US3083070A - Process for improving the dyeability of polymeric material - Google Patents

Process for improving the dyeability of polymeric material Download PDF

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Publication number
US3083070A
US3083070A US734109A US73410958A US3083070A US 3083070 A US3083070 A US 3083070A US 734109 A US734109 A US 734109A US 73410958 A US73410958 A US 73410958A US 3083070 A US3083070 A US 3083070A
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fibers
hydroxylamine
treatment
sample
boiled
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Ferdinand L Schouteden
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Gevaert Photo Producten NV
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Gevaert Photo Producten NV
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/388Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
    • G03C7/3882Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific polymer or latex
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J45/00Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/30Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18Monocomponent 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
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38Monocomponent 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
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/58Treating 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 nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/63Treating 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 nitrogen or compounds thereof, e.g. with nitrides with hydroxylamine or hydrazine
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/376Oximes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/673Inorganic compounds
    • D06P1/67308Hydroxylamine or derivatives thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/70Material containing nitrile groups
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/22Effecting variation of dye affinity on textile material by chemical means that react with the fibre
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/34Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45Nitrogen-containing groups
    • D21H17/455Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/053Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/775Photosensitive materials characterised by the base or auxiliary layers the base being of paper
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/795Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/835Macromolecular substances therefor, e.g. mordants
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/22Subtractive cinematographic processes; Materials therefor; Preparing or processing such materials
    • G03C7/25Dye-imbibition processes; Materials therefor; Preparing or processing such materials
    • 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
    • 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
    • Y10S8/93Pretreatment before dyeing
    • Y10S8/931Washing or bleaching

Definitions

  • Uie at This invention relates to the dyeing of fibers, yarns, fabrics and other shaped articles substantially consisting of polymers containing nitrile groups, as defined hereinafter.
  • polyacrylonitrile fibers possess outstanding properties, yet the expansion of their technical application is strongly limited by the difiiculties which arise when dyeing these fibers and by the tendency of these fibers to take up static electricity.
  • cuprous ion technique which consists in dyeing these fibers in the presence of cuprous ions
  • Treatments which superficially change the formed fibers by chemical reaction are for instance: saponification (H. Rein, Angew. Chem. 60 (1948), 159/161), and treatment with organic amines (British Patent No. 700,172) in the presence of sulphonic acid (British Patent No. 712,235) or other mineral substances with acid character.
  • Another object is the manufacture of White shaped articles consisting substantially of polymers containing acrylonitrile units with improved dyeability.
  • Still another object is the provision of a process for dyeing polyacrylonitrile fibrous material.
  • the present invention particularly relates to shaped articles as, for instance, powders, films, fibers, yarns and fabrics, consisting of polymers containing nitrile groups.
  • the latter comprise polymers or copolymers, including graft and block copolymers, of acrylonitrile, methacrylonitrile and vinylidene cyanide, and they comprise also cyanoethylated polymers, in the first instance cyanoethylated cellulose, and mixtures of the above polymers with other polymers.
  • the process may also be applied successfully to copolymers containing less than 50 percent acrylonitrile units.
  • the present invention is especially concerned with the treatment of polyacrylonitrile polymers with an aqueous hydroxylamine solution it must be pointed out that the hydroxylamine treatment may also be carried out in alcoholic medium or even by treating the polymers in solution with hydroxylamine.
  • the degree of conversion needed in order to obtain fibers with very good dyeability may vary within wide limits; in some extreme cases a degree of conversion of 10% may be desirable, but in most cases the optimum is about 0.5-5%.
  • the degree of conversion is defined as the ratio:
  • Weight of polymer converted assuming that the polymer consists exclusively of acrylonitrile and that 1 CN group reacts with l NH OH molecule.
  • hydroxylamine is too unstable to be available commercially
  • hydroxylamine salts being salts of weak bases, are substantially hydrolyzed and the amount of hyclroxylamine liberated in this way enables the reaction to set in Without liberating the hydroxylamine from its salts by addition of strong bases.
  • hydroxylamine treatment may be carried out over practically the 'whole pH range, preferably between 2 and 10.
  • polyarnines substances having in their molecule at least two NH groups as well as their derivatives containing at least one amino group capable of being acylated.
  • amines may be mentioned: diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5 diaminopentane, 1,6 diarnino- 3 hexane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, aminoethylethanolarriine, diethylaminoeth-ylamine.
  • the polyamine may be added to the reaction medium simultaneously with the by droxylamine. If desired, this step may include the addition of the dyestuif. f 7
  • reaction temperature for both the hydroxylarnine aiid polyamine treatments may vary Within wide limits. Conveniently both the treatments and dyeing are.ef-
  • the chemical treatments may be carried out at' temperatures from 50 C. to 125 0., preferably between 75 and 105 C. Also the dyeing operation may be carried out between these temperature limits, conveniently between 90 C. and the boiling point of theb'ath; if desired, the different operations may be carried out under pressure at higher temperatures.
  • fibrous material may be treated in a bath or the material may be part of a close circuit wherein the liquid is pumped through a bed of iibers.
  • the treat-merit with hydroxylamine and with polyamine's may also be applied immediately after spinning.
  • the discoloration which appears during the treatment of the fibers with polyamines may be removed by a treatment with diluted aqueous solution of strong acids such as sulphuric acid, hydrochloric acid, phosphoric acid, oxalic and malei'c acid.
  • This treatment likewise involves an increase of the heat stability.
  • the fibers improved according, to the present invention may be dyed with a wide variety of dyes'belonging to difierent classes including acid, direct, disperse, vat, metalliz'able and metal complex dyes, also mixtures of dyes may be used. Although the aflinity for cationic dyes seems notto be increased, yet the fibers remain dyeable with these dyes. Also the Cuprous ion technique. may be used. Likewise noncolored substances, for example clearing and finishing agents, may be fi'ried on the fibrous material.
  • the reaction with hydroxylamine and with polyamines will be followed by the dyeing operation, but both may also be carried out in the same bath without changing the main liquid, simply by altering the com-'- position to the end in view.
  • the dyeing is carried out in an acid medium which may be obtained by addition of inorganic or of organic acid;
  • dyeing assistants, relustering agents and buffering mixtures may be used.
  • the present invention can be put into practice in any known dyeing process including printing, although it is the purpose to improve the afiinity for dyes, it is also accompanied by a greater water-absorption which considerably diminishes the receptivity for static electricity.
  • EXAMPLE 1 100 g. polyacrylonitrile powder (obtained by emulsion polymerization) are boiled for 2 /2 hours in a solution consisting of 750' ml. water and 5 g. hydroxylaminesulphate (sample A). pH of the solution before the treatment: 3.7, after the treatment: 5.0. i
  • samples of the washed powder (A) are boiled for 1 hour in a 1% aqueous solution of ethylenediamine (sample B), hexamethylenediamine (sample C) and diethylaminoetliylamine (sample D).
  • sample B ethylenediamine
  • sample C hexamethylenediamine
  • the samples A, B, C and D are boiled for /2 hour in a dye bath containing 0.2% Fast Red A.V. (CI. 15620) in H 30 N/l0.
  • the dye uptake amounts to: 5% for sample A, 16% for sample B, and 14% 'for samples C and D.
  • EXAMPLE 3 1100 g. polyacrylonitrile as in Example 1 are treated for 2 hours with 1000 ml. of an aqueous solution containing 10 g. hydroxylaminesulphate and 4 g. NaOH (this quantity of NaOH is sufiicient to liberate 80% of the hydroxylamine)- pH before treatment: 6.7; after the treatment: 8.5.
  • the difierent samples are then dyed in the same dye bath consisting of 0.2% Fast Red A.V. (CI. 15620) in H 50, N/lO. V
  • the dye uptake amounts to: 10% for A and B, 20% for C, 30% for D and 40% for E.
  • EXAMPLE 4 i '10 g. polyacrylonitrile staple fibers (manufactured by Cassella) are boiled for /2 hour in a solution containing 0.5 g. of hydroxylamine hydrochloride, 0.32 g. anhydrous sodium carbonate and 150 ml. water. Thefibers are then thoroughly washed. After removing the excess of water they are boiled for /2 hour with an aqueous diethylaminoethylamine 2% solution. Next, they are rinsed again and pressed out. They possess a yellow color.
  • EXAMPLE 5 l V V g. Orlon 42 (a copolymer mainly consisting of acrylonitrile manufactured by Du. Pont de Nemours) staple fibers are boiled up in an aqueous solution of a Wetting agent, rinsed and centrifuged.- Then the fibers are treated wih an aqueous solution consisting of 1250 ml. water, 5 g. hydroxylaminesulphate and 1.6 g. anhydrous sodium carbonate. The quantity of sodium carbonate sufiices to liberate 45% of the hydroxylamine. Next the fibers are boiled for '1 hour in 1 liter 0.5% aqueous'soluticn of diethylaminoethylamine.
  • the Slightly yellow"discoloration of the fibers may be removed by treating them for 5 minutes with a 5% oxalic acid solution. -If-insteadof' this last treatment a 5 g. sample of the fibers is boiled for 1 hour in a solution containing 150 ml. water, 0.5 ml. formic acid and 0.25 ml. Calcocid M 9863, black dyeings are obtained.
  • EXAMPLE 6 g. polyacrylonitrile staple fibers (manufactured by Cassella) are treated for 1 hour at 90 C. with a solu tion composed of 1 20 cm. of demineralized water, 0.3 g. hydroxylaminesulphate, 0.2 g. of ethylenediamine and 0.14 g. of NaOH. After adding cm. H SO /N and 0.5 g. Neolan Yellow (CI. 19010), the mixture is boiled for /2 hour. The fibers are deeply yellow colored.
  • EXAMPLE 8 10 g. Darlan (registered trademark for a copolymer mainly consisting of vinylidene cyanide manufactured by B. F. Goodrich) staple fibers are boiled for 30 minutes in a solution composed of 125 ml. water, 1 g. hydroxylaminesulphate and 0.45 g. NaOH. After adding2 m1. of ethylenediamine solution 70% the mixture is boiled for 30 minutes. Afterwards the pH is brought to 2 by adding sulphuric acid; then 0.25 g. Fast Red AV (C.'I. No. 176) is added and the mixture is further boiled for 30 minutes. Now the bath is practically exhausted.
  • Darlan registered trademark for a copolymer mainly consisting of vinylidene cyanide manufactured by B. F. Goodrich
  • EXAMPLE 9 This example is an alternative of Example 8 and is characterized thereby that the ethylenediamine and the hydroxylamine are added together from the beginning of the reaction. After this treatment the solution is acidified, whereafter Black Tetracide NBA (Cl. 20740) (an acid dyestufi manufactured by Soc. Carbochimique de Tertre) is added and further boiled for /2 hour.
  • Black Tetracide NBA (Cl. 20740) (an acid dyestufi manufactured by Soc. Carbochimique de Tertre) is added and further boiled for /2 hour.
  • the fibers are homogeneously black dyed.
  • EXAMPLE 10 10 g. Orlon-42 staple fibers (registered trademark of Du Pont de Nemours for staple fibers from a copolymer mainly consisting of acrylonitrile) are boiled for minutes in a solution composed of: 150 ml. water, 0.3 g. hydroxylamine sulphate (3% on the weight of fibers) and 0.14 g. NaOH (sufficient to liberate 95% hydroxylamine).
  • Blue Formalan 26 (trade name for metal complex dyestufi manufactured by the Soc. Carbochimique de Tertre) and such a quantity of sulphuric acid whereby the pH of the solution is brought at about 3 are added to the bath.
  • EXAMPLE 11 100 g. polyacrylonitrile monofilaments are treated during 15 minutes in a 1% Hostapon T (registered trademark for a wetting agent consisting of oleyl methyl tauride sodium salt manufactured by Farbwerke Hoechst,
  • sample A Part of sample A, above, is treated for 3 hours at 90-95 C. in a solution consisting of 1500-ml. water, 5 g. hydroxylaminesulphate' and 2.2 g. NaOH (the quantity of NaOH suffices to neutralize 90% of the hydroxylamine) (sample B).
  • Process for improving the dyeability of shaped articles formed from a polymeric substance selected from the group consisting of cyanoethylated cellulose, polyacrylonitrile, polymethacrylonitrile, polyvinylidene cyanide, copolymers mainly consisting essentially of acrylonitrile and copolymers mainly consisting essentially of vinylidene cyanide which comprise the steps of (1) treating said articles for /2 to 2 /2 hours in a solution containing free hydroxylamine in a concentration between 0.12 and 0.4% and (2) after the hydroxylamine treatment to obtain from about 0.5 to 10% conversion of the nitrile groups in said article, further treatment of said article with a 0.16 to 3% aqueous solution of ethylenediamine at 50-125 C. for from /2 to 3 /2 hours.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Toxicology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Artificial Filaments (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Optical Filters (AREA)
  • Coloring (AREA)
US734109A 1955-03-30 1958-05-09 Process for improving the dyeability of polymeric material Expired - Lifetime US3083070A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9305/55A GB833204A (en) 1957-03-08 1955-03-30 Improvements in or relating to the dyeability of treated polymeric material
NL850116X 1957-03-08
NL852483X 1957-03-08
BE2038176 1959-07-01

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US (1) US3083070A (xx)
BE (5) BE565400A (xx)
CH (2) CH334656A (xx)
DE (3) DE1149169B (xx)
FR (2) FR1147427A (xx)
GB (6) GB786960A (xx)
LU (1) LU33836A1 (xx)
NL (4) NL88955C (xx)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3210371A (en) * 1961-07-18 1965-10-05 Toho Rayon Kk Process for manufacturing imidazolines or bisimidazolines
US3383240A (en) * 1964-06-19 1968-05-14 Monsanto Co Flame resistant composition and method of treating acrylic containing textile fibers therewith and the resulting product
US3462238A (en) * 1966-04-07 1969-08-19 Monsanto Co Process of whitening acrylic fibers
WO2018004773A3 (en) * 2016-06-10 2018-01-25 Gill Gary A Converting acrylic fibers to amidoxime-carboxylate containing polymer adsorbents for sequestering uranium and other elements from water

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US3087914A (en) * 1958-07-01 1963-04-30 Gevaert Photo Prod Nv Process for the preparation of polymers containing amidoxime groups
NL287835A (xx) * 1962-01-17
US3145073A (en) * 1962-04-18 1964-08-18 Gagliardi Domenick Donald Treatment of polyolefin articles and resulting products
CH464524A (de) * 1963-07-17 1968-10-31 Nippon Rayon Kk Verfahren zur Verbesserung der Anfärbbarkeit von Fasern und Formartikeln aus Polypropylen
DE3035134A1 (de) * 1979-09-19 1981-04-09 Aligena AG, Basel Poroese, modifizierte, fuer die ultrafiltration geeignete membranen auf der basis von polyacrylnitrilen, verfahren zu ihrer herstellung und ihre verwendung
US4247615A (en) 1980-03-06 1981-01-27 Eastman Kodak Company Continuous-tone dyed diazo imaging process
CH649718A5 (de) * 1981-03-25 1985-06-14 Aligena Ag Verfahren zur herstellung von semipermeablen membranen aus polymeren auf acrylnitrilbasis, die nach diesem verfahren hergestellten membranen und ihre verwendung.
JPS5941307A (ja) * 1982-09-01 1984-03-07 Sumitomo Chem Co Ltd キレート樹脂の製造方法
JPS61254603A (ja) * 1985-05-02 1986-11-12 Kyoritsu Yuki Kogyo Kenkyusho:Kk カチオン化澱粉の製造方法
AU586246B2 (en) * 1985-05-16 1989-07-06 Ge Chemicals, Inc Hydroxylamine coagulant for acrylonitrile removal
DE3630192A1 (de) * 1986-09-04 1988-03-10 Michail Petrovic Zverev Verfahren zur herstellung von anionenaustauscherfasern

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US2785003A (en) * 1954-11-15 1957-03-12 Louis J Zaravsey Hold-down clip devices for vehicle convertible top covers
US2792276A (en) * 1954-01-28 1957-05-14 Pacific Mills Treatment of polyacrylonitrile material with hydroxylamine salts
US2893812A (en) * 1959-07-07 Dyeing of mixed textile materials

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US2792276A (en) * 1954-01-28 1957-05-14 Pacific Mills Treatment of polyacrylonitrile material with hydroxylamine salts
US2785003A (en) * 1954-11-15 1957-03-12 Louis J Zaravsey Hold-down clip devices for vehicle convertible top covers

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US3210371A (en) * 1961-07-18 1965-10-05 Toho Rayon Kk Process for manufacturing imidazolines or bisimidazolines
US3383240A (en) * 1964-06-19 1968-05-14 Monsanto Co Flame resistant composition and method of treating acrylic containing textile fibers therewith and the resulting product
US3462238A (en) * 1966-04-07 1969-08-19 Monsanto Co Process of whitening acrylic fibers
WO2018004773A3 (en) * 2016-06-10 2018-01-25 Gill Gary A Converting acrylic fibers to amidoxime-carboxylate containing polymer adsorbents for sequestering uranium and other elements from water

Also Published As

Publication number Publication date
GB838296A (en) 1960-06-22
FR1153961A (fr) 1958-03-31
GB786960A (en) 1957-11-27
GB850116A (en) 1960-09-28
GB840797A (en) 1960-07-13
LU33836A1 (xx)
CH334656A (fr) 1958-12-15
GB852483A (en) 1960-10-26
BE565402A (xx)
DE1149169B (de) 1963-05-22
NL92192C (xx)
CH344844A (fr) 1960-02-29
DE1148072B (de) 1963-05-02
NL215200A (xx)
DE1130593B (de) 1962-05-30
NL200690A (xx)
BE569039A (xx)
NL88955C (xx)
GB863533A (en) 1961-03-22
BE541496A (xx)
FR1147427A (fr) 1957-11-25
BE565400A (xx)
BE546321A (xx)

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