US2648592A - Removing salts from polyacrylonitrile - Google Patents

Removing salts from polyacrylonitrile Download PDF

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Publication number
US2648592A
US2648592A US228759A US22875951A US2648592A US 2648592 A US2648592 A US 2648592A US 228759 A US228759 A US 228759A US 22875951 A US22875951 A US 22875951A US 2648592 A US2648592 A US 2648592A
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US
United States
Prior art keywords
salt
per cent
fibers
article
salts
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
US228759A
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English (en)
Inventor
George W Stanton
Theodore B Lefferdink
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.)
Dow Chemical Co
Original Assignee
Dow Chemical 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
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Priority to US228759A priority Critical patent/US2648592A/en
Priority to US319182A priority patent/US2648593A/en
Priority to DED15083A priority patent/DE1044346B/de
Priority to FR1082729D priority patent/FR1082729A/fr
Priority to CH326492D priority patent/CH326492A/de
Priority to NL178428A priority patent/NL81838C/xx
Priority to GB15167/53A priority patent/GB732008A/en
Application granted granted Critical
Publication of US2648592A publication Critical patent/US2648592A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D05—SEWING; EMBROIDERING; TUFTING
    • D05B—SEWING
    • D05B1/00—General types of sewing apparatus or machines without mechanism for lateral movement of the needle or the work or both
    • D05B1/08—General types of sewing apparatus or machines without mechanism for lateral movement of the needle or the work or both for making multi-thread seams
    • D05B1/18—Seams for protecting or securing edges
    • D05B1/20—Overedge seams
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S424/00—Drug, bio-affecting and body treating compositions
    • Y10S424/06—Chelate

Definitions

  • This invention relates to a method for removing metal salts from polymeric films or filaments composed chiefly of acrylonitrile. It is concerned particularly with such a method for minimizing the salt content of fibers of polyacrylonitrile which have been spun from aqueous saline solutions of the polymer.
  • the desired salt removal is effected after the fibers have been coagulated and stretched in the desired manner.
  • the fiber forming process may entail coagulation of the polymer solution as it is extruded into water, acid or dilute brine, followed by cold stretching or hot stretching, or both, with following or in tervening treatments of the fiber with water or other coagulant to reduce the salt content to a value usually between 2 and 5 per cent.
  • Such an amount of residual salt is not detrimental during a subsequent drying operation, though the presence of over 5 per cent salt usually causes the fibers to fuse when heated to C. or so during drying.
  • a much lower salt content is required when the fibers are to be used in making woven or knit goods which may be worn in contact with sensitive skins.
  • an agent capable of forming a complex with the metal ion or ions of the salt or salts in the fibers include chelating agents and other metal sequestering agents.
  • the preferred agents include the alkali metal salts of ethylene diamine tetraacetic acid and the alkali metal salts of the polyphosphoric acids.
  • the commoner polyvalent metal ions which may be present in the fibers, including those of zinc, calcium, magnesium, tin, aluminum, antimony, arsenic, bismuth, and others.
  • the treatment is carried out while the fibers are still wet from a prior step in the process, as it has been found that dried fibers containing salt lose it very slowly to a solution of one of the complex-forming or sequestering agents, as they do to plain water.
  • a solution was prepared consisting of 7 per cent by weight of polyacrylonitrile, having a Staudinger molecular weight of 76,100, 31.6 per cent zinc chloride, 23.2 per cent calcium chloride and 38.2 per cent water.
  • This solution having a viscosity of 300 poises,-was extruded through a 100-hole spinneret, having openings 0.0025 inch in diameter, into Water at C.
  • the socoagulated tow of filaments was cold-stretched in air 1.8 times its initial length, and was hotstretched in wet steam 2.4 times its cold-stretched length.
  • the tow of stretched fibers was washed for 10 seconds with water. Analysis of the product at various stages in the process to this point showed the following values:
  • the tow was dried to l per cent moisture content, and had 2.9 per cent zinc chloride and 1.7 per cent calcium chloride. Another portion of the wet tow was soaked in water for one minute, and, when dried, had 0.35 per cent zinc chloride and 0.22 per cent calcium chloride. When, however, the wet tow was led through a 10 per cent solution in water at pH 8 of the tetrasodium salt of ethylene diamine tetracetic acid for one minute, the subsequently dried fibers had 0.04 per cent zinc chloride and 0.08 per cent calcium chloride. By way of contrast, if the tow was dried before being exposed to the solution of sequestering or chelating agent, soaking in such a solution for 18 hours still left over 1 per cent total salt in the redried fibers.
  • the invention has been illustrated with respect to the treatment of fibers produced by wet spinning of aqueous saline solutions of polyacrylonitrile. It is applicable as well to the removal of salts from such other products as films made by extrusion and coagulation of such saline solutions.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Artificial Filaments (AREA)
US228759A 1951-05-28 1951-05-28 Removing salts from polyacrylonitrile Expired - Lifetime US2648592A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US228759A US2648592A (en) 1951-05-28 1951-05-28 Removing salts from polyacrylonitrile
US319182A US2648593A (en) 1951-05-28 1952-10-27 Removing salts from polyacrylonitrile
DED15083A DE1044346B (de) 1951-05-28 1953-05-18 Verfahren zur Herstellung von Gebilden aus Polyacrylnitril
FR1082729D FR1082729A (fr) 1951-05-28 1953-05-18 Perfectionnements relatifs au procédé de fabrication d'articles mis en forme
CH326492D CH326492A (de) 1951-05-28 1953-05-19 Verfahren zur Herstellung geformter Erzeugnisse, wie Fäden oder Filme, aus Acrylnitrilpolymeren
NL178428A NL81838C (pm) 1951-05-28 1953-05-19
GB15167/53A GB732008A (en) 1951-05-28 1953-06-01 Improvements in or relating to the purification of polyacrylonitrile filaments and films

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US228759A US2648592A (en) 1951-05-28 1951-05-28 Removing salts from polyacrylonitrile
US319182A US2648593A (en) 1951-05-28 1952-10-27 Removing salts from polyacrylonitrile
GB15167/53A GB732008A (en) 1951-05-28 1953-06-01 Improvements in or relating to the purification of polyacrylonitrile filaments and films

Publications (1)

Publication Number Publication Date
US2648592A true US2648592A (en) 1953-08-11

Family

ID=32303003

Family Applications (2)

Application Number Title Priority Date Filing Date
US228759A Expired - Lifetime US2648592A (en) 1951-05-28 1951-05-28 Removing salts from polyacrylonitrile
US319182A Expired - Lifetime US2648593A (en) 1951-05-28 1952-10-27 Removing salts from polyacrylonitrile

Family Applications After (1)

Application Number Title Priority Date Filing Date
US319182A Expired - Lifetime US2648593A (en) 1951-05-28 1952-10-27 Removing salts from polyacrylonitrile

Country Status (6)

Country Link
US (2) US2648592A (pm)
CH (1) CH326492A (pm)
DE (1) DE1044346B (pm)
FR (1) FR1082729A (pm)
GB (1) GB732008A (pm)
NL (1) NL81838C (pm)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2879204A (en) * 1956-05-05 1959-03-24 Roussel Uclaf Vitamin b12 recovery process
US2879203A (en) * 1956-05-09 1959-03-24 Roussel Uclaf Recovery of vitamin b12 from diluted solutions
US2904391A (en) * 1956-09-10 1959-09-15 Courtaulds Ltd Production of polyacrylonitrile threads, fibres, filaments and the like
US2916348A (en) * 1956-08-21 1959-12-08 American Cyanamid Co Production of polyacrylonitrile filaments
US3003993A (en) * 1959-10-19 1961-10-10 Eastman Kodak Co Process for color stabilizing acrylonitrile polymers by washing with ethylene diamine tetraacetic acid
US3056169A (en) * 1959-09-28 1962-10-02 Du Pont Process of preparing shaped articles of acrylonitrile polymer containing silver insoluble particles
US3057811A (en) * 1958-04-25 1962-10-09 American Cyanamid Co Self-insolubilizing mineral pigment coating compositions for paper comprising a water-soluble anionic polymer adhesive and a water-soluble alum-sequestering agent complex
US3081273A (en) * 1960-07-13 1963-03-12 Celanese Corp Solution of terephthalamide polymer in solvent comprising antimony trichloride and process for preparing same
US3121765A (en) * 1960-09-24 1964-02-18 Toho Rayon Kk Process for the manufacture of acrylic synthetic fiber
US3154509A (en) * 1960-07-13 1964-10-27 Celanese Corp Solutions of polymers in solvent comprising antimony trichloride and process for preparing same
US3415611A (en) * 1965-10-28 1968-12-10 Dow Chemical Co Method of improving heat stability of acrylonitrile polymer fibers
US4650624A (en) * 1984-05-22 1987-03-17 Bayer Aktiengesellschaft Process for the production of filaments and fibres from acrylonitrile polymers

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2878200A (en) * 1956-05-23 1959-03-17 Chemstrand Corp Stabilized acrylonitrile polymer composition and method of preparing same
US2878208A (en) * 1956-05-23 1959-03-17 Chemstrand Corp Acrylonitrile polymer composition stabilized with formaldehyde, ethylenediamine tetraacetic acid and sodium salts thereof, and an inorganic acid, and method of making same
US2878204A (en) * 1956-05-23 1959-03-17 Chemstrand Corp Acrylonitrile polymer composition stabilized with metal formaldehyde sulfoxylate, ethylenediamine tetra-acetic acid and sodium salts thereof, and an inorganic acid, and method of making same
US3030235A (en) * 1958-03-13 1962-04-17 American Viscose Corp Discoloration-resistant regenerated cellulose articles
US3079213A (en) * 1958-06-02 1963-02-26 Yardney International Corp Antimicrobial treatment of organic materials and composition therefor
DE1181367B (de) * 1960-06-08 1964-11-12 Toho Rayon Kabushiki Kaisha Verfahren zur Herstellung von Faeden aus Acrylnitrilpolymeren oder Mischpolymeren mit wenigstens 85% Acrylnitril durch Nassspinnen
CS148810B1 (pm) * 1969-06-13 1973-05-24

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2425191A (en) * 1944-07-13 1947-08-05 American Cyanamid Co Polymerization of acrylates, methacrylates alone or in mixtures, and products thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2425191A (en) * 1944-07-13 1947-08-05 American Cyanamid Co Polymerization of acrylates, methacrylates alone or in mixtures, and products thereof

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2879204A (en) * 1956-05-05 1959-03-24 Roussel Uclaf Vitamin b12 recovery process
US2879203A (en) * 1956-05-09 1959-03-24 Roussel Uclaf Recovery of vitamin b12 from diluted solutions
US2916348A (en) * 1956-08-21 1959-12-08 American Cyanamid Co Production of polyacrylonitrile filaments
US2904391A (en) * 1956-09-10 1959-09-15 Courtaulds Ltd Production of polyacrylonitrile threads, fibres, filaments and the like
US3057811A (en) * 1958-04-25 1962-10-09 American Cyanamid Co Self-insolubilizing mineral pigment coating compositions for paper comprising a water-soluble anionic polymer adhesive and a water-soluble alum-sequestering agent complex
US3056169A (en) * 1959-09-28 1962-10-02 Du Pont Process of preparing shaped articles of acrylonitrile polymer containing silver insoluble particles
US3003993A (en) * 1959-10-19 1961-10-10 Eastman Kodak Co Process for color stabilizing acrylonitrile polymers by washing with ethylene diamine tetraacetic acid
US3081273A (en) * 1960-07-13 1963-03-12 Celanese Corp Solution of terephthalamide polymer in solvent comprising antimony trichloride and process for preparing same
US3154509A (en) * 1960-07-13 1964-10-27 Celanese Corp Solutions of polymers in solvent comprising antimony trichloride and process for preparing same
US3121765A (en) * 1960-09-24 1964-02-18 Toho Rayon Kk Process for the manufacture of acrylic synthetic fiber
DE1267783B (de) * 1960-09-24 1968-05-09 Toho Rayon Kabushiki Kaisha Co Verfahren zum Herstellen von Fasern aus einem Acrylnitrilpolymerisat
US3415611A (en) * 1965-10-28 1968-12-10 Dow Chemical Co Method of improving heat stability of acrylonitrile polymer fibers
US4650624A (en) * 1984-05-22 1987-03-17 Bayer Aktiengesellschaft Process for the production of filaments and fibres from acrylonitrile polymers

Also Published As

Publication number Publication date
US2648593A (en) 1953-08-11
NL81838C (pm) 1956-06-15
FR1082729A (fr) 1954-12-31
GB732008A (en) 1955-06-15
CH326492A (de) 1957-12-31
DE1044346B (de) 1958-11-20

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