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WO1993013112A1 - Method of bleaching alkyl and/or alkenyl glycosides - Google Patents

Method of bleaching alkyl and/or alkenyl glycosides Download PDF

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Publication number
WO1993013112A1
WO1993013112A1 PCT/EP1992/002894 EP9202894W WO9313112A1 WO 1993013112 A1 WO1993013112 A1 WO 1993013112A1 EP 9202894 W EP9202894 W EP 9202894W WO 9313112 A1 WO9313112 A1 WO 9313112A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
bleaching
alkenyl
alcohol
stabilizers
Prior art date
Application number
PCT/EP1992/002894
Other languages
German (de)
French (fr)
Inventor
Paul Schulz
Rainer Eskuchen
Herbert Esser
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19914142592 external-priority patent/DE4142592A1/en
Priority claimed from DE19924200850 external-priority patent/DE4200850A1/en
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1993013112A1 publication Critical patent/WO1993013112A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60—Sugars; Derivatives thereof
    • A61K8/604—Alkylpolyglycosides; Derivatives thereof, e.g. esters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/42—Separation; Purification; Stabilisation; Use of additives
    • C07C303/44—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
    • C07H15/10—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical containing unsaturated carbon-to-carbon bonds

Definitions

  • the invention relates to a process for bleaching alkyl and / or alkenyl oligoglycosides, in which the bleaching is carried out with peroxygen compounds in the presence of aluminum ions, alkali silicates, sugar acids and / or organic complexing agents as stabilizers.
  • European Patent EP 0 165 721 B1 suggests treating alkyl glycosides first with hydrogen peroxide or other peroxygen compounds and then with an SO 2 source.
  • a process for bleaching alkyl glucosides is known from European patent application EP 0 338 151 A1, in which the products are subjected to a hydrogenation, for example with sodium boranate.
  • the object of the invention was therefore to develop an improved process for bleaching alkyl and / or alkenyl oligoglyosides which is free from the disadvantages described.
  • the invention relates to a process for bleaching alkyl and / or alkenyl glycosides with the aid of peroxygen compounds, which is characterized in that the bleach is selected in the presence of stabilizers from the group consisting of aluminum ions, alkali metal silicates, sugar acids and organic complexing agents is formed.
  • stabilizers from the group consisting of aluminum ions, alkali metal silicates, sugar acids and organic complexing agents.
  • R! for an aliphatic, linear or branched alkyl and / or alkenyl radical with 6 to 22 carbon atoms
  • the glycose unit [G] can be derived from aldoses or ketoses. Because of the better reactivity, the reducing saccharides, the aldoses, are preferably used. Among the aldoses, glucose is particularly suitable because of their easy access and technical availability.
  • the preferred bleached alkyl and / or alkenyl oligoglycosides are therefore the alkyl and / or alkenyl oligoglucosides.
  • the alkyl radical R 1 can be derived from primary alcohols having 6 to 22, preferably 12 to 18, carbon atoms. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palm oleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, arachyl alcohol, technical alcohols, gadoleyl alcohol, and mixtures thereof, gadoleyl alcohol of natural fats and oils, for example palm oil, palm kernel oil, coconut oil or beef tallow.
  • capronic alcohol caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palm oleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol,
  • alkyl oligoglycosides of the formula (I) in which R 1 is an alkyl radical having 12 to 18 carbon atoms. ato en, [G] stands for a glucose residue and / or p for numbers from 1.1 to 3.0.
  • the bleaching is carried out in the presence of peroxygen compounds.
  • peroxygen compounds Typical examples of this are perborates, percarbonates and in particular hydrogen peroxide, which can be used in the form of an aqueous 5 to 70, preferably 15 to 35% by weight solution.
  • concentration of the peroxygen compounds can be 1 to 5, preferably 2 to 3% by weight, based on the solids content of the alkyl or alkenyl oligoglycoside paste to be bleached.
  • Aluminum ions, alkali silicates, sugar acids and / or organic complexing agents come into consideration as stabilizers.
  • the aluminum ions can be added to the peroxygen compounds in the form of salts, for example sulfates, carbonates, silicates or phosphates.
  • alkali silicates are sodium and / or potassium silicates (“water glass”), in which an average of 2 to 4 moles of silicon dioxide per mole of alkali oxide.
  • sugar acids gluconic acid, glucaric acid, glucoronic acid and glucoheptonic acid and their alkali and alkaline earth salts are particularly suitable.
  • organic complexing agents are phosphonic acids, such as, for example, diethylenetriaminepentamethylphosphonic acid.
  • the stabilizers can be used individually or in combination in concentrations of 0.1 to 5.0, preferably 0.5 to 3.0 and in particular 1.0 to 2.0% by weight, based on the solids content of the alkyl to be bleached. or alkenyl oligoglycoside paste - are used.
  • the surface-active compounds are mixed with the peroxygen compounds and the stabilizers. This can take place at ambient temperature or else at the bleaching temperature, the latter being 80 to 120, preferably 90 to 100 ° C.
  • the alkyl or alkenyl oligoglycosides obtainable by the process according to the invention are light-colored and are suitable for the production of detergents, dishwashing detergents and cleaning agents and for products for hair and body care, in which they are present in amounts of 0.1 to 50, preferably 1 to 10 wt .-% - based on the agent - may be included.
  • the water of reaction was continuously distilled off and the reaction was stopped after the water separation had ended and the residual content of unreacted glucose in the mixture was less than 1% by weight, based on the starting amount.
  • the reaction mixture was then neutralized with magnesium oxide, the excess coconut fatty alcohol was separated off under reduced pressure (approx. 1 mbar) and at a temperature of 180 ° C. using a thin-film evaporator and the residue was pasted with water.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Genetics & Genomics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Biotechnology (AREA)
  • Molecular Biology (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
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  • Saccharide Compounds (AREA)

Abstract

The invention concerns a method of bleaching alkyl and/or alkenyl glycosides with peroxy compounds to give a pale colour, the bleaching reaction being carried out in the presence of stabilizers selected from the group comprising aluminium ions, alkali-metal silicates, saccharic acids and organic complexing agents.

Description

Verfahren zur Bleiche von Alkyl- und/oder Alkenyloligoglykosiden Process for bleaching alkyl and / or alkenyl oligoglycosides
Gebiet der ErfindungField of the Invention
Die Erfindung betrifft ein Verfahren zur Bleiche von Alkyl- und/oder Alkenyloligoglykosiden, bei dem man die Bleiche mit Persauerstoffverbindungen in Gegenwart von Aluminiumionen, Alkalisilicaten, Zuckersäuren und/oder organischen Komplex¬ bildnern als Stabilisatoren durchführt.The invention relates to a process for bleaching alkyl and / or alkenyl oligoglycosides, in which the bleaching is carried out with peroxygen compounds in the presence of aluminum ions, alkali silicates, sugar acids and / or organic complexing agents as stabilizers.
Stand der TechnikState of the art
Oberflächenaktive Alkyl- und/oder Alkenyloligoglykoside sind als Rohstoffe für die Herstellung von Waschmitteln bereits seit langem bekannt. Ihre Herstellung erfolgt üblicherweise durch säurekatalysierte Acetalisierung von Zuckern (Glykosen) - insbesondere Glucose - mit Fettalkoholen. Zur Einstellung des Glucosepolymerisationsgrades wird die Alkoholkomponente im Überschuß eingesetzt, das freiwerdende Reaktionswasser kontinuierlich aus dem Reaktionsgleichgewicht entfernt und die Reaktion abgebrochen, wenn die Glucose praktisch voll¬ ständig abreagiert hat. Anschließend wird der saure Katalysator neutralisiert, der überschüssige Fettalkohol destillativ abgetrennt und der Rückstand mit Wasser angepastet. Stellvertretend für die große Zahl von Verfahren zum Stand der Technik sei hier auf die Druckschriften US 3,839,318, US 3,450, 690 und EP 0 132 046 AI verwiesen.Surface-active alkyl and / or alkenyl oligoglycosides have long been known as raw materials for the production of detergents. They are usually produced by acid-catalyzed acetalization of sugars (glycoses) - especially glucose - with fatty alcohols. To adjust the degree of glucose polymerization, the alcohol component is used in excess, the water of reaction released is continuously removed from the reaction equilibrium and the reaction is stopped when the glucose has reacted virtually completely. Then the acid The catalyst is neutralized, the excess fatty alcohol is removed by distillation and the residue is mixed with water. Representative of the large number of prior art processes, reference is made here to the publications US Pat. No. 3,839,318, US Pat. No. 3,450,690 and EP 0 132 046 A1.
Die Abtrennung überschüssigen Fettalkohols von den Glykosiden bedarf hoher Temperaturen und stark verminderter Drücke. Üb¬ licherweise arbeitet man in Destillationsapparaturen, bei denen die Verdampfung aus einer dünnen Schicht bei einer Temperatur von 160 bis 220°C und einem Betriebsdruck von ca. 0,1 bar erfolgt. Trotz aller Anstrengungen, die Alkoholab¬ trennung möglichst schonend durchzuführen, finden unter den Destillationsbedingungen Zersetzungs- und Kondensationsreak¬ tionen statt, die in aller Regel eine unerwünschte Verfärbung der Produkte hervorrufen.The separation of excess fatty alcohol from the glycosides requires high temperatures and greatly reduced pressures. Usually one works in distillation apparatuses in which the evaporation takes place from a thin layer at a temperature of 160 to 220 ° C and an operating pressure of approx. 0.1 bar. Despite all efforts to carry out the alcohol separation as gently as possible, decomposition and condensation reactions take place under the distillation conditions, which generally cause undesired discoloration of the products.
In der Vergangenheit hat es nicht an Versuchen gemangelt, hellfarbige Alkyl- bzw. Alkenyloligoglykoside herzustellen. Neben präventiven Maßnahmen, wie beispielsweise Minimierung des Restzuckergehaltes, stehen dabei Verfahren zur Bleiche der Produkte, insbesondere unter Verwendung von Wasserstoff¬ peroxid, im Vordergrund.There has been no shortage of attempts in the past to produce light-colored alkyl or alkenyl oligoglycosides. In addition to preventive measures, such as, for example, minimizing the residual sugar content, the focus here is on processes for bleaching the products, in particular using hydrogen peroxide.
So wird beispielsweise in der Europäischen Patentschrift EP 0 165 721 Bl vorgeschlagen, Alkylglykoside zunächst mit Was¬ serstoffperoxid oder anderen Persauerstoffverbindungen und anschließend mit einer Sθ2-Quelle zu behandeln.For example, European Patent EP 0 165 721 B1 suggests treating alkyl glycosides first with hydrogen peroxide or other peroxygen compounds and then with an SO 2 source.
Aus der Europäischen Patentanmeldung EP 0 338 151 AI ist ein Verfahren zur Bleiche von Alkylglucosiden bekannt, bei dem man die Produkte einer Hydrierung, beispielsweise mit Na- triumboranat, unterwirft.A process for bleaching alkyl glucosides is known from European patent application EP 0 338 151 A1, in which the products are subjected to a hydrogenation, for example with sodium boranate.
Die genannten Verfahren des Stands der Technik sind jedoch insgesamt nicht zufriedenstellend. Die Bleiche von Alkyl- bzw. Alkenyloligoglykosiden unter reduzierenden Bedingungen ist mit hohem technischen Aufwand verbunden und daher aus ökonomischen Gründen unvorteilhaft. Bei Einsatz von Wasser¬ stoffperoxid müssen Stabilisatoren, beispielsweise Magnesi¬ umoxid, mitverwendet werden, die die Bleichwirkung unter¬ stützen und einen spontanen Zerfall des H2O2 verhindern. Un¬ ter den üblichen Lagerbedingungen (pH = 11,5) kommt es jedoch häufig zu unerwünschten Austrübungen, die auf die Anwesenheit schwer löslicher Stabilisatoren zurückzuführen ist.However, the prior art methods mentioned are overall unsatisfactory. The bleaching of alkyl or alkenyl oligoglycosides under reducing conditions is associated with high technical outlay and is therefore disadvantageous for economic reasons. When using hydrogen peroxide, stabilizers, for example magnesium oxide, must be used, which support the bleaching effect and prevent spontaneous decomposition of the H2O2. Under the usual storage conditions (pH = 11.5), however, undesirable clouding often occurs, which is due to the presence of poorly soluble stabilizers.
Die Aufgabe der Erfindung bestand somit darin, ein verbes¬ sertes Verfahren zur Bleiche von Alkyl- und/oder Alkenyl- oligoglyosiden zu entwickeln, das frei von den geschilderten Nachteilen ist.The object of the invention was therefore to develop an improved process for bleaching alkyl and / or alkenyl oligoglyosides which is free from the disadvantages described.
Beschreibung der ErfindungDescription of the invention
Gegenstand der Erfindung ist ein Verfahren zur Bleiche von Alkyl- und/oder Alkenylglykosiden mit Hilfe von Persauer¬ stoffverbindungen, das sich dadurch auszeichnet, daß man die Bleiche in Gegenwart von Stabilisatoren ausgewählt aus der Gruppe, die von Aluminiumionen, Alkalisilicaten, Zuckersäuren und organischen Komplexbildnern gebildet wird, durchführt. Überraschenderweise wurde gefunden, daß Aluminiumionen, Al- kalisilicate, Zuckersäuren und/oder organische Komplexbildner Wasserstoffperoxid in gleicher Weise wie beispielsweise Mag¬ nesiumionen stabilisieren, die resultierenden Alkyl- bzw. Alkenyloligoglykosid-Pasten jedoch bei pH-Werten größer 10 klar bleiben und auch bei längerer Lagerung nicht austrüben.The invention relates to a process for bleaching alkyl and / or alkenyl glycosides with the aid of peroxygen compounds, which is characterized in that the bleach is selected in the presence of stabilizers from the group consisting of aluminum ions, alkali metal silicates, sugar acids and organic complexing agents is formed. Surprisingly, it was found that aluminum ions, alkali silicates, sugar acids and / or organic complexing agents stabilize hydrogen peroxide in the same way as, for example, magnesium ions, but the resulting alkyl or alkenyl oligoglycoside pastes remain clear at pH values greater than 10 and also at longer ones Do not cloud storage.
Die zu bleichenden Alkyl- und/oder Alkenylglykoside folgen der Formel (I),The alkyl and / or alkenyl glycosides to be bleached follow the formula (I)
Rl-0-[G]p (I) R l-0- [G] p (I)
in derin the
R! für einen aliphatischen, linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoff¬ atomen,R! for an aliphatic, linear or branched alkyl and / or alkenyl radical with 6 to 22 carbon atoms,
[G] für eine Glykose-Einheit mit 5 oder 6 Kohlenstoffatomen und[G] for a glycose unit with 5 or 6 carbon atoms and
p für eine Zahl von 1 bis 10p for a number from 1 to 10
steht.stands.
Die Glycose-Einheit [G] kann sich von Aldosen bzw. Ketosen ableiten. Vorzugsweise werden wegen der besseren Reaktions¬ fähigkeit die reduzierend wirkenden Saccharide, die Aldosen, verwendet. Unter den Aldosen kommt wegen ihrer leichten Zu¬ gänglichkeit und technischen Verfügbarkeit insbesondere die Glucose in Betracht. Die bevorzugt gebleichten Alkyl- und/ oder Alkenyloligoglykoside sind daher die Alkyl- und/oder Alkenyloligoglucoside.The glycose unit [G] can be derived from aldoses or ketoses. Because of the better reactivity, the reducing saccharides, the aldoses, are preferably used. Among the aldoses, glucose is particularly suitable because of their easy access and technical availability. The preferred bleached alkyl and / or alkenyl oligoglycosides are therefore the alkyl and / or alkenyl oligoglucosides.
Die Indexzahl p in der allgemeinen Formel (I) gibt den Oli- gomerisierungsgrad, d. h. die Verteilung von Mono- und Oli- goglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muß und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyl- bzw. Alkenyloligo- glykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyl- und/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0 verwendet. Besonders bevorzugt sind solche Alkyl- und/oder Alkenyloligoglykoside, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbe¬ sondere zwischen 1,2 und 1,4 liegt.The index number p in the general formula (I) gives the degree of oligomerization, ie. H. the distribution of mono- and oligoglycosides is present and stands for a number between 1 and 10. While p must always be an integer in a given compound and can above all assume the values p = 1 to 6, the value p is for certain alkyl or alkenyl oligoglycoside is an analytically calculated quantity, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. Those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are particularly preferred.
Der Alkylrest R1 kann sich von primären Alkoholen mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen ableiten. Ty¬ pische Beispiele sind Capronalkohol, Caprylalkohol, Caprin- alkohol, Laurylalkohol, Myristylalkohol, Cetylalkohol, Palm- oleylalkohol, Stearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Ara- chylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol sowie deren technische Mischungen auf Basis von natürlichen Fetten und Ölen, beispielsweise Palmöl, Palmkernöl, Kokosöl oder Rindertalg.The alkyl radical R 1 can be derived from primary alcohols having 6 to 22, preferably 12 to 18, carbon atoms. Typical examples are capronic alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palm oleyl alcohol, stearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, arachyl alcohol, technical alcohols, gadoleyl alcohol, and mixtures thereof, gadoleyl alcohol of natural fats and oils, for example palm oil, palm kernel oil, coconut oil or beef tallow.
Bevorzugt ist der Einsatz von Alkyloligoglykosiden.der Formel (I), in der R1 für einen Alkylrest mit 12 bis 18 Kohlenstoff- ato en, [G] für einen Glucoserest und/oder p für Zahlen von 1,1 bis 3,0 steht.Preferred is the use of alkyl oligoglycosides of the formula (I) in which R 1 is an alkyl radical having 12 to 18 carbon atoms. ato en, [G] stands for a glucose residue and / or p for numbers from 1.1 to 3.0.
Die Bleiche wird in Gegenwart von Persauerstoffverbindungen durchgeführt. Typische Beispiele hierfür sind Perborate, Per- carbonate und insbesondere Wasserstoffperoxid, das in Form wäßriger, 5 bis 70, vorzugsweise 15 bis 35 gew.-%iger Lösung zum Einsatz gelangen kann. Die Konzentration der Persauer¬ stoffverbindungen kann 1 bis 5, vorzugsweise 2 bis 3 Gew.-% - bezogen auf den Feststoffgehalt der zu bleichenden Alkyl- bzw. Alkenyloligoglykosid-Paste - betragen.The bleaching is carried out in the presence of peroxygen compounds. Typical examples of this are perborates, percarbonates and in particular hydrogen peroxide, which can be used in the form of an aqueous 5 to 70, preferably 15 to 35% by weight solution. The concentration of the peroxygen compounds can be 1 to 5, preferably 2 to 3% by weight, based on the solids content of the alkyl or alkenyl oligoglycoside paste to be bleached.
Als Stabilisatoren kommen Aluminiumionen, Alkalisilicate, Zuckersäuren und/oder organische Komplexbildner in Betracht.Aluminum ions, alkali silicates, sugar acids and / or organic complexing agents come into consideration as stabilizers.
Die Aluminiumionen können den Persauerstoffverbindungen in Form von Salzen, beispielsweise Sulfaten, Carbonaten, Sili- caten oder Phosphaten zugesetzt werden.The aluminum ions can be added to the peroxygen compounds in the form of salts, for example sulfates, carbonates, silicates or phosphates.
Typische Beispiele für Alkalisilicate sind Natrium- und/oder Kaliumsilicate ("Wasserglas"), bei denen auf ein Mol Alkali¬ oxid durchschnittlich 2 bis 4 Mol Siliciu dioxid entfallen.Typical examples of alkali silicates are sodium and / or potassium silicates (“water glass”), in which an average of 2 to 4 moles of silicon dioxide per mole of alkali oxide.
Unter den Zuckersäuren eignen sich insbesondere Gluconsäure, Glucarsäure, Glucoronsäure und Glucoheptonsäure sowie deren Alkali- und Erdalkalisalze.Among the sugar acids, gluconic acid, glucaric acid, glucoronic acid and glucoheptonic acid and their alkali and alkaline earth salts are particularly suitable.
Typische Beispiele für organische Komplexbildner sind Phos- phonsäuren, wie beispielsweise Diethylentriaminpentamethyl- phosphonsäure. Die Stabilisatoren können einzeln oder in Kombination in Konzentrationen von jeweils 0,1 bis 5,0, vorzugsweise 0,5 bis 3,0 und insbesondere 1,0 bis 2,0 Gew.-% - bezogen auf den Feststoffgehalt der zu bleichenden Alkyl- bzw. Alkenyloligo- glykosid-Paste - eingesetzt werden.Typical examples of organic complexing agents are phosphonic acids, such as, for example, diethylenetriaminepentamethylphosphonic acid. The stabilizers can be used individually or in combination in concentrations of 0.1 to 5.0, preferably 0.5 to 3.0 and in particular 1.0 to 2.0% by weight, based on the solids content of the alkyl to be bleached. or alkenyl oligoglycoside paste - are used.
Zur Bleiche werden die oberflächenaktiven Verbindungen mit den Persauerstoffverbindungen und den Stabilisatoren ver¬ setzt. Dies kann bei Umgebungstemperatur oder aber auch bei der Bleichtemperatur erfolgen, wobei letztere 80 bis 120, vorzugsweise 90 bis 100°C betragen kann.For bleaching, the surface-active compounds are mixed with the peroxygen compounds and the stabilizers. This can take place at ambient temperature or else at the bleaching temperature, the latter being 80 to 120, preferably 90 to 100 ° C.
Es empfiehlt sich, die Bleiche über einen Zeitraum von 0,1 bis 5, vorzugsweise 1 bis 3 h durchzuführen. Des weiteren hat es sich als optimal erwiesen, hierbei einen pH-Wert von 7 bis 14, vorzugsweise 9 bis 11 einzustellen.It is advisable to carry out the bleaching over a period of 0.1 to 5, preferably 1 to 3, hours. Furthermore, it has proven to be optimal to set a pH of 7 to 14, preferably 9 to 11.
Gewerbliche AnwendbarkeitIndustrial applicability
Die nach dem erfindungsgemäßen Verfahren erhältlichen Alkyl- bzw. Alkenyloligoglykoside sind hellfarbig und eignen sich zur Herstellung von Wasch-, Spül- und Reinigungsmitteln sowie für Produkte zur Haar- und Körperpflege, in denen sie in Mengen von 0,1 bis 50, vorzugsweise 1 bis 10 Gew.-% - bezogen auf die Mittel - enthalten sein können.The alkyl or alkenyl oligoglycosides obtainable by the process according to the invention are light-colored and are suitable for the production of detergents, dishwashing detergents and cleaning agents and for products for hair and body care, in which they are present in amounts of 0.1 to 50, preferably 1 to 10 wt .-% - based on the agent - may be included.
Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern, ohne ihn darauf einzuschränken. BeispieleThe following examples are intended to explain the subject matter of the invention in more detail without restricting it. Examples
I. Herstellung einer C-]2-1 -Kokosalkylglucosid-PasteI. Preparation of a C-] 2-1 coconut alkyl glucoside paste
In einem 2-1-Dreihalskolben mit Rührer, Destillationsaufsatz und Innenthermometer wurden 180 g (1 Mol) wasserfreie Glucose und 870 g (4,5 mol) Ci2/i4-Kokosfettalkohol (Lorol(R) S, Hy- roxylzahl 290, Fa.Henkel KGaA, Düsseldorf, FRG) vorgelegt und unter einem verminderten Druck von ca. 20 mbar auf 110°C er¬ hitzt. Anschließend wurde die Reaktionsmischung mit 0,1 bis 0,5 Gew.-% - bezogen auf die Glucose - Sulfobernsteisäure in Form einer 5 gew.-%igen Lösung in Kokosfettalkohol versetzt. Zur Verlagerung des Gleichgewichtes wurde das Reaktionswasser kontinuierlich abdestilliert und die Reaktion abgebrochen, nachdem die Wasserabscheidung beendet war und der Restgehalt an nicht umgesetzter Glucose in der Mischung weniger als 1 Gew,-% - bezogen auf die Ausgangsmenge - betrug. Danach wurde die Reaktionsmischung mit Magnesiumoxid neutralisiert, der überschüssige Kokosfettalkohol unter vermindertem Druck (ca. 1 mbar) und einer Temperatur von 180°C mit Hilfe eines Dünn¬ schichtverdampfers abgetrennt und der Rückstand mit Wasser angepastet.180 g (1 mol) of anhydrous glucose and 870 g (4.5 mol) of Ci2 / i4 coconut oil alcohol (Lorol ( R ) S, hydrogenation number 290, Fa.) Were placed in a 2-1 three-necked flask with stirrer, distillation attachment and internal thermometer. Henkel KGaA, Düsseldorf, FRG) and heated to 110 ° C under a reduced pressure of approx. 20 mbar. Then 0.1 to 0.5% by weight, based on the glucose, of sulfosuccinic acid in the form of a 5% by weight solution in coconut oil alcohol was added to the reaction mixture. To shift the equilibrium, the water of reaction was continuously distilled off and the reaction was stopped after the water separation had ended and the residual content of unreacted glucose in the mixture was less than 1% by weight, based on the starting amount. The reaction mixture was then neutralized with magnesium oxide, the excess coconut fatty alcohol was separated off under reduced pressure (approx. 1 mbar) and at a temperature of 180 ° C. using a thin-film evaporator and the residue was pasted with water.
Anschließend wurde die Paste mit Natronlauge auf pH = 9 bis 10 eingestellt und bei 90°C mit 1,5 bis 2 Gew.-% Wasser¬ stoffperoxid (30 gew.-%ige wäßrige Lösung) - bezogen auf die Paste - sowie den Stabilisatoren versetzt und über 1 bis 1,5 h gerührt. Die Ergebnisse sind in Tab.l zusammengefaßt. Tab.1; Bleiche von Kokosalkylglucosid Prozentangabe als Gew.-%The paste was then adjusted to pH = 9 to 10 with sodium hydroxide solution and at 90 ° C. with 1.5 to 2% by weight of hydrogen peroxide (30% by weight aqueous solution) - based on the paste - and the stabilizers added and stirred for 1 to 1.5 h. The results are summarized in Tab. 1. Tab. 1; Bleaching of coconut alkyl glucoside Percentage as% by weight
Figure imgf000011_0001
Figure imgf000011_0001
Legende; c(H2θ2) = Konzentration WasserstoffperoxidLegend; c (H2θ2) = concentration of hydrogen peroxide
St = Stabilisator c(St) = Konzentration Stabilisator t = BleichdauerSt = stabilizer c (St) = concentration stabilizer t = bleaching time
T = BleichtemperaturT = bleaching temperature
NatriumsilicatSodium silicate
(Portil(R) 37/40, Fa.Henkel KGaA)(Portil ( R ) 37/40, Henkel KGaA)
B Aluminiumsulfat C Aluminiumsulfat/KaliumgluconatB aluminum sulfate C aluminum sulfate / potassium gluconate
Gewichtsverhältnis 2 : 1 Weight ratio 2: 1

Claims

PatentansprücheClaims
Verfahren zur Bleiche von Alkyl- und/oder Alkenylglyko- siden mit Hilfe von Persauerstoffverbindungen, dadurch gekennzeichnet, daß man die Bleiche in Gegenwart von Stabilisatoren ausgewählt aus der Gruppe, die von Alu¬ miniumionen, Alkalisilicaten, Zuckersäuren und organi¬ schen Komplexbildnern gebildet wird, durchführt.Process for bleaching alkyl and / or alkenyl glycosides with the aid of peroxygen compounds, characterized in that the bleach in the presence of stabilizers is selected from the group formed by aluminum ions, alkali metal silicates, sugar acids and organic complexing agents. carries out.
Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man Alkyl- und/oder Alkenylglykoside der Formel (I) einsetzt.Process according to Claim 1, characterized in that alkyl and / or alkenyl glycosides of the formula (I) are used.
Rl_0-[G]p (I) R l_0- [G] p (I)
in derin the
Rl für einen aliphatischen, linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlen¬ stoffatomen,Rl for an aliphatic, linear or branched alkyl and / or alkenyl radical with 6 to 22 carbon atoms,
[G] für eine Glykose-Einheit mit 5 oder 6 Kohlenstoff¬ atomen und[G] for a glycose unit with 5 or 6 carbon atoms and
p für eine Zahl von 1 bis 10p for a number from 1 to 10
steht. 3. Verfahren nach den Ansprüchen 1 und 2, dadurch gekenn¬ zeichnet, daß man die Persauerstoffverbindungen in Kon¬ zentrationen von 0,1 bis 5 Gew.-% - bezogen auf den Feststoffgehalt der zu bleichenden Alkyl- bzw. Alkenyl- oligoglykosid-Paste - einsetzt.stands. 3. Process according to claims 1 and 2, characterized gekenn¬ characterized in that the peroxygen compounds in concentrations from 0.1 to 5 wt .-% - based on the solids content of the alkyl or alkenyl oligoglycoside paste to be bleached - sets in.
4. Verfahren nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man die Stabilisatoren in Konzentrationen von jeweils 0,1 bis 5 Gew.-% - bezogen auf den Feststoffgehalt der zu bleichenden Alkyl- bzw. Alkenyloligoglykosid-Paste - einsetzt.4. The method according to at least one of claims 1 to 3, characterized in that the stabilizers in concentrations of 0.1 to 5 wt .-% - based on the solids content of the alkyl or alkenyl oligoglycoside paste to be bleached - used.
5. Verfahren nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Bleiche bei einer Temperatur von 80 bis 120°C durchführt.5. The method according to at least one of claims 1 to 4, characterized in that one carries out the bleaching at a temperature of 80 to 120 ° C.
6. Verfahren nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die Bleiche über einen Zeitraum von 0,1 bis 5 h durchführt.6. The method according to at least one of claims 1 to 5, characterized in that the bleaching is carried out over a period of 0.1 to 5 h.
7. Verf hren nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man die Bleiche bei einem pH-Wert von 7 bis 14 durchführt. 7. The method according to at least one of claims 1 to 6, characterized in that the bleaching is carried out at a pH of 7 to 14.
PCT/EP1992/002894 1991-12-21 1992-12-14 Method of bleaching alkyl and/or alkenyl glycosides WO1993013112A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DEP4142592.8 1991-12-21
DE19914142592 DE4142592A1 (en) 1991-12-21 1991-12-21 Bleaching surface active cpd. with peroxy cpd. - in presence of alkaline earth ions, zinc ions or alkali silicate as booster
DE19924200850 DE4200850A1 (en) 1992-01-15 1992-01-15 Bleaching alkyl and/or alkenyl glycoside with peroxy cpd. - in presence of stabiliser e.g. aluminium ions and alkali silicate(s), with prod. used for washing and rinsing compsn.
DEP4200850.6 1992-01-15

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