EP0108321A2 - Application of low molecular organic compounds as viscosity regulators for highly viscous technical tenside concentrates - Google Patents

Application of low molecular organic compounds as viscosity regulators for highly viscous technical tenside concentrates Download PDF

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Publication number
EP0108321A2
EP0108321A2 EP83110590A EP83110590A EP0108321A2 EP 0108321 A2 EP0108321 A2 EP 0108321A2 EP 83110590 A EP83110590 A EP 83110590A EP 83110590 A EP83110590 A EP 83110590A EP 0108321 A2 EP0108321 A2 EP 0108321A2
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EP
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Prior art keywords
acid
concentrates
viscosity
esters
salts
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EP83110590A
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German (de)
French (fr)
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EP0108321A3 (en
EP0108321B1 (en
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Karl Dr. Schmid
Horst Dr. Baumann
Hans Josef Rommerskirchen
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT83110590T priority Critical patent/ATE27175T1/en
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Publication of EP0108321A3 publication Critical patent/EP0108321A3/en
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/03—Organic sulfoxy compound containing
    • 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
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/03—Organic sulfoxy compound containing
    • Y10S516/04—Protein or carboxylic compound containing

Definitions

  • aqueous slurries which contain a large part of the detergent constituents or also all detergent constituents. From an economic point of view, it is important that the slurry is as rich in detergent components as possible, i.e. is as low in liquid fiber as possible. The lowest possible amount of water is therefore used to prepare the slurries. Concentration is limited by the highest possible viscosity at which the slurry can just be processed.
  • anionic surfactants which are mostly used as paste-like concentrates in the form of their alkali or ammonium salts in the production of the detergent slurries.
  • the surfactant content of technical concentrates is, for example in the case of the ⁇ -sulfotalg fatty acid methyl ester, about 30% by weight. Pastes with a higher surfactant content can no longer be processed.
  • a special feature of the rheological behavior of surfactant concentrates is that they do not react to the addition of water with a reduction in viscosity, but first with a thickening to a gel-like state, which poses further problems for the processor. For example, it is often not. easy to get formed lumps of gel back into solution, or it clogs valves of pumps and containers.
  • DE-OS 22 51 405 describes the salts of certain carboxylic acids, in particular hydroxycarboxylic acids, as viscosity regulators.
  • sulfonated aromatic compounds are suitable for these purposes.
  • DE-OS 23 26 006 mentions sulfates or sulfonates of aliphatic, optionally substituted hydrocarbons as viscosity regulators. The addition of lower alkanols is also listed as a possibility for reducing the viscosity in the publications mentioned.
  • Object of the present invention is therefore the provision of substances for improving the F l ware- behavior of aqueous technical anionic surfactant concentrates, in particular of ⁇ -sulfo fatty acid esters, so that they are processed as previously in higher concentrations or when diluted with water, no increase in the Have viscosity.
  • viscosity regulator for highly viscous technical surfactant concentrates of the type of synthetic anionic surfactants, in particular of ⁇ -sulfofatty acid esters with at least 30% by weight of ⁇ -sulfofatty acid esters, the viscosity regulator being used in amounts of 1-15% by weight, based on the amount of surfactant , adds, so that a reduction in the viscosity of the concentrates to a maximum of 10,000 mPas at 70 ° C occurs, can achieve the desired effects.
  • surfactant content can be adjusted to values of approximately approximately 60% by weight in the industrial production of the surfactant concentrates without the viscosity being the upper limit of approximately 10,000 mPas permissible for processability exceeds, whereby surfactant concentrates with lower water ballast are obtained.
  • these concentrates are diluted, the temporary increase in viscosity which is otherwise observed does not occur, which is also advantageous for processing.
  • the viscosity regulators are preferably added to the aqueous industrial anionic surfactant concentrates in amounts of approx. 10% by weight, i.e. in particular 7 to 12% by weight, based on the surfactant content, the desired viscosity reduction of the concentrate being determined by the amounts of the viscosity regulator added.
  • the compounds suitable as viscosity regulators are derived, for example, from acetic acid, succinic acid or malonic acid.
  • the sodium salts of the compound mentioned are particularly suitable.
  • Examples of the combinations mentioned are the sodium salts of monochloroacetic acid, ot-sulfosuccinic acid, ⁇ -sulfomalonic acid, ⁇ -sulfoacetic acid, ⁇ -sulfoacetic acid methyl ester, cyanoacetic acid and ethyl cyanoacetate.
  • the compounds mentioned can be added individually or in a mixture.
  • the viscosity-reducing effect is particularly pronounced at low pH values, for example at pH values below 7. This is in some cases another advantage of the use of the compounds mentioned according to the invention.
  • the addition of other compounds with electron-withdrawing groups also reduces the viscosity of anionic surfactant concentrates; Examples of such compounds are the sodium salts of vinyl sulfonate and nitrilotriacetic acid.
  • Dipropylene glycol monomethyl ether is also suitable as a viscosity regulator.
  • This type d) compound of the aforementioned viscosity regulators is an ether alcohol which contains two propylene glycol units and a methoxy group.
  • Viscosity regulation is a particular problem for concentrates of ⁇ -sulfofatty acid esters, since concentrates with a surfactant content of more than about 30% by weight are no longer easy to process. Without the viscosity problem, it would be technically possible to produce surfactant concentrates with up to about 80% by weight of surfactant. The reduction in viscosity of ⁇ -sulfofatty acid ester concentrates is therefore a particular object of the present invention.
  • the ⁇ -sulfofatty acid esters to the concentrates of which the viscosity regulators mentioned are added, are derived from fatty acids with 10 to 20, preferably 12 to 18, carbon atoms and from aliphatic alcohols with 1 to 10, preferably 1 to 4, carbon atoms in the molecule.
  • the sulfo group is introduced either by sulfonation of the fatty acid and subsequent esterification of the carboxyl group with alcohol or by sulfonation of a corresponding fatty acid ester. According to both methods, esters of sulfo fatty acids are obtained which contain the sulfo acid group in the ⁇ -position.
  • Particularly suitable ⁇ -sulfofatty acid esters are the alkali or ammonium salts of ethyl and especially the methyl ester of tallow fatty acid with a sulfo group in the ⁇ -position, the acid component of the fatty acid esters consisting essentially of saturated C 16 and C 18 fatty acids.
  • the salts are prepared by neutralizing the acidic esters with the appropriate bases.

Abstract

An aqueous anionic surfactant concentrate containing certain low molecular weight organic compounds as viscosity regulators and a method of regulating the viscosity of highly viscous concentrates, e.g. alpha -sulfo fatty acid ester surfactants in concentrations about 30% by weight. The viscosity regulators are selected from: (a) a C1-C6-alkyl monocarboxylic acid substituted in the alpha -position by a halogen, cyano or sulfo group, a salt thereof, or an ester thereof with a C1-C6-alkanol, (b) a C1-C6-alkylene dicarboxylic acid substituted in the alpha -position by a halogen, cyano or sulfo group, a salt thereof, or an ester thereof with a C1-C6-alkanol, (c) nitrilotriacetic acid and its salts, (d) an ether alcohol containing from 2 to 4 alkylene glycol units and 1 alkoxy group, (e) and mixtures thereof.

Description

Bei der Herstellung von pulverförmigen oder körnigen Wasch- und Reinigungsmitteln nach dem im großtechnischen Maßstab gebräuchlichen Heißsprühverfahren geht man von wäßrigen Aufschlämmungen ("Slurry" genannt) aus, die einen großen Teil der Waschmittelbestandteile oder auch alle Waschmittelbestandteile enthalten. Unter wirtschaftlichen Gesichtspunkten ist es wichtig, daß der Slurry möglichst reich an Waschmittelbestandteilen, d.h. möglichst arm an flüssigen Ballaststoffen ist. Man verwendet zum Ansetzen des Slurries daher die geringstmögliche Wassermenge. Der Konzentrierung sind aber Grenzen durch die höchstmögliche Viskosität, bei welcher der Slurry gerade noch verarbeitet werden kann, gesetzt.In the production of powdery or granular detergents and cleaning agents according to the hot spray process customary on an industrial scale, aqueous slurries (called "slurry") are used which contain a large part of the detergent constituents or also all detergent constituents. From an economic point of view, it is important that the slurry is as rich in detergent components as possible, i.e. is as low in liquid fiber as possible. The lowest possible amount of water is therefore used to prepare the slurries. Concentration is limited by the highest possible viscosity at which the slurry can just be processed.

Ein wesentlicher Bestandteil der meisten Wasch- und Reinigungsmittel sind anionische Tenside, die bei der Herstellung des Waschmittel-Slurries meist als pastenförmige Konzentrate in Form ihrer Alkali- oder Ammoniumsalze eingesetzt werden. Der Tensidgehalt technischer Konzentrate liegt zum Beispiel im Fall der α -Sulfotalgfettsäuremethylester bei ca. 30 Gew.-%. Pasten mit höherem Tensidgehalt lassen sich aber nicht mehr verarbeiten.An essential component of most detergents and cleaning agents are anionic surfactants, which are mostly used as paste-like concentrates in the form of their alkali or ammonium salts in the production of the detergent slurries. The surfactant content of technical concentrates is, for example in the case of the α-sulfotalg fatty acid methyl ester, about 30% by weight. Pastes with a higher surfactant content can no longer be processed.

Eine Besonderheit im rheologischen Verhalten von Tensid- konzentraten besteht darin, daß sie auf die Zugabe von Wasser nicht mit einer Viskositätsverminderung, sondern zunächst mit einer Verdickung zu einem gelartigen Zustand reagieren, woraus für den Verarbeiter weitere Probleme erwachsen. Beispielsweise ist es häufig nicht . einfach, gebildete Gelklumpen wieder in Lösung zu bringen, oder es verstopfen Ventile von Pumpen und Behältern.A special feature of the rheological behavior of surfactant concentrates is that they do not react to the addition of water with a reduction in viscosity, but first with a thickening to a gel-like state, which poses further problems for the processor. For example, it is often not. easy to get formed lumps of gel back into solution, or it clogs valves of pumps and containers.

Zur Lösung dieser Probleme sind verschiedene Vorschläge bekannt geworden. In der DE-OS 22 51 405 beispielsweise werden die Salze bestimmter Carbonsäuren, insbesondere Hydroxycarbonsäuren als Viskositätsregulatoren beschrieben. Nach der Lehre der DE-OS 23 05 554 sind sulfonierte aromatische Verbindungen für diese Zwecke geeignet. Die DE-OS 23 26 006 nennt Sulfate oder Sulfonate von aliphatischen, gegebenenfalls substituierten Kohlenwasserstoffen als Viskositätsregulatoren. Auch der Zusatz von niederen Alkanolen wird als Möglichkeit zur Viskositätsverminderung in den genannten Druckschriften aufgeführt. Ferner wird der Zusatz der altbekannten Hydrotrope wie zum Beispiel Cumolsulfonat, oder von sauren Phosporsäureestern (De-AS 16 17 160) oder von mehrwertigen Alkoholen, bestimmten Carbonsäuren und/oder Estern dieser Verbindungen beschrieben (EP-OS 8 060). Aus der europäischen Offenlegungsschrift Nr. 24 711 ist bekannt, zur Verbesserung des Fließverhaltens von anionischen Tensidkonzentraten Sulfate von bestimmten Polyalkyletherglykolen zuzusetzen.Various proposals have been made to solve these problems. DE-OS 22 51 405, for example, describes the salts of certain carboxylic acids, in particular hydroxycarboxylic acids, as viscosity regulators. According to the teaching of DE-OS 23 05 554, sulfonated aromatic compounds are suitable for these purposes. DE-OS 23 26 006 mentions sulfates or sulfonates of aliphatic, optionally substituted hydrocarbons as viscosity regulators. The addition of lower alkanols is also listed as a possibility for reducing the viscosity in the publications mentioned. Furthermore, the addition of the well-known hydrotropes such as cumene sulfonate, or of acidic phosphoric acid esters (DE-AS 16 17 160) or of polyhydric alcohols, certain carboxylic acids and / or esters of these compounds is described (EP-OS 8 060). It is known from European Patent Application No. 24 711 to add sulfates of certain polyalkyl ether glycols to improve the flow behavior of anionic surfactant concentrates.

Manche der in der Literatur genannten Zusätze wirken nicht bei allen Tensid-Konzentraten, andere müssen in hoher Konzentration eingesetzt werden, und wieder andere, wie niedere Alkanole, erniedrigen den Flammpunkt der Konzentrate.Some of the additives mentioned in the literature do not work with all surfactant concentrates, others have to be used in high concentrations, and still others, such as lower alkanols, lower the flash point of the concentrates.

Aufgabe der vorliegenden Erfindung ist daher die Bereitstellung von Substanzen zur Verbesserung des Fließ- verhaltens von wäßrigen technischen Aniontensid-Konzentraten, insbesondere von α-Sulfofettsäureestern, so daß diese in höheren Konzentrationen als bisher verarbeitbar sind bzw. beim Verdünnen mit Wasser kein Ansteigen der Viskosität aufweisen.Object of the present invention is therefore the provision of substances for improving the F l ieß- behavior of aqueous technical anionic surfactant concentrates, in particular of α-sulfo fatty acid esters, so that they are processed as previously in higher concentrations or when diluted with water, no increase in the Have viscosity.

Es wurde nun gefunden, daß man durch die Verwendung von niedermolekularen organischen Verbindungen, umfassend eine oder mehrere Verbindungen der folgenden Gruppen:

  • a) in α-Stellung durch Halogen-,Cyan- oder Sulfogruppen substituierte C1- bis C6-Alkylmonocarbon- säuren, deren Salze oder deren Ester mit C1- bis C6-Alkanolen, insbesondere mit Ethanol oder Methanol,
  • b) in α-Stellung durch Halogen-, Cyan- oder Sulfogruppen substituierte C1-bis C6-Alkylendicarbon- säuren, deren Salze oder deren Ester mit C1- bis C6-Alkanoleri, insbesondere mit Ethanol oder Methanol,
  • c) Nitrilotriessigsäure und deren Salze,
  • d) Etheralkohole mit 2 bis 4 Alkylenglykoleinheiten und einer Alkoxygruppe, insbesondere einer Methoxy-oder Ethoxy-Gruppe
It has now been found that by using low molecular weight organic compounds comprising one or more compounds of the following groups:
  • a) C 1 -C 6 -alkyl monocarboxylic acids substituted in the α-position by halogen, cyano or sulfo groups, their salts or their esters with C 1 -C 6 -alkanols, in particular with ethanol or methanol,
  • b) C 1 -C 6 -alkylenedicarboxylic acids substituted in the α-position by halogen, cyano or sulfo groups, their salts or their esters with C 1 -C 6 -alkanols, in particular with ethanol or methanol,
  • c) nitrilotriacetic acid and its salts,
  • d) ether alcohols with 2 to 4 alkylene glycol units and an alkoxy group, in particular a methoxy or ethoxy group

als Viskositätsregler für hochviskose technische TensidKonzentrate vom Typ der synthetischen anionischen Tenside, insbesondere von α -Sulfofettsäureestern mit wenigstens 30 Gew.-% α-Sulfofettsäureester, wobei man den Viskositätsregler in Mengen von 1 - 15 Gew.-%, bezogen auf die Tensid-Menge, zusetzt, so daß eine Viskositätsverminderung der Konzentrate auf höchstens 10 000 mPas bei 70 °C eintritt, die gewünschten Effekte erzielen kann.as a viscosity regulator for highly viscous technical surfactant concentrates of the type of synthetic anionic surfactants, in particular of α-sulfofatty acid esters with at least 30% by weight of α-sulfofatty acid esters, the viscosity regulator being used in amounts of 1-15% by weight, based on the amount of surfactant , adds, so that a reduction in the viscosity of the concentrates to a maximum of 10,000 mPas at 70 ° C occurs, can achieve the desired effects.

D.h., man kann die Viskosität der Konzentrate bei der jeweiligen Verarbeitungstemperatur, d.h. bei der Temperatur, bei der die Tensidkonzentrate hergestellt, gepumpt, mit anderen Waschmittelbestandteilen vermischt oder versprüht werden, was man im allgemeinen zwischen 60 und 90 °C vornimmt, auf eine für eine Verarbeitung geeignete Viskosität von höchstens 10 000 mPas vermindern. D. h., to the viscosity of the concentrates at the particular processing temperature, ie the temperature at which manufactured the surfactant concentrates, pumped, mixed with other detergent components or be sprayed, which is carried out generally between 60 and 90 ° C, to a for Reduce a processing suitable viscosity of at most 10,000 mPas.

Ein weiterer, sehr wesentlicher Vorteil der erfindungsgemäßen Verwendung besteht darin, daß man bei der technischen Herstellung der Tensidkonzentrate den Tensidgehalt auf Werte bis annähernd etwa 60 Gew.-% einstellen kann, ohne daß die Viskosität die für die Verarbeitbarkeit zulässige Obergrenze von etwa 10 000 mPas übersteigt, wodurch Tensidkonzentrate mit geringerem Wasserballast erhalten werden. Beim Verdünnen dieser Konzentrate tritt zudem nicht der sonst zu beobachtende vorübergehende Anstieg der Viskosität auf, was für die Verarbeitung ebenfalls von Vorteil ist.Another very important advantage of the use according to the invention is that the surfactant content can be adjusted to values of approximately approximately 60% by weight in the industrial production of the surfactant concentrates without the viscosity being the upper limit of approximately 10,000 mPas permissible for processability exceeds, whereby surfactant concentrates with lower water ballast are obtained. When these concentrates are diluted, the temporary increase in viscosity which is otherwise observed does not occur, which is also advantageous for processing.

Die Viskositätsregler setzt man den wäßrigen technischen Aniontensid-Konzentraten vorzugsweise in Mengen von ca. 10 Gew.-%, d.h. insbesondere 7 - 12 Gew.-%, bezogen auf den Tensidgehalt, zu, wobei man durch die Mengen des zugesetzten Viskositätsreglers die erwünschte Viskositätserniedrigung des Konzentrats bestimmt. Die als Viskositätsregler geeigneten Verbindungen leiten sich beispielsweise von Essigsäure, Bernsteinsäure oder Malonsäure ab. Besonders geeignet sind die Natriumsalze der genannten Verbindung. Beispiele für die genannten Verbinaungen sind die Natriumsalze der Monochloressigsäure, der ot-Sulfobernsteinsäure, der α-Sulfomalonsäure, der α-Sulfoessigsäure, des α-Sulfoessigsäuremethylesters, der Cyanessigsäure sowie der Cyanessigsäureethylester.The viscosity regulators are preferably added to the aqueous industrial anionic surfactant concentrates in amounts of approx. 10% by weight, i.e. in particular 7 to 12% by weight, based on the surfactant content, the desired viscosity reduction of the concentrate being determined by the amounts of the viscosity regulator added. The compounds suitable as viscosity regulators are derived, for example, from acetic acid, succinic acid or malonic acid. The sodium salts of the compound mentioned are particularly suitable. Examples of the combinations mentioned are the sodium salts of monochloroacetic acid, ot-sulfosuccinic acid, α-sulfomalonic acid, α-sulfoacetic acid, α-sulfoacetic acid methyl ester, cyanoacetic acid and ethyl cyanoacetate.

Die genannten Verbindungen können einzeln oder auch im Gemisch zugesetzt werden. Die viskositätsvermindernde Wirkung ist besonders stark ausgeprägt bei niedrigen pH-Werten, beispielsweise bei pH-Werten unter 7. Dies ist in manchen Fällen.ein weiterer Vorteil der erfindungsgemäßen Verwendung der genannten Verbindungen. Auch der Zusatz von anderen Verbindungen mit elektronenziehenden Gruppen bewirkt eine Viskositätsverminderung von Aniontensid-Konzentraten; Beispiele für derartige Verbindungen sind die Natriumsalze von Vinylsulfonat und Nitrilotriessigsäure. Ebenfalls geeignet ist Dipropylenglykolmonomethylether als Viskositätsregler. Diese Verbindung des Typs d) der vorgenannten Viskositätsregler stellt einen Etheralkohol dar, der zwei Propylenglykoleinheiten und eine Methoxygruppe enthält. Verbindungen des Typs d), bei denen die Alkylengruppe Ethylenglykol-oder Trimethylenglykol-Einheiten darstellen, sind ebenso geeignet wie Verbindungen, deren Alkoxygruppen Ethoxy-, Propoxy- oder Butoxygruppen sind. Etheralkohole mit Propylenglykoleinheiten und Methoxygruppen sind aber bevorzugt. Besonders bewährt haben sich 10 Gew.-%ige Zusätze der Natriumsalze von Nitrilotriessigsäure, α-Sulessigsäuremethylester, Chloressigsäure und Cyanessigsäureethylester. Sie sind daher bevorzugt.The compounds mentioned can be added individually or in a mixture. The viscosity-reducing effect is particularly pronounced at low pH values, for example at pH values below 7. This is in some cases another advantage of the use of the compounds mentioned according to the invention. The addition of other compounds with electron-withdrawing groups also reduces the viscosity of anionic surfactant concentrates; Examples of such compounds are the sodium salts of vinyl sulfonate and nitrilotriacetic acid. Dipropylene glycol monomethyl ether is also suitable as a viscosity regulator. This type d) compound of the aforementioned viscosity regulators is an ether alcohol which contains two propylene glycol units and a methoxy group. Compounds of type d) in which the alkylene group represents ethylene glycol or trimethylene glycol units are just as suitable as compounds whose alkoxy groups are ethoxy, propoxy or butoxy groups. However, ether alcohols with propylene glycol units and methoxy groups are preferred. 10% by weight additions of the sodium salts of nitrilotriacetic acid, methyl α-sulacetic acid, chloroacetic acid and ethyl cyanoacetate have proven particularly useful. They are therefore preferred.

Die Viskositätsregulierung ist für Konzentrate von α-Sulfofettsäureestern ein besonderes Problem, da bereits Konzentrate mit mehr als etwa 30 Gew.-% Tensidgehalt nicht mehr gut verarbeitbar sind. Ohne das Viskositätsproblem wäre es technisch möglich, Tensidkonzentrate mit bis zu etwa 80 Gew.-% Tensid-Gehalt herzustellen. Die Viskositätsverminderung von α-Sulfofettsäureester-Konzentraten ist daher ein besonderes Ziel der vorliegenden Erfindung.Viscosity regulation is a particular problem for concentrates of α-sulfofatty acid esters, since concentrates with a surfactant content of more than about 30% by weight are no longer easy to process. Without the viscosity problem, it would be technically possible to produce surfactant concentrates with up to about 80% by weight of surfactant. The reduction in viscosity of α-sulfofatty acid ester concentrates is therefore a particular object of the present invention.

Die α-Sulfofettsäureester, zu deren Konzentraten man die genannten Viskositätsregler zusetzt, leiten sich von Fettsäuren mit 10 bis 20, vorzugsweise 12 bis 18 Kohlenstoffatomen und von aliphatischen Alkoholen mit 1 bis 10, vorzugsweise 1 bis 4 Kohlenstoffatomen im Molekül ab. Die Einführung der Sulfogruppe erfolgt entweder durch Sulfonierung der Fettsäure und anschließende Veresterung der Carboxylgruppe mit Alkohol oder durch Sulfonierung eines entsprechenden Fettsäureesters. Nach beiden Verfahren werden Ester von Sulfofettsäuren erhalten, die die Sulfosäuregruppe in α-Stellung enthalten. Besonders geeignete α-Sulfofettsäureester sind die Alkali- oder Ammoniumsalze des Ethyl- und insbe-sondere des Methylesters von Talgfettsäure mit einer Sulfogruppe in α-Stellung, wobei die Säurekomponente der Fettsäureester im wesentlichen aus gesättigten C16- und C18-Fettsäuren besteht. Die Salze werden durch Neutralisation der sauren Ester mit den entsprechenden Basen hergestellt.The α-sulfofatty acid esters, to the concentrates of which the viscosity regulators mentioned are added, are derived from fatty acids with 10 to 20, preferably 12 to 18, carbon atoms and from aliphatic alcohols with 1 to 10, preferably 1 to 4, carbon atoms in the molecule. The sulfo group is introduced either by sulfonation of the fatty acid and subsequent esterification of the carboxyl group with alcohol or by sulfonation of a corresponding fatty acid ester. According to both methods, esters of sulfo fatty acids are obtained which contain the sulfo acid group in the α-position. Particularly suitable α-sulfofatty acid esters are the alkali or ammonium salts of ethyl and especially the methyl ester of tallow fatty acid with a sulfo group in the α-position, the acid component of the fatty acid esters consisting essentially of saturated C 16 and C 18 fatty acids. The salts are prepared by neutralizing the acidic esters with the appropriate bases.

B e i s p i e l eExample

Im folgenden wird die Wirksamkeit von Viskositätsreglern an ca. 50 bis ca. 60 Gew.-%igen Konzentraten des Na-Salzes von α-Sulfo-Talgfettsäuremethylester gezeigt. Dabei dampfte man eine entsprechende 30 Gew.-%ige Paste (Sulfiergrad 97,4 %) bis zur Trockne ein. Das erhaltene Pulver diente zum Ansetzen der Konzentrate mit den in der folgenden Tabelle angegebenen und durch Epton-Titration überprüften Konzentrationen. Den Konzentraten setzte man die folgenden Viskositätsregler zu:

  • A = α-Sulfoessigsäuremethylester, Natriumsalz
  • B = Chloressigsäure, Natriumsalz
  • C = Cyanessigsäureethylester
The effectiveness of viscosity regulators on about 50 to about 60% by weight concentrates of the sodium salt of methyl α-sulfo tallow fatty acid is shown below. A corresponding 30% by weight paste (degree of sulfonation 97.4%) was evaporated to dryness. The powder obtained was used to prepare the concentrates at the concentrations given in the table below and checked by Epton titration. The following viscosity regulators were added to the concentrates:
  • A = methyl α-sulfoacetate, sodium salt
  • B = chloroacetic acid, sodium salt
  • C = ethyl cyanoacetate

Die Konzentrate mit den Viskositätsreglern wurden auf dem Dampfbad erhitzt, bis man klare Flüssigkeiten erhielt. Nach Entschäumen dieser Flüssigkeiten in einer Zentrifuge wurden deren Viskositäten in einem Höppler-Kugelfallviskosimeter bei verschiedenen Temperaturen bestimmt. Die erzielte Viskositätsverringerung ist in der folgenden Tabelle aufgeführt. Vergleichbare Ergebnisse erhielt man mit α-Sulfobernsteinsäureethylester, α-Sulfoadipinsäuremethylester oder der α-Chlorvaleriansäure.

Figure imgb0001
The concentrates with the viscosity regulators were heated on the steam bath until clear liquids were obtained. After defoaming these liquids in a centrifuge, their viscosities were determined in a Höppler falling ball viscometer at various temperatures. The viscosity reduction achieved is shown in the following table. Comparable results were obtained with ethyl α-sulfosuccinate, methyl α-sulfoadipate or α-chloro-valeric acid.
Figure imgb0001

Claims (5)

1. Verwendung von niedermolekularen organischen Verbindungen, umfassend eine oder mehrere Verbindungen der folgenden Gruppen: a) in α-Stellung durch Halogen-, Cyan- oder Sulfogruppen substituierte C1- bis C6-Alkylmono- carbonsäuren, deren Salze oder deren Ester mit C1- bis C5-Alkanolen, insbesondere mit Ethanol oder Methanol, b) in α-Stellung durch Halogen-, Cyan- oder Sulfogruppen substituierte C1- bis C6-Alkylendi- . carbonsäuren, deren Salze oder deren Ester mit C1- bis C6-Alkanolen, insbesondere mit Ethanol oder Methanol, c) Nitrilotriessigsäure und deren Salze, d) Etheralkohole mit 2 bis 4 Alkylenglykoleinheiten und einer Alkoxygruppe, insbesondere einer Methoxy- oder Ethoxy-Gruppe
als Viskositätsregler für hochviskose technische TensidKonzentrate vom Typ der synthetischen anionischen Tenside, insbesondere von α-Sulfofettsäureestern mit wenigstens 30 Gew.-% des Na-Salzes von α-Sulfofettsäureester, wobei man den Viskositätsregeler in Mengen von 1 - 15 Gew.-%, bezogen auf die Tensid-Menge, zusetzt, so daß eine Viskositätsverminderung der Konzentrate auf höchstens 10-000 mPas bei 70 °C eintritt.1. Use of low molecular weight organic compounds comprising one or more compounds of the following groups: a) C 1 to C 6 alkyl monocarboxylic acids substituted in the α position by halogen, cyano or sulfo groups, their salts or their esters with C 1 to C 5 alkanols, in particular with ethanol or methanol, b) C 1 - to C 6 -alkylenedi- substituted in the α-position by halogen, cyano or sulfo groups. carboxylic acids, their salts or their esters with C 1 to C 6 alkanols, in particular with ethanol or methanol, c) nitrilotriacetic acid and its salts, d) ether alcohols with 2 to 4 alkylene glycol units and an alkoxy group, in particular a methoxy or ethoxy group
as a viscosity regulator for highly viscous technical surfactant concentrates of the type of synthetic anionic surfactants, in particular of α-sulfofatty acid esters with at least 30% by weight of the Na salt of α-sulfofatty acid esters, the viscosity regulator being obtained in amounts of 1-15% by weight to the amount of surfactant, so that the viscosity of the concentrates decreases to a maximum of 10,000 mPas at 70 ° C. 2. Verwendung der Verbindungen nach Anspruch 1 als Viskositätsregler in Mengen von 7 - 12 Gew.-%, bezogen auf den Tensid-Gehalt der Konzentrate.2. Use of the compounds according to claim 1 as a viscosity regulator in amounts of 7-12% by weight, based on the surfactant content of the concentrates. 3. Verwendung der Natriumsalze der α-Sulfobernsteinsäure, der α-Sulfomalonsäure, der α-Sulfoessigsäure, der Cyanessigsäure und insbesondere der Monochloressigsäure, des α-Sulfoessigsäuremethylesters, der Nitrilotriessigsäure sowie des Cyanessigsäureethylesters nach den Ansprüchen 1 und 2 als Viskositätsregler für Konzentrate von Aniontensiden, insbesondere von α-Sulfofettsäureestern.3. Use of the sodium salts of α-sulfosuccinic acid, α-sulfomalonic acid, α-sulfoacetic acid, cyanoacetic acid and in particular monochloroacetic acid, methyl α-sulfoacetic acid, nitrilotriacetic acid and ethyl cyanoacetate according to Claims 1 and 2 as viscosity regulators for concentrates of anionic surfactants especially of α-sulfofatty acid esters. 4. Verwendung der Verbindungen nach den Ansprüchen 1 bis 3 als Viskositätsregler in α-Sulfofettsäureester-Konzentraten mit pH-Werten unter 7.4. Use of the compounds according to claims 1 to 3 as viscosity regulators in α-sulfofatty acid ester concentrates with pH values below 7. 5. Verwendung der Verbindungen nach den Ansprüchen 1 bis 4 als Viskositätsregler für Konzentrate von α-Sulfo- (hydrierter Talg-) fettsäureethyl- und insbesondere -methylester in Form ihrer Alkali-oder Ammoniumsalze.5. Use of the compounds according to claims 1 to 4 as a viscosity regulator for concentrates of α-sulfo (hydrogenated tallow) fatty acid and in particular methyl esters in the form of their alkali metal or ammonium salts.
EP83110590A 1982-11-02 1983-10-24 Application of low molecular organic compounds as viscosity regulators for highly viscous technical tenside concentrates Expired EP0108321B1 (en)

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