EP0343504A1 - Foam-depressing polyglycol ethers for cleaning products - Google Patents
Foam-depressing polyglycol ethers for cleaning products Download PDFInfo
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- EP0343504A1 EP0343504A1 EP89108904A EP89108904A EP0343504A1 EP 0343504 A1 EP0343504 A1 EP 0343504A1 EP 89108904 A EP89108904 A EP 89108904A EP 89108904 A EP89108904 A EP 89108904A EP 0343504 A1 EP0343504 A1 EP 0343504A1
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- Prior art keywords
- foam
- radical
- carbon atoms
- cleaning
- polyglycol ethers
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
- C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
- C11D1/721—End blocked ethers
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating compositions
Definitions
- the invention relates to the use of selected end group capped polyethylene glycol ethers as foam-suppressing additives in low-foam cleaning agents.
- the new auxiliaries of the invention should in particular also be suitable for cleaning foam processes which generate a lot of foam, for example machine dishwashing for household and commercial use, or e.g. to suppress unwanted foam formation during machine cleaning of bottles in the beverage industry.
- Cleaning agents intended for use in trade and industry in particular those for cleaning metal, glass and ceramic surfaces, generally contain substances which are able to counteract undesirable foam development.
- foam-suppressing additives is in most cases due to the fact that the contaminants detached from the substrates and accumulating in the cleaning baths act as foaming agents, for example in the dish washing of the foam formed from foods or in the bottle washing that caused by the detachment and the decomposition of labels by foam formed by caustic soda.
- anti-foam Means may also be necessary due to the fact that the cleaning agents themselves contain components that give rise to undesirable foam formation under the given working conditions.
- anionic surfactants widely used in cleaning agents.
- Addition products of alkylene oxides with organic compounds with reactive hydrogen atoms in the molecule have long been used as foam-suppressing additives.
- adducts of propylene oxide with aliphatic polyalcohols - see for example DE-PS 12 80 455 and DE-PS 16 21 592 - and with aliphatic polyamines - cf. for example DE-PS 12 89 597 and DE-PS 16 21 593 - as well as addition products of ethylene oxide and propylene oxide with aliphatic polyamines, especially ethylenediamine - cf. DE-PS 19 44 569 - proven in practice.
- these alkylene oxide addition products also have the alkali stability which is usually required for use in commercial and industrial cleaning agents.
- the compounds in this class are not sufficiently biodegradable to meet the applicable legal requirements.
- R1O- (CH2CH2O) n -R2 being in this formula R1 is a straight-chain or branched alkyl radical or alkenyl radical with 8 to 18 carbon atoms, R2 is an alkyl radical with 4 to 8 carbon atoms and n is a number from 7 to 12 mean.
- R 1 is a fatty alcohol radical having 12 to 18 carbon atoms and R 2 is the n-butyl radical, in which n stands for the number 10, has proven particularly useful in practice.
- the teaching of the present invention is based on the surprising finding that even more effective auxiliaries of the type concerned here can be obtained by slightly varying the structure of the last-mentioned end group-sealed fatty alcohol polyethylene glycol ethers.
- it is not only possible to set a general increase in activity while maintaining the physiological harmlessness and biodegradability of these foam-suppressing additives with the now described varied ethylene glycol ethers, in particular, improved working in the lower temperature range, for example in the area of the room temperature, is revealed or only slightly elevated temperatures.
- foam-suppressing additives are often to be carried out at low temperatures, for example in order to carry out an energy-saving pre-cleaning.
- Conventional, foam-suppressing additives are often characterized by the fact that they are very effective in combating foam in the temperature range of approximately 50 ° C. and above, but their use at temperatures of approximately 20 ° C. leads to comparatively weaker foam damping.
- the additives according to the invention described below develop particular effectiveness precisely at low temperatures and also exhibit this property when they are blended with structurally similar, known components.
- the invention accordingly relates to the use of polyethylene glycol ethers of the general formula (I) R1O- (CH2CH2O) n -R2 (I) in the R1 is a straight-chain or branched alkyl or alkenyl radical having 8 to 14 carbon atoms, R2 is an alkyl radical with 8 to 10 carbon atoms and n is a number from 2 to 8 mean, as foam-suppressing additives for low-foam cleaning agents.
- R2 C8-alkyl radical, the numerical value from 2 to 6 applies to n.
- the preferred compounds of general formula (I) contain a radical R1 of the type specified with 8 to 10 carbon atoms.
- the preferred radical R2 in the compounds according to the invention is the decyl radical, in particular the n-decyl radical.
- the preferred values for n in the general formula (I) are 2 to 6 and in particular 4 to 6.
- the carbon number of this residue is compared to that The above-described residues increased, and is at least 8 carbon atoms.
- the end group-capped fatty alcohol polyglycol ethers of the formula (I) are prepared in accordance with the specifications of DE-OS 33 15 951.
- the fatty alcohols of higher carbon number described above are advantageously reacted with ethylene oxide in a molar ratio of 1: 2 to 1: 8 and then etherified the hydroxyl groups present in the reaction product obtained.
- the reaction with ethylene oxide takes place under the known alkoxylation conditions, preferably in the presence of suitable alkaline catalysts.
- the etherification of the free hydroxyl groups is preferably carried out under the known conditions of Williamson's ether synthesis with straight-chain or branched C8 to C10 alkyl halides.
- n-decyl radical for the radical R2 from the general formula (I) is of particular importance in the course of the inventive action.
- examples of such a final etherification are accordingly n-decyl halides, such as n-decyl iodide.
- the invention is not restricted to this; further examples are n-octyl chloride, 2-ethylhexyl chloride, n-nonyl chloride, i-nonyl chloride and n-decyl chloride.
- alkyl halide and alkali in a stoichiometric excess, for example from 10 to 50%, over the hydroxyl groups to be etherified.
- polyglycol ethers of the formula (I) are used in which n denotes a number from 4 to 6.
- the end group-capped polyglycol ethers of the formula (I) to be used according to the invention are in an important Aus imple mentation form in admixture with structurally identical polyethylene glycol ethers, in which, however, the radical R 1 is a straight-chain or branched alkyl or alkenyl radical having 8 to 18 carbon atoms and n is a number from 7 to 12, and preferably from 8 to 10.
- the invention thus provides to blend the polyglycol ethers described here with the foam-suppressing additives from DE-OS 33 15 951.
- Mixing ratios of the two types in the range from 10 to 90 to 90 to 10% by weight, in particular in weight ratios from 60 to 40 to 40 to 60% by weight, are suitable for this embodiment.
- One area of application for such mixtures is, for example, machine bottle cleaners or cleaning agents for the dairy industry.
- end group-capped polyglycol ethers of the formula (I) which are now to be used according to the invention are also notable for high alkali and acid stability. Their foam-preventing effect in alkaline and neutral cleaning liquors is strengthened in the specified sense, moreover they also meet the legal requirements for biodegradability.
- Another area of application for the end group-capped polyglycol units of the formula (I) are, for example, liquid or powder detergents for automatic dishwashing for household and commercial use.
- the use of these substances in powder cleaners has the additional effect that these substances act as anti-caking agents ("anticaking agents") in such a way that on the one hand they prevent the powder grains from sticking together when the powder products are stored and thus maintain good flowability of the powders and on the other hand can bind the dust that forms as abrasion when moving the powder.
- the end group-capped polyglycol ethers of the formula (I) are sprayed in a controlled manner onto the dry, moving and therefore well-mixed solid granulate constituents, which consist of builders, alkali metal carbonates and silicates. Lödige and Eirich mixers can be used as granulators.
- the cleaning agents in which the end group-capped polyglycol ethers of the invention are used can contain the constituents customary in such agents, such as wetting agents, builders and complexing agents, alkalis or acids, corrosion inhibitors and optionally also organic solvents.
- Non-ionic surface-active compounds such as polyglycol ethers which are obtained by adding ethylene oxide to alcohols, in particular fatty alcohols, alkylphenols, fatty amines and carboxamides, and anionic surfactants such as alkali metal, amine and alkylolamine salts of fatty acids, alkylsulfonic acids, alkylsulfonic acids and alkylbenzenesulfonic acids are considered as wetting agents.
- the builders can include alkali metal orthophosphates, polymer phosphates, silicates, borates, carbonates, polyacrylates and gluconates, as well as citric acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, 2-hydroxyalkane-1,1-diphosphonic acid and ethylenediphosphonic acid, Contain phosphonoalkane polycarboxylic acids such as phosphonobutane tricarboxylic acid and alkali metal salts of these acids.
- Highly alkaline cleaning agents in particular those for bottle cleaning, contain considerable mega caustic alkali in the form of sodium and / or potassium hydroxide. If special cleaning effects are desired, the cleaning agents can be organic solvents, for example alcohols, gasoline fractions and chlorinated hydrocarbons and free alkylolamines.
- cleaning agents are once understood to mean the aqueous solutions intended for direct application to the substrate to be cleaned, but the term cleaning agents also includes the concentrates and solid mixtures intended for the preparation of the application solutions.
- the ready-to-use solutions can be acidic to strongly alkaline; they are generally used at temperatures of around 20 to 90 ° C.
- test foamer a 1% aqueous solution of the triethernolamine salt of tetrapropylene benzene sulfonate
- test foamer 1 ml of a 1% aqueous solution of the triethernolamine salt of tetrapropylene benzene sulfonate
- the volume formed which is formed by liquid and foam, is determined.
- further test foamers are then metered in in portions of 1 ml and the volume of liquid and foam formed after 30 sec is determined. This gradual cycle of metering the test foam and volume determination after 30 sec until the surfactant solution in the measuring cylinder is foamed to 2,000 ml.
- the end group-sealed polyglycol ethers to be used according to the invention give effective effects even in low concentrations. They are preferably added to the cleaning agents in amounts such that their concentration in the ready-to-use solutions is approximately in the range from 50 to 500 ppm.
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Abstract
Description
Die Erfindung betrifft die Verwendung ausgewählter Endgruppenverschlossener Polyethylenglykolether als schaumdrückende Zusätze in schaumarmen Reinigungsmitteln. Die neuen Hilfsmittel der Erfindung sollen insbesondere auch dazu geeignet sein, bei stark schaumerzeugenden Reinigungsprozessen, beispielsweise bei der maschinellen Geschirrspülung für Haushalt und Gewerbe, oder z.B. bei der maschinellen Reinigung von Flaschen in der Getränkeindustrie eine unerwünschte Schaumbildung zu unterdrücken.The invention relates to the use of selected end group capped polyethylene glycol ethers as foam-suppressing additives in low-foam cleaning agents. The new auxiliaries of the invention should in particular also be suitable for cleaning foam processes which generate a lot of foam, for example machine dishwashing for household and commercial use, or e.g. to suppress unwanted foam formation during machine cleaning of bottles in the beverage industry.
Für die Verwendung in Gewerbe und Industrie bestimmte Reinigungsmittel, insbesondere solche für die Reinigung von Metall-, Glas- und Keramikoberflächen, enthalten in der Regel Substanzen, die in der Lage sind, einer unerwünschten Schaumentwicklung entgegenzuwirken. Der Einsatz von schaumdrückenden Zusätzen ist in den meisten Fällen dadurch bedingt, daß die von den Substraten abgelösten und in den Reinigungsbädern sich ansammelnden Verunreinigungen als Schaumbildner wirken, wie z.B. bei der Geschirreinigung der aus Nahrungsmitteln entstehende Schaum bzw. bei der Flaschenwäsche der durch das Ablösen und die Zersetzung von Etiketten durch Natronlauge gebildete Schaum. Daneben kann die Verwendung von Antischaum mitteln auch aufgrund der Tatsache erforderlich sein, daß die Reinigungsmittel selbst Bestandteile enthalten, die unter den vorgegebenen Arbeitsbedingungen zu unerwünschter Schaumbildung Anlaß geben. Ein Beispiel hierfür sind die in Reinigungsmitteln in weitem Umfang eingesetzten Aniontenside.Cleaning agents intended for use in trade and industry, in particular those for cleaning metal, glass and ceramic surfaces, generally contain substances which are able to counteract undesirable foam development. The use of foam-suppressing additives is in most cases due to the fact that the contaminants detached from the substrates and accumulating in the cleaning baths act as foaming agents, for example in the dish washing of the foam formed from foods or in the bottle washing that caused by the detachment and the decomposition of labels by foam formed by caustic soda. In addition, the use of anti-foam Means may also be necessary due to the fact that the cleaning agents themselves contain components that give rise to undesirable foam formation under the given working conditions. An example of this are the anionic surfactants widely used in cleaning agents.
Als schaumdrückende Zusätze werden seit langem Anlagerungsprodukte von Alkylenoxiden an organische Verbindungen mit reaktiven Wasserstoffatomen im Molekül eingesetzt. Hier haben sich insbesondere Anlagerungsprodukte von Propylenoxid an aliphatische Polyalkohole - siehe beispielsweise DE-PS 12 80 455 und DE-PS 16 21 592 - und an aliphatische Polyamine - vgl. beispielsweise DE-PS 12 89 597 und DE-PS 16 21 593 -sowie Anlagerungsprodukte von Ethylenoxid und Propylenoxid an aliphatische Polyamine, insbesondere Ethylendiamin - vgl. DE-PS 19 44 569 - in der Praxis bewährt. Diese Alkylenoxidanlagerungsprodukte besitzen neben einer guten schaumdrückenden Wirkung auch die für die Anwendung in gewerblichen und industriellen Reinigungsmitteln zumeist erforderliche Alkalistabilität. Die Verbindungen dieser Klasse sind jedoch nicht hinreichend biologisch abbaubar, um den geltenden gesetzlichen Vorschriften zu genügen.Addition products of alkylene oxides with organic compounds with reactive hydrogen atoms in the molecule have long been used as foam-suppressing additives. Here, in particular, adducts of propylene oxide with aliphatic polyalcohols - see for example DE-PS 12 80 455 and DE-PS 16 21 592 - and with aliphatic polyamines - cf. for example DE-PS 12 89 597 and DE-PS 16 21 593 - as well as addition products of ethylene oxide and propylene oxide with aliphatic polyamines, especially ethylenediamine - cf. DE-PS 19 44 569 - proven in practice. In addition to a good foam-suppressing effect, these alkylene oxide addition products also have the alkali stability which is usually required for use in commercial and industrial cleaning agents. However, the compounds in this class are not sufficiently biodegradable to meet the applicable legal requirements.
Eine Klasse hochwirksamer und gleichzeitig biologisch abbaubarer Entschäumungshilfsmittel ist in der DE-OS 33 15 951 beschrieben. Geschildert wird dort die Verwendung von Endgruppen-verschlossenen Polyethylenglykolethern der Formel (I)
R₁O-(CH₂CH₂O)n -R₂
wobei in dieser Formel
R₁ einen geradkettigen oder verzweigten Alkylrest oder Alkenylrest mit 8 bis 18 C-Atomen,
R₂ einen Alkylrest mit 4 bis 8 C-Atomen und
n eine Zahl von 7 bis 12
bedeuten.A class of highly effective and at the same time biodegradable defoaming agents is described in DE-OS 33 15 951. The use of end-capped polyethylene glycol ethers of the formula (I) is described there.
R₁O- (CH₂CH₂O) n -R₂
being in this formula
R₁ is a straight-chain or branched alkyl radical or alkenyl radical with 8 to 18 carbon atoms,
R₂ is an alkyl radical with 4 to 8 carbon atoms and
n is a number from 7 to 12
mean.
In der Praxis besonders bewährt hat sich ein Produkt dieser Art, in dem der Rest R₁ einen Fettalkoholrest mit 12 bis 18 C-Atomen und R₂ den n-Butylrest bedeuten, wobei n für die Zahl 10 steht.A product of this type in which the radical R 1 is a fatty alcohol radical having 12 to 18 carbon atoms and R 2 is the n-butyl radical, in which n stands for the number 10, has proven particularly useful in practice.
Die Lehre der vorliegenden Erfindung geht von der überraschenden Erkenntnis aus, daß man noch wirkungsvollere Hilfsmittel der hier betroffenen Art dadurch erhlaten kann, daß die zuletzt erwähnten Endgruppen-verschlossenen Fettalkoholpolyethylenglykolether in ihrer Struktur leicht varriert werden. Im Sinne des erfindungsgemäßen Handelns ist es dabei nicht nur möglich, eine allgemeine Wirkungssteigerung unter Erhalt der physiologischen Unbedenklichkeit und biologischen Abbaubarkeit dieser schaumdrückenden Zusatzstoffe einzustellen, mit den jetzt beschriebenen variierten Ethylenglykolethern erschließt sich insbesondere ein verbessertes Arbeiten im niedrigeren Temperaturbereich, beispielsweise also im Bereich der Raumtemperatur oder nur schwach erhöhter Temperaturen.The teaching of the present invention is based on the surprising finding that even more effective auxiliaries of the type concerned here can be obtained by slightly varying the structure of the last-mentioned end group-sealed fatty alcohol polyethylene glycol ethers. In the sense of the action according to the invention, it is not only possible to set a general increase in activity while maintaining the physiological harmlessness and biodegradability of these foam-suppressing additives, with the now described varied ethylene glycol ethers, in particular, improved working in the lower temperature range, for example in the area of the room temperature, is revealed or only slightly elevated temperatures.
Hier liegt gegenüber den vorbekannten schaumdrückenden Zusätzen eine sehr wichtige Erweiterung. Es ist bekannt, daß in gewerblichen Reinigungsprozessen häufig Spülprozesse gerade bei niedrigen Temperaturen durchgeführt werden sollen, um beispielsweise eine energiesparende Vorreinigung durchzuführen. Konventionelle, schaumdrückende Zusatzstoffe zeichnen sich häufig dadurch aus, daß sie im Temperaturbereich von etwa 50 °C und darüber sehr wirkungsvoll der Schaumbekämpfung dienen, ihre Einsatz bei Temperaturen von etwa 20 °C führt aber zu einer vergleichsweise schwächeren Schaumdämpfung. Überraschenderweise zeigt sich, daß die im Nachfolgenden beschriebenen erfindungsgemäßen Zusatzstoffe gerade bei niedrigen Temperaturen besondere Wirksamkeit entfalten und diese Eigenschaft auch dann zeigen, wenn sie mit strukturähnlichen, vorbekannten Komponenten verschnitten werden.This is a very important extension compared to the known foam-suppressing additives. It is known that in industrial cleaning processes, rinsing processes are often to be carried out at low temperatures, for example in order to carry out an energy-saving pre-cleaning. Conventional, foam-suppressing additives are often characterized by the fact that they are very effective in combating foam in the temperature range of approximately 50 ° C. and above, but their use at temperatures of approximately 20 ° C. leads to comparatively weaker foam damping. Surprisingly, it has been shown that the additives according to the invention described below develop particular effectiveness precisely at low temperatures and also exhibit this property when they are blended with structurally similar, known components.
Gegenstand der Erfindung ist dementsprechend die Verwendung von Polyethylenglykolethern der allgemeinen Formel (I)
R₁O-(CH₂CH₂O)n -R₂ (I)
in der
R₁ einen geradkettigen oder verzweigten Alkyl- oder Alkenylrest mit 8 bis 14 C-Atomen,
R₂ einen Alkylrest mit 8 bis 10 C-Atomen und
n eine Zahl von 2 bis 8
bedeuten,
als schaumdrückende Zusätze für schaumarme Reinigungsmittel. Für die Ausführungsform R₂ = C₈-Alkylrest gilt für n der Zahlenwert von 2 bis 6.The invention accordingly relates to the use of polyethylene glycol ethers of the general formula (I)
R₁O- (CH₂CH₂O) n -R₂ (I)
in the
R₁ is a straight-chain or branched alkyl or alkenyl radical having 8 to 14 carbon atoms,
R₂ is an alkyl radical with 8 to 10 carbon atoms and
n is a number from 2 to 8
mean,
as foam-suppressing additives for low-foam cleaning agents. For the embodiment R₂ = C₈-alkyl radical, the numerical value from 2 to 6 applies to n.
Die bevorzugten Verbindungen der allgemeinen Formel (I) enthalten einen Rest R₁ der angegebenen Art mit 8 bis 10 C-Atomen. Als bevorzugter Rest R₂ liegt in den erfindungsgemäßen Verbindungen der Decylrest vor und zwar insbesondere der n-Decylrest. Die bevorzugten Werte für n in der allgemeinen Formel (I) liegen bei 2 bis 6 und insbesondere bei 4 bis 6.The preferred compounds of general formula (I) contain a radical R₁ of the type specified with 8 to 10 carbon atoms. The preferred radical R₂ in the compounds according to the invention is the decyl radical, in particular the n-decyl radical. The preferred values for n in the general formula (I) are 2 to 6 and in particular 4 to 6.
Die entscheidende Abwandlung der erfindungsgemäßen Polyethylenglykolether der allgemeinen Formel (I) gegenüber den strukturähnlichen Verbindungen der zuvor genannten DE-OS 33 15 951 liegt in der Variation des Restes R₂. Erfindungsgemäß ist die Kohlenstoffzahl dieses Restes gegenüber den vorbeschriebenen Resten erhöht, und liegt bei wenigstens 8 C-Atomen.The decisive modification of the polyethylene glycol ether of the general formula (I) according to the invention compared to the structure-like compounds of the aforementioned DE-OS 33 15 951 lies in the variation of the rest R₂. According to the invention, the carbon number of this residue is compared to that The above-described residues increased, and is at least 8 carbon atoms.
Die Herstellung der Endgruppen-verschloseenen Fettalkoholpolyglykolether der Formel (I) erfolgt entsprechend den Angaben der DE-OS 33 15 951. So setzt man zweckmäßigerweise die vorstehend beschriebenen Fettalkohole höherer Kohlenstoffzal mit Ethylenoxid im Molverhältnis von 1 : 2 bis 1 : 8 um und verethert anschließend die im erhaltenen Reaktionsprodukt vorhandenen Hydroxylgruppen. Die Umsetzung mit Ethylenoxid erfolgt dabei unter den bekannten Alkoxylierungsbedingungen, vorzugsweise in Gegenwart von geeigneten alkalischen Katalysatoren. Die Veretherung der freien Hydroxylgruppen wird bevorzugt unter den bekannten Bedingungen der Williamson'schen Ethersynthese mit geradkettigen oder verzweigten C₈ bis C₁₀-Alkylhalogeniden durchgeführt. Besondere Bedeutung kommt im Rahmen des erfindungsgemäßen Handelns dem n-Decylrest für den Rest R₂ aus der allgemeinen Formel (I) zu. Beispiele für eine solche abschließende Veretherung sind dementsprechend n-Decylhalogenide, wie n-Decyliodid. Die Erfindung ist allerdings hierauf nicht beschränkt, weitere Beispiele sind n-Octylchlorid, 2-Ethylhexylchlorid, n-Nonylchlorid, i-Nonylchlorid und n-Decylchlorid.The end group-capped fatty alcohol polyglycol ethers of the formula (I) are prepared in accordance with the specifications of DE-OS 33 15 951. The fatty alcohols of higher carbon number described above are advantageously reacted with ethylene oxide in a molar ratio of 1: 2 to 1: 8 and then etherified the hydroxyl groups present in the reaction product obtained. The reaction with ethylene oxide takes place under the known alkoxylation conditions, preferably in the presence of suitable alkaline catalysts. The etherification of the free hydroxyl groups is preferably carried out under the known conditions of Williamson's ether synthesis with straight-chain or branched C₈ to C₁₀ alkyl halides. The n-decyl radical for the radical R₂ from the general formula (I) is of particular importance in the course of the inventive action. Examples of such a final etherification are accordingly n-decyl halides, such as n-decyl iodide. However, the invention is not restricted to this; further examples are n-octyl chloride, 2-ethylhexyl chloride, n-nonyl chloride, i-nonyl chloride and n-decyl chloride.
Dabei kann es zweckmäßig sein, Alkylhalogenid und Alkali im stöchiometrischen Überschuß, beispielsweise von 10 bis 50 %, über die zu verethernden Hydroxylgruppen einzusetzen.It may be expedient here to use alkyl halide and alkali in a stoichiometric excess, for example from 10 to 50%, over the hydroxyl groups to be etherified.
In einer bevorzugten Ausführungsform der Erfindung werden Polyglykolether der Formel (I) eingesetzt, in denen n eine Zahl von 4 bis 6 bedeutet.In a preferred embodiment of the invention, polyglycol ethers of the formula (I) are used in which n denotes a number from 4 to 6.
Die erfindungsgemäß zu verwendenden Endgruppen-verschlossenen Polyglykolether der Formel (I) werden in einer wichtigen Aus führungsform in Abmischung mit sturkturgleichen Polyethylenglykolethern eingesetzt, in denen jedoch der Rest R₁ einen geradkettigen oder verzweigten Alkyl- oder Alkenylrest mit 8 bis 18 C-Atomen bedeutet und n eine Zahl von 7 bis 12, und bevorzugt von 8 bis 10 ist. In dieser Ausführungsform sieht damit die Erfindung vor, die hier beschriebenen Polyglykolether mit den schaumdrückenden Zusatzstoffen aus der DE-OS 33 15 951 zu verschneiden. Geeignet sind für diese Ausführungsform Mischungsverhältnisse der beiden Typen im Bereich von 10 bis 90 zu 90 bis 10 Gew.-%, insbesondere in Gewichtsverhältnissen von 60 bis 40 zu 40 bis 60 Gew.-%. Ein Anwendungsgebiet für solche Mischungen sind z.B. die maschinellen Flaschenreiniger oder Reinigungsmittel für die Milchwirtschaft.The end group-capped polyglycol ethers of the formula (I) to be used according to the invention are in an important Aus imple mentation form in admixture with structurally identical polyethylene glycol ethers, in which, however, the radical R 1 is a straight-chain or branched alkyl or alkenyl radical having 8 to 18 carbon atoms and n is a number from 7 to 12, and preferably from 8 to 10. In this embodiment, the invention thus provides to blend the polyglycol ethers described here with the foam-suppressing additives from DE-OS 33 15 951. Mixing ratios of the two types in the range from 10 to 90 to 90 to 10% by weight, in particular in weight ratios from 60 to 40 to 40 to 60% by weight, are suitable for this embodiment. One area of application for such mixtures is, for example, machine bottle cleaners or cleaning agents for the dairy industry.
Auch die erfindungsgemäß jetzt zu verwendenden Endgruppen-verschlossenen Polyglykolether der Formel (I) zeichnen sich durch eine hohe Alkali- und Säurestabilität aus. Ihre schaumverhindernde Wirkung in alkalischen und neutralen Reinigungsflotten ist im angegebenen Sinne verstärkt, darüberhinaus erfüllen sie die gesetzlichen Anforderungen an die biologische Abbaubarkeit.The end group-capped polyglycol ethers of the formula (I) which are now to be used according to the invention are also notable for high alkali and acid stability. Their foam-preventing effect in alkaline and neutral cleaning liquors is strengthened in the specified sense, moreover they also meet the legal requirements for biodegradability.
Ein weiteres Anwendungsgebiet für die erfindungsgemäßen Endgruppen-verschlossenen Polyglykolehter der Formel (I) sind z.B. flüssige oder pulverförmige Reinigungsmittel für die maschinelle Geschirrspülung für Haushalt und Gewerbe. Dabei hat die Verwendung dieser Substanzen bei Pulverreinigern den zusätzlichen Effekt, daß diese Substanzen als Antibackmittel ("Anticakingmittel") in der Weise wirken, daß sie einerseits das Zusammenkleben der Pulverkörner bei Lagerung der Pulverprodukte verhindern und somit eine gute Rieselfähigkeit der Pulver erhalten und andererseits auch den beim Bewegen der Pulver als Abrieb sich bildenden Staub zu binden vermögen. Die erfindungsgemäßen Endgruppen-verschlossenen Polyglykolether der Formel (I) werden dabei in kontrollierter Weise auf die trockenen bewegten und dadurch gut gemischten festen Granulatbestandteile, welche aus Gerüstsubstanzen, Alkalimetallcarbonaten und Silikaten bestehen, aufgesprüht. Als Granulatoren können Lödige- und Eirich-Mischer verwendet werden.Another area of application for the end group-capped polyglycol units of the formula (I) are, for example, liquid or powder detergents for automatic dishwashing for household and commercial use. The use of these substances in powder cleaners has the additional effect that these substances act as anti-caking agents ("anticaking agents") in such a way that on the one hand they prevent the powder grains from sticking together when the powder products are stored and thus maintain good flowability of the powders and on the other hand can bind the dust that forms as abrasion when moving the powder. The end group-capped polyglycol ethers of the formula (I) are sprayed in a controlled manner onto the dry, moving and therefore well-mixed solid granulate constituents, which consist of builders, alkali metal carbonates and silicates. Lödige and Eirich mixers can be used as granulators.
Die Reinigungsmittel, in denen die Endgruppen-verschlossenen Polyglykolether der Erfindung zur Anwendung kommen, können die in solchen Mitteln üblichen Bestandteile wie Netzmittel, Gerüstsubstanzen und Komplexbildner, Alkalien oder Säuren, Korrosionsinhibitoren und gegebenenfalls auch organische Lösungsmittel enthalten. Als Netzmittel kommen nichtionogene oberflächenaktive Verbindungen wie Polyglykolether, die durch Anlagerung von Ethylenoxid an Akohole, insbesondere Fettalkohole, Alkylphenole, Fettamine und Carbonsäureamide erhalten werden, sowie anionaktive Netzmittel wie Alkalimetall-, Amin-und Alkylolaminsalze von Fettsäuren, Alkylschwfelsäuren, Alkylsulfonsäuren und Alkylbenzolsulfonsäuren in Betracht. An Gerüstsubstanzen und Komplexbildnern können die Reinigungsmittel vor allem Alkalimetallorthophosphate, -polymerphosphate, -silikate, -borate, -carbonate, -polyacrylate und -glukonate sowie Citronensäure, Nitrilotriessigsäure, Ethylendiamintetraessigsäure, 2-Hydroxyalkan-1,1-diphosphonsäuren und Ethylendiamintetra-(methylenphosphonsäure), Phosphonoalkanpolycarbonsäuren wie z.B. Phosphonobutantricarbonsäure und Alkalimetallsalze dieser Säuren enthalten. Hochalkalische Reinigungsmittel, insbesondere solche für die Flaschenreinigung, enthalten beträchtliche Megnen Ätzalkali in Form von Natrium- und/oder Kaliumhydroxid. Wenn besondere Reinigungseffekte gewünscht werden, können die Reinigungsmittel organische Lösungsmittel, beispielsweise Alkohole, Benzinfraktionen und chlorierte Kohlenwasserstoffe sowie freie Alkylolamine enthalten.The cleaning agents in which the end group-capped polyglycol ethers of the invention are used can contain the constituents customary in such agents, such as wetting agents, builders and complexing agents, alkalis or acids, corrosion inhibitors and optionally also organic solvents. Non-ionic surface-active compounds such as polyglycol ethers which are obtained by adding ethylene oxide to alcohols, in particular fatty alcohols, alkylphenols, fatty amines and carboxamides, and anionic surfactants such as alkali metal, amine and alkylolamine salts of fatty acids, alkylsulfonic acids, alkylsulfonic acids and alkylbenzenesulfonic acids are considered as wetting agents. The builders can include alkali metal orthophosphates, polymer phosphates, silicates, borates, carbonates, polyacrylates and gluconates, as well as citric acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, 2-hydroxyalkane-1,1-diphosphonic acid and ethylenediphosphonic acid, Contain phosphonoalkane polycarboxylic acids such as phosphonobutane tricarboxylic acid and alkali metal salts of these acids. Highly alkaline cleaning agents, in particular those for bottle cleaning, contain considerable mega caustic alkali in the form of sodium and / or potassium hydroxide. If special cleaning effects are desired, the cleaning agents can be organic solvents, for example alcohols, gasoline fractions and chlorinated hydrocarbons and free alkylolamines.
Unter Reinigungsmitteln werden im Zusammenhang mit der Erfindung einmal die zur direkten Anwendung auf die zu reinigenden Stubstrate bestimmten wäßrigen Lösungen verstanden, daneben umfaßt der Begriff Reinigungsmittel aber auch die zur Herstellung der Anwendungslösungen bestimmten Konzentrate und feste Mischungen.In connection with the invention, cleaning agents are once understood to mean the aqueous solutions intended for direct application to the substrate to be cleaned, but the term cleaning agents also includes the concentrates and solid mixtures intended for the preparation of the application solutions.
Die gebrauchsfertigen Lösungen können sauer bis stark alkalisch sein; sie werden in der Regel bei Temperaturen von etwa 20 bis 90 °C eingesetzt.The ready-to-use solutions can be acidic to strongly alkaline; they are generally used at temperatures of around 20 to 90 ° C.
In den nachfolgenden Beispielen wird die Schaumdämpfung der erfindungsgemäß ausgewählten Zusatzstoffe - und im Vergleich dazu strukturähnlicher, jedoch nicht in den Rahmen der Erfindung fallender Zusatzstoffe - nach folgenden Prüfmethoden ermittelt, wie nachstehend beschrieben wird:
In the following examples, the foam attenuation of the additives selected according to the invention - and, in comparison, structurally similar additives, but not falling within the scope of the invention - is determined using the following test methods, as described below:
In einem doppelwandigen 2 l-Meßzylinder werden 300 ml einer 1 %igen wäßrigen Natronlauge auf 20 °C temperiert. Anschließend wird der jeweils ausgewählte schaumdrückende Zusatzstoff in den nachfolgend angegebenen Mengen zugesetzt. Mit Hilfe einer Laborschlauchpumpe wird die Flüssigkeit mit einer Umwälzgeschwindigkeit von 4 l pro Minute umgepumpt. Dabei wird die Prüflösung ca. 5 mm über den Boden des Meßzylinders mittels eines 55 cm langen Glasrohres (Innendurchmesser 8,5 mm, Außendurchmesser 11 mm), das mit der Pumpe über einen Silikonschlauch verbunden ist, angesaugt und über ein zweites Glasrohr (Länge 20 cm), das an der 2 000 ml-Marke angebracht ist, in freiem Fall zurückgeführt.300 ml of a 1% aqueous sodium hydroxide solution are heated to 20 ° C. in a double-walled 2 l measuring cylinder. The selected foam-suppressing additive is then added in the amounts specified below. With the help of a laboratory hose pump, the liquid is pumped at a circulation rate of 4 l per minute. The test solution is sucked in approx. 5 mm above the bottom of the measuring cylinder by means of a 55 cm long glass tube (inner diameter 8.5 mm, outer diameter 11 mm), which is connected to the pump via a silicone hose, and through a second glass tube (length 20 cm) attached to the 2,000 ml mark in free fall.
Nach 30 sec dosiert man zunächst 1 ml einer 1 %igen wäßrigen Lösung des Triethernolaminsalzes von Tetrapropylenbenzolsulfonat (in den nachfolgenden Tabellen als "Testschäumer" bezeichnet) in die Flotte und bestimmt nach weiteren 30 sec das entstandene Volumen, das durch Flüssigkeit und Schaum gebildet wird. In Zeitabständen von jeweils 1 min wird nachfolgend weiterer Testschäumer jeweils in Portionen von 1 ml zudosiert und das nach 30 sec entstandene Volumen aus Flüssigkeit und Schaum bestimmt. Diesen stufenweisen Zyklus von Zudosierung des Testschäumers und Volumenbestimmung nach 30 sec behält man so lange bei, bis die Tensidlösung im Meßzylinder auf 2 000 ml aufgeschäumt ist.After 30 seconds, 1 ml of a 1% aqueous solution of the triethernolamine salt of tetrapropylene benzene sulfonate (referred to in the tables below as "test foamer") is first metered into the liquor and, after a further 30 seconds, the volume formed, which is formed by liquid and foam, is determined. At intervals of 1 min each, further test foamers are then metered in in portions of 1 ml and the volume of liquid and foam formed after 30 sec is determined. This gradual cycle of metering the test foam and volume determination after 30 sec until the surfactant solution in the measuring cylinder is foamed to 2,000 ml.
Die erfindungsgemäß zu verwendenden Endgruppen-verschlossenen Polyglykolether geben bereits in geringen Konzentrationen wirkungsvolle Effekte. Bevorzugt werden sie den Reinigungsmitteln in solchen Mengen zugesetzt, daß ihre Konzentration in den gebrauchsfertigen Lösungen etwa im Bereich von 50 bis 500 ppm liegt.
Weiterhin wurde die schaumdämpfende Wirkung der Produkte A und B nach folgender Methode bestimmt:
Es wurde jeweils eine Reinigungslösung von einem Liter hergestellt, welche 4 g eines verquirlten Volleis (Eiweiß + Eidotter), 3 g eines Geschirrspülreinigers der folgenden Rezeptur
500 g Natriummetasilikat, wasserfrei
370 g Pentanatriumtripolyphosphat-hexahydrat
70 g Natriumcarbonat, wasserfrei
80 g Wasserglas (Na₂ : SiO₃ = 1 : 33) in 120 g Wasser
10 g Trichlorisocyanursäure
und 0,5 g des Produktes A (Beispiel 1) bzw. des Produktes B (Vergleichsbeispiel 1) in 992,5 g Wasser von 16 °dH enthielt.Furthermore, the foam-suppressing effect of products A and B was determined using the following method:
In each case, a cleaning solution of one liter was prepared, which was 4 g of whisked whole egg (egg white + egg yolk), 3 g of a dishwasher cleaner of the following recipe
500 g sodium metasilicate, anhydrous
370 g pentasodium tripolyphosphate hexahydrate
70 g sodium carbonate, anhydrous
80 g water glass (Na₂: SiO₃ = 1: 33) in 120 g water
10 g trichloroisocyanuric acid
and 0.5 g of product A (example 1) or product B (comparative example 1) in 992.5 g of water at 16 ° dH.
450 ml dieser Reinigungslösung werden dann in einen doppelwandigen Meßzylinder von 2 000 ml Fassungsvermögen auf 20 °C temperiert. Mit Hilfe einer Laborschlauchpumpe wird diese Lösung mit einem Glasrohr vom Boden des Meßzylinders angesaugt. Die Rückführung der Flüssigkeit erfolgt über ein zweites Rohr, dessen unteres Ende in der Höhe der Oberkante des Meßzylinders endet. Die Flüssigkeit wird mit einer Geschwindigkeit von 4 l/min umgepumpt und fällt in den Meßzylinder zurück. Durch dieses Umpumpen der Flüssigkeit entsteht Schaum. Nach 1, 2, 3, 4, 5, 7 und 10 min werden die Volumina abgelesen, welche sich aus Schaum und Flüssigkeit nach diesen Zeiten gebildet haben.
Claims (3)
R₁O-(CH₂CH₂O)n -R₂ (I)
in der
R₁ einen geradkettigen oder verzweigten Alkyl- oder Alkenylrest mit 8 bis 14 C-Atomen, R₂ einen Alkylrest mit 8 bis 10 C-Atomen und n eine Zahl von 2 bis 8
mit der Maßgabe bedeuten, daß für die Ausführungsform R₂ = C₈-Alkylrest n eine Zahl von 2 bis 6 bedeutet, als schaumdrückende Zusätze für schaumarme Reinigungsmittel.1. Use of polyethylene glycol ethers of the general formula (I)
R₁O- (CH₂CH₂O) n -R₂ (I)
in the
R₁ is a straight-chain or branched alkyl or alkenyl radical having 8 to 14 carbon atoms, R₂ is an alkyl radical having 8 to 10 carbon atoms and n is a number from 2 to 8
with the proviso that for the embodiment R₂ = C₈-alkyl radical n is a number from 2 to 6, as foam-suppressing additives for low-foam cleaning agents.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3818014 | 1988-05-27 | ||
| DE3818014A DE3818014A1 (en) | 1988-05-27 | 1988-05-27 | FOAM-PRESSING ALKYL POLYGLYCOLETHER FOR CLEANING AGENTS (II) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0343504A1 true EP0343504A1 (en) | 1989-11-29 |
Family
ID=6355234
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89108904A Withdrawn EP0343504A1 (en) | 1988-05-27 | 1989-05-18 | Foam-depressing polyglycol ethers for cleaning products |
| EP89905675A Withdrawn EP0415970A1 (en) | 1988-05-27 | 1989-05-18 | Anti-froth alkyl polyglycol ethers for detergents (ii) |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89905675A Withdrawn EP0415970A1 (en) | 1988-05-27 | 1989-05-18 | Anti-froth alkyl polyglycol ethers for detergents (ii) |
Country Status (5)
| Country | Link |
|---|---|
| EP (2) | EP0343504A1 (en) |
| JP (1) | JPH03504612A (en) |
| DE (1) | DE3818014A1 (en) |
| WO (1) | WO1989011524A1 (en) |
| ZA (1) | ZA894026B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991009925A2 (en) * | 1989-12-22 | 1991-07-11 | Henkel Kommanditgesellschaft Auf Aktien | Use of a combination of non-ionic surface-active agents |
| WO2000050551A1 (en) * | 1999-02-22 | 2000-08-31 | The Procter & Gamble Company | Automatic dishwashing compositions comprising selected nonionic surfactants |
| US7012052B1 (en) | 1999-02-22 | 2006-03-14 | The Procter & Gamble Company | Automatic dishwashing compositions comprising selected nonionic surfactants |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3928602A1 (en) * | 1989-08-30 | 1991-03-07 | Henkel Kgaa | ALKALISTABLE AND STRONG ALKALINE-MOLDABLE ANTI-FOAM AGENTS FOR COMMERCIAL CLEANING, ESPECIALLY FOR BOTTLE AND CIP CLEANING |
| EP2726452B1 (en) | 2011-08-17 | 2016-04-06 | Dow Global Technologies LLC | Biorenewable biodegradable surfactants |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1012821A (en) * | 1962-02-06 | 1965-12-08 | Rohm & Haas | Polyethenoxy ethers |
| US3684723A (en) * | 1964-04-21 | 1972-08-15 | Lever Brothers Ltd | Detergent composition |
| GB1445716A (en) * | 1973-04-24 | 1976-08-11 | Diversey Ltd | Cleaning compositions |
| EP0124815A2 (en) * | 1983-05-02 | 1984-11-14 | Henkel Kommanditgesellschaft auf Aktien | Use of polyglycol ethers as foam-depressing additives in cleaning agents producing little foam |
-
1988
- 1988-05-27 DE DE3818014A patent/DE3818014A1/en not_active Withdrawn
-
1989
- 1989-05-18 EP EP89108904A patent/EP0343504A1/en not_active Withdrawn
- 1989-05-18 WO PCT/EP1989/000543 patent/WO1989011524A1/en not_active Application Discontinuation
- 1989-05-18 JP JP1505476A patent/JPH03504612A/en active Pending
- 1989-05-18 EP EP89905675A patent/EP0415970A1/en not_active Withdrawn
- 1989-05-26 ZA ZA894026A patent/ZA894026B/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1012821A (en) * | 1962-02-06 | 1965-12-08 | Rohm & Haas | Polyethenoxy ethers |
| US3684723A (en) * | 1964-04-21 | 1972-08-15 | Lever Brothers Ltd | Detergent composition |
| GB1445716A (en) * | 1973-04-24 | 1976-08-11 | Diversey Ltd | Cleaning compositions |
| EP0124815A2 (en) * | 1983-05-02 | 1984-11-14 | Henkel Kommanditgesellschaft auf Aktien | Use of polyglycol ethers as foam-depressing additives in cleaning agents producing little foam |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991009925A2 (en) * | 1989-12-22 | 1991-07-11 | Henkel Kommanditgesellschaft Auf Aktien | Use of a combination of non-ionic surface-active agents |
| WO1991009925A3 (en) * | 1989-12-22 | 1992-01-09 | Henkel Kgaa | Use of a combination of non-ionic surface-active agents |
| TR25486A (en) * | 1989-12-22 | 1993-05-01 | Henkel Kgaa | USING A COMBINATION WITH NON-IONIC TENSIDS |
| WO2000050551A1 (en) * | 1999-02-22 | 2000-08-31 | The Procter & Gamble Company | Automatic dishwashing compositions comprising selected nonionic surfactants |
| US7012052B1 (en) | 1999-02-22 | 2006-03-14 | The Procter & Gamble Company | Automatic dishwashing compositions comprising selected nonionic surfactants |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0415970A1 (en) | 1991-03-13 |
| DE3818014A1 (en) | 1989-11-30 |
| JPH03504612A (en) | 1991-10-09 |
| WO1989011524A1 (en) | 1989-11-30 |
| ZA894026B (en) | 1990-01-31 |
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