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EP0025165A1 - Quaternary esters of hydroxyalkylamido amines, a process for their preparation and their utilization as fabric softening rinsing agents - Google Patents

Quaternary esters of hydroxyalkylamido amines, a process for their preparation and their utilization as fabric softening rinsing agents Download PDF

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Publication number
EP0025165A1
EP0025165A1 EP19800105053 EP80105053A EP0025165A1 EP 0025165 A1 EP0025165 A1 EP 0025165A1 EP 19800105053 EP19800105053 EP 19800105053 EP 80105053 A EP80105053 A EP 80105053A EP 0025165 A1 EP0025165 A1 EP 0025165A1
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Prior art keywords
alkyl
formula
hydrogen
methyl
compound
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German (de)
French (fr)
Inventor
Wolfgang Dr. Wagemann
Adolf Dr. May
Hans-Walter Dr. Bücking
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • 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

Definitions

  • the invention relates to quaternary esters of hydroxyalkylamidoamines having the general formula 1.
  • R 1 and P 3 are alkyl or alkenyl with 7 to 24 C atoms, R 2 alkyl or hydroxyalkyl with 1 to 4 C atoms or benzyl, R 4 is hydrogen or methyl, R 5 is hydrogen or alkyl with 1 to 6 C atoms , m 2 or 3, n is a number from 1 to 8 and X is a halogen, alkyl sulfate or alkyl phosphate anion.
  • R 1 and R 3 are alkyl having 15 to 22 carbon atoms
  • R 2 is methyl
  • R 4 is hydrogen
  • R 5 is hydrogen or methyl
  • m 3 is a number from 1 to 3
  • X. is a chloride or methosulfate anion.
  • These compounds are prepared by first using a diamine of the general formula 2 in an equimolar amount with a carboxylic acid of the general formula 3 implements.
  • the resulting amidoamine of Formula 4 is in the second reaction step with an alkylene oxide of formula 5 to the hydroxyalkylamidoamine of the formula 6 implemented.
  • This compound is esterified with a fatty acid R 3 COOH and reacted in the last step with an alkylating agent of the formula R 2 X to the quaternary esters according to the invention.
  • the reaction of the diamine (2) in the first stage with the carboxylic acid (3) is carried out in an inert solvent or, preferably, in bulk at temperatures from 120 to 200 ° C., preferably at 140 to 180 ° C. with simultaneous removal of the water of reaction formed. It goes without saying that derivatives such as acid chlorides or acid anhydrides can also be used instead of the free acids. The complete course of the reaction is controlled via the acid number.
  • the resulting amidoamines (4) are in a known manner with an alkylene oxide such as ethylene oxide or propylene oxide, mixtures of these two or with both agents successively, but preferably with ethylene oxide alone to the Hydroxialkylamidoaminen (6).
  • an alkylene oxide such as ethylene oxide or propylene oxide
  • the esterification of the hydroxiamidoamines (6) is carried out by known methods in higher-boiling inert solvents such as toluene or xylene or preferably in bulk with stoichiometric or slightly sub-stoichiometric amounts of a fatty acid R 3 COOH.
  • the reflux temperature of the reaction mixture is expediently chosen as the reaction temperature and the water of reaction formed is removed azeotropically.
  • the water of reaction is distilled off directly from the reaction mixture.
  • the reaction temperatures here are 140 to 220 ° C, preferably 150 to 180 ° C.
  • An acid catalyst such as p-toluenesulfonic acid is used to accelerate the reaction. The completeness of the reaction is checked by determining the acid number.
  • esters of hydroxyalkylamidoamines thus obtained are then dissolved in an alcohol or, preferably, dispersed in water and reacted with an alkylating agent R 2 X at temperatures below 100 ° C., preferably at 40 to 80 ° C., to give the quaternary products according to the invention.
  • This reaction can also be carried out without any solvent.
  • the pure compounds of the formula (1) are obtained.
  • the process is carried out in aqueous dispersion, with 20% aqueous dispersions of the compounds (1) being obtained directly, which, after appropriate dilution with water and preparation, can be used directly as fabric softener.
  • Diamines of the formula (2) used with preference are the industrially available products tallow fat propylene diamine or stearyl propylene diamine. But it is according to the inven It is equally possible to use other diamines with a more or less wide alkyl chain distribution. Such diamines are produced in a known manner by adding acrylonitrile to primary fatty amines and then catalytically hydrogenating the propionitriles. For the amidation with the carboxylic acid 3, formic acid or acetic acid is preferably used.
  • Fatty acids suitable for esterification are natural or synthetic products such as Palmitic acid, stearic acid, behenic acid or branched chain compounds from oxo synthesis such as e.g. Isostearic acid or mixtures of the ones mentioned, e.g. accrued from natural cuts derived from coconut oil or tallow.
  • the alkylating agent used is preferably methyl chloride or dimethyl sulfate.
  • the crfindungsdorfen compounds of formula (1) are suitable as a laundry Weichs p ülstoff and be in the form of aqueous dispersions with an active substance content of 1 to 15 wt .-%, usually 4 - 10 wt .-% of compounds of formula 1 following the wash the textile material in the last rinsing bath. The textile material is then dried.
  • These fabric softeners can also contain other substances and auxiliaries that are commonly used in fabric softeners. These include, for example, cationic or nonionic surface-active substances, electrolytes, acidifying agents, organic complexing agents, optical brighteners or solubilizers as well as colorants and fragrances.
  • the products are used to additionally influence the handle of the goods or other properties of the textiles to be treated or to adjust the viscosity, regulate the pH or increase the cold stability of the solutions.
  • the compounds according to the invention give any textile materials, especially those made from natural or regenerated cellulose, wool cellulose acetate, triacetate, polyamide, polyacrylonitrile, polyester, polypropylene, a pleasant and soft feel.
  • Use as a laundry treatment agent for terry and underwear is particularly advantageous.
  • the mixture is stirred at 140 ° C. for 2 hours and allowed to cool.
  • a medium-strong nitrogen stream is passed through the reaction mixture at 50 ° C. under vacuum for 1 hour.
  • 235 g of pourable, viscous product are obtained, which is transferred to a glass flask.
  • 122 g (0.45 mol) of technical stearic acid, 0.3 g of p-toluenesulfonic acid and 0.25 g of hydrazine hydrate are added and the mixture is heated to 170 ° C. with a blanket of nitrogen. Water distills off via a descending cooler. After four hours of stirring at 170 ° C., the acid number is less than 5.
  • Example 1 The procedure described in Example 1 is followed with the following amounts: To simplify matters, the entire synthesis can be carried out in an autoclave. In this case, devices for dropping and distilling off must be attached during the condensation steps.
  • A statistical mixture of 1 mol -CH 2 -CH 2 -O- and 0.7 mol

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Quaternary esters of hydroxyalkylamidoamines of the formula 1 <IMAGE> where R1 and R3 are alkyl or alkenyl of 7 to 24 carbon atoms, R2 is alkyl or hydroxyalkyl of 1 to 4 carbon atoms or benzyl, R4 is hydrogen or methyl, R5 is hydrogen or alkyl of 1 to 6 carbon atoms, m is 2 or 3, n is from 1 to 8, and X is a halogen, alkylsulphate or alkylphosphate anion, are useful as final rinse fabric softeners.

Description

Gegenstand der Erfindung sind quaternäre Ester von Hydroxialkylamidoaminen mit der allgemeinen Formel 1.

Figure imgb0001
wobei R1 und P3 Alkyl oder Alkenyl mit 7 bis 24 C-Atomen, R2 Alkyl oder Hydroxialkyl mit 1 bis 4 C-Atomen oder Benzyl, R4 Wasserstoff oder Methyl, R5 Wasserstoff oder Alkyl mit 1 bis 6 C-Atomen, m 2 oder 3, n eine Zahl von 1 bis 8 und X ein Halogen-, Alkylsulfat-, oder Alkylphosphatanion bedeuten.The invention relates to quaternary esters of hydroxyalkylamidoamines having the general formula 1.
Figure imgb0001
 where R 1 and P 3 are alkyl or alkenyl with 7 to 24 C atoms, R 2 alkyl or hydroxyalkyl with 1 to 4 C atoms or benzyl, R 4 is hydrogen or methyl, R 5 is hydrogen or alkyl with 1 to 6 C atoms , m 2 or 3, n is a number from 1 to 8 and X is a halogen, alkyl sulfate or alkyl phosphate anion.

Bevorzugt sind solche Verbindungen der Formel 1, worin R1 und R3 Alkyl oder Alkenyl mit 15 bis 22 C-Atomen, R2 Alkyl oder Hydroxialkyl mit 1 oder 2 C-Atomen oder Benzyl, R4 Wasserstoff, R5 Wasserstoff oder Methyl, m = 3, n eine Zahl von 1 bis 5 und X ein Chlorid-, Bromid- oder Methosulfat-Anion bedeuten.Preferred compounds of the formula 1 are those in which R 1 and R 3 are alkyl or alkenyl having 15 to 22 C atoms, R 2 alkyl or hydroxyalkyl having 1 or 2 C atoms or benzyl, R 4 is hydrogen, R 5 is hydrogen or methyl, m = 3, n is a number from 1 to 5 and X is a chloride, bromide or methosulfate anion.

Insbesondere bevorzugt sind solche Verbindungen der Formel 1, worin R1 und R3 Alkyl mit 15 bis 22 C-Atomen, R2 Methyl, R4 Wasserstoff, R5 Wasserstoff oder Methyl, m 3, n eine Zahl von 1 bis 3 und X ein Chlorid- oder Methosulfat-Anion bedeuten.Particularly preferred are those compounds of the formula 1 in which R 1 and R 3 are alkyl having 15 to 22 carbon atoms, R 2 is methyl, R 4 is hydrogen, R 5 is hydrogen or methyl, m 3, n is a number from 1 to 3 and X. is a chloride or methosulfate anion.

Diese Verbindungen werden hergestellt, indem man zunächst ein Diamin der allgemeinen Formel 2

Figure imgb0002
in äquimolaror Menge mit einer Carbonsäure der allgemeinem Formel 3
Figure imgb0003
umsetzt. Das resultierende Amidoamin der Formel 4
Figure imgb0004
wird im zweiten Reaktionsschritt mit einem Alkylenoxid der Formel 5
Figure imgb0005
zum Hydroxialkylamidoamin der Formel 6
Figure imgb0006
umgesetzt.These compounds are prepared by first using a diamine of the general formula 2
Figure imgb0002
 in an equimolar amount with a carboxylic acid of the general formula 3
Figure imgb0003
 implements. The resulting amidoamine of Formula 4
Figure imgb0004
 is in the second reaction step with an alkylene oxide of formula 5
Figure imgb0005
 to the hydroxyalkylamidoamine of the formula 6
Figure imgb0006
 implemented.

Diese Verbindung wird mit einer Fettsäure R3COOH verestert und im letzten Schritt mit einem Alkylierungsagens der Formel R2X zu den erfindungsgemäßen quaternären Estern umgesetzt.This compound is esterified with a fatty acid R 3 COOH and reacted in the last step with an alkylating agent of the formula R 2 X to the quaternary esters according to the invention.

Die Reaktion des Diamins (2) in der ersten Stufe mit der Carbonsäure (3) erfolgt in einem inerten Lösungsmittel oder bevorzugt in Substanz bei Temperaturen von 120 bis 200°C, bevorzugt bei 140 bis 180°C unter gleichzeitigem Entfernen des gebildeten Reaktionswassers. Es versteht sich, daß anstelle der freien Säuren auch Derivate wie Säurachloride oder Säureanhydride Verwendung finden können. Der vollständige Reaktionsablauf wird über die Säurezahl kontrolliert.The reaction of the diamine (2) in the first stage with the carboxylic acid (3) is carried out in an inert solvent or, preferably, in bulk at temperatures from 120 to 200 ° C., preferably at 140 to 180 ° C. with simultaneous removal of the water of reaction formed. It goes without saying that derivatives such as acid chlorides or acid anhydrides can also be used instead of the free acids. The complete course of the reaction is controlled via the acid number.

Die resultierenden Amidoamine (4) werden in bekannter Weiso mit einem Alkylenoxid wie Ethylenoxid oder Propylenoxid, Gemischen dieser beiden oder mit beiden Agenzien nacheinander, bevorzugt jedoch mit Ethylenoxid allein zu den Hydroxialkylamidoaminen (6) umgesetzt.The resulting amidoamines (4) are in a known manner with an alkylene oxide such as ethylene oxide or propylene oxide, mixtures of these two or with both agents successively, but preferably with ethylene oxide alone to the Hydroxialkylamidoaminen (6).

Die Veresterung der Hydroxiamidoamine (6) wird nach bekannten Verfahren in höhersiedenden inerten Lösungsmitteln wie Toluol oder Xylol oder bevorzugt in Substanz mit stöchiometrischen oder leicht unterstöchiometrischen Mengen einer Fettsäure R3COOH durchgeführt. Bei Veresterung in einem Lösungsmittel wählt man als Reaktionstemperatur zweckmäßigerweise die Rückflußtemperatur des Reaktionsgemisches und entfernt das gebildete Reaktionswasser azeotrop. Bei Veresterung in Substanz wird das Reaktionswasser direkt aus der Reaktionsmischung abdestilliert. Die Reaktionstemperaturen liegen hier bei 140 bis 220°C, bevorzugt bei 150 bis 180°C. Zur Beschleunigung der Reaktion verwendet man einen sauren Katalysator wie z.B. p-Toluolsulfonsäure. Die Vollständigkeit der Reaktion wird über die Bestimmung der Säurezahl kontrolliert.The esterification of the hydroxiamidoamines (6) is carried out by known methods in higher-boiling inert solvents such as toluene or xylene or preferably in bulk with stoichiometric or slightly sub-stoichiometric amounts of a fatty acid R 3 COOH. When esterifying in a solvent, the reflux temperature of the reaction mixture is expediently chosen as the reaction temperature and the water of reaction formed is removed azeotropically. In the case of esterification in bulk, the water of reaction is distilled off directly from the reaction mixture. The reaction temperatures here are 140 to 220 ° C, preferably 150 to 180 ° C. An acid catalyst such as p-toluenesulfonic acid is used to accelerate the reaction. The completeness of the reaction is checked by determining the acid number.

Die so erhaltenen Ester der Hydroxialkylamidoamine werden dann in einem Alkohol gelöst oder bevorzugt in Wasser dispergiert und mit einem Alkylierungsmittel R2X bei Temperaturen unter 100°C, vorzugsweise bei 40 bis 80°C zu den erfindungsgemäßen quaternären Produkten umgesetzt. Man kann diese Reaktion auch ohne jedes Lösungsmittel durchführen. Nach Abdestillieren des Wassers oder des Lösungsmittels erhält man so die reinen Verbindungen der Formel (1). Nach einer bevorzugten Ausführungsform der Erfindung arbeitet man in wäßriger Dispersion, wobei direkt 20 %ige wäßrige Dispersionen der Verbindungen (1) anfallen, die nach entsprechender Verdünnung mit Wasser und Konfektionierung direkt als Wäscheweichspülmittel verwendet werden können.The esters of hydroxyalkylamidoamines thus obtained are then dissolved in an alcohol or, preferably, dispersed in water and reacted with an alkylating agent R 2 X at temperatures below 100 ° C., preferably at 40 to 80 ° C., to give the quaternary products according to the invention. This reaction can also be carried out without any solvent. After distilling off the water or the solvent, the pure compounds of the formula (1) are obtained. According to a preferred embodiment of the invention, the process is carried out in aqueous dispersion, with 20% aqueous dispersions of the compounds (1) being obtained directly, which, after appropriate dilution with water and preparation, can be used directly as fabric softener.

Bevorzugt eingesetzte Diamine der Formel (2) sind die technisch verfügbaren Produkte Talgfettpropylendiamin oder Stearylpropylendiamin. Es ist aber gemäß der Erfindung ebensogut möglich, andere Diamine mit mehr oder weniger breiter Alkylkettenverteilung zu verwenden. Solche Diamine werden in bekannter Weise durch Anlagerung von Acrylnitril an primäre Fettamine und anschließende katalytische Hydrierung der Propionitrile hergestellt. Zur Amidierung mit der Carbonsäure 3 setzt man bevorzugt Ameisensäure oder Essigsäure ein.Diamines of the formula (2) used with preference are the industrially available products tallow fat propylene diamine or stearyl propylene diamine. But it is according to the inven It is equally possible to use other diamines with a more or less wide alkyl chain distribution. Such diamines are produced in a known manner by adding acrylonitrile to primary fatty amines and then catalytically hydrogenating the propionitriles. For the amidation with the carboxylic acid 3, formic acid or acetic acid is preferably used.

Zur Veresterung geeignete Fettsäuren sind Produkte auf natürlicher oder synthetischer Basis wie z.B. Palmitinsäure, Stearinsäure, Behensäure oder verzweigtkettige Verbindungen aus der Oxo-Synthese wie z.B. Isostearinsäure bzw. Gemische der genannten, wie sie z.B. aus natürlichen Schnitten anfallen, die sich vom Cocosöl oder Talg ableiten. Als Alkylierungsmittel verwendet man zweckmäßigerweise bevorzugt Methylchlorid oder Dimethylsulfat.Fatty acids suitable for esterification are natural or synthetic products such as Palmitic acid, stearic acid, behenic acid or branched chain compounds from oxo synthesis such as e.g. Isostearic acid or mixtures of the ones mentioned, e.g. accrued from natural cuts derived from coconut oil or tallow. The alkylating agent used is preferably methyl chloride or dimethyl sulfate.

Die crfindungsgemäßen Verbindungen der Formel (1) eignen sich als Wäscheweichspülmittel und werden in Form wäßriger Dispersionen mit einem Wirksubstanzgehalt von 1 bis 15 Gew.-%, meist 4 - 10 Gew.-% der Verbindungen der Formel 1 im Anschluß an die Wäsche des Textilmaterials in das letzte Spülbad gegeben. Danach wird das Textilmaterial getrocknet. Diese Wäscheweichspülmittel können außerdem noch weitere Substanzen und Hilfsmittel enthalten wie sie üblicherweise in Wäscheweichspülmitteln mitverwendet werden. Hierzu gehören z.B. kationische oder nichtionische oberflächenaktive Substanzen, Elektrolyte, Absäuerungsmittel, organische Komplexbildner, Optische Aufheller oder Lösungsvermittlcr sowie Farb- und Duftstoffe. Die Produkte dienen zur zusätzlichen Beeinflussung des Warengriffs oder sonstiger Eigenschaften der zu behandelnden Textilien oder zur Viskositätseinstellung, der pH-Regulierung oder zur Erhöhung der Kältestabilität der Lösungen.The crfindungsgemäßen compounds of formula (1) are suitable as a laundry Weichs p ülmittel and be in the form of aqueous dispersions with an active substance content of 1 to 15 wt .-%, usually 4 - 10 wt .-% of compounds of formula 1 following the wash the textile material in the last rinsing bath. The textile material is then dried. These fabric softeners can also contain other substances and auxiliaries that are commonly used in fabric softeners. These include, for example, cationic or nonionic surface-active substances, electrolytes, acidifying agents, organic complexing agents, optical brighteners or solubilizers as well as colorants and fragrances. The products are used to additionally influence the handle of the goods or other properties of the textiles to be treated or to adjust the viscosity, regulate the pH or increase the cold stability of the solutions.

Die Verbindungen gemäß der Erfindung verleihen beliebigen Textilmaterialien, besonders solchen aus natürlicher oder regenerierter Cellulose, Wolle Celluloseacetat, Triacetat, Polyamid, Polyacrylnitril, Polyester, Polypropylen einen angenehmen und weichen Griff. Besonders vorteilhaft ist der Einsatz als Wäschenachbehandlungsmittel für Frottee- und Leibwäsche.The compounds according to the invention give any textile materials, especially those made from natural or regenerated cellulose, wool cellulose acetate, triacetate, polyamide, polyacrylonitrile, polyester, polypropylene, a pleasant and soft feel. Use as a laundry treatment agent for terry and underwear is particularly advantageous.

Beispiel 1:Example 1:

180 g (0,5 Mol) technisches Talgfettpropylendiamin werden aufgeschmolzen. Bei 70°C tropft man 23,5 g (0,5 Mol) 98 %ige Ameisensäure hinzu und verrührt gut. Nun wird Stickstoff übergelagert und innerhalb von 15 Minuten auf 155°C aufgeheizt. Das gebildete Reaktionswasser destilliert über einen absteigenden Kühler ab. Nach zweistündigem Rühren bei 155°C ist die Säurezahl kleiner als 1. Das Produkt wird in einen Autoklav überführt. Man gibt 0,6 g frisch gepulvertes Natriumhydroxid zu, heizt auf 145°C und drückt bei einem Maximaldruck von 4 bar insgesamt 44 g (1 Mol) Ethylenoxid auf. Nach vollständiger Zugabe wird 2 Stunden bei 140°C nachgerührt und abkühlen gelassen. Zur Entfernung eventuell noch vorhandener Reste an Ethylenoxid wird bei 50°C unter Vakuum 1 Stunde ein mittelstarker Stickstoffstrom durch die Reaktionsmischung geleitet. Man erhält 235 g gießbares, viskoses Produkt, das in einen Glaskolben überführt wird. Man gibt 122 g (0,45 Mol) technische Stearinsäure, 0,3 g p-Toluolsulfonsäure und 0.25 g Hydrazinhydrat zu und erhitzt unter Überlagerung mit Stickstoff auf 170°C. Dabei destilliert Wasser über einen absteigenden Kühler ab. Nach vierstündigem Rühren bei 170°C ist die Säurezahl kleiner als 5. Man erhält 348 g einer wachsartigen, gelblichen Masse, die in aufgeschmolzenem Zustand wieder in einen Autoklav überführt wird. Unter gutem Rühren fügt man 1400 ml 70°C heißes Wasser portionsweise zu, so daß eine feine Dispersion des Esters gebildet wird. Der Autoklav wird verschlossen und bei 70°C solange Methylchlorid aufgedrückt bis ein konstanter Druck von 4 bar erhalten wird. Nach dem Abkühlen und Entspannen wird zur Entfernung von CH3Cl-Resten dreimal mit Stickstoff gespült. Man erhält eine 20 %ige wäßrige Dispersion des erfindungsgemäßen Produktes. Der Quaternisierungsgrad beträgt mehr als 95 %.180 g (0.5 mol) of technical tallow fat propylene diamine are melted. At 70 ° C., 23.5 g (0.5 mol) of 98% formic acid are added dropwise and the mixture is stirred well. Now nitrogen is superimposed and heated to 155 ° C within 15 minutes. The water of reaction formed distills off via a descending condenser. After stirring for two hours at 155 ° C., the acid number is less than 1. The product is transferred to an autoclave. 0.6 g of freshly powdered sodium hydroxide is added, the mixture is heated to 145 ° C. and a total of 44 g (1 mol) of ethylene oxide is pressed in at a maximum pressure of 4 bar. After the addition is complete, the mixture is stirred at 140 ° C. for 2 hours and allowed to cool. To remove any residual ethylene oxide that may still be present, a medium-strong nitrogen stream is passed through the reaction mixture at 50 ° C. under vacuum for 1 hour. 235 g of pourable, viscous product are obtained, which is transferred to a glass flask. 122 g (0.45 mol) of technical stearic acid, 0.3 g of p-toluenesulfonic acid and 0.25 g of hydrazine hydrate are added and the mixture is heated to 170 ° C. with a blanket of nitrogen. Water distills off via a descending cooler. After four hours of stirring at 170 ° C., the acid number is less than 5. 348 g of a waxy, yellowish mass are obtained which, in the molten state, are transferred back to an autoclave. With good stirring, 1400 ml of 70 ° C hot water are added in portions, so that a fine dis persion of the ester is formed. The autoclave is closed and methyl chloride is pressed in at 70 ° C. until a constant pressure of 4 bar is obtained. After cooling and relaxing, the mixture is flushed three times with nitrogen to remove CH 3 Cl residues. A 20% aqueous dispersion of the product according to the invention is obtained. The degree of quaternization is more than 95%.

Beispiel 2Example 2

Es wird nach dem in Beispiel 1 beschriebenen Verfahren mit folgenden Einsatzmengen vorgegangen:

Figure imgb0007
Zur Vereinfachung kann die gesamte Synthese im Autoklaven durchgeführt werden. Bei den Kondensationsschritten müssen in diesem Falle Vorrichtungen zum Zutropfen und Abdestillieren angebracht werden.The procedure described in Example 1 is followed with the following amounts:
Figure imgb0007
 To simplify matters, the entire synthesis can be carried out in an autoclave. In this case, devices for dropping and distilling off must be attached during the condensation steps.

Beispiel 3Example 3

Analog Beispiel 1 mit folgenden Einsatzprodukten:

Figure imgb0008
Figure imgb0009
Dem suspendierten Ester werden bei 70°C (0,49 Mol) Dimethylsulfat zugetropft (pH = 3). Nach zweistündigem Nachrühren wird mit 2n-NaOH auf pH = 6 eingestellt (Quaternisierungsgrad > 97 %).Analogous to example 1 with the following input products:
Figure imgb0008
Figure imgb0009
 Dimethyl sulfate (pH = 3) is added dropwise to the suspended ester at 70 ° C. (0.49 mol). After stirring for two hours, the pH is adjusted to 6 using 2N NaOH (degree of quaternization> 97%).

Beispiel 4Example 4

Es wird analog Beispiel 1 vorgegangen:

Figure imgb0010
The procedure is analogous to Example 1:
Figure imgb0010

Beispiel 5Example 5

Es wird analog Beispiel 1 vorgegangen:

Figure imgb0011
Figure imgb0012
Die Konstitution der nach den Beispielen 1 bis 5 erhaltenen Verbindungen der Formel 1 ist aus der folgenden Tabelle ersichtlich:The procedure is analogous to Example 1:
Figure imgb0011
Figure imgb0012
 The constitution of the compounds of formula 1 obtained according to Examples 1 to 5 can be seen from the following table:

Beispiel 1:Example 1:

Figure imgb0013
Figure imgb0013

Beispiel 2:Example 2:

Figure imgb0014
A = statistisches Gemisch aus 1 Mol -CH2-CH2-O-und 0,7 Mol
Figure imgb0015
Figure imgb0014
 A = statistical mixture of 1 mol -CH 2 -CH 2 -O- and 0.7 mol
Figure imgb0015

Beispiel 3:Example 3:

Figure imgb0016
Figure imgb0016

Beispiel 4:Example 4:

Figure imgb0017
Figure imgb0017

Beispiel 5:Example 5:

Figure imgb0018
Figure imgb0018

Claims (5)

1. Verfahren zur Herstellung der Verbindungen der Formel 1
Figure imgb0023
wobei R1 und R3 Alkyl oder Alkenyl mit 7 bis 24 C-Atomen, R2 Alkyl oder Hydroxialkyl mit 1 bis 4 C-Atomen oder Benzyl, R4 Wasserstoff oder Methyl, R5 Wasserstoff oder Alkyl mit 1 bis 6 C-Atomen, m 2 oder 3, n eine Zahl von 1 bis 8 und X ein Halogen-, Alkylsulfat-, oder Alkylphosphatanion bedeuten, dadurch gekennzeichnet, daß man zunächst eine Verbindung der Formel 2
Figure imgb0024
mit einer Verbindung der Formel 3
Figure imgb0025
umsetzt, die resultierende Verbindung mit einer Verbindung der Formel 6
Figure imgb0026
umsetzt, das Produkt mit einer Fettsäure R3COOH verestert und anschließend mit einem Alkylierungsmittel R2X quaternisiert.1. Process for the preparation of the compounds of formula 1
Figure imgb0023
 where R 1 and R 3 are alkyl or alkenyl with 7 to 24 C atoms, R 2 alkyl or hydroxyalkyl with 1 to 4 C atoms or benzyl, R 4 is hydrogen or methyl, R 5 is hydrogen or alkyl with 1 to 6 C atoms , m 2 or 3, n is a number from 1 to 8 and X is a halogen, alkyl sulfate or alkyl phosphate anion, characterized in that a compound of the formula 2
Figure imgb0024
 with a compound of formula 3
Figure imgb0025
 reacting the resulting compound with a compound of formula 6
Figure imgb0026
 reacted, the product esterified with a fatty acid R 3 COOH and then quaternized with an alkylating agent R 2 X. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man eine Verbindung der Formel 1 herstellt, wobei R1 und R3 Alkyl oder Alkenyl mit 15 bis 22 C-Atomen, R2 Alkyl oder Hydroxialkyl mit 1 oder 2 C-Atomen oder Benzyl, R4 Wasserstoff, R5 Wasserstoff oder Methyl, m = 3, n eine Zahl von 1 bis 5 und X ein Chorid-, Bromid- oder Methosulfat-Anien bedeuten.2. The method according to claim 1, characterized in that one produces a compound of formula 1, wherein R 1 and R 3 alkyl or alkenyl having 15 to 22 carbon atoms, R 2 alkyl or hydroxyalkyl with 1 or 2 carbon atoms or benzyl , R 4 is hydrogen, R 5 is hydrogen or methyl, m = 3, n is a number from 1 to 5 and X is a choride, bromide or methosulfate anien. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man eine Verbindung der Formel 1 herstellt, wobei R1 und R3 Alkyl mit 15 bis 22 C-Atomen, R2 Methyl, R4 Wasserstoff, R5 Wasserstoff oder Methyl, m= 3, n eine Zahl von 1 bis 3 und X ein Chlorid oder Methosulfat-Anion bedeuten.3. The method according to claim 1, characterized in that one produces a compound of formula 1, wherein R 1 and R 3 alkyl having 15 to 22 carbon atoms, R 2 methyl, R 4 hydrogen, R 5 hydrogen or methyl, m = 3, n is a number from 1 to 3 and X is a chloride or methosulfate anion. 4. Verwendung der Verbindungen der Formel 1 nach Anspruch 1 als Wäscheweichspülmittel.4. Use of the compounds of formula 1 according to claim 1 as fabric softener.
EP19800105053 1979-09-07 1980-08-26 Quaternary esters of hydroxyalkylamido amines, a process for their preparation and their utilization as fabric softening rinsing agents Withdrawn EP0025165A1 (en)

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DE19792936121 DE2936121A1 (en) 1979-09-07 1979-09-07 QUATERNAERE ESTERS OF HYDROXIALKYLAMIDOAMINES, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF AS A SOFT SOFT DETERGENT
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EP0316701A3 (en) * 1987-11-14 1990-10-17 Henkel Kommanditgesellschaft auf Aktien Quaternary amidoammonium salts, process for their preparation and their use
EP0643128A1 (en) * 1993-09-10 1995-03-15 Kao Corporation Aqueous fabric softener composition, novel quaternary ammonium salt, and process for the preparation of said salt
EP0707059A3 (en) * 1994-10-14 2001-04-18 Kao Corporation Liquid softener composition, use thereof and process for preparing a quaternary ammonium salt

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US4737741A (en) * 1986-10-20 1988-04-12 Hughes Aircraft Company Orthogonal mode electromagnetic wave launcher
JPH0618287B2 (en) * 1987-01-28 1994-03-09 富士通株式会社 Ultra-small broadband antenna
SE9001862D0 (en) * 1990-05-23 1990-05-23 Berol Nobel Ab NEW NUCLEAR CONTAINING SOCIETIES, PROCEDURES FOR THEIR PREPARATION AND USE OF SOCIETIES
DE4135115A1 (en) * 1991-10-24 1993-04-29 Trigon Chemie Gmbh New cationic quat. ammonium chloride surfactants - used as brighteners, conditioners and disinfectants, e.g. for textiles
CA3016025C (en) 2016-03-01 2021-01-26 Ecolab Usa Inc. Sanitizing rinse based on quat-anionic surfactant synergy
MX2019001666A (en) 2016-08-11 2019-07-04 Ecolab Usa Inc INTERACTION BETWEEN QUATERNARY ANTIMICROBIAL COMPOUNDS AND ANIONIC SURFACTANTS.

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Publication number Priority date Publication date Assignee Title
EP0316701A3 (en) * 1987-11-14 1990-10-17 Henkel Kommanditgesellschaft auf Aktien Quaternary amidoammonium salts, process for their preparation and their use
EP0643128A1 (en) * 1993-09-10 1995-03-15 Kao Corporation Aqueous fabric softener composition, novel quaternary ammonium salt, and process for the preparation of said salt
US5476597A (en) * 1993-09-10 1995-12-19 Kao Corporation Liquid softener composition, novel quaternary ammonium salt, and process for the preparation of said salt
US5580481A (en) * 1993-09-10 1996-12-03 Kao Corporation Aqueous fabric softener composition, novel quaternary ammonium salt, and process for the preparation of said salt
EP0707059A3 (en) * 1994-10-14 2001-04-18 Kao Corporation Liquid softener composition, use thereof and process for preparing a quaternary ammonium salt
EP1445303A3 (en) * 1994-10-14 2004-10-20 Kao Corporation Liquid softener composition

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