US2432448A - Bleaching polyacrylonitrile - Google Patents

Bleaching polyacrylonitrile Download PDF

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Publication number
US2432448A
US2432448A US572261A US57226145A US2432448A US 2432448 A US2432448 A US 2432448A US 572261 A US572261 A US 572261A US 57226145 A US57226145 A US 57226145A US 2432448 A US2432448 A US 2432448A
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United States
Prior art keywords
yarn
bleaching
acrylonitrile
color
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.)
Expired - Lifetime
Application number
US572261A
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English (en)
Inventor
Richards John Cadwallader
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and 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 to BE465917D priority Critical patent/BE465917A/xx
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US572261A priority patent/US2432448A/en
Priority to GB4999/46A priority patent/GB605770A/en
Priority to FR927217D priority patent/FR927217A/fr
Application granted granted Critical
Publication of US2432448A publication Critical patent/US2432448A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/20Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen
    • D06L4/22Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using inorganic agents
    • D06L4/23Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using inorganic agents using hypohalogenites
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S260/00Chemistry of carbon compounds
    • Y10S260/28Peroxide
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/06Resin bleach

Definitions

  • This invention relates to the removal of color from shaped articles comprising a polymer of acrylonitrile and is particularly concerned with the bleaching of yarn composed of acrylonitrile polymer.
  • Polymers of acrylonitrile such as acrylonitrile polymers in which the polymers are composed entirely of acrylonitrile, and interpolymers and copolymers of acrylonitrile with other materials such as vinyl chloride, vinyl acetate, acrylic acid, its esters and homologues, styrene, butadiene, isobutylene and other polymerizable substances, especially those containing olefinic and diolefinic linkages, although potentially of great value on account of their highly desirable properties, are insoluble in ordinary organic solvents when the polymers contain at least 85% by Weight of acrylonitrile (vinyl cyanide) in the polymer molecule.
  • One method which may be used to produce polyacrylonitrile yarn is the so-called wet spinning process which comprises extruding a solution of polyacrylonitrile through a perforated nozzle (spinneret) into a bath composed of a liquid which will readily leach out the solvent from the polymer solution and coagulate or precipitate the polymer from its solution, the yarn being carried through the bath for a period of time sufiicient to solidify the polymer to the desired extent and being subjected, if desired, to a stretching operation, preferably while it is in the gel state, in order to increase tenacity as well as .otherwise to improve physical properties by orienting the micelles of which the filaments are composed.
  • Yarn produced by means of this wet spinning process has excellent physical properties, but does not possess that degree of freedom from color which is required by the exacting standards of the textile industry. Moreover, the
  • the bleaching of color from filaments, fibers and the like do not efiect the desired elimination of color from polyacrylonitrile yarn.
  • the yellowish or golden-brown color present in polyacrylonitrile articles occurs either during polymerization or processing of the polymer prior to or during shaping of the polymer to the desired form and may be caused by prolonged treatment of the polymer at high temperature, e. g. C. and above.
  • the invention will be described most particularly with reference to yarn composed of continuous filaments, but it will b 'understood that this is merely by way of illustration since the invention may also be applied to staple fibers, thin transparent films such as may be used as wrapping tissue, monofils, artificial straw, hollow pellicles such as tubing, and other industrialproducts composed of acrylonitrile polymer.
  • the objects of the invention are accomplished in general by extruding a solution of polyacrylonitrile through a spinneret submerged in a liquid which will rapidly coagulate the polymer, passing the bundle of filaments through the bath of coagulating liquid for a distance sufficient to solidify or set the filaments, preferably collecting the yarn so formed on a bobbin or other suitable collecting device, maintaining it in the gel state, i. e. before the gel structure has collapsed, as for example while the yarn still possesses a large amount of absorbed coagulating bath liquid, e. g.
  • a Yarn to be treated in accordance with the present invention may be prepared as follows:
  • a solution of 18 parts of polyacrylonitrlle possessing an average molecular weight of 120,000, as determined from viscosity measurements by the Staudinger formula, in 82 parts of dimethyl formamide is extruded at a temperature of 100 0. through a ten-hole spinneret into a spinning bath consisting of glycerol heated to"'a temperature of C., the solution being ex- 153 wa 1 i.
  • the yarn On leaving the bath, the yarn is passed without slippage about a positively driven feed :wheel possessing a peripheral speed of 3,600 inches per minute, the yarn being subsequently collected'on a rotating, perforated bobbin possessing thesame peripheral speed as the feed wheel.
  • the bobbin and gel yarn wound thereon are then placed on a chuck and submitted to pressure washing with water until the glycerol is removed from the yarn.
  • the yarn is wound into skeins from the collectingbobbin and washed in running water until free from glycerol.
  • the yarns used in the following examples have been freed from glycerol in the manner described in this paragraph, the retained wash water maintaining the yarn in the swollen condition.
  • Example I Acrylonitrile polymer yarn, prepared by a process such as that described'in Example A and Wound on the perforated collecting bobbin which permits the passage of fluid through the bobbin and yarn, .is soaked, while still in the gel state, in water containing hydrogen peroxide at a temperature of 75 C. for ten minutes, is washed with distilled water and dried at 40 0.; the dried yarnis then'heat-treated while relaxed and free to shrink at 105 C. ,forfive minutes, to increase ya nelongation.
  • the yarn bleached in accordance with this example shows a color of 0.5 as contrasted with dried yarn (otherwise prepared and processed in thesame way except that the bleaching treatment was omitted), exhibiting a color of .4, and the dry tenacity of 5.2 grams per denier and the dry elongation of about 18% possessed by the dried, unbleached yarn are substantially unaf fected'by the bleaching treatment.
  • Example 11 Skeins of gel acrylonitrile polymer yarn prepared by aprocess similar to Example A are subjected "to soaking in a 10% aqueous solution of hydrogen peroxide for five minutes at 80 (3., followed by washing with distilled water, drying and heat-treating as in Example I, and show-a color of'0.5 on the same color scale used in Example I.
  • the same degree of freedom from color isobtained by soaking the skeins of yarn-for one minute at 80 C. in the same aqueous hydrogen peroxide solution.
  • the bleaching treatment effects no marked change in yarn tenacity and elongation.
  • Example III Yarn skeins identical with the'gel, unbleached yarn used in Example 11 are soaked, while still in the gel state, for ten minutes at 80 C. in 3% aqueous solution of hydrogen peroxide, are washedin distilled water, dried and heat-treated as in Example I, and show a color of 0.5 on the same color scale used in Example I, with no substantial decrease in tenacity and elongation.
  • the same yarn, in the form of skeins is subjected to 1% aqueous hydrogen peroxide solution for one minute, followed by washing and drying, and shows a a color in water.
  • Example IV Yarn skeins identical with the gel, unbleached .yarn-processedin accordance with Examples 11 and III are soaked, while still in the gel state,
  • Example V 'Acrylonitrile polymer yarn similar to thatproducedin accordance with Example A and wound on a perforated bobbin, is soaked, while still'in the gel state, on the bobbin, in 2.5 liters of the hypochlorite solution of Examples IVby heating the yarn and solution in a beaker for twenty minutes until a temperature of 68 C. was reached. This temperature is maintained :2 C. for ten minutes, after which the yarn :is thoroughly washed with tap water, twisted, skeined, dried and subjected, while relaxed, to heat-treatment at a temperature'of 114 'C. for twelve .minutes. Yarn tenacity and elongation are not materially affected by the bleaching treatment and the-bleached yarn is almost completely white ascompared with-the light goldenbrown color of the same yarn which had not been subjected to the bleaching treatment.
  • the acrylonitrile polymer for use with this invention is preferably prepared by the ammonium persulfate catalyzed polymerization of monomeric acrylonitrile dissolved or emulsified It can, however, .be prepared by any other suitable type of polymerization reaction, such as *for example the emulsion type reaction disclosed by U. S. Patent No. 2,160,054 to Bauer et al.
  • the polymer preferably possesses a molecular weight within the range of 15,000 to 250,000 'oreven higher, as calculated from viscosity measurements :by the Staudinger equation:
  • U iii weight (as calculated by the above equation) of approximately 60,000. Increasing or decreasing the amount of the catalyst, while maintaining the other conditions constant, decreases or increases the molecular weight of the polymer.
  • glycerol as the coagulating medium in the wet spinning process for forming polyacrylonitrile yarn
  • other coagulating liquids for example water, organic solvents such as alcohol, ether, etc., or aqueous solutions of salts, alkalies or acids may be used.
  • the tension spinning of acrylonitrile polymers from solution, involving the use of coagulating baths which may, for example, comprise glycerol is described and claimed in the copending application of William W. Watkins, Serial No. 496,476, filed July 23, 1943.
  • the acrylonitrile polymer yarn must be wet spun and must be maintained in the gel state up to and through the bleaching treatment;
  • the coagulating bath liquid for example glycerol
  • another swelling liquid for example water and other liquids which can be used as coagulating bath liquids for acrylonitrile polymers, but the yarn must not be allowed to lose its swollen condition prior to bleaching.
  • the examples illustrate the removal of glycerolby washing with water, this procedure representing an inexpensive and preferred expedient to remove from the yarn relatively non-volatile materials present in the coagulating bath.
  • the bleaching solutions used in accordance with the present invention must be maintained within certain concentrations.
  • an aqueous solution of hydrogen peroxide is used as the bleaching agent, the hydrogen peroxide must be within the range of 1% to based on the weight of the total aqueous solution and is preferably present in a concentration of 3% to-10%.
  • hypochlorous acid solution may readily be prepared by dissolving a material such as sodium hypochlorite, or calcium hypochlorite, or other soluble hypochlorite, in water, acidifying with a mineral acid such as hydrochloric or sulfuric acid to a pH of less than 7.0 and preferably 5.0 or less, the term available chlorine signifying the chlorine present as hypochlorous acid.
  • a mineral acid such as hydrochloric or sulfuric acid
  • Adequate bleaching can be obtained in accordance with the present invention only by maintaining a temperature during the bleaching period of between 50 and 100 C. The higher the temperature, the shorter the necessary period of contact between the yarn and the bleaching solution. Normally, adequate bleaching is accomplished in a few minutes at the higher temperature and in less than an hour at the lower end of the temperature range.
  • the preferred temperature is about 70 to C. and the preferred time of bleaching is about one to thirty minutes.
  • the wet spun, gel yarn of polyacrylonitrile may be bleached in a substantially continuous manner after the coagulation thereof and before the yarn is collected on a bobbin, bucket or other collecting device.
  • the gel yarn may be collected, for example on a bobbin in a bobbin spinning process, or in a bucket in a bucket spinning process, and the resultant gel yarn cake subjected to treatment with the bleaching solution.
  • a preferred method of bleaching yarn in accordance with this invention comprises skeining the yarn with the skeining reel dipping in water or even submerged under water to insure the retention of the yarn in its swollen, gel state. The skein's of gel yarn are then dipped into the bleaching solution,
  • polyacrylonitrile yarn, filaments, fibers, film, monofilaments, artificial straw, hollow tubing and other structures can .be bleached to a satisfactory colorless or white character Without deleterious action on the structure.
  • the step which comprises subjecting said article in the gel state, at a temperature of 50 to C. for a time sufiicient for bleaching and less than one hour to treatment with an aqueous solution taken from the class consisting of hydrogen peroxide in 1% to 10% concentration by weight and hypochlorous acid in a, concentration corresponding to 0.05% to 0.5% by weight available chlorine.
  • the step which comprises subjecting Said yarn in the gel state, at a temperature of 50 to 100 C. and for a period of about one to thirty minutes, to treatment with an aqueous solution taken from the class consisting of hydrogen peroxide in 1% to 10% concentration by weight and hypochlorous. acid in a concentration corresponding to 0.05% to 0.5% by weight available chlorine,
  • the step which comprises subjecting said yarn in the gel state, at a temperature of 50 to 100 C. for a time sufiicient for bleaching and less than one hour, to treatment with an aqueous solution of hydrogen peroxide in 1% to 10% concentration by weight.
  • the step which comprises subjecting said yarn in the gel state, at a; temperature of 50 to 100 C. for a time sufiicient for bleaching and less than one hour, to treatment with an aqueous solution of hypochlorous acid in a concentration corresponding to 0.05% to 0.5% by Weight available chlorine.
  • the step which comprises subjecting said yarn in the gel state, at a temperature-of 70 to 80 C. for a time sufficient for bleaching and less than one hourfto treatment with an aqueous solution of hydrogen peroxide in 3% to 10% concentration by weight.
  • the step which 8 comprises subjecting said yarn in the gel state, at atemperature of 70 to 80 C. for a time sufiicient for bleaching and less than one hour, to treatment with an aqueous solution of hypochlorous

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Artificial Filaments (AREA)
US572261A 1945-01-10 1945-01-10 Bleaching polyacrylonitrile Expired - Lifetime US2432448A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE465917D BE465917A (ko) 1945-01-10
US572261A US2432448A (en) 1945-01-10 1945-01-10 Bleaching polyacrylonitrile
GB4999/46A GB605770A (en) 1945-01-10 1946-02-18 Removal of colour from shaped articles comprising a polymer or copolymer of acrylonitrile
FR927217D FR927217A (fr) 1945-01-10 1946-05-22 Procédé de blanchiment

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US572261A US2432448A (en) 1945-01-10 1945-01-10 Bleaching polyacrylonitrile

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BE (1) BE465917A (ko)
FR (1) FR927217A (ko)
GB (1) GB605770A (ko)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2507142A (en) * 1947-07-10 1950-05-09 Stabelan Chemical Company Stabilization of polymeric organic compounds
US2641524A (en) * 1949-07-13 1953-06-09 American Viscose Corp Acrylonitrile-vinyl amine interpolymers and method of making
US2720440A (en) * 1952-12-26 1955-10-11 Du Pont Bleaching polyacrylonitrile fibers
DE1027176B (de) * 1953-03-24 1958-04-03 Bayer Ag Verfahren zum kontinuierlichen Bleichen von nach dem Trockenspinnverfahren hergestellten Polyacrylnitrilbaendern
US2882121A (en) * 1954-12-07 1959-04-14 Stevensons Dyers Ltd Permonosulfuric acid for bleaching synthetic polymer textiles
US2946762A (en) * 1956-11-01 1960-07-26 American Cyanamid Co Aqueous solution containing a bisulfite and acrylonitrile polymer having basic amino groups
US2946761A (en) * 1956-11-01 1960-07-26 American Cyanamid Co Aqueous solution containing acyrlonitrile polymer and a bisulfite
US3031428A (en) * 1956-11-19 1962-04-24 Goodrich Co B F Spinning dope solutions of a vinylidene cyanide interpolymer and method of making
US3124413A (en) * 1964-03-10 Method of making essentially colorless
US3127233A (en) * 1964-03-31 Cross referenci
US3460897A (en) * 1965-06-25 1969-08-12 Dow Chemical Co Mild alkaline oxidation treatment of polyacrylonitrile fibers or films to improve flexibility and dyeability
US4139697A (en) * 1977-04-06 1979-02-13 Tenneco Chemicals, Inc. Color stabilization of vinyl chloride resins
US4220754A (en) * 1976-05-25 1980-09-02 Tenneco Chemicals, Inc. Process for the purification of polyvinyl chloride with oxidizing agents

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE930891C (de) * 1951-05-01 1955-07-28 Phrix Werke Ag Verfahren zur Nachbehandlung von nach dem Trockenspinnverfahren hergestellten, fertig verstreckten Gebilden aus Polyacrylnitril oder Mischpolymerisaten des Acrylnitrils
BE532074A (ko) * 1953-09-24

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB437271A (en) * 1934-03-28 1935-10-28 John William Croom Crawford Improvements in or relating to the polymerisation of derivatives of unsaturated organic acids
US2021763A (en) * 1932-02-24 1935-11-19 Rohm & Haas Manufacture of artificial products
FR802840A (fr) * 1935-06-05 1936-09-16 Cie Nat Matieres Colorantes Procédé de préparation de produits de condensation de cétones
US2116210A (en) * 1936-10-21 1938-05-03 Du Pont Regenerated cellulose structures and method for preparing same
GB518970A (en) * 1938-09-05 1940-03-13 John William Croom Crawford Manufacture of polymerisation products derived from acrylic acid derivatives
US2292737A (en) * 1937-09-13 1942-08-11 Blomer Alfred Chlorine containing synthetic resins
US2295660A (en) * 1938-07-06 1942-09-15 Hubert Emil Method of improving the heat stability of polyvinyl chloride articles

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2021763A (en) * 1932-02-24 1935-11-19 Rohm & Haas Manufacture of artificial products
GB437271A (en) * 1934-03-28 1935-10-28 John William Croom Crawford Improvements in or relating to the polymerisation of derivatives of unsaturated organic acids
FR802840A (fr) * 1935-06-05 1936-09-16 Cie Nat Matieres Colorantes Procédé de préparation de produits de condensation de cétones
US2116210A (en) * 1936-10-21 1938-05-03 Du Pont Regenerated cellulose structures and method for preparing same
US2292737A (en) * 1937-09-13 1942-08-11 Blomer Alfred Chlorine containing synthetic resins
US2295660A (en) * 1938-07-06 1942-09-15 Hubert Emil Method of improving the heat stability of polyvinyl chloride articles
GB518970A (en) * 1938-09-05 1940-03-13 John William Croom Crawford Manufacture of polymerisation products derived from acrylic acid derivatives

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3124413A (en) * 1964-03-10 Method of making essentially colorless
US3127233A (en) * 1964-03-31 Cross referenci
US2507142A (en) * 1947-07-10 1950-05-09 Stabelan Chemical Company Stabilization of polymeric organic compounds
US2641524A (en) * 1949-07-13 1953-06-09 American Viscose Corp Acrylonitrile-vinyl amine interpolymers and method of making
US2720440A (en) * 1952-12-26 1955-10-11 Du Pont Bleaching polyacrylonitrile fibers
DE1027176B (de) * 1953-03-24 1958-04-03 Bayer Ag Verfahren zum kontinuierlichen Bleichen von nach dem Trockenspinnverfahren hergestellten Polyacrylnitrilbaendern
US2882121A (en) * 1954-12-07 1959-04-14 Stevensons Dyers Ltd Permonosulfuric acid for bleaching synthetic polymer textiles
US2946761A (en) * 1956-11-01 1960-07-26 American Cyanamid Co Aqueous solution containing acyrlonitrile polymer and a bisulfite
US2946762A (en) * 1956-11-01 1960-07-26 American Cyanamid Co Aqueous solution containing a bisulfite and acrylonitrile polymer having basic amino groups
US3031428A (en) * 1956-11-19 1962-04-24 Goodrich Co B F Spinning dope solutions of a vinylidene cyanide interpolymer and method of making
US3460897A (en) * 1965-06-25 1969-08-12 Dow Chemical Co Mild alkaline oxidation treatment of polyacrylonitrile fibers or films to improve flexibility and dyeability
US4220754A (en) * 1976-05-25 1980-09-02 Tenneco Chemicals, Inc. Process for the purification of polyvinyl chloride with oxidizing agents
US4139697A (en) * 1977-04-06 1979-02-13 Tenneco Chemicals, Inc. Color stabilization of vinyl chloride resins

Also Published As

Publication number Publication date
FR927217A (fr) 1947-10-23
BE465917A (ko)
GB605770A (en) 1948-07-29

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