EP0186896A2 - Use of alkane sulphates as viscosity regulators for high viscous concentrates of anionic surfactants - Google Patents

Use of alkane sulphates as viscosity regulators for high viscous concentrates of anionic surfactants Download PDF

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Publication number
EP0186896A2
EP0186896A2 EP85116508A EP85116508A EP0186896A2 EP 0186896 A2 EP0186896 A2 EP 0186896A2 EP 85116508 A EP85116508 A EP 85116508A EP 85116508 A EP85116508 A EP 85116508A EP 0186896 A2 EP0186896 A2 EP 0186896A2
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Prior art keywords
concentrates
viscosity
weight
viscosity regulators
acid ester
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German (de)
French (fr)
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EP0186896A3 (en
EP0186896B1 (en
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Karl-Heinz Linde
Dietrich Dr. Klötzer
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • 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
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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

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 these slurries are as rich in detergent components as possible and 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 slurries can just be processed.
  • anionic surfactants which are mostly used as paste-like concentrates in the form of their alkali metal or ammonium salts in the production of detergent slurries.
  • the surfactant content of the technical concentrates is, for example in the case of the ⁇ -sulphotalg fatty acid methyl ester sodium salts, around 30% by weight. Pastes with a higher surfactant content can be practically only with great difficulty or no longer process at all.
  • a peculiarity in the rheological behavior of these anionic 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, from which further problems arise for the processor, for example in that valves and Clogged pipes or that gel clumps formed can only be brought back into solution after mechanical comminution.
  • DE-OS 22 51 405 describes the salts of certain carboxylic acids, in particular salts of hydroxycarboxylic acids, as viscosity regulators.
  • sulfonated aromatic compounds are suitable for this purpose.
  • DE-OS 23 26 006 mentions sulfates or sulfonates of aliphatic, optionally substituted hydrocarbons having 1 to 6 carbon atoms as viscosity regulators. The addition of lower alcohols is as a way to Viskosticiansver - reduction given in the cited references.
  • hydrotropes such as cumene sulfonate, or of acidic phosphoric acid esters (DE-AS 16 17 160), polyhydric alcohols, certain carboxylic acids and / or esters of these compounds is described (EP-OS 8 060).
  • sulfates of certain polyalkylene ether glycols to improve the flow behavior of anionic surfactant concentration is known from EP-OS 24 711.
  • aqueous technical anionic surfactant concentrates in particular of ⁇ -sulfofatty acid ester salt concentrates
  • the solution of the problem consists in the use of Alkalimetallalkansulfonaten with an average carbon number of 11 to 21 as viscosity regulators for aqueous highly concentrated technical anionic surfactant concentrates, in particular for CC-sulfofatty acid ester salt concentrates, which at least 30 G ew .-% ⁇ -sulfofatty acid ester contained.
  • the viscosity regulators are used in amounts of 0.5 to 10% by weight, based on the surfactant content, so that the concentrates at 40 ° C. have a viscosity of at most 10,000 mPas.
  • the alkali metal alkanesulfonates used according to the invention as viscosity regulators are known substances which are readily soluble in water and have long been used as washing raw materials which are insensitive to water hardness because of their good wetting, foaming and washing properties. These substances are generally produced by sulfochlorination of n-paraffins with a corresponding carbon number and subsequent saponification of the alkanesulfochlorides formed with alkali metal hydroxides.
  • the sodium alkane sulfonates are of particular interest in the context of the invention.
  • the alkanesulfonates mentioned consist predominantly of salts of alkane monosulfonic acids, in addition there are portions (about 15 to 50% by weight of the detergent active substance) of di- and polysulfonates.
  • the monosulfonate portion in turn mainly consists of secondary alkanesulfonates, the sulfonate groups of which are bound to the individual carbon atoms of the alkane chain in an arbitrary distribution.
  • the currently commercially available alkanesulfonates are obtained from relatively narrow n-paraffin sections, for example from fractions with an average chain length of 13, 15 and 20 to 21 carbon atoms.
  • the alkanesulfonates used are manufactured by a process that largely excludes chlorination of the carbon chain.
  • Corresponding commercial products are available in the form of concentrated solutions, pastes and solid products for the use according to the invention.
  • the products mentioned can be used individually or in a mixture as a viscosity regulator.
  • Combinations of Alkane sulfonates with average chain lengths of 13, 15 and 20 to 21 carbon atoms can be of particular importance.
  • Viscosity regulation is a particular problem with concentrates of ⁇ -sulfofatty acid ester salts, since concentrates with more than about 30% by weight surfactant content are no longer easy to process. If the viscosity problem did not exist, it would be technically possible to produce surfactant concentrates with a surfactant content of up to approximately 80% by weight. The reduction in viscosity of ⁇ -sulfofatty acid ester salt concentrates is therefore a particular object of the present invention.
  • the oC-sulfofatty acid ester salt concentrates 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 acids and subsequent esterification of the carboxyl group with alcohol or by sulfonation of a corresponding fatty acid ester. Both processes result in esters of sulfofatty acids which contain the sulfofatty acid group in the ⁇ -position.
  • the oC-sulfofatty acid ester salts are preferably in the form of alkali metal and / or ammonium salts, in particular sodium salts.
  • the salts are prepared by neutralizing the acidic esters with the appropriate bases.
  • Particularly suitable oC-sulfofatty acid ester salts are derived from the ethyl and especially from the methyl ester of hydrogenated tallow fatty acid, the acid component of the fatty acid esters consisting essentially of saturated C 16 and C 18 fatty acids.
  • alkanesulfonates Through the use of alkanesulfonates according to the invention, a substantial improvement in the flow behavior of aqueous anionic surfactant concentrates, in particular of OC-sulfofatty acid ester salt concentrates, is achieved over the entire temperature range that is suitable for processing such concentrates.
  • the addition of the alkanesulfonates defined above has the effect that the viscosity of the surfactant concentrates is greatly reduced.
  • the framework formation responsible for the solidification of the mixtures is prevented; these surfactant concentrates are pastes that are flowable and pumpable even at normal temperature.
  • the addition of a viscosity regulator can be increased in order to achieve the desired reduction in viscosity. Otherwise, the reduction achieved with a certain amount of viscosity regulator increases with increasing temperature. However, an increase in the working temperature is generally not appropriate - if only for reasons of higher energy consumption.
  • Example 6 The sample from Example 6 was stored at room temperature for 7 days. A viscosity of 3,220 mPas was then measured at 23 ° C.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Steroid Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

Alkali metal alkane sulfonates containing on averge 11 to 21 carbon atoms are used as viscosity regulators for aqueous, highly concentrated commercial anionic surfactant concentrates, more especially for alpha -sulfofatty acid ester salt concentrates containing at least 30% by weight of alpha -sulfofatty acid ester salt. The viscosity regulators are used in quantities of from 0.5 to 10% by weight, based on the surfactant content, so that the concentrates have a viscosity at 40 DEG C. of at most 10,000 mPas.

Description

Bei der Herstellung von pulverförmigen oder körnigen Wasch- und Reinigungsmitteln nach dem im großtechnischen Maßstab gebräuchlichen Heißsprühverfahren geht man von wäßrigen Aufschlämmungen ("Slurries") aus, die einen großen Teil der Waschmittelbestandteile oder auch alle Waschmittelbestandteile enthalten. Unter wirtschaftlichen Gesichtspunkten ist es wichtig, daß diese Aufschlämmungen möglichst reich an Waschmittelbestandteilen und möglichst arm an flüssigen Ballaststoffen sind. Man verwendet daher zum Ansetzen der Slurries die geringstmögliche Wassermenge. Der Konzentrierung sind aber Grenzen gesetzt durch die höchstmögliche Viskosität, bei der die Slurries gerade noch verarbeitet werden können.In the production of powdery or granular detergents and cleaning agents according to the hot spraying process which is customary on an industrial scale, aqueous slurries 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 these slurries are as rich in detergent components as possible and 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 slurries can just be processed.

Ein wesentlicher Bestandteil der meisten Wasch- und Reinigungsmittel sind anionische Tenside, die bei der Herstellung der Waschmittel-Slurries meist als pastenförmige Konzentrate in Form ihrer Alkalimetall- oder Ammoniumsalze eingesetzt werden. Der Tensidgehalt der technischen Konzentrate liegt z.B. im Fall der α-sul- fotalgfettsäuremethylester-Natriumsalze bei ca. 30 Gew.-%. Pasten mit höherem Tensidgehalt lassen sich praktisch nur noch unter großen Schwierigkeiten oder überhaupt nicht mehr verarbeiten. Eine Besonderheit im rheologischen Verhalten dieser Aniontensid-Konzentrate 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 dadurch, daß sich Ventile und Rohrleitungen verstopfen oder daß sich gebildete Gelklumpen erst nach mechanischer Zerkleinerung wieder in Lösung bringen lassen.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 metal or ammonium salts in the production of detergent slurries. The surfactant content of the technical concentrates is, for example in the case of the α-sulphotalg fatty acid methyl ester sodium salts, around 30% by weight. Pastes with a higher surfactant content can be practically only with great difficulty or no longer process at all. A peculiarity in the rheological behavior of these anionic 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, from which further problems arise for the processor, for example in that valves and Clogged pipes or that gel clumps formed can only be brought back into solution after mechanical comminution.

Zur Lösung dieser Probleme sind bereits verschiedene Vorschläge bekannt geworden. So beschreibt beispielsweise die DE-OS 22 51 405 die Salze bestimmter Carbonsäuren, insbesondere Salze von Hydroxycarbonsäuren als Viskositätsregulatoren. Nach der Lehre der DE-OS 23 05 554 sind sulfonierte aromatische Verbindungen für diesen Zweck geeignet. Die DE-OS 23 26 006 nennt Sulfate oder Sulfonate von aliphatischen, gegebenenfalls substituierten Kohlenwasserstoffen mit 1 bis 6 Kohlenstoffatomen als Viskositätsregulatoren. Auch der Zusatz von niederen Alkoholen wird als Möglichkeit zur Viskositätsver- minderung in den genannten Druckschriften aufgeführt. Ferner wird der Zusatz der altbekannten Hydrotrope wie z.B. Cumolsulfonat, oder von sauren Phosphorsäureestern (DE-AS 16 17 160), mehrwertigen Alkoholen, bestimmten Carbonsäuren und/oder Estern dieser Verbindungen beschrieben (EP-OS 8 060). Die Verwendung von Sulfaten bestimmter Polyalkylenetherglykole zur Verbesserung des Fließverhaltens von Aniontensid-Konzentration ist aus der EP-OS 24 711 bekannt.Various proposals have already been made to solve these problems. For example, DE-OS 22 51 405 describes the salts of certain carboxylic acids, in particular salts of hydroxycarboxylic acids, as viscosity regulators. According to the teaching of DE-OS 23 05 554, sulfonated aromatic compounds are suitable for this purpose. DE-OS 23 26 006 mentions sulfates or sulfonates of aliphatic, optionally substituted hydrocarbons having 1 to 6 carbon atoms as viscosity regulators. The addition of lower alcohols is as a way to Viskositätsver - reduction given in the cited references. The addition of the well-known hydrotropes such as cumene sulfonate, or of acidic phosphoric acid esters (DE-AS 16 17 160), polyhydric alcohols, certain carboxylic acids and / or esters of these compounds is described (EP-OS 8 060). The use of sulfates of certain polyalkylene ether glycols to improve the flow behavior of anionic surfactant concentration is known from EP-OS 24 711.

Von den in der Literatur genannten Zusätzen wirken manche nicht bei allen Tensidkonzentraten, andere müssen in hohen Konzentrationen eingesetzt werden, und wieder andere, wie beispielsweise niedere Alkanole, erniedrigen den Flammpunkt der Konzentrate.Some of the additives mentioned in the literature do not work for 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.

Es war daher Aufgabe der vorliegenden Erfindung, Substanzen zur Verbesserung des Fließverhaltens von wäßrigen technischen Aniontensid-Konzentraten, insbesondere von α-Sulfofettsäureestersalz-Konzentraten bereitzustellen, so daß diese Konzentrate auch in höheren Konzentrationen als bisher verarbeitbar sind oder daß bei gleicher, noch für eine Verarbeitung geeigneten Viskosität, Konzentrate mit höherem Feststoffgehalt eingesetzt werden können. Auf der anderen Seite sollte auch erreicht werden, daß hochkonzentrierte Aniontensid-Konzentrate, insbesondere oC-Sulfofettsäureestersalz-Konzentrate beim Verdünnen mit Wasser keinen Anstieg ihrer Viskosität durchlaufen.It was therefore an object of the present invention to provide substances for improving the flow behavior of aqueous technical anionic surfactant concentrates, in particular of α-sulfofatty acid ester salt concentrates, so that these concentrates can also be processed in higher concentrations than hitherto, or at the same level, still for processing suitable viscosity, concentrates with a higher solids content can be used. On the other hand, it should also be ensured that highly concentrated anionic surfactant concentrates, in particular oC-sulfofatty acid ester salt concentrates, do not undergo an increase in their viscosity when diluted with water.

Die Lösung der Aufgabe besteht in der Verwendung von Alkalimetallalkansulfonaten mit einer mittleren Kohlenstoffzahl von 11 bis 21 als Viskositätsregler für wäßrige hochkonzentrierte technische Aniontensid-Konzentrate, insbesondere für CC-Sulfofettsäureestersalz-Konzentrate, die wenigstens 30 Gew.-% α-Sulfofettsäureestersalz enthalten. Dabei setzt man die Viskositätsregler in Mengen von 0,5 bis 10 Gew.-%, bezogen auf den Tensidgehalt, ein, so daß die Konzentrate bei 400C eine Viskosität von höchstens 10 000 mPas aufweisen.The solution of the problem consists in the use of Alkalimetallalkansulfonaten with an average carbon number of 11 to 21 as viscosity regulators for aqueous highly concentrated technical anionic surfactant concentrates, in particular for CC-sulfofatty acid ester salt concentrates, which at least 30 G ew .-% α-sulfofatty acid ester contained. The viscosity regulators are used in amounts of 0.5 to 10% by weight, based on the surfactant content, so that the concentrates at 40 ° C. have a viscosity of at most 10,000 mPas.

Bei den erfindungsgemäß als Viskositätsregler eingesetzten Alkalimetallalkansulfonaten handelt es sich um bekannte, in Wasser leicht lösliche Stoffe, die wegen ihres guten Netz-, Schaum- und Waschvermögens seit langem als Wasserhärte-unempfindliche Waschrohstoffe Verwendung finden. Diese Substanzen werden in der Regel durch Sulfochlorierung von n-Paraffinen entsprechender Kohlenstoffzahl und nachfolgende Verseifung der entstandenen Alkansulfochloride mit Alkalimetallhydroxiden hergestellt. Im Rahmen der Erfindung sind insbesondere die Natriumalkansulfonate von Interesse.The alkali metal alkanesulfonates used according to the invention as viscosity regulators are known substances which are readily soluble in water and have long been used as washing raw materials which are insensitive to water hardness because of their good wetting, foaming and washing properties. These substances are generally produced by sulfochlorination of n-paraffins with a corresponding carbon number and subsequent saponification of the alkanesulfochlorides formed with alkali metal hydroxides. The sodium alkane sulfonates are of particular interest in the context of the invention.

Die genannten Alkansulfonate bestehen überwiegend aus Salzen von Alkanmonosulfonsäuren, daneben sind Anteile (etwa 15 bis 50 Gew.-% der Waschaktivsubstanz) an Di-und Polysulfonaten vorhanden. Der Monosulfonatanteil besteht seinerseits hauptsächlich aus sekundären Alkansulfonaten, deren Sulfonatgruppen in willkürlicher Verteilung an die einzelnen Kohlenstoffatome der Alkankette gebunden sind. Die derzeit handelsüblichen Alkansulfonate werden aus relativ engen n-Paraffinschnitten gewonnen, beispielsweise aus Fraktionen mit einer durchschnittlichen Kettenlänge von 13, 15 und 20 bis 21 Kohlenstoffatomen. Die zur Verwendung kommenden Alkansulfonate sind nach Verfahren hergestellt, die eine Chlorierung der Kohlenstoffkette weitgehend ausschließt. Entsprechende Handelsprodukte stehen in Form von konzentrierten Lösungen, Pasten und festen Produkten für die erfindungsgemäße Verwendung zur Verfügung. Die genannten Produkte können einzeln oder auch im Gemisch als Viskositätsregler eingesetzt werden. Kombinationen von Alkansulfonaten mit mittleren Kettenlängen von 13, 15 und 20 bis 21 Kohlenstoffatomen kann besondere Bedeutung zukommen.The alkanesulfonates mentioned consist predominantly of salts of alkane monosulfonic acids, in addition there are portions (about 15 to 50% by weight of the detergent active substance) of di- and polysulfonates. The monosulfonate portion in turn mainly consists of secondary alkanesulfonates, the sulfonate groups of which are bound to the individual carbon atoms of the alkane chain in an arbitrary distribution. The currently commercially available alkanesulfonates are obtained from relatively narrow n-paraffin sections, for example from fractions with an average chain length of 13, 15 and 20 to 21 carbon atoms. The alkanesulfonates used are manufactured by a process that largely excludes chlorination of the carbon chain. Corresponding commercial products are available in the form of concentrated solutions, pastes and solid products for the use according to the invention. The products mentioned can be used individually or in a mixture as a viscosity regulator. Combinations of Alkane sulfonates with average chain lengths of 13, 15 and 20 to 21 carbon atoms can be of particular importance.

Die Viskositätsregulierung ist bei Konzentraten von α-Sulfofettsäureestersalzen ein besonderes Problem, da bereits Konzentrate mit mehr als etwa 30 Gew.-% Tensidgehalt nicht mehr gut verarbeitbar sind. Würde das Viskositätsproblem nicht bestehen, wäre es technisch möglich, Tensidkonzentrate mit bis zu ca. 80 Gew.-% Tensidgehalt herzustellen. Die Viskositätsverminderung von α-Sulfofettsäureestersalz-Konzentraten ist daher ein besonderes Ziel der vorliegenden Erfindung.Viscosity regulation is a particular problem with concentrates of α-sulfofatty acid ester salts, since concentrates with more than about 30% by weight surfactant content are no longer easy to process. If the viscosity problem did not exist, it would be technically possible to produce surfactant concentrates with a surfactant content of up to approximately 80% by weight. The reduction in viscosity of α-sulfofatty acid ester salt concentrates is therefore a particular object of the present invention.

Die oC-Sulfofettsäureestersalz-Konzentrate, deren Viskosität durch die erfindungsgemäße Verwendung von Alkansulfonaten vermindert werden kann, 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 Fettsäuren und anschließende Veresterung der Carboxylgruppe mit Alkohol oder durch Sulfonierung eines entsprechenden Fettsäureesters. Nach beiden Verfahren entstehen Ester von Sulfofettsäuren, die die Sulfofettsäuregruppe in α-Stellung enthalten. Die oC-Sulfofettsäureestersalze liegen vorzugsweise als Alkalimetall- und/oder Ammoniumsalze, insbesondere als Natriumsalze vor. Die Salze werden durch Neutralisation der sauren Ester mit den entsprechenden Basen hergestellt.The oC-sulfofatty acid ester salt concentrates, the viscosity of which can be reduced by the use of alkanesulfonates according to the invention, 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 acids and subsequent esterification of the carboxyl group with alcohol or by sulfonation of a corresponding fatty acid ester. Both processes result in esters of sulfofatty acids which contain the sulfofatty acid group in the α-position. The oC-sulfofatty acid ester salts are preferably in the form of alkali metal and / or ammonium salts, in particular sodium salts. The salts are prepared by neutralizing the acidic esters with the appropriate bases.

Besonders geeignete oC-Sulfofettsäureestersalze leiten sich vom Ethyl- und insbesondere vom Methylester der hydrierten Talgfettsäure ab, wobei die Säurekomponente der Fettsäureester im wesentlichen aus gesättigten C16-und C18-Fettsäuren besteht.Particularly suitable oC-sulfofatty acid ester salts are derived from the ethyl and especially from the methyl ester of hydrogenated tallow fatty acid, the acid component of the fatty acid esters consisting essentially of saturated C 16 and C 18 fatty acids.

Durch die erfindungsgemäße Verwendung von Alkansulfonaten wird eine wesentliche Verbesserung des Fließverhaltens von wäßrigen Aniontensid-Konzentraten, insbesondere von OC-Sulfofettsäureestersalz-Konzentraten, über den ganzen, für die Verarbeitung solcher Konzentrate in Betracht kommenden Temperaturbereich erzielt. Der Zusatz der vorstehend definierten Alkansulfonate bewirkt einerseits, daß die Viskosität der Tensidkonzentrate stark herabgesetzt wird. Darüberhinaus wird das insbesondere bei langkettigen CC-Sulfofettsäureestersalzen in Abwesenheit von Viskositätsreglern zu beobachtende "Aushärten" der frisch hergestellten Konzentrate zu festen, technisch kaum noch handhabbaren Massen beim Abkühlen auf und Stehenlassen bei Normaltemperatur vollkommen vermieden. In den mit den erfindungsgemäß zu verwendenden Alkansulfonaten versetzten Tensid-Konzentraten wird die für das Festwerden der Gemische verantwortliche Gerüstbildung verhindert; diese TensidKonzentrate stellen auch bei Normaltemperatur fließ- und pumpfähige Pasten dar.Through the use of alkanesulfonates according to the invention, a substantial improvement in the flow behavior of aqueous anionic surfactant concentrates, in particular of OC-sulfofatty acid ester salt concentrates, is achieved over the entire temperature range that is suitable for processing such concentrates. On the one hand, the addition of the alkanesulfonates defined above has the effect that the viscosity of the surfactant concentrates is greatly reduced. In addition, the "hardening" of the freshly prepared concentrates into solid, technically hardly manageable masses when cooling to and allowing to stand at normal temperature, which can be observed especially in the case of long-chain CC sulfofatty acid ester salts in the absence of viscosity regulators, is completely avoided. In the surfactant concentrates mixed with the alkanesulfonates to be used according to the invention, the framework formation responsible for the solidification of the mixtures is prevented; these surfactant concentrates are pastes that are flowable and pumpable even at normal temperature.

B e i s p i e l eExample Beispiele I bis 4Examples I to 4

Verschiedene Proben eines im großtechnischen Maßstab hergestellten Konzentrats des Natriumsalzes eines α-Sulfo-C16/C18-fettsäuremethylesters (mit ca. 60 Gew.-% Palmitinsäure und 40 Gew.-% Stearinsäure in dem als Ausgangsmaterial verwendeten Fettsäuremethylester) mit ca. 33 Gew.-% Waschaktivsubstanz wurden unterschiedliche Anteile

  • - eines Natriumalkansulfonats der durchschnittlichen Kettenlänge C15, mit einem mittleren Molekulargewicht von ca. 330, in Form einer 68 gewichtsprozentigen wäßrigen Lösung, in der der Di- und Polysulfonatanteil ca. 15 Gewichtsprozent der Waschaktivsubstanz ausmachte (Sulfonat A) und
  • - eines Natriumalkansulfonats der durchschnittlichen Kettenlänge C20-21' mit einem mittleren Molekulargewicht von ca. 400, in Form einer 65 gewichtsprozentigen wäßrigen Lösung, in der der Di- und Polysulfonatanteil ca. 42 bis 50 Gewichtsprozent der Waschaktivsubstanz ausmachte (Sulfonat B)

zugesetzt und die Viskosität der Proben bei 40°C mit Hilfe eines Viskosimeters nach Höppler bestimmt. Die dabei gefundenen Meßergebnisse sind in der nachstehenden Tabelle wiedergegeben.
Figure imgb0001
 Various samples of a concentrate of the sodium salt of an α-sulfo-C 16 / C 18 -fatty acid methyl ester (with approx. 60% by weight palmitic acid and 40% by weight stearic acid in the fatty acid methyl ester used as starting material) produced on an industrial scale with approx. 33 % By weight of detergent active were different proportions
  • - A sodium alkane sulfonate of average chain length C 15 , with an average molecular weight of about 330, in the form of a 68 weight percent aqueous solution, in which the di- and polysulfonate fraction made up about 15 percent by weight of the detergent substance (sulfonate A) and
  • - A sodium alkane sulfonate of average chain length C 20-21 ' with an average molecular weight of approx. 400, in the form of a 65% by weight aqueous solution in which the di- and polysulfonate fraction made up approx. 42 to 50% by weight of the detergent substance (sulfonate B)

added and the viscosity of the samples at 40 ° C with the aid of a Höppler viscometer. The measurement results found are shown in the table below.
Figure imgb0001

Bei höher konzentrierten Tensidlösungen kann der Zusatz an Viskositätsregler erhöht werden, um die gewünschte Viskositätsverminderung zu erreichen. Im übrigen nimmt die mit einer bestimmten Viskositätsreglermenge erzielte Verminderung mit steigender Temperatur zu. Eine Erhöhung der Arbeitstemperatur ist aber - schon aus Gründen des höheren Energieaufwandes - im allgemeinen nicht angebracht.In the case of more highly concentrated surfactant solutions, the addition of a viscosity regulator can be increased in order to achieve the desired reduction in viscosity. Otherwise, the reduction achieved with a certain amount of viscosity regulator increases with increasing temperature. However, an increase in the working temperature is generally not appropriate - if only for reasons of higher energy consumption.

Beispiele 5 bis 8Examples 5 to 8

Verschiedenen Proben eines im großtechnischen Maßstab hergestellten Konzentrats des Natriumsalzes eines α-Sulfo-C16/C18-fettsäuremethylesters (mit ca. 50 Gew.-% Palmitinsäure und ca. 50 Gew.-% Stearinsäure in dem als Ausgangsmaterial eingesetzten Fettsäuremethylester) mit ca. 31 Gew.-% Waschaktivsubstanz wurden unterschiedliche Mengen der in den Beispielen 1 bis 4 als Sulfonat A und Sulfonat B beschriebenen Natriumalkansulfonate zugesetzt und die Viskosität der Proben bei 400C mittels eines Höppler-Viskosimeters bestimmt. Die dabei gefundenen Meßergebnisse sind in der nachstehenden Tabelle II wiedergegeben.

Figure imgb0002
Various samples of a concentrate of the sodium salt of one produced on an industrial scale α-Sulfo-C 16 / C 18 -fatty acid methyl ester (with approx. 50% by weight palmitic acid and approx. 50% by weight stearic acid in the fatty acid methyl ester used as the starting material) with approx. 31% by weight detergent active ingredient sodium alkanesulfonates described in Examples 1 to 4 as sulfonate A and sulfonate B are added and the viscosity of the samples is determined at 40 ° C. using a Höppler viscometer. The measurement results found are shown in Table II below.
Figure imgb0002

Die Probe aus Beispiel 6 wurde 7 Tage lang bei Raumtemperatur gelagert. Danach wurde bei 23°C eine Viskosität von 3 220 mPas gemessen.The sample from Example 6 was stored at room temperature for 7 days. A viscosity of 3,220 mPas was then measured at 23 ° C.

Beispiele 9 bis 12Examples 9 to 12

Verschiedenen Proben eines im großtechnischen Maßstab hergestellten Konzentrats des Natriumsalzes eines α-Sulfo-C16/C18-fettsäuremethylesters (mit ca. 30 Gew.-% Palmitinsäure und ca. 70 Gew.-% Stearinsäure in dem als Ausgangsmaterial eingesetzten Fettsäuremethylester) mit ca. 29 Gew.-% Waschaktivsubstanz wurden mit unterschiedlichen Mengen der in den Beispielen 1 bis 4 als Sulfonat A und Sulfonat B beschriebenen Natriumalkansulfonate zugesetzt und die Viskosität der Proben bei 40°C mittels eines Höppler-Viskosimeters bestimmt. Die dabei gefundenen Meßergebnisse sind in der nachstehenden Tabelle III wiedergegeben.

Figure imgb0003
Various samples of a concentrate of the sodium salt of an α-sulfo-C 16 / C 18 -fatty acid methyl ester (with approx. 30 wt.% Palmitic acid and approx. 70 wt.% Stearic acid in the fatty acid methyl ester used as starting material) produced on an industrial scale with approx 29% by weight of washing-active substance were added with different amounts of the sodium alkanesulfonates described in Examples 1 to 4 as sulfonate A and sulfonate B, and the viscosity of the samples was determined at 40 ° C. using a Höppler viscometer. The measurement results found are shown in Table III below.
Figure imgb0003

Beispiele 13 bis 20Examples 13 to 20

Verschiedenen Proben eines im großtechnischen Maßstab hergestellten Konzentrats des Natriumsalzes eines α-Sulfo-C16/C18-fettsäuremethylesters (mit ca. 30 Gewichtsprozent Palmitinsäure und 70 Gewichtsprozent Stearinsäure in dem als Ausgangsmaterial eingesetzten Fettsäuremethylester) mit ca. 33 Gewichtsprozent Waschaktivsubstanz wurden unterschiedliche Mengen der in den Beispielen 1 bis 4 als Sulfonat A und Sulfonat B beschriebenen Natriumalkansulfonate sowie

  • - eines Natriumalkansulfonats der durchschnittlichen Kettenlänge C13, mit einem mittleren Molekulargewicht von ca. 350, in Form einer 68 gewichtsprozentigen wäßrigen Lösung, in der der Di-und Polysulfonatanteil ca. 15 Gewichtsprozent der Waschaktivsubstanz ausmachte (Sulfonat C)

zugesetzt und die Viskosität der Proben bei 40 °C mittels eines Höppler-Viskosimeters bestimmt. Die dabei gefundenen Meßergebnisse sind in der nachstehenden Tabelle IV wiedergegeben.Different samples of a concentrate of the sodium salt of an α-sulfo-C 16 / C 18 -fatty acid methyl ester (with approx. 30% by weight palmitic acid and 70% by weight stearic acid in the fatty acid methyl ester used as starting material) with approx. 33% by weight detergent substance were produced on an industrial scale sodium alkanesulfonates described in Examples 1 to 4 as sulfonate A and sulfonate B and
  • a sodium alkane sulfonate of average chain length C 13 , with an average molecular weight of approx. 350, in the form of a 68 weight percent aqueous solution in which the di- and polysulfonate fraction made up approx. 15 weight percent of the detergent substance (sulfonate C)

added and the viscosity of the samples at 40 ° C determined using a Höppler viscometer. The measurement results found are shown in Table IV below.

Figure imgb0004
Figure imgb0004

Claims (3)

1. Verwendung von Alkalimetallalkansulfonaten mit einer mittleren Kohlenstoffzahl von 11 bis 21 als Viskositätsregler für wäßrige hochkonzentrierte technische Aniontensid-Konzentrate, insbesondere für α-Sulfofettsäureestersalz-Konzentrate, die wenigstens 30 Gew.-% α-Sulfofettsäureestersalz enthalten, wobei man die Viskositätsregler in Mengen von 0,5 bis 10 Gew.-%, bezogen auf den Tensidgehalt einsetzt, so daß die Konzentrate bei 40°C eine Viskosität von höchstens 10 000 mPas aufweisen.1. Use of alkali metal alkanesulfonates with an average carbon number of 11 to 21 as a viscosity regulator for aqueous, highly concentrated technical anionic surfactant concentrates, in particular for α-sulfofatty acid ester salt concentrates which contain at least 30% by weight of α-sulfofatty acid ester salt, the viscosity regulator in amounts of 0.5 to 10 wt .-%, based on the surfactant content, so that the concentrates at 40 ° C have a viscosity of at most 10,000 mPas. 2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß Natriumalkansulfonate als Viskositätsregler eingesetzt werden.2. Use according to claim 1, characterized in that sodium alkane sulfonates are used as viscosity regulators. 3. Verwendung nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß die Viskositätsregler in Konzentraten von CC-Sulfotalgfettsäureethylestersalzen und insbesondere von α-Sulfotalgfettsäuremethyl- estersalzen eingesetzt werden, die als Alkalimetall- oder Ammoniumsalze vorliegen.3. Use according to claims 1 and 2, characterized in that the viscosity regulators are used in concentrates of C C-sulfotalgfatty acid ethyl ester salts and in particular of α-sulfotalgfatty acid methyl ester salts which are present as alkali metal or ammonium salts.
EP85116508A 1984-12-31 1985-12-23 Use of alkane sulphates as viscosity regulators for high viscous concentrates of anionic surfactants Expired - Lifetime EP0186896B1 (en)

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DE3447859 1984-12-31

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EP0328980A1 (en) * 1988-02-13 1989-08-23 Henkel Kommanditgesellschaft auf Aktien Process for the preparation of pastes of ester sulfonates with low viscosity
WO1991002045A1 (en) * 1989-08-09 1991-02-21 Henkel Kommanditgesellschaft Auf Aktien Aqueous anionic tenside concentrates with oleic acid sulphonates as viscosity controls
WO1991019775A1 (en) * 1990-06-15 1991-12-26 Henkel Kommanditgesellschaft Auf Aktien Use of salts of the sulphonation products of unsaturated fatty acids as viscosity reducers
EP0574086A2 (en) * 1992-06-08 1993-12-15 Colgate-Palmolive Company Alkyl sulfates as viscosity modifiers in anionic surfactant compositions
FR2714674A1 (en) * 1994-01-06 1995-07-07 Stepan Europe Hydrotropic agents and compositions containing them
WO2008155068A2 (en) * 2007-06-20 2008-12-24 Clariant Finance (Bvi) Limited Surfactant mixtures with synergistic characteristics

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FR2601960B1 (en) * 1986-07-25 1989-05-26 Lesieur Cotelle DETERGENT, VISCOUS, DILUABLE COMPOSITION AND PROCESS FOR OBTAINING SAME
DE3630533A1 (en) * 1986-09-08 1988-03-10 Henkel Kgaa NEW TENSIDE MIXTURES AND THEIR USE
DE3862837D1 (en) * 1987-07-28 1991-06-20 Lucas Ind Plc ROTATIONAL PART FOR A VEHICLE BRAKE WITH LIQUID COOLING.
US5152932A (en) * 1989-06-09 1992-10-06 The Procter & Gamble Company Formation of high active detergent granules using a continuous neutralization system
DE4032909A1 (en) * 1990-10-17 1992-04-23 Henkel Kgaa METHOD FOR PRODUCING ALKYL SULFATE PASTES WITH IMPROVED FLOWABILITY
US5538672A (en) * 1991-08-03 1996-07-23 Henkel Kommanditgesellschaft Auf Aktien Free-flowing water-containing alkyl sulfate pastes
WO2014072840A1 (en) 2012-11-12 2014-05-15 Galaxy Surfactants Ltd. Flowable, high active, aqueous fatty alkyl sulfates
MY179544A (en) * 2017-07-19 2020-11-10 Kl Kepong Oleomas Sdn Bhd A surfactant system

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EP0328980A1 (en) * 1988-02-13 1989-08-23 Henkel Kommanditgesellschaft auf Aktien Process for the preparation of pastes of ester sulfonates with low viscosity
US4943393A (en) * 1988-02-13 1990-07-24 Henkel Kommanditgesellschaft Auf Aktien Process for the manufacture of ester sulfonate pastes of low viscosity
WO1991002045A1 (en) * 1989-08-09 1991-02-21 Henkel Kommanditgesellschaft Auf Aktien Aqueous anionic tenside concentrates with oleic acid sulphonates as viscosity controls
WO1991019775A1 (en) * 1990-06-15 1991-12-26 Henkel Kommanditgesellschaft Auf Aktien Use of salts of the sulphonation products of unsaturated fatty acids as viscosity reducers
EP0574086A2 (en) * 1992-06-08 1993-12-15 Colgate-Palmolive Company Alkyl sulfates as viscosity modifiers in anionic surfactant compositions
EP0574086A3 (en) * 1992-06-08 1994-09-21 Colgate Palmolive Co Alkyl sulfates as viscosity modifiers in anionic surfactant compositions
FR2714674A1 (en) * 1994-01-06 1995-07-07 Stepan Europe Hydrotropic agents and compositions containing them
EP0662510A1 (en) * 1994-01-06 1995-07-12 Stepan Europe Hydrotropic agents and compositions containing them
WO2008155068A2 (en) * 2007-06-20 2008-12-24 Clariant Finance (Bvi) Limited Surfactant mixtures with synergistic characteristics
WO2008155068A3 (en) * 2007-06-20 2009-02-26 Clariant Int Ltd Surfactant mixtures with synergistic characteristics

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