Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General 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
  • D06P1/44—General 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
  • D06P1/655—Compounds containing ammonium groups
  • D06P1/66—Compounds containing ammonium groups containing quaternary ammonium groups
• • 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
  • Y10S8/90—Basic emulsifiers for dyeing
  • Y10S8/901—Quaternary ammonium salts
• • 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
  • Y10S8/906—Mixed cationic and nonionic emulsifiers for dyeing
• • 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
  • Y10S8/907—Nonionic emulsifiers for dyeing
• • 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

• the present invention provides a process for dyeing materials consisting of or containing polyacrylonitrile fibres or threads, which process comprises dyeing such a material in a dye bath containing a basic dyestuff under conditions for dyeing said polyacrylonitrile material with a basic dyestulf, the dyeing being effected in the presence of a quaternary ammonium compound which comprises:
• At least one aliphatic radical linking together two basic nitrogen atoms which aliphatic radical consists Patented Feb. 2, 1971 of an alkylene radical with 2 to 8 carbon atoms devoid of any hetero atoms or of a plurality of alkylene radicals each of from 2 to 8 carbon atoms separated from one another by a sulphur or oxygen atom,
• the number of basic nitrogen atoms at (a) is preferably 2 to 7, but may be much greater.
• the quaternary ammonium compounds of the present invention have a good affinity for the fibrous polyacrylonitrile material and favourably influence the uptake of the basic dyestuffs; in contradistinction to known dyeing assistants for regulating dyestuff uptake in similar situations, they do not produce any undesirable foam in aqueous solutions.
• dye baths they cause a slowing down in the uptake of basic dyestuffs by the fibrous material and are most suitable for regulating the uptake speed of basic dyestuffs in dyeing polyacrylonitrile fibres or threads.
• dyestulf quantity and dyeing temperature dyeing conditions normally used for dyeing polyacrylonitrile material with basic dyestuffs are oper ative.
• the dyeing may be effected with increasing temperature, at C. or under pressure, for example at 100-120" C., in a closed vessel.
• bath additives usual in dyeing with basic dyestuffs may be present, for example salts such as sodium sulphate, -chloride or -acetate or acids such as acetic acid, or also buffer solutions.
• the quaternary ammonium compounds of the invention may be employed in the form of pure compounds or as technical mixtures. Likewise, they may be used alone or in combination with suitable surface active compounds, such as for example surface active addition products of ethylene oxide and fatty amines, fatty alcohols, or alkylphenols.
• suitable surface active compounds such as for example surface active addition products of ethylene oxide and fatty amines, fatty alcohols, or alkylphenols.
• the amounts of the quaternary ammonium compounds to be used must be adjusted according to the circumstances of dyeing in each case, for example according to the nature and amount of the basic dyestuffs and according to the charatcer of the state of the fibrous material to be dyed. For example it amounts to 0.022% of the weight of the goods and may be added to the dye bath before or during the dyeing. It is also possible to pretreat the fibrous material with the quaternary compounds.
• the fibrous material to be dyed may be present in any desired form, e.g. as loose fibres, as yarn or as fabric; the fibrous material may consist of pure polyacrylonitrile or of mixed polymerizates containing a substantial proportion of polyacrylonitrile, e.g. mixed polymerizates of acrylonitrile with vinyl alcohol, vinyl acetate, acrylicand methacrylic acide esters, acrylic acid amides or vinyl chloride. Furthermore, it may be composed of a single type of fibres or of mixtures of such.
• dyestuffs suitable for use in the process of the invention are dyes of the diand triarylmethane series, the azine-, oxazine-, thiazineand thiazole series, xanthene dyestuffs, acridine dyestuffs, quoinoline dyestuffs, quinophthalone dyestuffs, cyanine-, methine-, azomethineand polymethine dyestuffs, basic azoand basic anthraquirione dyestuffs, nitroand naphthoquinoneimine dyestuffs as well as dyestuffs with cyclic imonium or external onium radical.
• the quaternary ammonium compounds of the present invention may be obtained in such a way that 1 mol of a dior polyamine, for example of the general formula wherein:
• n is or a whole number
• n is an integer and r is 3 or any higher integer, with the proviso that m+r must be equal to n+3,
• N-aralkylated polyamine in the form of the free amine is quaternized in manner known per se with a peralkylating agent which is suitable for introducing an alkyl radical with from 1 to 6 carbon atoms inclusive.
• Alkylene diamines for instance ethylene diamine, propylene diamine, hexylene diamine, diaminooctane, N-monomethylhexylene diamine, di (arninopropyl)- sulphide;
• dialkylene triamines (these are preferred amines I), for instance diethylene triamine which is especially suitable, dipropylene triamine, bis (aminopr0pyl)- methylamine, dihexylene triamine;
• polyalkylene polyamines for instance triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and hexaethylene heptamine and polyamines which may be obtained by the reduction of the addition products of acrylonitrile to amines, e.g. tetra- (aminopropyl)-pentaethylene hexamine.
• substitution products of these amines are suitable such as for example a tetraethylene pentamine in which a labile hydrogen atom has been replaced by a methyl, ethyl, B-cyanoethyL, hydroxyethylor mercaptoethyl radical; and also polyethylene polyamines of high degree of polymerization, e.g. polyethylene imine having a molecular weight of 30,000 to 40,000.
• amines which may be obtained by the addition of acrylonitrile to a polyol or another material containing active hydrogen and subsequent reduction of the nitrile groups, for instance 1,2,3-tri-(aminoproxy)- propane.
• Aralkylation agents of the naphthylalkyland the phenylalkyl series are, for example, 1-(chloromethyl)-naphthalene, 2-(chloromethyl)-naphthalene, 1- or 2-(2'-bromoethyl)-naphthalene, 2-, 3- or 4-methylbenzyl chloride, 2-, 3- or 4-ethylbenzyl bromide, 2-, 3- or 4-isopropylbenzyl chloride, fi-chloroand ,B-bromoethyl benzene, styrene oxide, 2-, 3- or 4-phenoxybenzyl chloride, phenoxyethyl chloride and especially benzyl chloride.
• peralkylating agents are alkyl halides and alkyl sulphates having alkyl radicals with from 1 to 6 carbon atoms, for instance n-hexyl iodide, n-butyl bromide, methyl bromide, ethyl iodide, diethyl sulphate and especially dimethyl sulphate.
• ammonium compounds of the invention are liquids of high viscosity or tough sticky pastes or solid crystalline materials. They are soluble in alcohol-Water mixtures, e.g. a mixture of isopropanol and water, or in water under conditions usual in dyeing with basic dyestuffs.
• Example 1 506 parts (4 mol) of benzyl chloride are added drop- Wise, while stirring, to a solution, heated to 80, of 74 parts (1 mol) of trimethylene diamine in 125 parts of Water. During this addition the temperature inside the reaction mixture should not rise above 100.
• the resulting water insoluble amine separates out and is removed; after recrystallization from ethanol it is obtained in crystalline form with a melting point of 404l (uncorrected) 434 parts (1 mol) of this crystalline amine are dissolved in 525 parts of benzene and heated to the boiling point of the benzene. 252 parts (2 mol) of dimethyl sulphate are added while stirring and kept for 45 hours at the reflux temperature of benzene. The resulting quaternary ammonuium compound is insoluble in benzene and separates in the form of a tough liquid. The supernatant benzene is decanted and the reaction product is freed of occluded benzene by vacuum distillation (about 20 mm.
• Example 2 When the trimethylene diamine in Example 1 is replaced with the corresponding quantity of octamethylene diamine dissolved in 250 parts of water and working is effected in the same way as in Example 1, after recrystallization from ethanol, there is obtained an amine melting at 79-80 (uncorrected) which gives a brown tough mass (ammonium compound No. 2) after quaternizing. This has the same properties as the ammonium compound No. 1.
• Example 3 103 parts (1 mol) of diethylene triamine are dissolved in 250 parts of water and heated to 80-90". 569 parts (4.5 mol) of benzyl chloride are added dropwise to this solution. The temperature of this reaction mixture should not exceed 100. After stirring for minutes at 90-100, 600 parts of a 30% sodium hydroxide solution (4.5 mol NaOH) are added and stirring is continued for a further 15 minutes.
• a 30% sodium hydroxide solution 4.5 mol NaOH
• the resulting water insoluble reaction product is separated and dried in a vacuum at about 15 mm. of Hg at The reaction product is a brown tough liquid.
• the resulting quaternized product (ammonium compound No. 3) is dissolved in isopropanol-water; it has good retarding properties.
• the quaternization with dimethyl sulphate can likewise be efiected in an inert solvent, for instance benzene, used in an amount of about 500 to 1,000 parts per mol of the amine to be quaternized.
• Example 4 110 parts (0.87 mol) of benzyl chloride are added dropwise with a speed such that the temperature does not exceed l20130 to 45 parts (about 0.145 mol) of a technical amine mixture consisting of 75% of bis-(hexamethylene) triamine, and higher homologs,
• One suitable method of carrying out the process of the invention comprises using as the dyeing adjuvant a quaternary ammonium compound which is a reaction product of:
• Example I 100 parts of polyacrylonitrile yarn in the form of a tow (More Dyeable Orlon 42, from the firm of Du Pont) are dyed in 5,000 parts of a dyebath containing 0.7 part of the dyestuff of the formula 39 2H4-H C H103 ammonium compounds of the invention; these compounds 01110-8039 are produced by following the procedure of the example shown in the last column. 2H5
• Example 12 3 parts of sodium acetate 2 parts of 40% acetic acid and To 95 parts by weight of a 22.5% aqueous solution of polyethylene imine with a molecular Weight of from 30,000 to 40,000 there are added dropwise 70 parts by weight of benzyl chloride at 90.
• the reaction is exothermic; the inside temperature of the reaction mixture should be between 100 and 110 C.
• stirring is effected for a further 1% hours at 95 to 100.
• Subsequently distillation is effected of the excess benzyl chloride with water in a slight vacuum (about 100 mm. of Hg); water must be added as soon as the product becomes viscous.
• a total of parts by weight of benzyl chloride are recovered to that 50 parts by weight of benzyl chloride had been used up.
• the lower aqueous layer is rejected, but the upper one is dried in a vacuum (15 mm. of Hg) at 105.
• the dried residue is light brown and very viscous.
• the fibrous material is put into the dyebath at 40, heating to -98 is effected during 45 minutes and dye ing at this temperature is effected for 60 minutes.
• adjuvant i.e. ammonium compound No. 1
• ammonium compound N0. 1 has a retarding and levelling effect on the uptake of the dyestuff so that a very level, light and wet stable red brown dyeing is obtained, Whereas without the addition of ammonium compound N0. 1 the dyestuff is taken up very quickly and the resulting dyeing is not level.
• Example II Working is effected in accordance with the data of Example I with the addition of ammonium compound No. 3 and the dyestuffs listed in the following table are used instead of dyestulf (A).
• the dyestuffs (B) and (C) correspond to the respective formulae yellow Example III 100 parts of polyacrylonitrile yarns of various origins (as listed in Table 3) are dyed in 5,000 parts of a dyebath containing 3 parts of sodium acetate, 2 parts of 40% acetic acid, 0.16 to 1.0 part of an ammonium compound A likewise level, light and wet stable dyeing results when the dyestuff Basic Red. 26 is used instead of the dyestufi (A).
• Example V 100 parts of polyacrylonitrile yarn in the form of a tow (type: More Dyeable Orlon 42 of the firm Du Pont) are dyed in 5,000 parts of a dyebath containing 0.7 part of dyestulf (A),
• dyestuff (A) instead of dyestuff (A) it is possible to use, for example, the following dyestuffs:
• the fibrous material is put into the bath at 40, heating to 9598 is effected during 45 minutes and dyeing at this temperature is carried out for minutes.
• the ad juvant addition has a retarding and levelling elfect on the uptake of the dyestutl so that a level, light and Wet stable dyeing results.
• a a dialkylene triamine with 4 to 16 carbon atoms in the molecule
• c a polyalkylene polyamine or a derivative thereof selected from triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and hexaethylene heptamine, tetra (amino-propyl)- pentaethylene hexamine and polyethylene polyamines of high degree of polymerization, and of molecular weight of about 30,000 to 40,000;
• an aralkylation or phenylalkylation agent selected from the group consisting of l-(chloromethyl)- naphthalene, 2-(chloromethyl)-naphthalene, 1- or 2- (2-bromoethyl)-naphthalene, 2-, 3- or 4-me'thylbenzyl chloride, 2-, 3- or 4-ethylbenzyl bromide, 2-, 3- or 4- isopropylbenzyl chloride, ,B-chloroand fl-bromoethyl benzene ,styrene oxide, 2-, 3- or 4-phenoxybenzyl chloride, phenoxyethyl chloride and benzy chloride;
• a quaternization agent selected from alkyl halides with up to 6 carbon atoms in the molecule and alkyl sulphates with up to 6 carbon atoms in the molecule.
• an aralkylation agent selected from the phenylalkyl and naphthylalkyl series, and
• a quaternization agent selected from alkyl halides with up to 6 carbon atoms in the molecule and alkyl sulphates with up to 6 carbon atoms in the molecule.
• an aralkylation agent selected from the phenylalkyl and naphthylalkyl series, and
• a quaternization agent selected from alkyl halides with up to 6 carbon atoms in the molecule and alkyl sulphates with up to 6 carbon atoms in the molecule.
• an aralkylation agent selected from the phenylalkyl and naphthylalkyl series, and
• a quaternization agent selected from alkyl halides with up to 6 carbon atoms in the molecule and alkyl sulphates with up to 6 carbon atoms in the molecule.
• an aralkylation agent selected from the phenylalkyl and naphthylalkyl series, and
• a quaternization agent selected from alkyl halides with up to 6 carbon atoms in the molecule and alkyl sulphates with up to 6 carbon atoms in the molecule.
• constituent (iii) is selected from n-hexyl iodide, n-butyl bromide, methyl bromide, ethyl iodide, diethyl sulphate and dimethyl sulphate.
• constituent (i) is a mixture of amines.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Coloring (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (1)

Publications (1)

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Family Applications (1)

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Cited By (5)

• 1966
  • 1966-12-28 CH CH1862966A patent/CH484319A/de not_active IP Right Cessation
  • 1966-12-28 CH CH1862966D patent/CH1862966A4/xx unknown
• 1967
  • 1967-12-11 US US689354A patent/US3560142A/en not_active Expired - Lifetime
  • 1967-12-26 ES ES348624A patent/ES348624A1/es not_active Expired
  • 1967-12-27 BE BE708560D patent/BE708560A/xx unknown
  • 1967-12-27 GB GB58701/67A patent/GB1160938A/en not_active Expired
  • 1967-12-28 DE DE19671643526 patent/DE1643526A1/de active Granted
  • 1967-12-28 FR FR1551361D patent/FR1551361A/fr not_active Expired

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