US2681265A - Spinning artificial filaments - Google Patents

Spinning artificial filaments Download PDF

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Publication number
US2681265A
US2681265A US62413A US6241348A US2681265A US 2681265 A US2681265 A US 2681265A US 62413 A US62413 A US 62413A US 6241348 A US6241348 A US 6241348A US 2681265 A US2681265 A US 2681265A
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US
United States
Prior art keywords
bath
spinning
dimethyl formamide
yarn
acrylonitrile
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.)
Expired - Lifetime
Application number
US62413A
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English (en)
Inventor
Howard M Hoxie
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.)
Akzo Nobel UK PLC
Original Assignee
American Viscose Corp
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
Application filed by American Viscose Corp filed Critical American Viscose Corp
Priority to US62413A priority Critical patent/US2681265A/en
Priority claimed from US123994A external-priority patent/US2622003A/en
Priority to GB30058/49A priority patent/GB663500A/en
Priority to BE492368D priority patent/BE492368A/xx
Priority to FR1000338D priority patent/FR1000338A/fr
Priority to DEA2000A priority patent/DE970677C/de
Priority to CH289952D priority patent/CH289952A/fr
Publication of US2681265A publication Critical patent/US2681265A/en
Application granted granted Critical
Anticipated expiration legal-status Critical
Assigned to WALTER E. HELLER & COMPANY, INC., A CORP. OF DEL. reassignment WALTER E. HELLER & COMPANY, INC., A CORP. OF DEL. AGREEMENT WHEREBY AETNA RELEASES AVTEX FROM ALL MORTAGES AND SECURITY INTERESTS IN SAID INVENTIONS AS OF JANUARY 11,1979, AND ASSIGNS TO ASSIGNEE THE ENTIRE INTEREST IN SAID MORTAGE AGREEMENT TO ASSIGNEE (SEE RECORDS FOR DETAILS). Assignors: AETNA BUSINESS CREDIT, INC., A CORP. OF N.Y., AVTEX FIBERS, INC, A CORP. OF NY, KELLOGG CREDIT CORP., A CORP. OF DEL.
Assigned to KELLOGG CREDIT CORPORATION A DE CORP. reassignment KELLOGG CREDIT CORPORATION A DE CORP. AGREEMENT WHEREBY SAID HELLER AND RAYONIER RELEASES ALL MORTGAGES AND SECURITY INTERESTS HELD BY AVTEX ON APRIL 28, 1978, AND JAN. 11, 1979, RESPECTIVELY AND ASSIGNS ITS ENTIRE INTEREST IN SAID MORT-AGAGE AGREEMENT TO ASSIGNEE (SEE RECORD FOR DETAILS) Assignors: AVTEX FIBERS INC., A NY CORP., ITT RAYONIER INCORPORATED, A DE CORP., WALTER E. HELLER & COMPANY, INC. A NY CORP.
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • 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
    • D01F6/40—Modacrylic fibres, i.e. containing 35 to 85% acrylonitrile

Definitions

  • This invention relates to the production of synthetic filaments or yarns comprising acrylonitrile polymers.
  • the patent literature contains statements to the effect that acrylonitrile polymers containing at least 85% by weight acrylonitrile in the polymer molecule can be formed into synthetic filaments or yarns by extruding a dimethyl formamide solution of the polymer into water at a temperature of 70 C., and stretching the filaments or yarns thus obtained to 6.3 times their original length.
  • an object of this invention to provide a new method of producing filaments and yarns from solutions of the acrylonitrile polymers in dimethyl formamide by a wet spinning procedure, whereby homogeneous filaments given a stretch of from 200 to 300%. merits withdrawn from the bath are coagulated so that they possess sufiicient plasticity to permit extension thereof under stretching, without rupture. It is known that stretching of the acrylonitrile polymer filaments efiects an improvement in the physical properties such as tenacity and resilience.
  • acrylonitrile polymer yarns produced by wet spinning a dimethyl iormamide solution of the polymer can be stretched at any the usual after the filaments have been withdrawn from the coaguwashing to remove the remaining solvent.
  • the filaments produced by the present method are generally stretched by 200 to 300% after they are withdrawn from the dimethyl formamide-water spinning bath prior to washing thereof.
  • This stretching can be accomplished at room temperature by passing the in dimethyl formamide and spun into a coagulating bath consisting of a water-dimethyl formamide mixture containing from 35 to volume per cent of dimethyl formamide in accordance
  • a coagulating bath consisting of a water-dimethyl formamide mixture containing from 35 to volume per cent of dimethyl formamide in accordance
  • the coagulating baths of the present invention are particularly useful in the spinning of dimethyl formamide solutions of acrylonitrile polymers containing at least 65% by weight acrylonitrile in the polymer molecule and having a molecular weight of 15,000 to 250,000 as determined by specific viscosity data using the standinger equation, since those polymers are suitable for the production of filaments and yarns which may be used for general textile purposes.
  • the advantages of the method of this invention are numerous and important. Spinning can be performed at room temperature, thus eliminating the need for means for heating the bath. Once the spinning operation has been initiated the only expedient required in order to maintain the composition of the spinning bath constant is the periodical or continuous addition of the calculated amounts of plain water, so that expensive bath recirculating and regenerating systems are entirely avoided. In addition, the solvent recovery procedure is simple since in order to recover the solvent, it is only necessary to distill ofi the water, which can be accomplished rapidly and at comparatively little exing bath consisting of 30%
  • the acrylonitrile polymers which are formed into filaments or yarns in accordance with the invention may be produced by any suitable polymerization procedure, e. g., by emulsion, suspension, bulk, or solution polymerization procedures.
  • Example I 13% dimethyl formamide solution of a copolymer which was prepared by the solution copoiymerization of acrylonitrile and 2-viny1 pyridine and which contained 15% of 2-vinyl pyridine by weight in the polymer molecule was extruded through a spinneret having 44 holes each having a diameter of 4 mils into a coagulatwater and 70% dimethyl formamide, by volume, at 23 C. After a bath travel of 9.5 inches, at a speed of 260 inches/min. the yarn was withdrawn from the bath and stretched 220% between two pairs of canted godets. The yarn was then washed with water, collected, and dried in air. It had a dry tenacity of 1.3 gms. per denier; dry extensibility, 25%. The yarn was then stretched 350% by passing it through a tube heated to 175 C. at a speed of 70 it./min. The resulting yarn had the following characteristics:
  • the concentration of dimethyl iormamide in the bath must be maintained at from to 80% by volume throughout the entire spinning operation.
  • the spinning bath comprises a mixture of, say, 67% dimethyl formamide and 33% water
  • amounts of dimethyl formamide greater than are do not have to be added, and it is necessary to add only a liter of water to the bath, for each liter of dimethyl formamide pumped in as dope, in order to maintain the necessary bath composition.
  • the filaments or yarns obtained by the present method compare favorably with, and in many cases are superior to, the yarns which can be obtained by spinning the solutions of the acrylonitrile polymers into organic solvents such as glycerol, or into salt solutions.
  • the tenacity and extensibility of the final heatstretched yarn are essentially the same as those of a yarn obtained by spinning the dimethyl formamide solution into glycerol or calcium chloride solution, at elevated temperatures, in spite of the fact that, prior to the final heating and stretching step, the tensile strength of the yarn was somewhat lower than thatv of yarns obtained when organic solvents or salt solutions were used to effect the coagulation.
  • the yarn produced by the present method exhibits excellent stability at high temperature, is not cemented, and can be dyed by means of wool dyes of the strong acid type, such as Wool Fast Scarlet.
  • the yarn is substantially free from voids when examined under a microscope which magnifies the cross section 500 times.
  • Example II A 15 solution of polyacrylonitrile in dimethyl formamide was extruded through a O-holeB-mil jet into a bath comprising 32% water and 68% dimethyl formamide by volume. After an immersion of five inches (speed- 260 in./min.) the yarn was withdrawn..from the bath, stretched 200%, washed in water, and dried.
  • This yarn had a tensile strength of 1.2 g./d. and an extensibility of 24%. 300% stretch was applied to the yarn duringits passage through a tube heated to C. The tenacity of. the heat-stretched yarn was i5 ms/denier. After relaxation in boiling water the tenacity was 3.82 gms./denier, the extensibility 13%, and the denier 74.
  • Example HI A copolymer containing 17% acrylamide and 83% acrylonitrile by weight was prepared by water solution polymerization. :A 12% solution Of this p l m in dim thyl formamide w s X- 2.
  • a method as in claim 1, wherein the acry- (speed 2-60 iii/mind the yarn was withdrawn 5 lonitrile polymer is a oopolymer of acrylonitrile from the bath, stretched 200%, washed, and and 2-viny1 pyridine containing by weight dried.
  • the yarn so obtained had a tenacity of of acrylonitrile in the polymer molecule.
  • a method for the production 01 yarns from 0 A method as in 0391111 1, wherein the a ya solution of a fiber-forming acrylonitrile polylollitlilo P ymer is a oopolymer of acrylonitrile mgr containing in th pglymer molecule, at least and an acrylic acid ester containing at least 65% 65 of acrylonitrile in dimethyl formamide whi h by weight of acrylonitrile in the polymer molecule.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Artificial Filaments (AREA)
US62413A 1948-11-27 1948-11-27 Spinning artificial filaments Expired - Lifetime US2681265A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US62413A US2681265A (en) 1948-11-27 1948-11-27 Spinning artificial filaments
GB30058/49A GB663500A (en) 1948-11-27 1949-11-23 Method of making shaped articles of an acrylonitrile polymer
BE492368D BE492368A (de) 1948-11-27 1949-11-24
FR1000338D FR1000338A (fr) 1948-11-27 1949-11-24 Procédé de filage de polymères de l'acrylonitrile
DEA2000A DE970677C (de) 1948-11-27 1950-06-21 Verfahren zur Herstellung von kuenstlichen Gebilden aus acrylnitrilhaltigen Polymerisationsprodukten
CH289952D CH289952A (fr) 1948-11-27 1950-07-13 Procédé de fabrication de produits extrudés à partir de polymères ou copolymères d'acrylonitrile.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US62413A US2681265A (en) 1948-11-27 1948-11-27 Spinning artificial filaments
US123994A US2622003A (en) 1949-10-27 1949-10-27 Method of making shaped articles of an acrylonitrile polymer

Publications (1)

Publication Number Publication Date
US2681265A true US2681265A (en) 1954-06-15

Family

ID=26742228

Family Applications (1)

Application Number Title Priority Date Filing Date
US62413A Expired - Lifetime US2681265A (en) 1948-11-27 1948-11-27 Spinning artificial filaments

Country Status (6)

Country Link
US (1) US2681265A (de)
BE (1) BE492368A (de)
CH (1) CH289952A (de)
DE (1) DE970677C (de)
FR (1) FR1000338A (de)
GB (1) GB663500A (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2784135A (en) * 1954-04-30 1957-03-05 American Cyanamid Co Process for the manufacture of polyacrylonitrile films and laminates
US3019077A (en) * 1960-02-09 1962-01-30 Union Carbide Corp Crystalline isotactic polystyrene fibers
US3066008A (en) * 1959-03-09 1962-11-27 Courtaulds Ltd Process for producing fibers from copolymers of acrylonitrile and vinylidene chloride
US3180913A (en) * 1962-03-19 1965-04-27 Monsanto Co Method for producing high shrinkage fibers

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE512121A (de) * 1951-06-18
BE521584A (de) * 1952-08-05
DE1069326B (de) * 1952-09-16 1959-11-19
DE1057285B (de) * 1955-08-18 1959-05-14 Dr Paul Halbig Verfahren zur Herstellung von Faeden oder Fasern aus Polymerisaten
GB937685A (en) * 1960-08-11 1963-09-25 Tohu Rayon Kabushiki Kaisha Method for producing filamentary tows from polymers and co-polymers of acrylonitrile
GB1002767A (en) * 1960-09-24 1965-08-25 Toho Rayon Kk Method for the manufacture of polyacrylonitrile
US3111366A (en) * 1961-09-01 1963-11-19 Japan Exlan Co Ltd Method for producing high shrinking acrylonitrile polymer fibres
GB2211462A (en) * 1987-10-23 1989-07-05 Joseph Crichton Duncan Fibre materials

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2236061A (en) * 1937-05-27 1941-03-25 Du Pont Method of making films, threads, and the like
US2360406A (en) * 1940-06-21 1944-10-17 Celanese Corp Manufacture of artificial filaments, films, and like materials
US2404723A (en) * 1944-11-10 1946-07-23 Du Pont Preparation of polymer solutions
US2404714A (en) * 1942-06-17 1946-07-23 Du Pont Polymer products
US2420565A (en) * 1943-02-20 1947-05-13 Carbide & Carbon Chem Corp Synthetic textile articles

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE237599C (de) *
DE177957C (de) *
FR426436A (fr) * 1911-02-16 1911-07-06 Heyden Chem Fab Nouveau procédé de fabrication de la soie artificielle et autres produits formés d'éthers d'acides gras de la cellulose, dénommés "celluloses acidylées"
GB179234A (en) * 1921-01-04 1922-05-04 British Cellulose And Chemical Improvements relating to the manufacture of artificial filaments, threads and films
US1560965A (en) * 1923-05-17 1925-11-10 Meigs Bassett & Slaughter Inc Process of spinning artificial silk and other filaments from cellulose materials
GB239622A (en) * 1924-06-20 1925-09-17 Courtaulds Ltd Improvements in the manufacture of threads, or filaments, from cellulose esters
BE450153A (de) * 1942-04-13
DE897313C (de) * 1951-03-30 1953-11-19 Siegfried Hoffmann-Daimler Kniegelenk fuer Oberschenkelkunstbeine

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2236061A (en) * 1937-05-27 1941-03-25 Du Pont Method of making films, threads, and the like
US2360406A (en) * 1940-06-21 1944-10-17 Celanese Corp Manufacture of artificial filaments, films, and like materials
US2404714A (en) * 1942-06-17 1946-07-23 Du Pont Polymer products
US2420565A (en) * 1943-02-20 1947-05-13 Carbide & Carbon Chem Corp Synthetic textile articles
US2404723A (en) * 1944-11-10 1946-07-23 Du Pont Preparation of polymer solutions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2784135A (en) * 1954-04-30 1957-03-05 American Cyanamid Co Process for the manufacture of polyacrylonitrile films and laminates
US3066008A (en) * 1959-03-09 1962-11-27 Courtaulds Ltd Process for producing fibers from copolymers of acrylonitrile and vinylidene chloride
US3019077A (en) * 1960-02-09 1962-01-30 Union Carbide Corp Crystalline isotactic polystyrene fibers
US3180913A (en) * 1962-03-19 1965-04-27 Monsanto Co Method for producing high shrinkage fibers

Also Published As

Publication number Publication date
FR1000338A (fr) 1952-02-11
CH289952A (fr) 1953-04-15
GB663500A (en) 1951-12-19
DE970677C (de) 1958-10-16
BE492368A (de) 1949-12-15

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Legal Events

Date Code Title Description
AS Assignment

Owner name: KELLOGG CREDIT CORPORATION A DE CORP.

Free format text: AGREEMENT WHEREBY SAID HELLER AND RAYONIER RELEASES ALL MORTGAGES AND SECURITY INTERESTS HELD BY AVTEX ON APRIL 28, 1978, AND JAN. 11, 1979, RESPECTIVELY AND ASSIGNS ITS ENTIRE INTEREST IN SAID MORT-AGAGE AGREEMENT TO ASSIGNEE;ASSIGNORS:WALTER E. HELLER & COMPANY, INC. A NY CORP.;ITT RAYONIER INCORPORATED, A DE CORP.;AVTEX FIBERS INC., A NY CORP.;REEL/FRAME:003959/0350

Effective date: 19800326

Owner name: WALTER E. HELLER & COMPANY, INC., A CORP. OF DEL.

Free format text: AGREEMENT WHEREBY AETNA RELEASES AVTEX FROM ALL MORTAGES AND SECURITY INTERESTS IN SAID INVENTIONS AS OF JANUARY 11,1979, AND ASSIGNS TO ASSIGNEE THE ENTIRE INTEREST IN SAID MORTAGE AGREEMENT TO ASSIGNEE;ASSIGNORS:AETNA BUSINESS CREDIT, INC., A CORP. OF N.Y.;AVTEX FIBERS, INC, A CORP. OF NY;KELLOGG CREDIT CORP., A CORP. OF DEL.;REEL/FRAME:003959/0250

Effective date: 19800326