US2788563A - New filaments of polymers or copolymers having a basis of acrylonitrile and process for their manufacture - Google Patents

New filaments of polymers or copolymers having a basis of acrylonitrile and process for their manufacture Download PDF

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US2788563A
US2788563A US326134A US32613452A US2788563A US 2788563 A US2788563 A US 2788563A US 326134 A US326134 A US 326134A US 32613452 A US32613452 A US 32613452A US 2788563 A US2788563 A US 2788563A
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Prior art keywords
acrylonitrile
basis
polymers
filament
filaments
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US326134A
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Stuchlik Rene Emile Fernand
Rosset Jean
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Crylor SA
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Crylor SA
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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
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247—Discontinuous hollow structure or microporous structure
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2973—Particular cross section
    • Y10T428/2975—Tubular or cellular

Definitions

  • the present invention relates to the manufacture of an improved type of filaments and other extruded articles from polymers and copolymers of acrylonitrile.
  • polymers having a basis of acrylonitrile may be spun from solutions in solvents having a basis of dimethylformamide and that these solutions can be extruded in evaporative medium at an elevated temperature in order to obtain textile articles such as filaments, threads, artificial horse hairs, tows, films, foils and analogous materials.
  • the walls of the spinning chamber are heated to a temperature of at least 100 C. and sometimes as high as 400 C.
  • filaments having a transverse section having an indented contour and in general having a porous structure which diminishes their density, all these characteristics being novel and according to the literature not being possessed by fibres having a basis of acrylonitrile polymers already known. It is known that the fibres having a basis of polyacrylonitrile actually known have a flattened transverse section in the form of dog bones or dumb bells (Rayon and Synthetic Textiles, 30, p. 91, April 1949) or of elliptic form (Textile Research Department American Viscose Corporation: Properties of Chemstrand Acrylic Fibre and Suggestions for Processing, March 1951, p. 2). In both these cases the surface of the filaments is perfectly smooth and without roughness.
  • the temperature at which the solution is extruded can vary within large limits and it is sometimes desirable to extrude at a temperature attaining 175 or even 200 C.
  • the process according to the present invention can be carried out by using either an evaporative chamber swept 2,788,563 Patented Apr. '16, 1957 by a current of air or by an arrangement similar to that described in U. S. Patent No. 2,472,842.
  • the annexed drawing shows a cross-section of the filament according to the present invention.
  • the filament is shown in the drawing as containing small irregular cellules 10 randomly distributed and formed as described herein. Certain of the cellules lie at the surface and form an indented contour for the filament.
  • Example 1 A polymer of acrylonitrile of specific viscosity 0.290 for which the minimum concentration calculated as above is is used. A composition consisting of 34.5 parts of this polymer and 65.5 parts of dimethylformamide is extruded through a spinneret of 32 holes of 0.15 mm. at a temperature of 128 C. into an evaporative chamber of which the walls are at C. and which is swept through by an air current at the same temperature produced by as piration applied to the base of the evaporative chamber.
  • the thread obtained has a titre of 800 decitex (720 deniers); it is stretched in the known fashion.
  • the density of these filaments determined at 20 C. by the method of floatation in an organic liquid and then measuring the density of this mixture in a pyknometer at 20 is 1.125. Their resistance to breaking is 3.5 g. per denier.
  • Example 2 A composition consisting of 36.9 parts of the same polymer as that described in Example 1 and 63.1 parts of dimethylformamide is heated to C. and extruded through a spinneret of 32 holes of 0.13 mm. diameter into a spinning apparatus of the type described in British Patent No. 605,579, the evaporating chamber being maintained at 55 C. and the heating chamber at 65 C.
  • the thread gathered up on emerging from the cell is stretched in the known manner.
  • the transverse section of the thread resembles that of the thread obtained according to Example 1.
  • Example 3 A polymer of specific viscosity 0.310 is used and it is spun under the conditions described in Example 1 of copending application 221,119, filed April 4, 1951, and now abandoned, except that the concentration used is 32%. Filaments having an indented cross section analogous to those of Examples 1 and 2 are obtained.
  • a synthetic filament consisting of a polymer of acrylonitrllc, said filament having in transverse section an indented contour and having a cellular structure throughout its length, the cellules containing no solid particles and having a very small cross-section in relation. to thatof the filament and being irregularly dispersed in themass of the filament.
  • a synthetic filament consisting of a polymer of acrylonitrile according to claim 1, the density of which is .”lowergthan. 1.13.

Description

April 1 1957 R. E. F. STUCHLIK ET AL 2,788,563
NEW FI ENTS OF POLYMERS OR COPOLYMERS HAVING A BASIS OF A LONITRILEF D PROCESS FOR THEIR MANUFACTURE d. Dec
- INVENTO lPf/VE f. 5' STUCf/L/ s EORNEY NEW FILAMENTS F POLYMERS OR. COPOLY- MERS HAVING A BASIS 0F ACRYLONITRILE AND PROCESS FOR THEIR MANUFACTURE Ren Emile Fenland Stuchlik, Viileurhanne, and Jean Rosset, Lyon, France, assignors, by mesa-e assignments, to Crylor, Paris, France, a corporation of France Application December 15, 1952, Serial No. 326,134
Claims priority, application France May 17, 1952 3 Claims. (CI. 28-82) The present invention relates to the manufacture of an improved type of filaments and other extruded articles from polymers and copolymers of acrylonitrile.
It is known that polymers having a basis of acrylonitrile may be spun from solutions in solvents having a basis of dimethylformamide and that these solutions can be extruded in evaporative medium at an elevated temperature in order to obtain textile articles such as filaments, threads, artificial horse hairs, tows, films, foils and analogous materials. According to these processes the walls of the spinning chamber are heated to a temperature of at least 100 C. and sometimes as high as 400 C.
It has now been found and this is the object of the present invention, that in a process for dry spinning by starting from solutions of polymers or copolymers having a basis of acrylonitrile in a solvent having a high boiling point and in particular those having a basis of dimethylformamide one can obtain filaments and other extruded articles having a new type of structure on condition that they are extruded at a temperature at least equal to 120 and that the solution has a concentration, expressed in parts of polymer or copolymer per 100 parts of the solution which is greater than the value 15 W empn 1cally determlned where sp represents the specific viscosity of the polymer in the solvent in question determined at a concentration of 0.2% and at a temperature of 20.
Under these conditions filaments are obtained having a transverse section having an indented contour and in general having a porous structure which diminishes their density, all these characteristics being novel and according to the literature not being possessed by fibres having a basis of acrylonitrile polymers already known. It is known that the fibres having a basis of polyacrylonitrile actually known have a flattened transverse section in the form of dog bones or dumb bells (Rayon and Synthetic Textiles, 30, p. 91, April 1949) or of elliptic form (Textile Research Department American Viscose Corporation: Properties of Chemstrand Acrylic Fibre and Suggestions for Processing, March 1951, p. 2). In both these cases the surface of the filaments is perfectly smooth and without roughness.
It has furthermore most surprisingly been found that it is possible under the working conditions indicated above to extrude solutions in an evaporative atmosphere of which the temperature is lower than 100, for example in certain cases 40 or even 30, which was completely unexpected owing to the fact that one is concerned with the evaporation of solvents having a high boiling point as for example dimethylformamide which boils at 153.
The temperature at which the solution is extruded can vary within large limits and it is sometimes desirable to extrude at a temperature attaining 175 or even 200 C.
The process according to the present invention can be carried out by using either an evaporative chamber swept 2,788,563 Patented Apr. '16, 1957 by a current of air or by an arrangement similar to that described in U. S. Patent No. 2,472,842.
The production of filaments having an indented cross section is of great technical value as it is known to everybody versed in the art that such a section is very much better adapted to textile working than a fiat section or one of the dog bone type. Furthermore-the employment of evaporative chambers havinga lower temperature constitutes a very valuable feature from the economic point of view.
The annexed drawing shows a cross-section of the filament according to the present invention.
The filament is shown in the drawing as containing small irregular cellules 10 randomly distributed and formed as described herein. Certain of the cellules lie at the surface and form an indented contour for the filament.
The following examples are given to illustrate how the invention can be carried out but are not limitat-ive. The parts denote parts by weight.
Example 1 A polymer of acrylonitrile of specific viscosity 0.290 for which the minimum concentration calculated as above is is used. A composition consisting of 34.5 parts of this polymer and 65.5 parts of dimethylformamide is extruded through a spinneret of 32 holes of 0.15 mm. at a temperature of 128 C. into an evaporative chamber of which the walls are at C. and which is swept through by an air current at the same temperature produced by as piration applied to the base of the evaporative chamber.
The thread obtained has a titre of 800 decitex (720 deniers); it is stretched in the known fashion.
Filaments are obtained having the transverse section shown by the accompanying drawing in which the indented contour of the threads and the numerous alveoles are clearly shown.
The density of these filaments, determined at 20 C. by the method of floatation in an organic liquid and then measuring the density of this mixture in a pyknometer at 20 is 1.125. Their resistance to breaking is 3.5 g. per denier.
Example 2 A composition consisting of 36.9 parts of the same polymer as that described in Example 1 and 63.1 parts of dimethylformamide is heated to C. and extruded through a spinneret of 32 holes of 0.13 mm. diameter into a spinning apparatus of the type described in British Patent No. 605,579, the evaporating chamber being maintained at 55 C. and the heating chamber at 65 C.
The thread gathered up on emerging from the cell is stretched in the known manner. The transverse section of the thread resembles that of the thread obtained according to Example 1.
Example 3 A polymer of specific viscosity 0.310 is used and it is spun under the conditions described in Example 1 of copending application 221,119, filed April 4, 1951, and now abandoned, except that the concentration used is 32%. Filaments having an indented cross section analogous to those of Examples 1 and 2 are obtained.
What we claim is:
1. A synthetic filament consisting of a polymer of acrylonitrllc, said filament having in transverse section an indented contour and having a cellular structure throughout its length, the cellules containing no solid particles and having a very small cross-section in relation. to thatof the filament and being irregularly dispersed in themass of the filament.
2. A synthetic filament consisting of a polymer of acrylonitrile according to claim 1, the density of which is ."lowergthan. 1.13.
3; "A'synthetic filament consisting of a polymer of acrylonitrile according to claim 1 having a breaking strength in excess 'of 3 grams per denier.
References Cited in the file of this patent UNITED STATES PATENTS

Claims (1)

1. A SYNTHETIC FILAMENT CONSISTING OF A POLYMER OF ACRYLONITRILE, SAID FILAMENT HAVING IN TRANSVERSE SECTION AN INDENTED CONTOUR AND HAVING A CELLULAR STRUCTURE THROUGHOUT ITS LENGTH, THE CELLULES CONTAINING NO SOLID PARTICLES AND HAVING A VERY SMALL CROSS-SECTION IN RELATION TO THAT OF THE FILAMENT AND BEING IRREGULARLY DISPERSED IN THE MASS OF THE FILAMENT.
US326134A 1952-05-17 1952-12-15 New filaments of polymers or copolymers having a basis of acrylonitrile and process for their manufacture Expired - Lifetime US2788563A (en)

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FR1061479X 1952-05-17

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BE (1) BE512490A (en)
CH (1) CH302492A (en)
DE (1) DE1061479B (en)
FR (2) FR1056662A (en)
GB (1) GB730902A (en)
NL (2) NL170861B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2948048A (en) * 1955-11-04 1960-08-09 Dow Chemical Co Oriented thermoplastic filament having a satiny appearance
US3047456A (en) * 1959-08-10 1962-07-31 Monsanto Chemicals Manufacture of paper products from fibers wet spun from polymer blends
US3047455A (en) * 1959-03-13 1962-07-31 Monsanto Chemicals Paper manufacture from synthetic non-cellulosic fibers
US3088188A (en) * 1960-01-04 1963-05-07 Monsanto Chemicals Manufacture of shaped objects of acrylonitrile polymer by wet spinning
US3322611A (en) * 1962-10-19 1967-05-30 Du Pont Porous fibers and processes of preparing same
US3889038A (en) * 1953-05-04 1975-06-10 Sol B Wiczer Coated filament and method of forming same
DE3210625A1 (en) * 1981-04-03 1982-10-28 Mitsubishi Rayon Co., Ltd., Tokyo ACRYLIC FIBER WITH IRREGULAR SECTION AND METHOD FOR THE PRODUCTION THEREOF
US4515859A (en) * 1982-09-16 1985-05-07 American Cyanamid Company Hydrophilic, water-absorbing acrylonitrile polymer fiber
US5344711A (en) * 1988-12-28 1994-09-06 Asahi Kasei Kogyo Kabushiki Kaisha Acrylic synthetic fiber and process for preparation thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2706522A1 (en) * 1977-02-16 1978-08-17 Bayer Ag HYDROPHILIC ACRYLIC FIBERS WITH IMPROVED GRINDABILITY
DE2736065A1 (en) * 1977-08-10 1979-02-22 Bayer Ag PROCESS FOR MANUFACTURING HYDROPHILIC FIBERS AND FIBERS BY THE DRY-THEN-WET SPINNING PROCESS

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2107668A (en) * 1930-07-22 1938-02-08 Du Pont Method of producing artificial silk
US2200946A (en) * 1937-09-16 1940-05-14 Bloch Godfrey Fabric-making material
US2339950A (en) * 1942-12-18 1944-01-25 Grand Rapids Fibre Cord Compan Cord or padding material
US2404714A (en) * 1942-06-17 1946-07-23 Du Pont Polymer products
US2472842A (en) * 1942-08-25 1949-06-14 Rhodiaceta Apparatus and method of dry spinning vinyl compounds
US2476293A (en) * 1944-10-03 1949-07-19 American Viscose Corp Artificial fiber
US2571457A (en) * 1950-10-23 1951-10-16 Ladisch Rolf Karl Method of spinning filaments
US2607751A (en) * 1948-03-02 1952-08-19 Du Pont Acrylonitrile polymer dissolved in a dicarboxylic acid anhydride
US2612679A (en) * 1950-10-23 1952-10-07 Ladisch Rolf Karl Filaments containing fillers

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB585368A (en) * 1943-07-28 1947-02-05 Du Pont Improved yarns, films, tubing and like articles of acrylonitrile polymer
US2585499A (en) * 1948-07-29 1952-02-12 Du Pont Production of shaped articles from acrylonitrile polymers

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2107668A (en) * 1930-07-22 1938-02-08 Du Pont Method of producing artificial silk
US2200946A (en) * 1937-09-16 1940-05-14 Bloch Godfrey Fabric-making material
US2404714A (en) * 1942-06-17 1946-07-23 Du Pont Polymer products
US2472842A (en) * 1942-08-25 1949-06-14 Rhodiaceta Apparatus and method of dry spinning vinyl compounds
US2339950A (en) * 1942-12-18 1944-01-25 Grand Rapids Fibre Cord Compan Cord or padding material
US2476293A (en) * 1944-10-03 1949-07-19 American Viscose Corp Artificial fiber
US2607751A (en) * 1948-03-02 1952-08-19 Du Pont Acrylonitrile polymer dissolved in a dicarboxylic acid anhydride
US2571457A (en) * 1950-10-23 1951-10-16 Ladisch Rolf Karl Method of spinning filaments
US2612679A (en) * 1950-10-23 1952-10-07 Ladisch Rolf Karl Filaments containing fillers

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3889038A (en) * 1953-05-04 1975-06-10 Sol B Wiczer Coated filament and method of forming same
US2948048A (en) * 1955-11-04 1960-08-09 Dow Chemical Co Oriented thermoplastic filament having a satiny appearance
US3047455A (en) * 1959-03-13 1962-07-31 Monsanto Chemicals Paper manufacture from synthetic non-cellulosic fibers
US3047456A (en) * 1959-08-10 1962-07-31 Monsanto Chemicals Manufacture of paper products from fibers wet spun from polymer blends
US3088188A (en) * 1960-01-04 1963-05-07 Monsanto Chemicals Manufacture of shaped objects of acrylonitrile polymer by wet spinning
US3322611A (en) * 1962-10-19 1967-05-30 Du Pont Porous fibers and processes of preparing same
DE3210625A1 (en) * 1981-04-03 1982-10-28 Mitsubishi Rayon Co., Ltd., Tokyo ACRYLIC FIBER WITH IRREGULAR SECTION AND METHOD FOR THE PRODUCTION THEREOF
US4515859A (en) * 1982-09-16 1985-05-07 American Cyanamid Company Hydrophilic, water-absorbing acrylonitrile polymer fiber
US5344711A (en) * 1988-12-28 1994-09-06 Asahi Kasei Kogyo Kabushiki Kaisha Acrylic synthetic fiber and process for preparation thereof

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BE512490A (en)
NL170861B (en)
GB730902A (en) 1955-06-01
CH302492A (en) 1954-10-31
FR1056662A (en) 1954-03-01
DE1061479B (en) 1959-07-16
FR64012E (en) 1955-10-17
NL97529C (en)

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