and other adsorbable materials. Increased water adsorption provides greater comfort in wearing fabrics made from such fiber.
  • the hollow or open structure also provides greater bulk than conventional fiber of the same denier. Esthetic qualities such as handle or feel are also desirably altered by the hollow or open structure and suitable structures can provide greater cover in fabric constructions than conventional structures of the same denier. Fabrics constructed from the open structure fiber dry quicker than fabrics constructed from closed structure fiber because of their greater surface area. Thus, although the desirability of hollow and open structure fibers is generally recognized, suitable processes for preparing such fiber have been difficult to provide and only limited amounts of fiber of hollow and open structures have become available.
  • a process for preparing acrylonitrile polymer fiber which comprises extruding a homogeneous single phase fusion melt of acrylonitrile polymer and water through a spinnerette directly into a steam-prcssurized solidification zone maintained under conditions of saturation, temperature and pressure which controls the release of water from the nascent extrudate and maintain the extrudate in plastic state and stretching said extrudate while it remains within the solidification zone to provide orientation of the polymer molecules characterized by employing a spinnerette the orifices of which have been partially blocked by means of a solid insert therein whereby hollow or open structure fibers are provided.
  • the process of the present invention provides acrylonitrile polymer fiber of infinite varieties of hollow and open structures.
  • the spinnerette modifications necessary to provide hollow or open structure fiber is readily accomplished by means of removable solid inserts which partially block part of the orifice volume in accordance with the type of fiber structure desired.
  • Figures 1-4 represent a first embodiment for preparing open structure fiber
  • Figures 5-9 represent a second embodiment for providing open structure fiber
  • Figures 10-15 represent an embodiment for preparing hollow fibers. More specifically:
  • a homogoncous single phase fusion melt of a fiber-forming acrylonitrile polymer and water is prepared in accordance with conventional procedures.
  • This fusion melt is then extruded through a spinncrette assembly which has been modified with solid inserts that block a portion of the orifice volume so as to provide a hollow or open structure in the resulting extrudate.
  • Such extrusion is conducted in such a manner that the extrudate which is in the form of filaments issues directly into a steam--pressurized solidification zone maintained under conditions which prevent formation of a sheath-core structure within the solid polymer area and minimize formation of a density gradient and voids therein.
  • the steam will be maintained under conditions of saturation, temperature and pressure which control the rate of release of water from the nascent extrudate and maintain the extrudate in plastic state. Such conditions are described in the art. While the nascent extrudate remains in the solidification zone, it is subjected to orientation stretching at stretch ratios adequate to provide desirable textile properties in the fiber produced. Such stretching can be accomplished within the steam-pressurized solidification zone because under the steam conditions maintained therein sufficient water remains within the extrudate to maintain the extrudate in plastic state. Stretching may be accomplished in one or more stages while within the solidification zone and can lead to fine denier filaments as well as highly desirable physical properties for textile applications.
  • the acrylonitrile polymer-water fusion melt when spun through a spinnerette directly into a solidfying medium solidifies rapidly without forming sticky surfaces and retains with high conformity the shape of the orifices without the need for any special provisions such as injection of secondary fluid to retain hollow structure.
  • a variety of fiber shapes and hollow or open configurations can be employed in producing fiber having excellent conformity to the shape-forming orifices including those providing hollow structures.
  • a hydrophilic acrylonitrile polymer is employed as the fiber-forming polymer.
  • a polymer will contain acrylonitrile units and will have hydrophilic moieties associated therewith.
  • hydrophilic moieties can be associated with an acrylonitrile polymer.
  • One method of introducing hydrophilic units into an acrylonitrile polymer composition is to copolymerize acrylonitrile with a hydrophilic comonomer, to provide a copolymer containing at least 50 weight percent of acrylonitrile units, from 1 to 10 weight percent of a hydrophilic monomer and any balance of one or more monomers copolymerizable with acrylonitrile.
  • Another method is to polymerize the acrylonitrile polymer composition in the presence of a redox initiator system that introduces acid groups at the polymer chain ends.
  • Yet another method is to polymerize the acrylonitrile polymer composition in the presence of a pre-formed hydrophilic polymer such as polyvinyl alcohol.
  • Still another method is to hydrolyze a small portion of the acrylonitrile units of a pre-formed acrylonitrile polymer to provide hydrophilic acrylic acid and/or acrylamide units. Further, one can modify a portion of the acrylonitrile units of a pre-formed acrylonitrile polymer by suitable reaction to provide hydrophilic groups, such as by reaction with ethylenediamine to provide imidazoline units. These and other methods known to those skilled in the art can be used alone or in combination to provide hydrophilic units associated with the acrylonitrile polymer composition used to prepare the fiber of the present invention.
  • An acrylonitrile polymer composition useful to provide the fiber in accordance with the invention may by a single polymer or a blend of compatible polymers so long as the composition provides a minimum of at least 50 weight percent acrylonitrile units and preferably has hydrophilic units associated therewith to achieve a transparent fiber. This transparency is reflected in a dye intensity of at least 60 and a shade change due to hot-wet processing of less than 25. Dye intensity is the reflectance of a dyed fiber of the present invention relative to the reflectance of a wet--spun fiber of the same polymer dyed with the same amount of the same dye.
  • Shade change due to hot-wet processing is the change in reflectance of the dyed fiber after a hot-wet processing step, such as oven drying the wet dyed fiber, compared to the air dried dyed fiber.
  • Individual compatible polymers in blends used need not contain the specified amounts of acrylonitrile units or hydrophilic moieties so long as the total blend composition provides the required amounts of such materials.
  • hydrophilic moieties are meant those portions of the acrylonitrile polymer composition that are hydrophilic and include such moieties as sulfonic acid groups, polyvinyl alcohol segments, repeating comonomer units and the like.
  • hydrophilic units are present in the acrylonitrile polymer composition in a manner appropriate for the particular hydrophilic moieties involved.
  • sulfonic acid groups may arise as end groups on polymer chains or as a functional group on a comonomer; polyvinyl alcohol moieties may be present as part of a grafted polymer; other hydrophilic moieties may arise as repeating units in a copolymer prepared from two or more monomers or as a result of hydrolyzing a suitable polymer; they may also arise as a result of suitable reaction of a pre-formed polymer; they may arise as a compatible polymer blend; and in such other methods as are known to those skilled in the art.
  • the term associated therewith is intended to include the various manners in which hydrophilic moieties are present in the acrylonitrile polymer composition since no other terminology is appropriate to cover all the manners described.
  • the amount of hydrophilic moieties in a given acrylonitrile composition will vary depending upon many factors.
  • the content of hydrophilic moieties will be influenced by the nature of the hydrophilic groups, the molecular weight of the polymer, the content of acrylonitrile in the polymer, the nature of the polymer composition, i.e. copolymer, graft, blend, etc., the presence or absence of more than one type of hydrophilic moieties, processing conditions and other variables.
  • useful amounts of hydrophilic moieties are those which as monomer units comprise about 1 to 10 weight percent of the total polymer weight.
  • useful contents of hydrophilic moieties can readily be found by trial following the teachings herein as a guide.
  • Suitable acrylonitrile polymers include homopolymers of acrylonitrile and copolymers of acrylonitrile and one or more of the following monomers.
  • Acrylic acid methacrylic acid, alpha-chloroacrylic acid, itaconic acid, vinyl sulfonic acid, styrene sulfonic acid, methallyl sulfonic acid, p-methoxyallyl benzene sulfonic acid, acrylamidomethylpropane sulfonic acid, ethylene- ⁇ , ⁇ --dicarboxylic acids and their salts; acrylamide, methacrylamide, dimethyl acrylamide, isopropyl acrylamide; allyl alcohol; 2-vinyl pyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine; vinylpyrrolidone; vinyl piperidone; 1,2-dihydroxypropyl methacrylate, hydroxyethyl methacrylate; 1-trimethylammonium--2-hydroxypropyl methacrylate methosulfate; and the like.
  • redox systems such as sodium per- persulfate-sodium bisulfite to initiate and control the polymerization.
  • redox systems such as sodium per- persulfate-sodium bisulfite to initiate and control the polymerization.
  • Such use results in sulfonic acid end groups on the polymer formed.
  • the proportion of sulfonic acid end groups in the polymer will vary with molecular weight of the polymer, higher proportions being present in polymers of low molecular weight. These sulfonic acid end groups should be taken into account when determining the content of hydrophilic moieties in the acrylonitrile polymer composition used to provide the fiber in accordance with the present invention.
  • Acrylonitrile polymer compositions containing sulfonic acid groups arising solely from the use of an appropriate redox system can be effectively employed to provide fiber in accordance with the present invention.
  • hydrophilic pre-formad polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, polyacrylamide, polyacrylic acid and the like are to be used to provide the acrylonitrile polymer composition, it is desirable that such pre-formed be added to the monomer composition to be polymerized to provide the acrylonitrile units.
  • Individual polymers of the composition may range in molecular weight from about 10,000 to 200,000 or more so long as the composition provides fiber of desirable properties.
  • a single phase fusion melt of acrylonitrile polymer composition and water results when suitable quantities of polymer composition and water are heated at elevated temperature and pressure sufficient to maintain water in liquid state.
  • the amount of water necessary will vary depending upon the polymer composition employed. For a given polymer composition, there will be a range of water contents that will provide the single phase fusion melt at the operating temperature and pressure. This can readily be determined from a phase diagram, which will also indicate the minimum melt temperature, i.e. the temperature at which the polymer begins to melt. Use of too low a water content or temperature will result in a separate phase of unmelted polymer.
  • a water content in the range of about 5-35 weight percent based on the total weight of polymer and water.
  • a hydrophilic polymer composition it is generally preferable to use a water content in the lower half of this range, i.e. about 5 to 20 weight percent.
  • the fusion melt should be obtained at a temperature safely below the deterioration or decomposition temperature of the polymer composition. Sufficient temperature and mixing should be employed to ensure that a homogeneous fusion melt is obtained. Useful temperatures are generally in the range of about 140-200°C.
  • the fusion melt is conveniently obtained in conjunction with spinning using a screw extruder coupled with a pump - and spinnerette.
  • a suitable procedure for melt spinning is described in U.S. Patent 3,991,153 issued November 9, 1976 to G. K. Klausner et al.
  • Other types of melt-spinning devices may be used such as a piston pump in conjunction with a spinnerette.
  • the homogeneous single phase fusion melt of acrylonitrile polymer composition and water is extruded througli a spinnetette directly into a steam-pressurized solidification zone maintained under conditions of saturation, temperature and pressure which control the release of water from the nascent extrudate and maintain the extrudate in plastic state.
  • the extrudate is solidified and remains in a state such that orientation stretching can be accomplished while the extrudate remains in the solidification zone.
  • the solidification zone is pressurized with saturated steam at a temperature which is about 10 to 30°C. below the minimum melt temperature of the polymer-water composition.
  • a preferred added processing stop in instances where a hydrophilic polymer composition is cmployed is to dry the extrudate in an oven under conditions specified by dry--bulb and wet-bulb temperatures. Generally, the dry-bulb will be in the range of 120-180°C. and the wet-bulb will be in the range of 60-100°C.
  • This drying step is preferably conducted before any uncontrolled or tensionless shrinkage of the extrudate has occurred. This drying step may be conducted on the extrudate in a frec-to-shrink condition or under tension.
  • Another preferred subsequent processing step is that of relaxing the extrudate in steam under pressure so as to achieve shrinkage of about 5-40%. This relaxing step should follow the drying step when such drying is effected.
  • the conventional spinnerette plate will contain a plurality of orifices and each orifice will have a counterbore to enable operative back pressure to be achieved.
  • Such spinnerettes should be of a material of construction, useful in melt spinning applications.
  • wire is inserted into the brifices of the spinnerette orifices to block a suitable portion thereof and contact the orifice surface at some point.
  • Wire of suitable-construction material and size is provided for insertion to provide the orifice modification desired.
  • a number of techniques for providing the wire modification of the orifices is possible. In one procedure, a single strand of suitable wire can be passed alternatively up and down through adjacent orifices until all orifices are modified and the wire ends are joined to secure the wire in position. Alternatively, such technique could be used in modifying with one wire strand only the orifices in one orifice row or in modifying only two adjacent orifices.
  • Another technique involves providing the wire in pre-cut and pre-shaped sections which then can be inserted through the counterbores to modify adjacent orifices while providing a secure fit. It is also possible to use more than one wire to block portions of one orifice and suitable securing procedures can involve multiple wires. Additional methods of securing the wires are possible and will readily occur to those skilled in the art.
  • the wires used to block a part of the spinnerette orifice may be of different size and shape depending upon the nature of blocking and the resulting fiber cross-section desired.
  • the wire should be of suitable size to fit within the orifice and leave sufficient opening for operability of the fiber spinning process.
  • Wire of round cross-section is most common and is useful for many desirable modifications of fiber cross-section. Additional shapes of useful wire cross-sections include triangular, square, rectangular, elliptical, hexagonal, and the like as well as irregular shapes. Additional variations arise from use of orifices of cross--sectional shapes other than round and placing different shaped wires therein. Combinations of several different shaped wires in an appropriate shaped orifice can lead to unusual fiber cross-sections providing maximization of those desirable properties for which shaped fiber cross-sections are desired.
  • Figure 1 represents a cross-sectional view of a portion of a conventional spinnerette plate showing two adjacent orifices and the countcr- bores associated therewith as well as top and bottom views of the orifices.
  • Figure 2 represents the same view as Figure 1 except that the orifices have been modified with wire in accordance with the present invention.
  • a round cross-section wire was employed which was bent to modify two orifices and was inserted in a manner in which the wire touches the wall of the orifice so as to provide an open-structure fiber cross-section. Spring tension in the bent wire keeps it securely placed in the two orifices.
  • Figure 3 shows enlarged boctom views of the modified orifices and Figure 4 shows the crescent-shaped cross-sections of the fiber obtained.
  • pins are designed so that they are of solid construction and occupy a fixed position within the counterbore.
  • the pins will be of such size as to enable extrusion composition to flow through the counterbores at operative back pressure to the orifice.
  • the pins will typically have an upper portion which fits into the counterbore and a lower portion which fits into the orifice.
  • the upper portion will be of suitable dimensions to assume a fixed position within the counterbore so that the lower portion remains suitably disposed in the orifice to provide the open structure fiber and enable adequate flow of extrusion composition through the counterbore and capillary.
  • the lower portion of the pin will be of suitable dimensions to fit within the orifice and contact a portion of the wall thereof while providing a desirable relationship between fiber wall and open structure therein.
  • Figure 5 represents a cross-section of a typical counterbore-orifice combination used in a typical spinnerette plate, as well as top and bottom views thereof.
  • the counterbore has a greatly enlarged diameter relative to that of the orifice and converges to the orifice diameter with proper sloping.
  • Figure 6 represents a side view of a preferred pin insert to provide open structure fibers when inserted within the counterbore-capillary combination as well as top and bottom views thereof.
  • the upper portion of the pin resembles a cylindrical rod which has been flattened along its length to provide clearance on two sides with the counterbore.
  • the top of the upper portion is leveled while the bottom thereof is tapered ' at a greater angle than the taper of the counterbore to connect the orifice and thus provides clearance for the extrusion material.
  • the bottom portion of the pin has a solid crcss--sectional shape that conforms to the shape of the orifice on one face which is positioned so as to contact a portion of the wall of the orifice and has additional shape to provide desirable open area within the extrudate issuing from the orifice and provide suitable fiber cross-sectional structure.
  • Figure 7 the insertion of the pin of Figure 6 in the counterbore-capillary combination of Figure 5 is shown in cross-section along with top and bottom views thereof.
  • Figure 8 is shown a variety of orifice shapes with various shapes of the lower portion of the insert pin that can be used in the process of the invention.
  • the pin shape may vary widely as may the orifice shape.
  • Figure 9 shows cross-sections of fiber obtained by the process of the invention using in the counterbore-capillary combinations pin inserts as shown in Figure 7.
  • Figure 10 represents a cross-section of a typical counterbore--capillary combination as well as top and bottom views thereof.
  • Figure 11 represents a side view of a preferred pin insert to provide hollow fibers when inserted within the counterbore--capillary combination as well as top and bottom views thereof.
  • the upper portion of the pin insert is to that of Figure G.
  • the lower portion is similar to that of Figure 6 but is centered and does not have conformity to the orifice wall since it does not contact such wall.
  • Figure 12 the insertion of the pin of Figure 11 in the counterbore-capillary combination of Figure 10 is shown in cross-section along with top and bottom views thereof. Clearance of the pin from the counterbore wall is shown in the top view and clearance between the tapers of the pin and counterbore are shown in the cross-section. In the bottom view the space between the two inner circles represents the wall thickness of the extrudate as spun.
  • Figure 13 is shown a variety of orifice shape with various shapes of the lower portion of the insert pin that can be used in providing hollow fibers.
  • the pin shape can vary widely as well as can the orifice shape.
  • Figure 14 represents a photomicrograph of fibers spun by the process of the invention using the pin modification shown in Figure 12, showing the hollow structure of fiber ends.
  • Figure 15 shows the greater wicking tendencies of hollow fibers comparied to solid fibers.
  • a conventional spinnerette plate having a plurality of orifices of 200 micron diameter was modified as shown in Figure 2 with 150 micron diameter wire resulting in free area remaining in the individual holes of about T3, 740 square microns. Modification was effected by cutting short lengths of the wire, about 1 inch, and feeding the ends through adjacent orifices from the counterbore side. The wire was then pulled tight which conformed the wire to the counterbore, cut to approximate length and filed to fit flush to the capillary exit.
  • the polymer had a kinematic molecular weight of 42,000.
  • the polymer, 86 parts, and water, 14 parts, were prepared as a fusion melt in an extruder at 160°C. and autogenous pressure and extruded through a spinnerette plate prepared as described above. Extrusion was directly into a steam-pressurized solidification chamber maintained at 13 pounds per square inch gauge with saturated steam and stretching was accomplished in the solidification chamber at a stretch ratio of 3.1 in a first stage and 8.3 in a second stage for a total stretch ratio of 25.7.
  • the resulting fiber of about 5 denier per filament had a cross-sectional shape as shown in Figure 4, which shape is termed crescent-shaped.
  • a conventional spinnerette plate having a plurality of orifices of 200 micron diameter was fitted with insert pins as shown in Figure 7.
  • Each pin was 175 microns in diameter resulting in free area remaining in the individual capillaries of about 7,363 square microns.
  • Example 1 The acrylonitrile polymer composition described in Example 1 was employed.
  • a mixture of 83 parts of the polymer, 17 parts water and 0.25 parts of a conventional glycol stearate type lubricant was converted into a fusion melt in an extruder at 175°C. and autogenous pressure and extruded through the . spinnerette plate modified as described above. Extrusion was directly into a steam-pressurized solidification chamber maintained at 11 pounds per square inch gauge with saturated steam. The filaments were stretched at a stretch ratio of 3 while in the solidification zone to give a fiber of about 4 0 denier per filament that had cross-sectional shape as shown in Figure 9 which shape is termed crescent-shaped.
  • a conventional spinnerette plate having a plurality of orifices of 300 micron diameter was fitted with insert pins as shown in Figure 12. Each pin was 175 micron in diameter resulting in free area remaining in the individual capillaries of about 46,633 square microns.
  • a mixture of 84.6 parts polymer, 15.4 parts water and 0.25 parts of a conventional glycol stearate type lubricant was converted to a fusion melt in an extruder at 167°C. and autogenous pressure and.extruded through the spinnerette plate prepared as described above directly into a steam--pressurized solidification chamber maintained at 13 pounds per square inch gauge with saturated steam.
  • the resulting filaments were stretched while in the solidification chamber at a stretch ratio of 9.2 in a first stage and 6.4 in a second stage of give a fiber of about 6.5 denier per filament.
  • the fiber was dried at 139°C. dry-bulb and 74°C. wet-bulb and steam-relaxed at 116°C.
  • the final denier fiber obtained was hollow as shown in Figure 14.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
EP79302908A 1979-02-21 1979-12-14 Procédé pour la fabrication de fibres de polymère d'acrylonitrile de structure creuse ou ouverte Withdrawn EP0014803A1 (fr)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
US1377379A 1979-02-21 1979-02-21
US1334279A 1979-02-21 1979-02-21
US13344 1979-02-21
US13346 1979-02-21
US06/013,346 US4261945A (en) 1979-02-21 1979-02-21 Method for providing shaped fiber
US06/013,353 US4278415A (en) 1979-02-21 1979-02-21 Apparatus for melt spinning hollow fibers
US06/013,344 US4316714A (en) 1979-02-21 1979-02-21 Apparatus for preparing open structure fibers
US13353 1979-02-21
US13773 1979-02-21
US13342 1993-04-05

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Publication Number Publication Date
EP0014803A1 true EP0014803A1 (fr) 1980-09-03

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EP79302908A Withdrawn EP0014803A1 (fr) 1979-02-21 1979-12-14 Procédé pour la fabrication de fibres de polymère d'acrylonitrile de structure creuse ou ouverte

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EP (1) EP0014803A1 (fr)
BR (1) BR8000588A (fr)
PL (1) PL222118A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0051203A1 (fr) * 1980-10-30 1982-05-12 Bayer Ag Procédé pour la fabrication des filaments et fibres creuses en polyacrylonitrile, filés à sec
EP0103743A2 (fr) * 1982-09-16 1984-03-28 American Cyanamid Company Fibre hydrophile, absorbant l'eau en polymère d'acrylonitrile
EP0232051A2 (fr) * 1986-01-21 1987-08-12 Clemson University Fibres de carbone de haute ténacité, filées par fusion et méthode pour leur préparation
CN108456943A (zh) * 2018-03-27 2018-08-28 蔡者 一种生产空心氨纶丝的喷头

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE914304C (de) * 1940-08-30 1954-07-01 Degussa Spinnduese zur Herstellung feiner kuenstlicher Hohlfaeden
FR2129887A3 (en) * 1971-03-18 1972-11-03 Sene Anciens Ets Plastic simulated hair - formed by extrusion and having crescent-shaped cross-section
GB1452400A (en) * 1973-02-05 1976-10-13 American Cyanamid Co Melt spinning of refractory polymers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE914304C (de) * 1940-08-30 1954-07-01 Degussa Spinnduese zur Herstellung feiner kuenstlicher Hohlfaeden
FR2129887A3 (en) * 1971-03-18 1972-11-03 Sene Anciens Ets Plastic simulated hair - formed by extrusion and having crescent-shaped cross-section
GB1452400A (en) * 1973-02-05 1976-10-13 American Cyanamid Co Melt spinning of refractory polymers

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0051203A1 (fr) * 1980-10-30 1982-05-12 Bayer Ag Procédé pour la fabrication des filaments et fibres creuses en polyacrylonitrile, filés à sec
EP0103743A2 (fr) * 1982-09-16 1984-03-28 American Cyanamid Company Fibre hydrophile, absorbant l'eau en polymère d'acrylonitrile
EP0103743A3 (en) * 1982-09-16 1986-02-19 American Cyanamid Company Hydrophilic, water-absorbing acrylonitrile polymer fiber
EP0232051A2 (fr) * 1986-01-21 1987-08-12 Clemson University Fibres de carbone de haute ténacité, filées par fusion et méthode pour leur préparation
EP0232051A3 (en) * 1986-01-21 1988-08-24 Clemson University High strength, melt spun carbon fibers and method for producing same
CN108456943A (zh) * 2018-03-27 2018-08-28 蔡者 一种生产空心氨纶丝的喷头

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PL222118A1 (fr) 1980-12-01
BR8000588A (pt) 1980-10-21

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