US3681004A - Polyacrylonitrile fibres - Google Patents

Polyacrylonitrile fibres Download PDF

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Publication number
US3681004A
US3681004A US2423A US3681004DA US3681004A US 3681004 A US3681004 A US 3681004A US 2423 A US2423 A US 2423A US 3681004D A US3681004D A US 3681004DA US 3681004 A US3681004 A US 3681004A
Authority
US
United States
Prior art keywords
fibre
salt
carboxylate
acrylic
fibres
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
US2423A
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English (en)
Inventor
Brian J D Torrance
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
Courtaulds PLC
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 Courtaulds PLC filed Critical Courtaulds PLC
Application granted granted Critical
Publication of US3681004A publication Critical patent/US3681004A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
    • 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
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
    • 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
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/927—Polyacrylonitrile fiber

Definitions

  • carboxylate acrylic fibres are of copolymers containing at least 85 percent by weight of acrylonitrile and at least 0.5 percent by weight of an ethylenically unsaturated carboxylic acid, for example acrylic acid, an a-alkyl acrylic acid such as methacrylic acid and an Ot-SllbStlIlltCd alkyl acrylic acid, such as itaconic acid.
  • an ethylenically unsaturated carboxylic acid for example acrylic acid, an a-alkyl acrylic acid such as methacrylic acid and an Ot-SllbStlIlltCd alkyl acrylic acid, such as itaconic acid.
  • ethylenically unsaturated monomers for example styrene, vinyl acetate, or an ester of acrylic or methacrylic acid for example methyl methacrylate or methyl acrylate.
  • a wet-spun, gelstate carboxylate acrylic fibre is impregnated with a solution of a salt of a metal from Group II of the Periodic Table, and the fibre is dried.
  • the preferred salts are those of Ca, Mg, Ba, Sr and Zn.
  • the salt is preferably a sulphonate such as p-toluene sulphonate or benzene sulphonateor an inorganic salt, for example sulphate, chloride or nitrate; the carboxylate salts,
  • Patented Aug. 1, 1972 for example acetate and benzoate, improve the resistance of the carboxylate acrylic fibre to a lesser extent.
  • the resistance to heat-discolouration is significantly increased even when only a proportion of the carboxylate groups in the carboxylate acrylic copolymer are incorporated in chelate groups.
  • the maximum resist ance is developed when all the available carboxylate groups (free acid groups and alkali metal salt groups) are deactivated.
  • the salt retained by the fibre should be from one half to twice that stoichiometrically required to form the chelate with the available carboxylate groups. Larger proportions are acceptable but do not significantly affect the outcome, except perhaps to accelerate the formation of the chelate.
  • the deactivation of the carboxylate groups as degradation catalysts following the impregnation of the gel-state fibre with the salt also reactivates the carboxylate groups as dye sites for basic dyes.
  • the gel state fibre is first dyed and then impregnated with the salt of the Group II metal.
  • Carboxylate groups already occupied by dye molecules are not significantly susceptible to reaction with the salt so that these groups are not available as they were before dyeing.
  • the reaction of the dyed fibre with the salt therefore involves only the supernumerary carboxylate groups, and the stoichiometric proportions of the salt should be calculated on this basis.
  • EXAMPLE 1 20 grams of never-dried carboxylate acrylic fibre con taining 2 percent by weight of acrylic acid on the dry fibre weight was immersed for 30 seconds in a 2 percent by weight zinc sulphate solution at 20 C. The fibres, after washing in demineralised water and drying in air at a temperature of 80 C., were 0.5 gm. heavier than another 20 gm. sample of untreated fibers which had been dried in the same way. The treated and untreated fibres were subjected to the heat stability test referred to above. The
  • Example 2 The procedure of Example 1 was followed, substituting other salt solutions for the zinc sulphate solution. The solutions are identified in the following table, together with the difference in temperatures at which the treated and untreated samples discoloured to the same extent and in the same time.
  • a method of improving the resistance to discolouration by heat of a wet-spun acrylic fibre containing carboxylic acid groups comprising impregnating the gel-state fibre with a solution of an uncolored, non-reducing salt of a metal of Group II of the Periodic Table.
  • a method as claimed in claim 1 comprising dyeing the gel-state fibre before impregnating it with the salt solution.
  • a method as claimed in claim 1 in which the salt retained by the fibre is from half to twice that stoichiometrically required to react with the available carboxylic acid groups of the fibre.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Artificial Filaments (AREA)
US2423A 1969-01-20 1970-01-12 Polyacrylonitrile fibres Expired - Lifetime US3681004A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB306769 1969-01-20

Publications (1)

Publication Number Publication Date
US3681004A true US3681004A (en) 1972-08-01

Family

ID=9751377

Family Applications (1)

Application Number Title Priority Date Filing Date
US2423A Expired - Lifetime US3681004A (en) 1969-01-20 1970-01-12 Polyacrylonitrile fibres

Country Status (8)

Country Link
US (1) US3681004A (enrdf_load_stackoverflow)
AU (1) AU1025470A (enrdf_load_stackoverflow)
BE (1) BE744681A (enrdf_load_stackoverflow)
CH (1) CH522049A (enrdf_load_stackoverflow)
DE (1) DE2002400A1 (enrdf_load_stackoverflow)
FR (1) FR2028740A1 (enrdf_load_stackoverflow)
GB (1) GB1288563A (enrdf_load_stackoverflow)
NL (1) NL7000345A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3917776A (en) * 1970-12-12 1975-11-04 Mitsubishi Rayon Co Process for producing carbon fiber
US4001382A (en) * 1974-02-04 1977-01-04 Japan Exlan Company Limited Process for producing carbon fibers having excellent physical properties
US4060650A (en) * 1975-06-24 1977-11-29 Kureha Kagaku Kogyo Kabushiki Kaisha Method for preventing or eliminating water-absorption whitening of a molded article containing an acrylonitrile polymer or copolymer
US4507257A (en) * 1982-03-18 1985-03-26 Hoechst Aktiengesellschaft Process for preparing acrylic filaments and fibers
US4524041A (en) * 1982-03-18 1985-06-18 Hoechst Aktiengesellschaft Processes for preparing thermostable fibers and filaments

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3917776A (en) * 1970-12-12 1975-11-04 Mitsubishi Rayon Co Process for producing carbon fiber
US4001382A (en) * 1974-02-04 1977-01-04 Japan Exlan Company Limited Process for producing carbon fibers having excellent physical properties
US4060650A (en) * 1975-06-24 1977-11-29 Kureha Kagaku Kogyo Kabushiki Kaisha Method for preventing or eliminating water-absorption whitening of a molded article containing an acrylonitrile polymer or copolymer
US4507257A (en) * 1982-03-18 1985-03-26 Hoechst Aktiengesellschaft Process for preparing acrylic filaments and fibers
US4524041A (en) * 1982-03-18 1985-06-18 Hoechst Aktiengesellschaft Processes for preparing thermostable fibers and filaments

Also Published As

Publication number Publication date
FR2028740A1 (enrdf_load_stackoverflow) 1970-10-16
AU1025470A (en) 1971-07-15
CH522049A (de) 1972-04-30
DE2002400A1 (de) 1970-07-23
NL7000345A (enrdf_load_stackoverflow) 1970-07-22
BE744681A (fr) 1970-07-01
GB1288563A (enrdf_load_stackoverflow) 1972-09-13

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