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EP1406722A1 - Aqueous preparations - Google Patents

Aqueous preparations

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Publication number
EP1406722A1
EP1406722A1 EP02764626A EP02764626A EP1406722A1 EP 1406722 A1 EP1406722 A1 EP 1406722A1 EP 02764626 A EP02764626 A EP 02764626A EP 02764626 A EP02764626 A EP 02764626A EP 1406722 A1 EP1406722 A1 EP 1406722A1
Authority
EP
European Patent Office
Prior art keywords
aqueous
nonionic surfactants
preparations
weight
contain
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP02764626A
Other languages
German (de)
French (fr)
Inventor
Hans-Christian Raths
Christian De Haut
Jean-Pierre Molitor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Health and Care Products France SAS
Original Assignee
Cognis France SAS
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
Application filed by Cognis France SAS filed Critical Cognis France SAS
Publication of EP1406722A1 publication Critical patent/EP1406722A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/44—Preparation of O-glycosides, e.g. glucosides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • 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
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37—Esters of carboxylic acids
    • 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
    • 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • 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
    • A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
    • A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
    • A61K8/9728—Fungi, e.g. yeasts
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/017—Mixtures of compounds
    • C09K23/018—Mixtures of two or more different organic oxygen-containing compounds

Definitions

  • the invention is in the field of biotechnology and relates to aqueous preparations containing biotechnologically produced surfactants and nonionic surfactants, a process for their preparation, the special use of the nonionic surfactants as extractants and the mixtures for the production of agrochemical or cosmetic preparations.
  • Fermentation can convert biomass, such as fats and oils, carbohydrates, hydrocarbons and the like, into surface-active substances, which are collectively referred to as "biosurfactants".
  • biosurfactants surface-active substances
  • the object of the present invention was therefore to provide an improved extraction process for working up biosurfactants from fermenter broths, in the course of which mixtures of the biosurfactants with the extraction agents are obtained which are commercially available, in particular in the field of agrochemistry or without further separation steps Cosmetics can be used.
  • the process should be characterized by the fact that it runs quickly and at low temperatures and thereby ensures a quantitative separation of the biosurfactants.
  • the invention relates to aqueous preparations containing
  • surface-active fermentation broths can be extracted quickly and quantitatively using nonionic surfactants if the extraction is carried out at the cloud point of the nonionic surfactants.
  • the resulting mixtures can be used directly commercially without further separation or workup and can be used, for example, as emulsifiers in agrochemicals or cosmetics.
  • biosurfactants are surface-active fermentation products.
  • the conversion of biomass into biosurfactants by fermentation can be carried out with the help of a large number of very different microorganisms.
  • Candida antarctica for example, is important for the production of mannosyl erytritol lipids (MEL).
  • MEL mannosyl erytritol lipids
  • the biosurfactants are rhamnolipids which are obtained by fermentation of carbohydrates with fats or oils and follow the general formula (I).
  • Nonionic surfactants are characterized by an inverse solubility behavior, i.e. they dissolve better in the cold than in the warmth. This effect is due to the fact that nonionic surfactants generally contain polyalkylene glycol ether chains, the ether oxides of which are hydrated in an aqueous environment via hydrogen bonds, which gives the molecule a high polarity and therefore good solubility. As the temperature rises, the hydrogen bonds are released, reducing the polarity and solubility and eliminating the nonionic surfactant from the aqueous phase. The temperature at which this excretion begins is typical of every nonionic surfactant and is referred to as the cloud point. Two micellar phases form below this temperature: a surfactant-rich and a surfactant-poor.
  • nonionic surfactants which have a cloud point in the range from 20 to 80 and in particular 25 to 50 ° C., with species having a particularly low cloud point, in particular in the range of room temperature, being of course particularly preferred because which allow the mixtures to be produced under very mild conditions.
  • the nonionic surfactants are fatty alcohol polyglycol ethers, which in particular follow the formula (II)
  • R 1 represents a linear or branched alkyl and / or alkenyl radical
  • R 2 represents hydrogen or methyl
  • n represents numbers from 1 to 30.
  • Typical examples are the addition products of an average of 1 to 5, preferably 2 to 3, moles of propylene glycol and / or 1 to 30, preferably 5 to 15, moles of ethylene oxide with fatty alcohols with 6 to 22 and in particular 12 to 18 carbon atoms, such as, for example, capron alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, cerium alcohol, oleyl alcohol, elaidyl alcohol, gadoleyl alcohol, arachyl alcohol, and technical beucyl alcohol, behenyl alcohol.
  • the nonionic surfactants can be prepared in a manner known per se on an industrial scale, that is to say by base-catalyzed addition of alkylene oxides to the corresponding fatty alcohols, resulting in substances with a conventionally broad homolog distribution.
  • fatty alcohol polyglycol ethers with a narrow homolog distribution are preferably used, since these are generally distinguished by particularly low cloud points.
  • the preparations can additionally contain electrolyte salts. These are preferably alkali or alkaline earth chlorides or sulfates.
  • the preparations according to the invention typically contain - based on the non-aqueous content -
  • the non-aqueous content of the preparations can be 10 to 50, preferably 20 to 30,% by weight.
  • the invention further relates to a process for the preparation of mixtures of surface-active fermentation products and nonionic surfactants, in which an aqueous solution of surface-active fermentation products with nonionic surfactants is extracted at their cloud point and the resulting lighter surfactant-containing phase is separated from the heavier aqueous phase.
  • the surface-active fermentation products are preferably directly fermenter broths. It has proven to be advantageous to add small amounts of electrolyte salts to the systems, since these support the phase separation and at the same time reduce the cloud point of the nonionic surfactants.
  • the subsequent separation can take place, for example, in a separator or by centrifugation, the surfactant-containing phase generally forming the lighter phase.
  • the heavier aqueous phase contains practically no more surfactant components.
  • Another object of the invention therefore relates to the use of nonionic surfactants as extractants for aqueous surface-active fermenter broths
  • aqueous mixtures obtainable in the sense of the invention have excellent surface-active properties and are in particular readily biodegradable and toxicologically harmless.
  • Another object of the invention therefore relates to their use, for example as emulsifiers, for the production of agrochemical or cosmetic preparations in which they are present in amounts of 0.1 to 30, preferably 1 to 20 and in particular 5 to 15% by weight can.
  • a rhamnolipid JBR 599, Jeneill Biosurfactant Co. Inc.
  • a rhamnolipid JBR 599, Jeneill Biosurfactant Co. Inc.

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  • Health & Medical Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
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  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
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  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Botany (AREA)
  • Genetics & Genomics (AREA)
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  • Dispersion Chemistry (AREA)
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  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
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Abstract

The invention relates to aqueous preparations containing (a) surface-active fermentation products and (b) non-ionic surfactants.

Description

Wässrige ZubereitungenAqueous preparations
Gebiet der ErfindungField of the Invention
Die Erfindung befindet sich auf dem Gebiet der Biotechnologie und betrifft wässrige Zubereitungen mit einem Gehalt an biotechnologisch hergestellten Tenside und nichtionischen Tensiden, einem Verfahren zu deren Herstellung, die spezielle Verwendung der nichtioni- sehen Tenside als Extraktionsmittel sowie der Gemische für die Herstellung von agrochemischen oder kosmetischen Zubereitungen.The invention is in the field of biotechnology and relates to aqueous preparations containing biotechnologically produced surfactants and nonionic surfactants, a process for their preparation, the special use of the nonionic surfactants as extractants and the mixtures for the production of agrochemical or cosmetic preparations.
Stand der TechnikState of the art
Durch Fermentation lässt sich Biomasse, wie beispielsweise Fette und Öle, Kohlenhydrate, Kohlenwasserstoffe und dergleichen in oberflächenaktive Stoffe umwandeln, die summarisch als „Biotenside" bezeichnet werden. Die Abtrennung von solchen Stoffen aus den Fermenter- brühen gestaltet sich jedoch oft sehr zeitaufwendig und kostenintensiv. In einer Reihe von Fällen hat sich der Einsatz von organischen Extraktionsmitteln, wie beispielsweise Methylenchlorid oder Essigester als möglich erwiesen, von erheblichem Nachteil ist jedoch, dass diese Stoffe anschließend wieder von den Biotensiden abgetrennt werden müssen, da ihre Mitverwendung beispielsweise im Bereich der Kosmetik natürlich unmöglich ist. Tatsächlich sind nicht einmal geringe Spuren an chlorierten Verbindungen tolerierbar. Im Fall der Rham- noiipide, die als extrazelluläre Tenside aus Glucose und nativen Triglyceriden hergestellt werden, gelingt aufgrund ihres anionischen Charakters auch eine Trennung durch Adsorption an Ionenaustauschern, allerdings ist ein solches Verfahren allenfalls im Labormaßstab sinnvoll durchführbar.Fermentation can convert biomass, such as fats and oils, carbohydrates, hydrocarbons and the like, into surface-active substances, which are collectively referred to as "biosurfactants". However, the removal of such substances from the fermenter broths is often very time-consuming and cost-intensive. In a number of cases, the use of organic extraction agents, such as methylene chloride or ethyl acetate, has proven to be possible, but it is a considerable disadvantage that these substances then have to be separated from the biosurfactants again, since their use, for example in the field of cosmetics, is of course impossible In fact, not even slight traces of chlorinated compounds can be tolerated, and in the case of rhamnoiipids, which are produced as extracellular surfactants from glucose and native triglycerides, their anionic character also enables separation by adsorption n on ion exchangers, but such a method can only be practiced on a laboratory scale.
In diesem Zusammenhang sei auf den Aufsatz von Hinze und Pramauro in Critical Review Anal. Chem. 24(2). 133-177 (1993) hingewiesen, aus dem die Extraktion von Proteinen mit zwitterionischen Tensiden und die Extraktion von Metallchelaten mit nichtionischen Tensiden an der Trübungspunkt bekannt ist. Von Minuth et al. wird in Biotechnol. Bioeng. 55(2 . 342ff (1997) über die Abtrennung von Biomasse aus wässrigen Zweiphasensystemen mit Hilfe der Zentrifugation berichtet.In this context, the article by Hinze and Pramauro in Critical Review Anal. Chem. 24 (2). 133-177 (1993), from which the extraction of proteins with zwitterionic surfactants and the extraction of metal chelates with nonionic surfactants at the cloud point is known. By Minuth et al. is in biotechnol. Bioeng. 55 (2. 342ff (1997) on the separation of biomass from aqueous two-phase systems using centrifugation.
Die Aufgabe der vorliegenden Erfindung hat somit darin bestanden, ein verbessertes Extrak- tionsverfahren zur Aufarbeitung von Biotensiden aus Fermenterbrühen zur Verfügung zu stellen, in dessen Verlauf Mischungen der Biotenside mit den Extraktionsmitteln erhalten werden, die ohne weitere Trennschritte kommerziell, insbesondere im Bereich der Agrochemie oder Kosmetik einsetzbar sind. Gleichzeitig sollte sich das Verfahren dadurch auszeichnen, dass es schnell und bei niedrigen Temperaturen abläuft und dabei eine quantitative Abtrennung der Biotenside sicherstellt.The object of the present invention was therefore to provide an improved extraction process for working up biosurfactants from fermenter broths, in the course of which mixtures of the biosurfactants with the extraction agents are obtained which are commercially available, in particular in the field of agrochemistry or without further separation steps Cosmetics can be used. At the same time, the process should be characterized by the fact that it runs quickly and at low temperatures and thereby ensures a quantitative separation of the biosurfactants.
Beschreibung der ErfindungDescription of the invention
Gegenstand der Erfindung sind wässrige Zubereitungen, enthaltendThe invention relates to aqueous preparations containing
(a) oberflächenaktive Fermentationsprodukte und(a) surface active fermentation products and
(b) nichtionische Tenside.(b) nonionic surfactants.
Überraschenderweise wurde gefunden, dass sich oberflächenaktive Fermentationsbrühen rasch und quantitativ mit Hilfe von nichtionischen Tensiden extrahieren lassen, wenn man die Extraktion am Trübungspunkt der Niotenside durchführt. Die resultierenden Gemische lassen sich ohne weitere Trennung bzw. Aufarbeitung direkt kommerziell nutzen und können Anwendung beispielsweise als Emulgatoren in der Agrochemie oder der Kosmetik finden.Surprisingly, it was found that surface-active fermentation broths can be extracted quickly and quantitatively using nonionic surfactants if the extraction is carried out at the cloud point of the nonionic surfactants. The resulting mixtures can be used directly commercially without further separation or workup and can be used, for example, as emulsifiers in agrochemicals or cosmetics.
Oberflächenaktive Fermentationsprodukte („Biotenside")Surface-active fermentation products ("biosurfactants")
Die Umwandlung von Biomasse in Biotenside durch Fermentation kann mit Hilfe einer Viel- zahl von ganz unterschiedlichen Mikroorganismen erfolgen. Bedeutung besitzt beispielsweise Candida antarctica für die Herstellung von Mannosyl-Erytritol-Lipiden (MEL). In einer bevorzugten Ausführungsform der Erfindung handelt es sich bei den Biotensiden jedoch um Rhamnolipide, die durch Fermentation von Kohlenhydraten mit Fetten oder Ölen enthalten werden und der allgemeinen Formel (I) folgen. The conversion of biomass into biosurfactants by fermentation can be carried out with the help of a large number of very different microorganisms. Candida antarctica, for example, is important for the production of mannosyl erytritol lipids (MEL). In a preferred embodiment of the invention, however, the biosurfactants are rhamnolipids which are obtained by fermentation of carbohydrates with fats or oils and follow the general formula (I).
Nichtionische TensideNonionic surfactants
Nichtionische Tenside zeichnen sich durch ein inverses Löslichkeitsverhalten aus, d.h. sie lösen sich in der Kälte besser als in der Wärme. Dieser Effekt ist darauf zurückzuführen, dass Niotenside in der Regel Polyalkylenglycoletherketten enthalten, deren Ethersauerstoffe in wässriger Umgebung über Wasserstoffbrückenbindungen hydratisiert vorliegen, was dem Molekül eine hohe Polarität und somit gute Löslichkeit verleiht. Mit steigender Temperatur werden die Wasserstoffbrücken gelöst, wodurch Polarität und Löslichkeit abnehmen und das Niotensid aus der wässrigen Phase ausgeschieden wird. Die Temperatur, an der diese Ausscheidung beginnt, ist für jedes Niotensid typisch und wird als Trübungspunkt bezeichnet. Unterhalb dieser Temperatur bilden sich zwei micellare Phasen aus : eine tensidreiche und eine tensidarme.Nonionic surfactants are characterized by an inverse solubility behavior, i.e. they dissolve better in the cold than in the warmth. This effect is due to the fact that nonionic surfactants generally contain polyalkylene glycol ether chains, the ether oxides of which are hydrated in an aqueous environment via hydrogen bonds, which gives the molecule a high polarity and therefore good solubility. As the temperature rises, the hydrogen bonds are released, reducing the polarity and solubility and eliminating the nonionic surfactant from the aqueous phase. The temperature at which this excretion begins is typical of every nonionic surfactant and is referred to as the cloud point. Two micellar phases form below this temperature: a surfactant-rich and a surfactant-poor.
Im Sinne der Erfindung kommen daher solche nichtionischen Tenside bevorzugt zum Einsatz, die einen Trübungspunkt im Bereich von 20 bis 80 und insbesondere 25 bis 50 °C aufweisen, wobei natürlich Spezies mit besonders niedrigem Trübungspunkt, insbesondere im Bereich der Raumtemperatur wiederum besonders bevorzugt sind, da die die Herstellung der Mi- schungen unter sehr milden Bedingungen erlauben. In der Regel handelt es sich bei den Niotensiden um Fettalkoholpolyglycolether, die insbesondere der Formel (II) folgenFor the purposes of the invention, preference is given to using nonionic surfactants which have a cloud point in the range from 20 to 80 and in particular 25 to 50 ° C., with species having a particularly low cloud point, in particular in the range of room temperature, being of course particularly preferred because which allow the mixtures to be produced under very mild conditions. As a rule, the nonionic surfactants are fatty alcohol polyglycol ethers, which in particular follow the formula (II)
R10(CH2CHR20)nH (II)R 1 0 (CH 2 CHR 2 0) n H (II)
in der R1 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest, R2 für Wasserstoff oder Methyl und n für Zahlen von 1 bis 30 steht. Typische Beispiele sind die Anlagerungsprodukte von durchschnittlich 1 bis 5, vorzugsweise 2 bis 3 Mol Propylenglykol und/oder 1 bis 30, vorzugsweise 5 bis 15 Mol Ethylenoxid an Fettalkohole mit 6 bis 22 und insbesondere 12 bis 18 Kohlenstoffatome, wie etwa Capronalkohol, Caprylalkohol, Caprinalkohol, Laurylal- kohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Ce- tearylalkohol, Oleylalkohol, Elaidylalkohol, Gadoleylalkohol, Arachylalkohol, Behenylalkohol, Erucylalkohol sowie deren technische Gemische. Die nichtionischen Tenside können in an sich bekannter großtechnischer Weise hergestellt werden, also durch basenkatalysierte Anlagerung von Alkylenoxiden an die entsprechenden Fettalkohole, wobei Stoffe mit einer konventionell breiten Homologenverteilung resultieren. Vorzugsweise werden jedoch Fettalko- holpolyglycolether mit eingeengter Homologenverteilung („Narrow-range ethoxylates, NRE") eingesetzt, da sich diese in der Regel durch besonders niedrige Trübungspunkte auszeich- nen. Ihre Herstellung erfolgt durch Alkoxylierung der Fettalkohole in Gegenwart spezieller, literaturbekannter Katalysatoren, wie z.B. calciniertem Hydrotalcit. Typische Beispiele sind C12/18-Kokosalkohol+5EO-NRE (Agrimul® NRE 1205) oder Myristylalkohol+6EO-NRE (Agrimul® 1406 NRE), die von der Cognis Deutschland GmbH im Handel erhältlich sind.in which R 1 represents a linear or branched alkyl and / or alkenyl radical, R 2 represents hydrogen or methyl and n represents numbers from 1 to 30. Typical examples are the addition products of an average of 1 to 5, preferably 2 to 3, moles of propylene glycol and / or 1 to 30, preferably 5 to 15, moles of ethylene oxide with fatty alcohols with 6 to 22 and in particular 12 to 18 carbon atoms, such as, for example, capron alcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, cerium alcohol, oleyl alcohol, elaidyl alcohol, gadoleyl alcohol, arachyl alcohol, and technical beucyl alcohol, behenyl alcohol. The nonionic surfactants can be prepared in a manner known per se on an industrial scale, that is to say by base-catalyzed addition of alkylene oxides to the corresponding fatty alcohols, resulting in substances with a conventionally broad homolog distribution. However, fatty alcohol polyglycol ethers with a narrow homolog distribution (narrow-range ethoxylates, NRE) are preferably used, since these are generally distinguished by particularly low cloud points. They are prepared by alkoxylating the fatty alcohols in the presence of special catalysts known from the literature, such as eg calcined hydrotalcite Typical examples are C12 / 18 coconut alcohol + 5EO-NRE (Agrimul® NRE 1205) or myristyl alcohol + 6EO-NRE (Agrimul® 1406 NRE), which are commercially available from Cognis Deutschland GmbH.
Elektrolytsalzeelectrolyte salts
In einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung können die Zubereitungen zusätzlich Elektrolytsalze enthalten. Dabei handelt es sich vorzugsweise um Al- kali- oder Erdalkalichloride oder -sulfate.In a further preferred embodiment of the present invention, the preparations can additionally contain electrolyte salts. These are preferably alkali or alkaline earth chlorides or sulfates.
Oberflächenaktive ZubereitungenSurface-active preparations
Typischerweise enthalten die erfindungsgemäßen Zubereitungen - bezogen auf den nicht- wässrigen Gehalt -The preparations according to the invention typically contain - based on the non-aqueous content -
(a) 10 bis 60, vorzugsweise 20 bis 40 Gew.-% oberflächenaktive Fermentationsprodukte,(a) 10 to 60, preferably 20 to 40% by weight of surface-active fermentation products,
(b) 40 bis 90, vorzugsweise 45 bis 80 Gew.-% nichtionische Tenside und (c) 0 bis 20, vorzugsweise 10 bis 15 Gew.-% Elektrolytsalze(b) 40 to 90, preferably 45 to 80% by weight of nonionic surfactants and (c) 0 to 20, preferably 10 to 15% by weight of electrolyte salts
mit der Maßgabe, dass sich die Mengenangaben zu 100 Gew.-% ergänzen. Der nicht- wässrige Gehalt der Zubereitungen kann dabei 10 bis 50, vorzugsweise 20 bis 30 Gew.-% betragen. Extraktionsverfahrenwith the proviso that the quantities add up to 100% by weight. The non-aqueous content of the preparations can be 10 to 50, preferably 20 to 30,% by weight. extraction process
Ein weiterer Gegenstand der Erfindung betrifft ein Verfahren zur Herstellung von Mischungen aus oberflächenaktiven Fermentationsprodukten und nichtionischen Tensiden, bei dem man eine wässrige Lösung oberflächenaktiver Fermentationsprodukte mit nichtionischen Tensiden an deren Trübungspunkt extrahier und die dabei entstehende leichtere tensidhaltige Phase von der schwereren wässrigen Phase abtrennt. Wie schon erläutert, handelt es sich bei den oberflächenaktiven Fermentationsprodukten vorzugsweise direkt um Fermenterbrühen. Es hat sich als vorteilhaft erwiesen, den Systemen geringe Mengen an Elektrolytsalzen hinzu- zufügen, da diese die Phasentrennung unterstützen und gleichzeitig den Trübungspunkt der Niotenside herabsetzen. Die anschließende Trennung kann beispielsweise in einem Separator oder durch Zentrifugieren erfolgen, wobei die tensidhaltige Phase in der Regel die leichtere Phase bildet. Die schwerere wässrige Phase enthält praktisch keine Tensidbestandteile mehr. Ein weiterer Gegenstand der Erfindung betrifft daher die Verwendung von nichtionischen Tensiden als Extraktionsmittel für wässrige oberflächenaktive FermenterbrühenThe invention further relates to a process for the preparation of mixtures of surface-active fermentation products and nonionic surfactants, in which an aqueous solution of surface-active fermentation products with nonionic surfactants is extracted at their cloud point and the resulting lighter surfactant-containing phase is separated from the heavier aqueous phase. As already explained, the surface-active fermentation products are preferably directly fermenter broths. It has proven to be advantageous to add small amounts of electrolyte salts to the systems, since these support the phase separation and at the same time reduce the cloud point of the nonionic surfactants. The subsequent separation can take place, for example, in a separator or by centrifugation, the surfactant-containing phase generally forming the lighter phase. The heavier aqueous phase contains practically no more surfactant components. Another object of the invention therefore relates to the use of nonionic surfactants as extractants for aqueous surface-active fermenter broths
Gewerbliche AnwendbarkeitIndustrial applicability
Die im Sinne der Erfindung erhältlichen wässrigen Mischungen besitzen ausgezeichnete o- berflächenaktive Eigenschaften und sind insbesondere leicht biologisch abbaubar sowie toxikologisch unbedenklich. Ein weiterer Gegenstand der Erfindung betrifft daher ihre Verwendung, beispielsweise als Emulgatoren, für die Herstellung von agrochemischen oder kosmetischen Zubereitungen, in denen sie in Mengen von 0,1 bis 30, vorzugsweise 1 bis 20 und insbesondere 5 bis 15 Gew.-% enthalten sein können. The aqueous mixtures obtainable in the sense of the invention have excellent surface-active properties and are in particular readily biodegradable and toxicologically harmless. Another object of the invention therefore relates to their use, for example as emulsifiers, for the production of agrochemical or cosmetic preparations in which they are present in amounts of 0.1 to 30, preferably 1 to 20 and in particular 5 to 15% by weight can.
BeispieleExamples
Beispiel 1. Eine wässerige Lösung eines Rhamnolipids (JBR 599, Jeneill Biosurfactant Co. Inc.) mit einer Konzentration von 40 g/l wurde mit 80 g/l C12/18-Kokosalkohol+5EO-NRE (Agrimul® 1205 NRE, Cognis) versetzt. Nach Zugabe von 10 Gew.-% Kochsalz und Erwärmen des Systems auf 50 °C ergab sich innerhalb weniger Minuten eine Phasentrennung (pH = 3,5). Die obere Tensidphase wurde abgetrennt und im Vergleich zur unteren wässrigen Phasen dünnschichtchromatographisch untersucht. Dabei wurde festgestellt, dass die wäss- rige Phase tensidfrei und die Extraktion damit quantitativ erfolgt war.Example 1. An aqueous solution of a rhamnolipid (JBR 599, Jeneill Biosurfactant Co. Inc.) with a concentration of 40 g / l was treated with 80 g / l C12 / 18 coconut alcohol + 5EO-NRE (Agrimul® 1205 NRE, Cognis) added. After adding 10% by weight of sodium chloride and heating the system to 50 ° C., the phases separated within a few minutes (pH = 3.5). The upper surfactant phase was separated off and examined by thin layer chromatography compared to the lower aqueous phases. It was found that the aqueous phase was free of surfactants and the extraction was thus quantitative.
Beispiel 2. Eine wässerige Lösung eines Rhamnolipids (JBR 599, Jeneill Biosurfactant Co. Inc.) mit einer Konzentration von 40 g/l wurde mit 70 g/l Myristylalkohol+6EO-NRE (Agrimul® 1406 NRE, Cognis) versetzt. Nach Zugabe von 8 Gew.-% Kochsalz und Erwärmen des Systems auf 45 °C ergab sich innerhalb weniger Minuten eine Phasentrennung (pH = 3,5). Die obere Tensidphase wurde abgetrennt und im Vergleich zur unteren wässrigen Phasen dünnschichtchromatographisch untersucht. Dabei wurde festgestellt, dass die wässrige Phase tensidfrei und die Extraktion damit quantitativ erfolgt war. Example 2. An aqueous solution of a rhamnolipid (JBR 599, Jeneill Biosurfactant Co. Inc.) with a concentration of 40 g / l was mixed with 70 g / l myristyl alcohol + 6EO-NRE (Agrimul® 1406 NRE, Cognis). After adding 8% by weight of sodium chloride and heating the system to 45 ° C., the phases separated within a few minutes (pH = 3.5). The upper surfactant phase was separated off and examined by thin layer chromatography compared to the lower aqueous phases. It was found that the aqueous phase was free of surfactants and the extraction was thus quantitative.

Claims

Patentansprüche claims
1. Wässrige Zubereitungen, enthaltend1. Aqueous preparations containing
(a) oberflächenaktive Fermentationsprodukten und(a) surface active fermentation products and
(b) nichtionische Tenside.(b) nonionic surfactants.
2. Zubereitungen nach Anspruch 1, dadurch gekennzeichnet, dass sie als Komponente (a) Rhamnolipide enthalten.2. Preparations according to claim 1, characterized in that they contain rhamnolipids as component (a).
3. Zubereitungen nach den Ansprüchen 1 und/oder 2, dadurch gekennzeichnet, dass sie als Komponente (b) nichtionische Tenside mit einem Trübungspunkt im Bereich von 20 bis 80 °C enthalten.3. Preparations according to claims 1 and / or 2, characterized in that they contain as component (b) nonionic surfactants with a cloud point in the range from 20 to 80 ° C.
4. Zubereitungen nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass sie als Komponente (b) Fettalkoholpolyglycolether enthalten.4. Preparations according to at least one of claims 1 to 3, characterized in that they contain fatty alcohol polyglycol ether as component (b).
5. Zubereitungen nach mindestens einem der Ansprüche 1 bis 4, dadurch gekenn- zeichnet, dass sie als Komponente (b) Fettalkoholpolyglycolether mit eingeengter5. Preparations according to at least one of claims 1 to 4, characterized in that they contain, as component (b), fatty alcohol polyglycol ether
Homologenverteilung enthalten.Homolog distribution included.
6. Zubereitungen nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass sie weiterhin Elektrolytsalze enthalten.6. Preparations according to at least one of claims 1 to 5, characterized in that they further contain electrolyte salts.
7. Zubereitungen nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass sie - bezogen auf den nicht-wässrigen Gehalt -7. Preparations according to at least one of claims 1 to 6, characterized in that - based on the non-aqueous content -
(a) 10 bis 60 Gew.-% oberflächenaktive Fermentationsprodukte, (b) 40 bis 90 Gew.-% nichtionische Tenside und(a) 10 to 60% by weight of surface-active fermentation products, (b) 40 to 90% by weight of nonionic surfactants and
(c) 0 bis 10 Gew.-% Elektrolytsalze(c) 0 to 10% by weight of electrolyte salts
mit der Maßgabe, dass sich die Mengenangaben zu 100 Gew.-% ergänzen.with the proviso that the quantities add up to 100% by weight.
8. Zubereitungen nach mindestens einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass sie einen nicht-wässrigen Gehalt von 10 bis 50 Gew.-% aufweisen. 8. Preparations according to at least one of claims 1 to 7, characterized in that they have a non-aqueous content of 10 to 50 wt .-%.
9. Verfahren zur Herstellung von Mischungen aus oberflächenaktiven Fermentationsprodukten und nichtionischen Tensiden, bei dem man eine wässrige Lösung oberflächenaktiver Fermentationsprodukte mit nichtionischen Tensiden an deren Trübungspunkt extrahier und die dabei entstehende leichtere tensidhaltige Phase von der schwereren wässrigen Phase abtrennt.9. A process for the preparation of mixtures of surface-active fermentation products and nonionic surfactants, in which an aqueous solution of surface-active fermentation products with nonionic surfactants is extracted at their cloud point and the resulting lighter surfactant-containing phase is separated from the heavier aqueous phase.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass man wässrige oberflächenaktive Fermenterbrühen einsetzt.10. The method according to claim 9, characterized in that aqueous surfactant fermenter broths are used.
11. Verfahren nach den Ansprüchen 9 und/oder 10, dadurch gekennzeichnet, dass man die Phasentrennung durch Zugabe von Elektrolytsalzen unterstützt.11. The method according to claims 9 and / or 10, characterized in that the phase separation is supported by the addition of electrolyte salts.
12. Verwendung von nichtionischen Tensiden als Extraktionsmittel für wässrige oberflächenaktive Fermenterbrühen.12. Use of nonionic surfactants as an extractant for aqueous surface-active fermenter broths.
13. Verwendung von Gemischen nach Anspruch 1 zur Herstellung von agrochemischen Zubereitungen.13. Use of mixtures according to claim 1 for the production of agrochemical preparations.
14. Verwendung von Gemischen nach Anspruch 1 zur Herstellung von kosmetischen Zube- reitungen. 14. Use of mixtures according to claim 1 for the production of cosmetic preparations.
EP02764626A 2001-07-13 2002-07-04 Aqueous preparations Withdrawn EP1406722A1 (en)

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FR0109360A FR2827192B1 (en) 2001-07-13 2001-07-13 PREPARATIONS CONTAINING NON-IONIC SURFACTANTS AS EXTRACTING AGENTS
FR0109360 2001-07-13
PCT/EP2002/007412 WO2003006146A1 (en) 2001-07-13 2002-07-04 Aqueous preparations

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112042858A (en) * 2020-09-15 2020-12-08 江西理工大学 Method for extracting biosurfactant of monascus pigment

Families Citing this family (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011090030B4 (en) 2011-12-28 2025-11-06 Evonik Operations Gmbh Aqueous hair and skin cleansing compositions containing biosurfactants
DE102013206314A1 (en) * 2013-04-10 2014-10-16 Evonik Industries Ag Cosmetic formulation containing copolymer as well as sulfosuccinate and / or biosurfactant
BR112015025049B1 (en) 2013-04-25 2021-03-09 Unilever Ip Holdings B.V. cleaning fluid composition
JP6866301B2 (en) * 2015-01-12 2021-04-28 ステパン カンパニー Manufacture of ramnolipide composition
EP3070155A1 (en) 2015-03-18 2016-09-21 Evonik Degussa GmbH Composition comprising peptidase and biosurfactant
BR112017027592A2 (en) 2015-06-25 2018-08-28 Basf Se process for electrolytically depositing a zinc or zinc alloy coating onto a metal substrate, zinc or zinc alloy coated metal substrate, and use of a zinc plating bath additive
CH712859A2 (en) 2016-08-29 2018-03-15 Remo Richli Washing, care and cleaning preparations containing polyoxyalkylene carboxylate and glycolipid biosurfactant.
CH712858A2 (en) 2016-08-29 2018-03-15 Remo Richli Mild preparations containing alkoxylated fatty acid amides and glycolipid biosurfactants.
CH712860A2 (en) 2016-08-29 2018-03-15 Remo Richli Agents with alkoxylated fatty acid amides and glycolipid biosurfactants.
US11464717B2 (en) 2017-02-10 2022-10-11 Evonik Operations Gmbh Oral care composition containing at least one biosurfactant and fluoride
CN110719951A (en) 2017-04-27 2020-01-21 赢创德固赛有限公司 Biodegradable cleaning composition
WO2018197623A1 (en) 2017-04-27 2018-11-01 Evonik Degussa Gmbh Biodegradable cleaning composition
US20210222085A1 (en) 2018-05-11 2021-07-22 Basf Se Detergent composition comprising rhamnolipids and/or mannosylerythritol lipids
DE102021214680A1 (en) 2021-12-20 2023-06-22 Henkel Ag & Co. Kgaa New combination of surfactants and detergents and cleaning agents containing them
EP4234671A1 (en) 2022-02-24 2023-08-30 Evonik Operations GmbH Compositions containing biosurfactants and a lipase from stachybotrys chlorohalonata
EP4482449A1 (en) 2022-02-24 2025-01-01 Evonik Operations GmbH New composition containing liposomes and biosurfactants
US20250171719A1 (en) 2022-02-24 2025-05-29 Evonik Operations Gmbh Bio based composition
EP4269530B1 (en) 2022-04-28 2024-11-20 Evonik Operations GmbH Multifunctional wax dispersant for subterranean chemical applications
EP4269531B1 (en) 2022-04-28 2024-09-11 Evonik Operations GmbH Multifunctional wax dispersant for subterranean chemical applications
WO2024002738A1 (en) 2022-06-28 2024-01-04 Evonik Operations Gmbh Composition comprising biosurfactant and persicomycin
CH720165A2 (en) 2022-10-26 2024-04-30 Chemtek Ug Compositions with N-acylglycamines
WO2024115213A1 (en) 2022-11-30 2024-06-06 Evonik Operations Gmbh Detergent compartment pouch comprising biosurfactants
EP4382090A1 (en) 2022-12-08 2024-06-12 Evonik Operations GmbH Cosmetical and pharmaceutical compositions containing bacillus strains or fermentation broths thereof
CN120390638A (en) 2022-12-21 2025-07-29 赢创斯特曼斯博士有限公司 Composition containing biosurfactant and deferoxamine
CN120813671A (en) 2023-03-16 2025-10-17 赢创运营有限公司 Area measurement biosurfactants on plastic articles
DE102023205205A1 (en) * 2023-06-05 2024-12-05 Henkel Ag & Co. Kgaa New surfactant combination and detergents and cleaning agents containing them
WO2024260751A1 (en) 2023-06-22 2024-12-26 Evonik Operations Gmbh Composition comprising biosurfactant and manganese
WO2025036642A1 (en) 2023-08-15 2025-02-20 Evonik Operations Gmbh Improved method for cleaning
FR3159328A3 (en) 2024-02-21 2025-08-22 L'oreal Cleaning wipe containing a hydrophobic polymer
FR3159518A3 (en) 2024-02-26 2025-08-29 L'oreal Cosmetic composition comprising a skin active agent
WO2025137014A1 (en) 2023-12-18 2025-06-26 L'oreal Mineral sunscreen and pigment dispersion comprising hydrophobic polymer
FR3159525A3 (en) 2024-02-27 2025-08-29 L'oreal mineral sunscreen composition COMPRISING A HYDROPHOBIC POLYMER
WO2025137065A1 (en) 2023-12-18 2025-06-26 L'oreal Cleansing wipe comprising hydrophobic polymer
WO2025137028A1 (en) 2023-12-18 2025-06-26 L'oreal Cosmetic emulsion comprising hydrophobic polymer
FR3159521A3 (en) 2024-02-26 2025-08-29 L'oreal Oil-in-water dispersion comprising
FR3159896A3 (en) 2024-03-06 2025-09-12 L'oreal PIGMENT DISPERSIONS WITH HYDROPHOBIC POLYMER
FR3159520A3 (en) 2024-02-26 2025-08-29 L'oreal Cosmetic emulsion comprising a hydrophobic polymer
EP4632053A1 (en) 2025-04-15 2025-10-15 Evonik Operations GmbH Method for treating a metal surface

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6037086B2 (en) * 1978-09-26 1985-08-24 花王株式会社 cosmetics
JPS5658532A (en) * 1980-07-04 1981-05-21 San Ei Chem Ind Ltd Production of fat and oil emulsifying liquid
US4943390A (en) * 1983-11-02 1990-07-24 Petroleum Fermentations N.V. Bioemulsifier-stabilized hydrocarbosols
US4728613A (en) * 1985-09-04 1988-03-01 Miles Laboratories, Inc. Method for the recovery of extracellular enzymes from whole fermentation beer
DE3643467A1 (en) * 1986-12-19 1988-06-30 Wintershall Ag METHOD FOR THE EXTRACELLULAR PRODUCTION OF NONIONIC BIOPOLYMERS AND THE USE THEREOF
CA2060698C (en) * 1991-02-12 1997-09-30 Peter J. Hall Detergent compositions
EP0574050A1 (en) * 1992-05-19 1993-12-15 Gist-Brocades N.V. Large scale separation and purification of fermentation product
FR2699928B1 (en) * 1992-12-30 1995-01-27 Inst Francais Du Petrole Composition containing a surfactant compound and sophorolipids and method for decontaminating a porous medium polluted by hydrocarbons.
FR2713655B1 (en) * 1993-12-15 1998-05-22 Inst Francais Du Petrole Method for decontaminating a porous medium polluted by hydrocarbons using a composition containing a surfactant compound and glycolipids.
BR9606987A (en) * 1995-01-27 1997-11-04 Genencor Int Processes for the recovery of a desired fermentation product to the preparation of a detergent powder
DE19628454B4 (en) * 1996-07-15 2006-02-16 MFH Marienfelde GmbH Unternehmen für Hygiene Rhamnolipid alginate polymer complex, microbiological process for its preparation, rhamnolipid alginate polymer complex preparations and their uses
DK0954524T3 (en) * 1996-09-11 2003-08-04 Pharmacia Ab Process for Purification of Apolipoproteins
ES2114506B1 (en) * 1996-10-04 1999-02-01 Consejo Superior Investigacion PROCEDURE FOR THE SELECTIVE PREPARATION OF DERIVATIVES OF MONOSACCHARIDES AND POLIOLS PARTIALLY ACYLATED.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03006146A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112042858A (en) * 2020-09-15 2020-12-08 江西理工大学 Method for extracting biosurfactant of monascus pigment
CN112042858B (en) * 2020-09-15 2022-11-29 江西理工大学 A kind of biosurfactant extraction method of monascus pigment

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