EP0825973A1 - Pivalic acid esters of alkoxylated aliphatic alcohols - Google Patents

Pivalic acid esters of alkoxylated aliphatic alcohols

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Publication number
EP0825973A1
EP0825973A1 EP96919771A EP96919771A EP0825973A1 EP 0825973 A1 EP0825973 A1 EP 0825973A1 EP 96919771 A EP96919771 A EP 96919771A EP 96919771 A EP96919771 A EP 96919771A EP 0825973 A1 EP0825973 A1 EP 0825973A1
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EP
European Patent Office
Prior art keywords
pivalic acid
acid esters
esters
pivalic
alcohol
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Withdrawn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
EP96919771A
Other languages
German (de)
French (fr)
Inventor
Richard Baur
Helmut GÜMBEL
Bernd Burkhart
Alfred Oftring
Gerhard Wolf
Johannes Perner
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BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0825973A1 publication Critical patent/EP0825973A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/24—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with monohydroxylic compounds

Definitions

  • the present invention relates to new pivalic acid esters of alkoxylated aliphatic alcohols of the general formula I
  • R is the remainder of an aliphatic alcohol with 6 to 30 C atoms
  • n an average value from 1 to 20
  • m an average value from 0 to 6.
  • the invention relates to the preparation of the compounds I, their use as surface-active substances, especially as a surfactant with foam-suppressing properties, and formulations with these surface-active substances.
  • DE-A 1 243 312 discloses esters of alkoxylated aliphatic alcohols, for example acetic acid or hydroxyisobutyric acid, as low-foaming nonionic surface-active compounds. However, they leave something to be desired when used as foam-suppressing surfactants. In particular, strong foaming is observed in machine cleaning processes.
  • the invention was therefore based on esters of alkoxylated aliphatic alcohols with improved foam-suppressing properties.
  • esters I defined at the outset were found.
  • Preferred alcohols R-OH from which the compounds I according to the invention are derived are preferably:
  • unbranched primary alkanols with 6 to 30 C atoms such as hexyl, heptyl, octyl, nonyl, decyl, undecyl alcohol and especially lauryl, myristyl, cetyl and stearyl alcohol
  • unbranched primary alkenols with 6 to 30 carbon atoms such as linolyl and linolenyl alcohol, especially oleyl alcohol.
  • These alcohols which are also called fatty alcohols, are mostly of natural origin and are therefore preferred. Mixtures of these alcohols, as in their natural occurrence, e.g. the coconut fatty alcohol, which is a mixture of lauryl alcohol and myristyl alcohol as main components.
  • alcohols and alcohol mixtures of synthetic provenance come into consideration, e.g. branched alkanols and alkenols such as 2-ethylhexyl, isooctyl, isononyl, 3-propylheptyl, isodecyl and isotridecyl alcohol.
  • branched alkanols and alkenols such as 2-ethylhexyl, isooctyl, isononyl, 3-propylheptyl, isodecyl and isotridecyl alcohol.
  • oxo alcohols which are obtained by hydroformylation of ⁇ -olefins and further reactions, are particularly suitable.
  • the degree of ethoxylation is preferably 4 to 12.
  • the polypropylene glycol ether group has an average degree of propoxylation of 0 to 6.
  • To prepare the compounds I 1 mol of the alcohol R-OH is reacted with n mol of ethylene oxide in a manner known per se and the esterification product is then esterified with pivalic acid or one of its functional derivatives.
  • the reaction with ethylene oxide takes place under the known alkoxylation conditions, preferably in the presence of an alkaline catalyst such as alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, in particular alkaline earth metal hydroxides such as calcium hydroxide, barium hydroxide and strontium hydroxide and hydrotalcite (Al 2 Mg 6 (OH) ⁇ 6 C0 3 -4H 2 0). If appropriate, it is then reacted with m mol of propylene oxide.
  • an alkaline catalyst such as alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, in particular alkaline earth metal hydroxides such as calcium hydroxide, barium hydroxide and strontium hydroxide and hydrotalcite (Al 2 Mg 6 (OH) ⁇ 6 C0 3 -4H 2 0).
  • pivalic anhydride and pivalic acid esters are suitable for acid-catalyzed esterification or transesterification, the numerous configurations of which are generally known with regard to the acid, the removal of the water of reaction, the temperature and the reaction time, so that further explanations are unnecessary.
  • the acid chloride is preferably used as the starting component.
  • the reaction can be carried out in the presence of an inert solvent such as toluene, acetone, diethyl ether, hexane, decane and petroleum ether, but is preferably solvent-free.
  • an inert solvent such as toluene, acetone, diethyl ether, hexane, decane and petroleum ether, but is preferably solvent-free.
  • the acid chloride in an equimolar amount to the alkoxylated alcohol, and the range from 40 to 80 ° C. is recommended for the reaction temperature.
  • the released hydrogen chloride can be bound with a base such as triethylamine or pyridine, but it is preferably removed by means of an inert gas stream, e.g. of a nitrogen stream.
  • reaction product is expediently freed from traces of acid, for example with sodium carbonate.
  • the pivalic acid esters I according to the invention have good surface-active properties, which enables their use in many areas of application. They are particularly notable for their considerably reduced foaming power and very good foam-suppressing action, compared to known esters of alkoxylated aliphatic alcohols. These properties enable use in areas of application in which foam formation is undesirable. They are therefore particularly suitable as agents for machine cleaning in the household and industry, either alone or in a mixture with other surface-active agents.
  • esters of the alkoxylated alcohols with other aliphatic carboxylic acids were prepared for comparison, specifically according to DE-A 1 243 312, Example 3.
  • the cloud point, the foaming power, the surface tension and the foam damping in the dishwasher were investigated as the application properties of the esters.
  • the cloud point was determined in accordance with DIN 53917. The temperature above which the solution becomes cloudy and is therefore present as a mixture of two liquid phases is determined. The lower the cloud temperature, the lower the foam capacity.
  • the foaming power was determined in accordance with DIN 53902 by measuring the foam volume in ml one minute after the end of foam generation.
  • the surface tension was determined in accordance with DIN 53924 by measuring the force in mN / m which is necessary to pull a horizontally suspended ring or bracket out of the liquid surface.
  • Foam is produced in a commercial household dishwasher by adding an egg, with a twelve-minute heating phase being carried out. During this time, the average number of revolutions of the spray arm per minute is determined. Foam formation reduces the number of revolutions due to the reduced recoil force and thus represents a measure of the suitability of surfactants in cleaning machines.
  • esters according to the invention are superior to those of the prior art (according to DE-A 1 243 312) in all their application properties.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Pivalic acid esters of alkoxylated aliphatic alcohols have formula (I), in which R stands for the residue of an aliphatic alcohol with 6 to 30 C atoms, A stands for the 1,2-propylene grouping, n stands for a mean value from 1 to 20 and m for a mean value from 0 to 6. The compounds (I) are useful as low foaming or anti-foaming surfactants.

Description

Pivalinsäureester alkoxylierter aliphatischer AlkoholePivalic acid esters of alkoxylated aliphatic alcohols
Beschreibungdescription
Die vorliegende Erfindung betrifft neue Pivalinsäureester alkoxy¬ lierter aliphatischer Alkohole der allgemeinen Formel IThe present invention relates to new pivalic acid esters of alkoxylated aliphatic alcohols of the general formula I
CH3 |CH 3 |
R-O- (CH2-CH20)n- (A-0)m-CO-C-CH3 IRO- (CH 2 -CH 2 0) n - (A-0) m -CO-C-CH 3 I
CH3 CH 3
in der die Variablen folgende Bedeutung haben:in which the variables have the following meaning:
R den Rest eines aliphatischen Alkohols mit 6 bis 30 C-AtomenR is the remainder of an aliphatic alcohol with 6 to 30 C atoms
A die 1,2-PropylengruppierungA the 1,2-propylene grouping
n einen Durchschnittswert von 1 bis 20n an average value from 1 to 20
m einen Durchschnittswert von 0 bis 6.m an average value from 0 to 6.
Außerdem betrifft die Erfindung die Herstellung der Verbindungen I, ihre Verwendung als oberflächenaktive Substanzen, vor allem als Tensid mit schaumdämpfenden Eigenschaften, sowie Formulierungen mit diesen oberflächenaktiven Substanzen.In addition, the invention relates to the preparation of the compounds I, their use as surface-active substances, especially as a surfactant with foam-suppressing properties, and formulations with these surface-active substances.
Aus der DE-A 1 243 312 sind Ester von alkoxylierten aliphatischen Alkoholen, beispielsweise der Essigsäure oder der Hydroxyisobut- tersäure, als schaumarme nicht-ionische grenzflächenaktive Verbindungen bekannt. Sie lassen jedoch bei ihrer Verwendung als schaumdämpfende Tenside zu wünschen übrig. So beobachtet man ins¬ besondere bei maschinellen Reinigungsprozessen eine starke Schaumbildung.DE-A 1 243 312 discloses esters of alkoxylated aliphatic alcohols, for example acetic acid or hydroxyisobutyric acid, as low-foaming nonionic surface-active compounds. However, they leave something to be desired when used as foam-suppressing surfactants. In particular, strong foaming is observed in machine cleaning processes.
Maschinell ablaufende Reinigungsprozesse finden sich hauptsäch- lieh in der Metallindustrie, in der Lebensmittelindustrie, im Gaststättengewerbe und im Haushalt. So müssen beispielsweise Metallgegenstände häufig nach ihrer Verarbeitung von Zieh- und Walzfetten befreit werden. In der Lebensmittelverarbeitung müssen alle Behältnisse und Arbeitsgeräte regelmäßig von Lebensmittel- rückständen gereinigt werden. Ein typisches Beispiel ist auch die maschinelle Flaschenreinigung in der Getränkeindustrie. Allen diesen Reinigungsprozessen ist gemeinsam, daß die dabei auftre- tende starke Flottenbewegung zur Schaumbildung führt und somit Tenside mit sehr guten schaumdämpfenden Eigenschaften erfordert.Mechanical cleaning processes are mainly found in the metal industry, in the food industry, in the catering trade and in the household. For example, metal objects often have to be freed from drawing and rolling greases after they have been processed. In food processing, all containers and tools must be cleaned regularly of food residues. A typical example is machine bottle cleaning in the beverage industry. It is common to all these cleaning processes that the Tending strong liquor movement leads to foam formation and thus requires surfactants with very good foam-suppressing properties.
Der Erfindung lagen daher Ester alkoxylierter aliphatischer Alkohole mit verbesserten schaumdämpfenden Eigenschaften als Aufgabe zugrunde.The invention was therefore based on esters of alkoxylated aliphatic alcohols with improved foam-suppressing properties.
Demgemäß wurden die eingangs definierten Ester I gefunden.Accordingly, the esters I defined at the outset were found.
Außerdem wurde ein Verfahren zur ihrer Herstellung, ihre Verwen¬ dung als oberflächenaktive Substanzen, vor allem als Tenside mit schaumdämpfenden Eigenschaften, sowie Formulierungen mit diesen oberflächenaktiven Substanzen gefunden.In addition, a process for their preparation, their use as surface-active substances, especially as surfactants with foam-suppressing properties, and formulations with these surface-active substances have been found.
Als Alkohole R-OH, von denen sich die erfindungsgemäßen Verbindungen I ableiten, kommen vorzugsweise in Betracht:Preferred alcohols R-OH from which the compounds I according to the invention are derived are preferably:
unverzweigte primäre Alkanole mit 6 bis 30 C-Atomen, wie Hexyl- , Heptyl-, Octyl-, Nonyl-, Decyl-, Undecylalkohol sowie vor allem Lauryl-, Myristyl-, Cetyl- und Stearylalkoholunbranched primary alkanols with 6 to 30 C atoms, such as hexyl, heptyl, octyl, nonyl, decyl, undecyl alcohol and especially lauryl, myristyl, cetyl and stearyl alcohol
unverzweigte primäre Alkenole mit 6 bis 30 C-Atomen, wie Linolyl- und Linolenylalkohol, darunter vor allem Oleyl- alkohol.unbranched primary alkenols with 6 to 30 carbon atoms, such as linolyl and linolenyl alcohol, especially oleyl alcohol.
Diese Alkohole, die auch als Fettalkohole bezeichnet werden, sind meist natürlichen Ursprungs und werden daher bevorzugt. Vor allem eignen sich auch Gemische dieser Alkohole, wie in ihren natürli¬ chen Vorkommen, z.B. der Kokosfettalkohol, der ein Gemisch aus Laurylalkohol und Myristylalkohol als Hauptkomponenten darstellt.These alcohols, which are also called fatty alcohols, are mostly of natural origin and are therefore preferred. Mixtures of these alcohols, as in their natural occurrence, e.g. the coconut fatty alcohol, which is a mixture of lauryl alcohol and myristyl alcohol as main components.
Weiterhin kommen Alkohole und Alkoholgemische synthetischer Pro¬ venienz in Betracht, z.B. verzweigte Alkanole und Alkenole wie 2-Ethylhexyl-, Isooctyl-, Isononyl-, 3-Propylheptyl-, Isodecyl- und Isotridecylalkohol. Besonders geeignet sind die sogenannten Oxoalkohole, die man durch Hydroformylierung von α-Olefinen und weitere Umsetzungen erhält.Furthermore, alcohols and alcohol mixtures of synthetic provenance come into consideration, e.g. branched alkanols and alkenols such as 2-ethylhexyl, isooctyl, isononyl, 3-propylheptyl, isodecyl and isotridecyl alcohol. The so-called oxo alcohols, which are obtained by hydroformylation of α-olefins and further reactions, are particularly suitable.
Die Polyethylenglycolethergruppe hat einen durchschnittlichen Alkoxylierungsgrad von n = 1 bis 20. Vorzugsweise beträgt der Ethoxylierungsgrad 4 bis 12.The polyethylene glycol ether group has an average degree of alkoxylation of n = 1 to 20. The degree of ethoxylation is preferably 4 to 12.
Die Polypropylenglycolethergruppe hat einen durchschnittlichen Propoxylierungsgrad von 0 bis 6. Bevorzugt werden Pivalinsäure- ester I, die diese Gruppierung nicht enthalten, da sie zusätzlich besonders gut biologisch abbaubar sind. Zur Herstellung der Verbindungen I setzt man 1 mol des Alkohols R-OH mit n mol Ethylenoxid in an sich bekannter Weise um und ver- estert anschließend das Alkoxilierungsprodukt mit Pivalinsäure oder einem ihrer funktioneilen Derivate. Die Umsetzung mit Ethylenoxid erfolgt dabei unter den bekannten Alkoxilierungsbe- dingungen, vorzugsweise in Gegenwart eines alkalischen Katalysa¬ tors wie Alkalimetallhydroxide wie Kaliumhydroxid und Natrium¬ hydroxid besonders Erdalkalimetallhydroxide wie Calciumhydroxid, Bariumhydroxid und Strontiumhydroxid sowie Hydrotalcit (Al2Mg6(OH)ι6C03-4H20) . Gegebenenfalls wird anschließend mit m mol Propylenoxid umgesetzt.The polypropylene glycol ether group has an average degree of propoxylation of 0 to 6. Preference is given to pivalic acid esters I which do not contain this group, since they are also particularly readily biodegradable. To prepare the compounds I, 1 mol of the alcohol R-OH is reacted with n mol of ethylene oxide in a manner known per se and the esterification product is then esterified with pivalic acid or one of its functional derivatives. The reaction with ethylene oxide takes place under the known alkoxylation conditions, preferably in the presence of an alkaline catalyst such as alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, in particular alkaline earth metal hydroxides such as calcium hydroxide, barium hydroxide and strontium hydroxide and hydrotalcite (Al 2 Mg 6 (OH) ι 6 C0 3 -4H 2 0). If appropriate, it is then reacted with m mol of propylene oxide.
Das so erhaltene Polyetherol wird mit der Pivalinsäure oder einem ihrer funktionellen Derivate umgesetzt. Hierzu eignen sich Piva- linsäureanhydrid und Pivalinsäureester zur sauer katalysierten Veresterung bzw. Umesterung, deren zahlreiche Ausgestaltungen hinsichtlich der Säure, der Entfernung des Reaktionswassers, der Temperatur und der Reaktionszeit allgemein bekannt sind, so daß sich nähere Ausführungen hierzu erübrigen.The polyetherol thus obtained is reacted with the pivalic acid or one of its functional derivatives. For this purpose, pivalic anhydride and pivalic acid esters are suitable for acid-catalyzed esterification or transesterification, the numerous configurations of which are generally known with regard to the acid, the removal of the water of reaction, the temperature and the reaction time, so that further explanations are unnecessary.
Vorzugsweise verwendet man das Säurechlorid als Ausgangs- komponente.The acid chloride is preferably used as the starting component.
Die Reaktion kann in der Gegenwart eines inerten Lösungsmittels wie Toluol, Aceton, Diethylether, Hexan, Decan und Petrolether vorgenommen werden, vorzugsweise jedoch lösungsmittelfrei.The reaction can be carried out in the presence of an inert solvent such as toluene, acetone, diethyl ether, hexane, decane and petroleum ether, but is preferably solvent-free.
Es ist zweckmäßig, das Säurechlorid in äquimolarer Menge zum alkoxylierten Alkohol einzusetzen, und für die Reaktionstempera- tur empfiehlt sich der Bereich von 40 bis 80°C. Man kann den frei¬ gesetzten Chlorwasserstoff mit einer Base wie Triethylamin oder Pyridin binden, entfernt ihn jedoch vorzugsweise mittels eines Inertgasstromes, z.B. eines StickstoffStromes.It is expedient to use the acid chloride in an equimolar amount to the alkoxylated alcohol, and the range from 40 to 80 ° C. is recommended for the reaction temperature. The released hydrogen chloride can be bound with a base such as triethylamine or pyridine, but it is preferably removed by means of an inert gas stream, e.g. of a nitrogen stream.
Im Anschluß an die Umsetzung wird das Reaktionsprodukt zweckmäßi¬ gerweise von Säurespuren befreit, beispielsweise mit Natrium- carbonat.Following the reaction, the reaction product is expediently freed from traces of acid, for example with sodium carbonate.
Die erfindungsgemäßen Pivalinsäureester I zeigen gute ober- flächenaktive Eigenschaften, was ihren Einsatz in vielen Anwen¬ dungsbereichen ermöglicht. Besonders zeichnen sie sich durch ein erheblich vermindertes Schaumvermögen sowie sehr gute schaum¬ dämpfende Wirkung aus, verglichen mit bekannten Estern alkoxy- lierter aliphatischer Alkohole. Diese Eigenschaften ermöglichen den Einsatz in Anwendungsgebieten, bei denen Schaumbildung uner¬ wünscht ist. Sie eignen sich daher besonders als Mittel für die maschinelle Reinigung in Haushalt und Industrie und zwar allein oder im Gemisch mit anderen oberflächenaktiven Mitteln.The pivalic acid esters I according to the invention have good surface-active properties, which enables their use in many areas of application. They are particularly notable for their considerably reduced foaming power and very good foam-suppressing action, compared to known esters of alkoxylated aliphatic alcohols. These properties enable use in areas of application in which foam formation is undesirable. They are therefore particularly suitable as agents for machine cleaning in the household and industry, either alone or in a mixture with other surface-active agents.
BeispieleExamples
A. Herstellung von Estern I und Estern des Standes der TechnikA. Preparation of Esters I and Esters of the Prior Art
1 mol eines mit n mol Ethylenoxid umgesetzten Alkohols ROH wurde bei 60°C unter Rühren und unter Durchleiten von Stickstoff1 mol of an alcohol reacted with n mol of ethylene oxide ROH was stirred at 60 ° C. and with nitrogen being passed through
(40 1/h) innerhalb von 30 Minuten allmählich mit Pivalinsäure- chlorid versetzt, wonach das Gemisch noch weitere 3 bis 5 Stunden unter diesen Bedingungen gehalten wurde. Mittels eines verstärk¬ ten StickstoffStromes (80 1/h) wurden anschließend die letzten HCl-Reste ausgetrieben, bis die Säurezahl konstant blieb {0,5 bis 1,0), wonach das Gemisch mit Natriumcarbonat neutralisiert wurde.(40 l / h) pivalic acid chloride was gradually added within 30 minutes, after which the mixture was kept under these conditions for a further 3 to 5 hours. The last HCl residues were then expelled using an increased nitrogen stream (80 l / h) until the acid number remained constant (0.5 to 1.0), after which the mixture was neutralized with sodium carbonate.
In gleicher Weise wurden zum Vergleich die Ester der alkoxy¬ lierten Alkohole mit anderen aliphatischen Carbonsäuren herge- stellt und zwar gemäß der DE-A 1 243 312, Beispiel 3.In the same way, the esters of the alkoxylated alcohols with other aliphatic carboxylic acids were prepared for comparison, specifically according to DE-A 1 243 312, Example 3.
In allen Fällen betrug die Ausbeute an den Estern praktisch 100 %. Einzelheiten zu diesen Beispielen und Vergleichsbeispielen sind der Tabelle zu entnehmen.In all cases the yield of the esters was practically 100%. Details of these examples and comparative examples can be found in the table.
B. Anwendungstechnische Eigenschaften der Ester I und der Ester des Standes der TechnikB. Application properties of the esters I and the esters of the prior art
TensidgrunddatenBasic surfactant data
Als anwendungstechnische Eigenschaften der Ester wurden der Trü¬ bungspunkt, das Schaumvermögen, die Oberflächenspannung und die Schaumdämpfung in der Geschirrspülmaschine untersucht.The cloud point, the foaming power, the surface tension and the foam damping in the dishwasher were investigated as the application properties of the esters.
Der Trübungspunkt wurde nach DIN 53917 bestimmt. Dabei wird die¬ jenige Temperatur ermittelt, oberhalb derer sich die Lösung trübt und somit als Mischung zweier flüssiger Phasen vorliegt. Je nie¬ driger die Trübungstemperatur, desto geringer ist das Schaumver¬ mögen.The cloud point was determined in accordance with DIN 53917. The temperature above which the solution becomes cloudy and is therefore present as a mixture of two liquid phases is determined. The lower the cloud temperature, the lower the foam capacity.
Das Schaumvermögen wurde nach DIN 53902 durch Messung des Schaum¬ volumens in ml eine Minute nach Beendigung der Schaumerzeugung bestimmt. Die Oberflächenspannung wurde nach DIN 53924 bestimmt, indem die Kraft in mN/m gemessen wird, welche notwendig ist, um einen hori¬ zontal aufgehängten Ring oder Bügel aus der Flüssigkeitsoberflä¬ che herauszuziehen.The foaming power was determined in accordance with DIN 53902 by measuring the foam volume in ml one minute after the end of foam generation. The surface tension was determined in accordance with DIN 53924 by measuring the force in mN / m which is necessary to pull a horizontally suspended ring or bracket out of the liquid surface.
Das Schaumdämpfungsverhalten in der Geschirrspülmaschine wird durch den sogenannten "Ei-Test" geprüft. Es wird in einer handel¬ süblichen Haushaltsgeschirrspülmaschine Schaum durch Zugabe eines Eies erzeugt, wobei eine zwölfminütige Aufheizphase durchlaufen wird. Während dieser Zeit wird die durchschnittliche Umdrehungs¬ zahl des Sprüharms pro Minute ermittelt. Durch Schaumbildung wird die Umdrehungszahl wegen der verringerten Rückstoßkraft vermin¬ dert und stellt somit ein Maß für die Tauglichkeit von Tensiden in Reinigungsmaschinen dar.The foam damping behavior in the dishwasher is checked by the so-called "egg test". Foam is produced in a commercial household dishwasher by adding an egg, with a twelve-minute heating phase being carried out. During this time, the average number of revolutions of the spray arm per minute is determined. Foam formation reduces the number of revolutions due to the reduced recoil force and thus represents a measure of the suitability of surfactants in cleaning machines.
Die einzelnen Werte sind der Tabelle zu entnehmen. Wie man er¬ kennt, sind die erfindungsgemäßen Ester denjenigen des Standes der Technik (gemäß DE-A 1 243 312) in allen anwendungStechnischen Eigenschaften überlegen. The individual values can be found in the table. As is known, the esters according to the invention are superior to those of the prior art (according to DE-A 1 243 312) in all their application properties.

Claims

Patentansprüche claims
1. Pivalinsäureester alkoxylierter aliphatischer Alkohole der allgemeinen Formel1. Pivalic acid esters of alkoxylated aliphatic alcohols of the general formula
' CH3 R-0- (CH2-CH20)n- (A-0)m-CO-C-CH3 I ' CH 3 R-0- (CH 2 -CH 2 0) n - (A-0) m -CO-C-CH 3 I
CH3 CH 3
in der die Variablen folgende Bedeutung haben:in which the variables have the following meaning:
R den Rest eines aliphatischen Alkohols mit 6 bis 30 C-AtomenR is the remainder of an aliphatic alcohol with 6 to 30 C atoms
A die 1,2-PropylengruppierungA the 1,2-propylene grouping
n einen Durchschnittswert von 1 bis 20n an average value from 1 to 20
m einen Durchschnittswert von 0 bis 6.m an average value from 0 to 6.
2. Pivalinsäureester nach Anspruch 1, in denen2. pivalic acid esters according to claim 1, in which
R einen nicht verzweigten Cβ-Ciβ-Alkyl- oder Alkenylrest bedeutetR represents an unbranched Cβ-Ciβ-alkyl or alkenyl radical
n für einen Durchschnittswert von 4 bis 12 undn for an average of 4 to 12 and
m für 0 steht.m stands for 0.
3. Gemische von verschiedenen Pivalinsäureestern I, die sich von unterschiedlichen Alkoholen R-OH ableiten.3. Mixtures of different pivalic acid esters I, which are derived from different alcohols R-OH.
4. Verfahren zur Herstellung der Pivalinsäureester I gemäß den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß man einen Alkohol R-OH in Gegenwart einer Base zunächst mit n mol Ethylenoxid und dann mit m mol Propylenoxid umsetzt und das so erhaltene Polyetherol mit Pivalinsäure oder einem funktio¬ neilen Derivat dieser Säure umsetzt.4. A process for the preparation of the pivalic acid esters I according to claims 1 to 3, characterized in that an alcohol R-OH is first reacted in the presence of a base with n mol of ethylene oxide and then with m mol of propylene oxide and the polyetherol thus obtained with pivalic acid or a functional derivative of this acid.
5. Verwendung der Pivalinsäureester I gemäß den Ansprüchen 1 bis 3 als oberflächenaktive Substanzen allein oder im Gemisch mit anderen oberflächenaktiven Mitteln. 5. Use of the pivalic acid esters I according to claims 1 to 3 as surface-active substances alone or in a mixture with other surface-active agents.
6. Verwendung der Pivalinsäureester I gemäß den Ansprüchen 1 bis 3 als schaumdämpfende Zusatzmittel zu Wasch- und Reinigungs¬ mitteln.6. Use of the pivalic acid ester I according to claims 1 to 3 as a foam-suppressing additive to detergents and cleaners.
7. Wasch- und Reinigungsmittel enthaltend die Pivalinsäure¬ ester I gemäß den Ansprüchen 1 bis 3. 7. washing and cleaning agents containing the pivalic esters I according to claims 1 to 3.
EP96919771A 1995-05-19 1996-05-11 Pivalic acid esters of alkoxylated aliphatic alcohols Withdrawn EP0825973A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19518476 1995-05-19
DE1995118476 DE19518476A1 (en) 1995-05-19 1995-05-19 Pivalic acid esters of alkoxylated aliphatic alcohols
PCT/EP1996/002029 WO1996036586A1 (en) 1995-05-19 1996-05-11 Pivalic acid esters of alkoxylated aliphatic alcohols

Publications (1)

Publication Number Publication Date
EP0825973A1 true EP0825973A1 (en) 1998-03-04

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EP96919771A Withdrawn EP0825973A1 (en) 1995-05-19 1996-05-11 Pivalic acid esters of alkoxylated aliphatic alcohols

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EP (1) EP0825973A1 (en)
JP (1) JPH11505235A (en)
DE (1) DE19518476A1 (en)
WO (1) WO1996036586A1 (en)

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Publication number Priority date Publication date Assignee Title
DE1243312B (en) * 1962-10-04 1967-06-29 Roehm & Haas Gmbh Low-foaming surface-active compounds
DE2257546A1 (en) * 1971-11-29 1973-06-07 Dow Chemical Co HYDRAULIC LIQUID
DE4225236A1 (en) * 1992-07-30 1994-02-03 Henkel Kgaa End-capped antifoams

Non-Patent Citations (1)

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Title
See references of WO9636586A1 *

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DE19518476A1 (en) 1996-11-21
WO1996036586A1 (en) 1996-11-21
JPH11505235A (en) 1999-05-18

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