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
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating 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
  • D06M13/402—Amides imides, sulfamic acids
  • D06M13/405—Acylated polyalkylene polyamines
• • 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
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating 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
  • D06M13/325—Amines
  • D06M13/332—Di- or polyamines
• • 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
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating 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
  • D06M13/46—Compounds containing quaternary nitrogen atoms
  • D06M13/467—Compounds containing quaternary nitrogen atoms derived from polyamines
• • 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
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2762—Coated or impregnated natural fiber fabric [e.g., cotton, wool, silk, linen, etc.]
  • Y10T442/277—Coated or impregnated cellulosic fiber fabric

Definitions

• the present invention relates to diquaternary ammonium salts, a process for their preparation and their use as textile finishing agents, the diquaternary ammonium salts according to the invention e.g. be prepared from dialkylaminoalkyl behenic acid amides and aliphatic epoxy compounds and thus have aliphatic bridge members between the two quaternary nitrogen atoms, which are always substituted by at least one hydroxyl group.
• DE-AS 1 092 878 discloses diquaternary ammonium salts which are prepared from dialkylaminoalkyl fatty acid amides and an epoxy compound, the fatty acids, however, having at most 18 carbon atoms as starting components.
• the known diquaternary ammonium salts are used as dyeing aids, in particular as leveling agents for dyeings on polyacrylonitrile fibers.
• diquaternary ammonium salts which e.g. from dialkylaminoalkyl behenic acid amides and aliphatic dihalo compounds, e.g. ⁇ , ⁇ '-Dibromodiethyl ether are produced and thus have aliphatic bridge members between the two quaternary nitrogen atoms, which are free of hydroxyl substituents.
• diquaternary ammonium salts are used in hair cosmetics, in particular shampoos and rinsing agents.
• Diquaternary ammonium salts have been found which, because of their properties, are used as textile finishing agents.
• alkylene radicals A 1 and A 2 in formula (1) are straight-chain or branched.
• 2,2-Dimethylpropylene also called neopentylene
• n-butylene tetramethylene
• n-propylene trimethylene
• Suitable substituents R 1 to R 4 are straight-chain or branched alkyl radicals, such as, for example, tert-butyl, isobutyl, n-butyl, isopropyl, n-propyl or, above all, ethyl or methyl.
• the corresponding hydroxyalkyl radicals for example hydroxyethyl, are also suitable .
• the alkoxyalkyl radicals each have 1 to 4 carbon atoms in the alkyl part and alkoxy part. Alkyoxyalkyl radicals thus contain a total of 2 to 8 carbon atoms. Examples include hydroxyethyl and ethoxyethyl. Unsubstituted alkyl radicals of the type indicated above are preferred
• Y 1 n ⁇ represents, if n is 1, the monovalent anion, and if n 2 is the divalent anion of a strong acid, in formula (1) depending on the value of n either 1 divalent anion or 2 monovalent anions are present.
• the monovalent or divalent anion of basically any water-soluble, inorganic or organic acid comes into consideration as the definition of Y 1 n ⁇ .
• the anion of an inorganic acid or an organic sulfonic acid is preferred.
• Halide, sulfate, methyl sulfate or ethyl sulfate ions are mentioned as representatives of such anions, with halide anions, especially the chloride anion, being of primary interest.
• the bridge member Zi in formula (1) is always interrupted by hydroxyl groups, especially 1 to 4 hydroxyl groups and optionally by 2 to 6 oxygen atoms, and preferably has 3 to 24 carbon atoms.
• Bridge members with, for example, 3 or 4 carbon atoms are mainly substituted by 1 or 2 hydroxy groups and are generally not interrupted by oxygen atoms, while bridge members with about 8 to 24 carbon atoms are primarily substituted by 2, 3 or 4 hydroxyl groups and preferably by oxygen atoms, especially by 2 up to 6 oxygen atoms are interrupted.
• Bridge members of particular interest are derived from an epihalohydrin, preferably epichlorohydrin, from an aliphatic diepoxide, especially a diepoxyalkane such as 1,2,3,4-diepoxybutane (also called butadiene dioxide) or 1,4-butanediol diglycidyl ether or a diglycidyl ether, that of an epihalohydrin, especially epichlorohydrin, and a lower alkylene glycol with preferably at most 4 carbon atoms, such as tetramethylene glycol (1,4-butanediol), dimethylethylene glycol (2,3-butanediol), trimethylene glycol (1,3-propanediol), especially propylene glycol (1,2-propanediol) or in particular ethylene glycol (1,2-ethanediol) is obtained, such diglycidyl ethers being monomers or oligomers which contain 2 to 4 units -CH 2
• the two leftovers in formula (1) stand for the rest of preferably technical behenic acid, which contains a smaller amount of, for example, arachidic acid and erucic acid and, above all, represents the hydrolysis product of the unsaturated C 22 acids from rapeseed oil.
• Such technical behenic acids have molecular weights of about 326 to about 354.
• the bridge members -At-Qt- on the one hand and ⁇ A 2 ⁇ Q 2 - on the other hand preferably have the same meanings in formula (1).
• the alkylene chain in Z 2 can be interrupted by 2 to 6 oxygen atoms.
• ammonium salts of formula (2) are prepared by adding about 2 moles of a dialkylaminoalkyl behenic acid amide or ester of the formula wherein A 1 , Q 1 , R s and R 6 have the meanings given, with about 1 mol of an epoxy compound of the formula wherein X 1 and X 2 have the meanings given and Z "optionally alkylene having 1 to 20 carbon atoms substituted by 1 or 2 hydroxyl groups and optionally interrupted by 2 to 6 oxygen atoms, or, if X 2 is an epoxy group, Z" also for is direct bond, in the presence of an acid of the formula where Y 2 and n have the meanings given.
• ammonium salts of formula (3) are prepared by adding about 2 moles of a dialkylaminoalkyl behenic acid amide or ester of the formula wherein Ai, 0 1 and Rs have the meanings given, with about 1 mol of an epoxy compound of the formula wherein Xi and X 2 have the meanings given and Z "is methylene or, if X 2 is an epoxy group, the direct bond or interrupted by 2 to 6 oxygen atoms and optionally substituted by 1 or 2 hydroxyl groups alkylene having 4 to 20 carbon atoms, in the presence an acid of the formula where Y 3 and n have the meanings given.
• ammonium salts of formula (4) are prepared by adding about 2 moles of a dialkylaminoalkyl behenic acid amide or ester of the formula wherein Aa, 0 1 and R 7 have the meanings given, with 1 mol of epichlorohydrin, 1,2,3,4-diepoxybutane, 1,4-butanediol diglycidyl ether or a diglycidyl ether, which is obtained from ethylene glycol and epichlorohydrin, in the presence of an acid Formula- where Y 4 ⁇ has the meanings given.
• dialkylaminoalkyl behenic acid amides or esters of the formulas (7), (8), (11), (14) and (17) are known per se and are prepared by known methods by adding behenic acid with approximately equimolar amounts of corresponding dialkylaminoalkylamines or dialkylaminoalkanols elevated temperature above 100 ° C, for example 150 to 180 ° C, with removal from the reaction mixture of the water formed by the reaction.
• the reaction of the compounds of formulas (7), (8) and (9) in the presence of the acid of formula (10) are preferably carried out at elevated temperature, e.g. 50 to 90 ° C, generally in an aqueous medium and optionally in the presence of a polar solvent, preferably a low molecular weight amide or ether, such as e.g. Dimethylformamide, diethylene glycol monobutyl ether or especially a low molecular weight alkanol such as e.g. Ethanol, especially butylgycol or especially isopropanol.
• a polar solvent preferably a low molecular weight amide or ether, such as e.g. Dimethylformamide, diethylene glycol monobutyl ether or especially a low molecular weight alkanol such as e.g. Ethanol, especially butylgycol or especially isopropanol.
• the ammonium salts according to the invention are used as water repellents, wrinkle-free
• the textile material which is finished according to the invention can be processed in any processing stage, i.e. as yarns, staple fibers, continuous threads, non-wovens, especially as woven or knitted fabrics, dyed or undyed, treated with or without an optical brightener or available as a further processed garment.
• Fully synthetic, semi-synthetic and natural fibers can be considered as textile fibers. Mixtures of synthetic and natural fibers are also possible.
• Examples of synthetic fibers are rayon, rayon, viscose, cellulose di- and triacetate, polyacrylonitrile, acrylonitrile copolymers, polyamide, in particular fibers made of poly-2-caprolactam, polyhexylmethylene diamide adipate or poly- ⁇ -aminoundecanoic acid and polyester, in particular fibers, which differ from the Derive terephthalic acid, e.g. Poly (ethylene glycol terephthalate) or poly (1,4-cyclohexylenedimethylene terephthalate), and examples of natural fibers include linen, hemp, ramie, wool and cotton.
• Derive terephthalic acid e.g. Poly (ethylene glycol terephthalate) or poly (1,4-cyclohexylenedimethylene terephthalate)
• natural fibers include linen, hemp, ramie, wool and cotton.
• wool, polyacrylonitrile, polyamide, polyester or cotton fabrics or knits as well as fabrics or knitted fabrics made from mixtures of the fibers mentioned can be refined.
• preparations which contain a diquaternary ammonium salt according to the invention are applied to the textile materials by customary processes.
• the preparations can be sprayed or puffed onto the textile materials.
• the textile materials are preferably padded with the preparations or treated by the exhaust process.
• the application takes place at room temperature or at elevated temperatures of, for example, 30 to 100 ° C. for about 5 to 120 minutes.
• the textile materials are then dried at room temperature or preferably at an elevated temperature, for example at 50 to 150 ° C.
• the diquaternary ammonium salts according to the invention are expediently used in amounts of 0.05 to 5% by weight, preferably 0.1 to 4% by weight, based on the textile material to be finished.
• the diquaternary ammonium salts according to the invention have the essential advantage of bringing about good finishing effects of the above-mentioned various types which can be applied to a large number of textile materials.
• dialkylaminoalkyl behenic acid amides or esters with the corresponding amine numbers are obtained in an analogous manner if behenic acid is reacted with the dialkylaminoalkylamines or dialkylaminoalkanols also listed in Table I:
• Example 1 A solution of 12.3 g of concentrated hydrochloric acid in 73 g of water and 43 g of isopropanol are added at 60 ° C. to 106.25 g of dimethylaminoethylbehenic acid amide according to preparation instruction B (0.25 mol). 11.6 g of epichlorohydrin (0.125 mol) are then added over the course of 15 minutes, and the temperature is then raised to 75 ° C. The reaction solution is kept at this temperature for 10 hours while stirring. After this time, the amine and epoxy values are 0. The reaction solution is then evaporated to dryness. 122 g of the diquaternary ammonium compound of the formula are obtained
• Example 2 101 g of dimethylamino-n-propylbehenic acid ester according to specification C (0.25 mol) are mixed at 60 ° C. with a solution of 12.3 g of concentrated hydrochloric acid in 73 g of water and 43 g of isopropanol. 11.6 g of epichlorohydrin (0.125 mol) are then added over the course of 15 minutes, and the temperature is then raised to 75 ° C. The reaction solution is kept at this temperature for 10 hours while stirring. After this time, the amine and epoxy values are 0. The reaction product is then evaporated to dryness.
• Example 3 A solution of 12.3 g of concentrated hydrochloric acid in 73 g of water and 43 g of isopropanol is added at 60 ° C. to 104.5 g of diethylaminoethylbehenic acid amide according to instruction D (0.25 mol). 11.6 g of epichlorohydrin (0.125 mol) are then added over the course of 15 minutes, and the temperature is then raised to 75 ° C. The reaction solution is kept at this temperature for 10 hours while stirring. After this time, the amine and epoxy values are 0. Then the reaction solution is evaporated to dryness. 120 g of the diquaternary ammonium compound of the formula are obtained
• Example 4 109.75 g of dimethylamino-n-propylbehenic acid amide according to instruction A (0.25 mol) are dissolved in 44 g of isopropanol with heating and then a solution of 12.3 g of concentrated hydrochloric acid in 74 g of water is added. 11.6 g of epichlorohydrin (0.125 mol) are added at 55 ° C. in the course of 15 minutes. The temperature of the reaction solution is then raised to 75 ° C. and the reaction solution is kept at this temperature for 3 hours with stirring. After this time, the amine and epoxy values are 0. 251 g of a 50% strength reaction solution of the diquaternary ammonium compound of the formula which is waxy at room temperature are obtained
• Example 5 65.6 g of dimethylamino-n-propylbehenic acid amide according to instruction A (0.15 mol) are melted at 80 ° C., and 14.8 g of 37% hydrochloric acid in 758.6 g of water are added. 16.35 g of 1,4-butanediol diglycidyl ether, which has an epoxide number of 4.6 (0.075 mol), are then added to the reaction mixture at 60 ° C. in the course of 10 minutes. The reaction mixture is then heated to 70 ° C. and kept at this temperature with stirring for one hour. After this time, the amine and epoxide values are 0. 855 g of a 10% strength solution of the diquaternary ammonium salt of the formula are obtained
• Example 6 65.6 g of dimethylamino-n-propylbehenic acid amide (0.15 mol) according to instruction A are melted at 80 ° C. and 5.1 g of sulfuric acid in 1083.6 g of water are added. 16.35 g (0.075 mol) of 1,4-butanediol diglycidyl ether, which has an epoxide number of 4.6, are then added to the reaction mixture at 60 ° C. in the course of 10 minutes. The reaction mixture is then heated to 70 ° C. and kept at this temperature with stirring for 10 hours. After this time the amine value is 28 and the epoxy value 0. 1170 g of a 7% solution are obtained which predominantly contains the diquaternary ammonium salt of the following formula:
• Example 7 45.8 g of dimethylaminoneopentylbehenic acid amide (0.1 mol) according to instruction E are heated together with 9.9 g of concentrated hydrochloric acid in 500.4 g of water to an internal temperature of 75 ° C. Then 10.9 g (0.05 mol) of 1,4-butanediol diglycidyl ether, which has an epoxide number of 4.6, are added in the course of 15 minutes and the mixture is stirred at 77-78 ° C. for 12 hours and epoxy values 0. 567 g of a 10% solution of the diquaternary ammonium salt of the formula are obtained:
• Example 8 42.3 g of diisopropylaminoethyl behenic acid amide (0.1 mol) according to instruction F are heated to 75 ° C. together with 9.9 g of concentrated hydrochloric acid in 479.8 g of water. Then 10.9 g (0.05 mol) of 1,4-butanediol dyglycidyl ether, which has an epoxide number of 4.6, are added within 15 minutes and the mixture is stirred at 75 ° C. for 12 hours. After this time, the amine and Epoxy values 0. 542 g of a 10% solution of the diquaternary ammonium salt of the formula are obtained
• Example 9 1 kg of cotton jersey is treated in the liquor ratio 1:30 in the exhaust process with a liquor at 40 ° C. for 20 minutes, which contains 4% of the diquaternary ammonium salt according to Example 4 and has a pH of 5.5 by adding acetic acid .
• the jersey is then dried without rinsing.
• To check the sewability use a long-fiber mower made of polyester with a sewing machine (Overlock Union Spezial type 39500) at 6000 stitches / min. a seam of 50 cm is attached. A needle with a Nm 70 tip is used. The number of holes along the seam is assessed. It was compared to a cotton jersey that was not treated.
• Table II The results are summarized in Table II below:
• Example 10 The knitted fabrics tested for sewability in Example 9 were also subjected to a soiling test. Dry soiling is assessed according to the following test: substrate; Size 9 x 12 cm (several test specimens) filter dust 15% on product weight apparatus Turbula running time 30 min. vacuum with a vacuum cleaner
• Example 11 100 kg of cotton jersey in 4000 liters of water, which contains a commercial wetting agent, are pretreated at 50 ° C. in a reel runner.
• the jersey After a further 45 min. at 80 ° C the jersey is rinsed with hot and then with cold water and then with 4000 liters of a liquor in a liquor ratio of 1:40 for 20 min. Washed at cooking temperature, the 4 kg of an adduct of 1 mole of nonylphenol and 9 moles of ethylene contains oxide and 4 kg of diquaternary ammonium salt according to Example 4. The jersey is then rinsed and dried again. In the monsanto picture as a measure for the wrinkle-free finishing of the treated jersey, the grade 4 is obtained. If the jersey is treated as stated above, but without the addition of the diquaternary ammonium salt in the dyebath and in the post-wash liquor, grade 2 is obtained in the monsanto picture.
• Example 13 A washing machine with a filling of approx. 4 kg is loaded with the following material:

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1986
  • 1986-11-03 EP EP86810499A patent/EP0221855B1/de not_active Expired - Lifetime
  • 1986-11-03 DE DE8686810499T patent/DE3672564D1/de not_active Expired - Lifetime
  • 1986-11-07 ZA ZA868483A patent/ZA868483B/xx unknown
  • 1986-11-08 JP JP61264917A patent/JPS62174042A/ja active Granted
• 1988
  • 1988-11-10 US US07/270,378 patent/US4906413A/en not_active Expired - Fee Related

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