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EP0623164B1 - Use as hydraulic fluids of esterification products of oleic acid with 2-alkyl-1-alkanols - Google Patents

Use as hydraulic fluids of esterification products of oleic acid with 2-alkyl-1-alkanols Download PDF

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Publication number
EP0623164B1
EP0623164B1 EP93902039A EP93902039A EP0623164B1 EP 0623164 B1 EP0623164 B1 EP 0623164B1 EP 93902039 A EP93902039 A EP 93902039A EP 93902039 A EP93902039 A EP 93902039A EP 0623164 B1 EP0623164 B1 EP 0623164B1
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Prior art keywords
hydraulic fluids
esterification products
alkyl
alkanols
oleic acid
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EP93902039A
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German (de)
French (fr)
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EP0623164A1 (en
Inventor
Dietrich Pirck
Hans-Dieter Grasshoff
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Wintershall Dea International AG
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RWE Dea AG fuer Mineraloel und Chemie
RWE Dea AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/34—Esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/286—Esters of polymerised unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/047—Thioderivatives not containing metallic elements
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

  • the invention relates to environmentally compatible liquids for vibration damping and level control, particularly in vehicles, consisting of one or more basic liquids and additives.
  • selected mineral oil fractions are used in combination with suitable lubricant additives as liquids for vibration damping and level control, particularly in vehicles, hereinafter also referred to as automotive hydraulic fluids.
  • suitable lubricant additives as liquids for vibration damping and level control, particularly in vehicles, hereinafter also referred to as automotive hydraulic fluids.
  • These generally meet the requirements with regard to vibration damping properties and aging resistance. However, they are not biodegradable sufficiently quickly, nor do they satisfy ecotoxiologically. Rather, they represent a considerable environmental impact. Because of the regularly occurring, uncontrollable loss of oil, particularly in the case of shock absorbers, environmentally friendly shock absorber fluids are urgently needed.
  • PCT publication WO 88/05808 describes hydraulic fluids based on natural triglycerides and a combination of vegetable oils with synthetic esters as control fluid for lowering or increasing the viscosity.
  • the low-temperature behavior remains clearly above the values required for automotive hydraulics.
  • rapeseed and sunflower oil have high lubricity and excellent viscosity-temperature behavior (VT behavior).
  • VT behavior viscosity-temperature behavior
  • aging and low-temperature behavior are unsatisfactory, so that these substances cannot be used.
  • Polyethylene glycols have a limited use in general industrial hydraulics. However, these materials are not suitable for use in motor vehicles, since cold flow behavior and compatibility with conventional lubricants are inadequate.
  • the task was therefore to provide liquids for vibration damping and level control, which meet both the necessary technical and strict ecological requirements, in particular with regard to biodegradability.
  • esterification products of oleic acid and 2alkyl-1-alkanols with 12 to 20 carbon atoms are used as biodegradable base liquids with ecologically compatible additives as liquids for vibration damping and level control, in particular in vehicles.
  • the alkanol components preferably contain 12 to 16 carbon atoms.
  • oleates are used whose alkanol components are mixtures of such alcohols.
  • the liquids contain basic liquids known per se in addition to the basic liquid or liquids according to the invention.
  • the base liquids according to the invention are prepared in a manner known per se by esterification, for example in the presence of zirconium or titanium contacts and entraining agents and by means of the stripping process. They preferably contain ester mixtures of oleic acid.
  • the following compounds are used as preferred representatives of the 2-alkyl-1-alkanols: 2-butyloctanol, 2-hexyldecanol, 2-butyldecanol, 2-octyldecanol, 2-hexyloctanol, 2-hexyldodecanol, 2-octyldodecanol.
  • the esterification products are added with customary additives, in particular up to 5% by weight of ecologically compatible additives based on the total hydraulic fluid, i.a. Protection against aging, wear protection, corrosion protection and anti-foam components. These components are selected according to the requirements of the relevant area of application, e.g. in damping systems for cars, commercial vehicles, railways.
  • the synthetic oleatester B has the following composition: 2-butyl octanol oleate 15% 2-butyl decanol oleate 50% 2-hexyl decanol oleate 35% The biodegradation rate is almost 100%.
  • Table 3 shows the VT curve between -40 ° C and +120 ° C compared to a conventional shock absorber oil (standard oil).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

The invention concerns hydraulic fluids for, in particular, vibration damping and level control in vehicles. The hydraulic fluids proposed consist essentially of esterification products of singly unsaturated fatty acids and 2-alkyl-1-alkanols. These liquids meet the requirements placed on hydraulic fluids for engineering use, one of their particular qualities being good biodegradability.

Description

Die Erfindung bezieht sich auf umweltverträgliche Flüssigkeiten zur Schwingungsdämpfung und Niveauregulierung insbesondere bei Fahrzeugen bestehend aus einer oder mehreren Basisflüssigkeiten und Additiven.The invention relates to environmentally compatible liquids for vibration damping and level control, particularly in vehicles, consisting of one or more basic liquids and additives.

Nach dem derzeitigen Stand der Technik werden als Flüssigkeiten zur Schwingungsdämpfung und Niveauregulierung insbesondere bei Fahrzeugen, im folgenden auch Kraftfahrzeughydraulikflüssigkeiten genannt, ausgewählte Mineralölfraktionen in Kombination mit geeigneten Schmierstoffadditiven eingesetzt. Diese genügen im allgemeinen den gestellten Anforderungen im Hinblick auf Schwingungsdämpfungseigenschaften und Alterungsbeständigkeit. Sie sind aber weder ausreichend schnell biologisch abbaubar noch befriedigen sie in ökotoxiologischer Hinsicht. Sie stellen vielmehr eine erhebliche Umweltbelastung dar. Wegen insbesondere bei Stoßdämpfern regelmäßig auftretender, nicht kontrollierbarer Ölverluste werden umweltfreundliche Stoßdämpferflüssigkeiten dringend benötigt.According to the current state of the art, selected mineral oil fractions are used in combination with suitable lubricant additives as liquids for vibration damping and level control, particularly in vehicles, hereinafter also referred to as automotive hydraulic fluids. These generally meet the requirements with regard to vibration damping properties and aging resistance. However, they are not biodegradable sufficiently quickly, nor do they satisfy ecotoxiologically. Rather, they represent a considerable environmental impact. Because of the regularly occurring, uncontrollable loss of oil, particularly in the case of shock absorbers, environmentally friendly shock absorber fluids are urgently needed.

Es wurde daher zunächst versucht, die betreffenden Mineralölprodukte durch Naturstoffe wie zum Beispiel pflanzliche Öle zu ersetzen.It was therefore first attempted to replace the mineral oil products in question with natural substances such as vegetable oils.

In der PCT-Veröffentlichung WO 88/05808 werden hydraulische Flüssigkeiten auf Basis von natürlichen Triglyceriden sowie eine Kombination von pflanzlichen Ölen mit synthetischen Estern als Stellflüssigkeit zur Absenkung oder Erhöhung der Viskosität beschrieben. Das Tieftemperaturverhalten bleibt jedoch auch hier deutlich oberhalb der für die Kfz-Hydraulik erforderlichen Werte.PCT publication WO 88/05808 describes hydraulic fluids based on natural triglycerides and a combination of vegetable oils with synthetic esters as control fluid for lowering or increasing the viscosity. However, the low-temperature behavior remains clearly above the values required for automotive hydraulics.

Beispielsweise zeigen Raps- und Sonnenblumenöl eine hohe Schmierfähigkeit sowie ein ausgezeichnetes Viskositäts-Temperatur-Verhalten (VT-Verhalten). Alterungs- und Tieftemperaturverhalten sind jedoch unbefriedigend, so daß auf diese Stoffe nicht ausgewichen werden kann.For example, rapeseed and sunflower oil have high lubricity and excellent viscosity-temperature behavior (VT behavior). However, aging and low-temperature behavior are unsatisfactory, so that these substances cannot be used.

Einen begrenzten Einsatz in der allgemeinen Industrie-Hydraulik finden Polyethylenglykole. Für den Einsatz in Kraftfahrzeugen aber sind diese Stoffe nicht geeignet, da Kältefließverhalten und Verträglichkeit mit konventionellen Schmierstoffen unzureichend sind.Polyethylene glycols have a limited use in general industrial hydraulics. However, these materials are not suitable for use in motor vehicles, since cold flow behavior and compatibility with conventional lubricants are inadequate.

Schließlich hat man auch für den Schwingsungsdämpfergebrauch gesättigte Dicarbonsäureester und Polyolester untersucht, die zwar eine noch ausreichende Abbaurate und gute thermische Stabilität zeigen, jedoch einen Viskositätsindex (VI) aufweisen, der deutlich unterhalb der Werte für die natürlichen Ölsäureester liegt. Weiterhin ist das Elastomerquellverhalten gegenüber dem technisch üblichen NBR-Material (Nitrilkautschuk) nicht vertretbar.Finally, saturated dicarboxylic acid esters and polyol esters have also been investigated for use in vibration dampers, although they still show a sufficient degradation rate and good thermal stability, but have a viscosity index (VI) which is significantly below the values for the natural oleic acid esters. Furthermore, the elastomer swelling behavior compared to the technically customary NBR material (nitrile rubber) is not justifiable.

In US-A-2 757 139 aus dem Jahr 1953 sind synthetische Esteröle als Schmiermittel für den Einsatz in Flugzeuggasturbinen offenbart. Der experimentelle Teil dieser Patentschrift bezieht sich ausschließlich auf Ester von Kokusnuß-Fettsäuren mit C₁₆, C₂₆ Guerbet-Alkoholen, die als Turbinenschmieröle geprüft wurden. Die beschriebenen Ester weisen einen für die erfindungsgemäße Anwendung unzureichenden VI-Wert (maximal 148 ) auf, wobei erhebliche Mengen VIVerbesserer zugesetzt werden müssen, um Werte über 150 zu erreichen. Ebenso sind deren Fließ- und Kälteverhalten unzureichend. Ökologische Anforderungen werden dort nicht gestellt.US-A-2 757 139, 1953, discloses synthetic ester oils as lubricants for use in aircraft gas turbines. The experimental part of this patent relates exclusively to esters of coconut fatty acids with C₁₆, C₂₆ Guerbet alcohols, which have been tested as turbine lubricating oils. The esters described have an inadequate VI value (maximum of 148) for the use according to the invention, with significant amounts of VI improvers having to be added in order to achieve values above 150. Their flow and cold behavior are also inadequate. There are no ecological requirements there.

Es bestand somit die Aufgabe, Flüssigkeiten zur Schwingungsdämpfung und Niveauregulierung bereitzustellen, die sowohl den erforderlichen technischen als auch strengen ökologischen Anforderungen insbesondere hinsichtlich der biologischen Abbaubarkeit gerecht werden.The task was therefore to provide liquids for vibration damping and level control, which meet both the necessary technical and strict ecological requirements, in particular with regard to biodegradability.

Erfindungsgemäß wird die gestellte Aufgabe dadurch gelöst, daß Veresterungsprodukte aus Ölsäure und 2Alkyl-1-alkanolen mit 12 bis 20 Kohlenstoffatomen als biologisch abbaubare Basisflüssigkeiten mit ökologisch verträglichen Additiven als Flüssigkeiten zur Schwingungsdämpfung und Niveauregulierung insbesondere bei Fahrzeugen zur Anwendung kommen.According to the invention, the object is achieved in that esterification products of oleic acid and 2alkyl-1-alkanols with 12 to 20 carbon atoms are used as biodegradable base liquids with ecologically compatible additives as liquids for vibration damping and level control, in particular in vehicles.

Bevorzugt enthalten die Alkanolkomponenten 12 bis 16 Kohlenstoffatome. Es werden insbesondere Oleate eingesetzt, deren Alkanolkomponente Gemische solcher Alkohole sind.The alkanol components preferably contain 12 to 16 carbon atoms. In particular, oleates are used whose alkanol components are mixtures of such alcohols.

Gemäß einer Ausführungsform der Erfindung sind in den Flüssigkeiten neben der oder den erfindungsgemäßen Basisflüssigkeiten an sich bekannte Basisflüssigkeiten enthalten.According to one embodiment of the invention, the liquids contain basic liquids known per se in addition to the basic liquid or liquids according to the invention.

Überraschend wurde gefunden, daß Veresterungsprodukte der Ölsäure mit den genannten 2-Alkyl-1-alkanolen als Flüssigkeiten neben ausgezeichneter biologischer Abbaubarkeit und der hervorragenden ökologischen Verträglichkeit auch die technischen Anforderungen in sehr befriedigender Weise erfüllen. Hierzu zählen insbesondere folgende Kriterien:

  • a) Viskositätslage von etwa 20 bis 35 mm/s bei 20°C
  • b) optimales Viskositäts-Temperatur-Verhalten (VT), Viskositätsindex (VI) von mindestens 150,
  • c) gutes Kältefließverhalten bei -40°C, max. 2000 mPa.s, Pour Point unter -40°C,
  • d) geringe Flüchtigkeit, 1 h/ 150°C / <5 %,
  • e) ausreichende thermische Alterungsstabilität bis 130°C mindestens, und
  • f) ausreichende Dichtungsmaterialbeständigkeit.
It has surprisingly been found that esterification products of oleic acid with the 2-alkyl-1-alkanols mentioned as liquids, in addition to excellent biodegradability and outstanding ecological compatibility, also meet the technical requirements in a very satisfactory manner. These include the following criteria in particular:
  • a) Viscosity position of about 20 to 35 mm / s at 20 ° C
  • b) optimal viscosity-temperature behavior (VT), viscosity index (VI) of at least 150,
  • c) good cold flow behavior at -40 ° C, max. 2000 mPa.s, pour point below -40 ° C,
  • d) low volatility, 1 h / 150 ° C / <5%,
  • e) sufficient thermal aging stability up to 130 ° C at least, and
  • f) sufficient sealing material resistance.

Hinsichtlich der ökologischen Verträglichkeit werden folgende Ansprüche gestellt:

  • a) höchstmögliche biologische Abbaubarkeit nach CECL-33-T82 von mindestens 80 %,,
  • b) Wassergefährdungsklasse, WGK = 0,
  • c) keine Einzelkomponenten dürfen einer Gefahrenstoffkennzeichnung unterliegen oder eine WGK von > 1 besitzen.
Diese Anforderungen werden von den erfindungsgemäßen Hydraulikflüssigkeiten erfüllt. Insbesondere sind hierbei hervorzuheben
  • die sehr hohe biologische Abbaurate
  • die überraschend gute thermische Alterungsstabilität, sowie
  • das günstige Viskositäts-Temperatur-Verhalten (VT)
  • das hervorragende Kältefließverhalten bei -40°C
The following demands are made with regard to ecological compatibility:
  • a) highest possible biodegradability according to CECL-33-T82 of at least 80% ,,
  • b) water hazard class, WGK = 0,
  • c) No individual components may be subject to hazardous substance labeling or have a WGK of> 1.
These requirements are met by the hydraulic fluids according to the invention. In particular, it should be emphasized here
  • the very high biodegradation rate
  • the surprisingly good thermal aging stability, as well
  • the favorable viscosity-temperature behavior (VT)
  • the excellent cold flow behavior at -40 ° C

Die erfindungsgemäßen Basisflüssigkeiten werden in an sich bekannter Weise durch Veresterung hergestellt, etwa in Gegenwart von Zirkon- bzw. Titankontakten und Schleppmitteln sowie mittels Strippverfahren. Sie enthalten vorzugsweise Estergemische der Ölsäure.The base liquids according to the invention are prepared in a manner known per se by esterification, for example in the presence of zirconium or titanium contacts and entraining agents and by means of the stripping process. They preferably contain ester mixtures of oleic acid.

Als bevorzugte Vertreter der 2-Alkyl-1-alkanole werden folgende Verbindungen eingesetzt:
   2-Butyloctanol, 2-Hexyldecanol, 2-Butyldecanol, 2-Octyldecanol, 2-Hexyloctanol, 2-Hexyldodecanol, 2-Octyldodecanol. Die eingesetzten 2-Alkyl-1-alkanole haben die allgemeine Formel

Figure imgb0001
mit der linearen Hauptkette R1= Alkyl mit 8 bis 12 C-Atomen, vorzugsweise 8 bis 10 C-Atomen, und verzweigt mit der linearen Seitenkette R₂= Alkyl mit 4 bis 8 C-Atomen vorzugsweise 4 bis 6 C-Atomen. Sie sind unter der Bezeichnung Guerbet-Alkohole bekannt und in technischen Verfahren zugänglich.The following compounds are used as preferred representatives of the 2-alkyl-1-alkanols:
2-butyloctanol, 2-hexyldecanol, 2-butyldecanol, 2-octyldecanol, 2-hexyloctanol, 2-hexyldodecanol, 2-octyldodecanol. The 2-alkyl-1-alkanols used have the general formula
Figure imgb0001
 with the linear main chain R 1 = alkyl with 8 to 12 C atoms, preferably 8 to 10 C atoms, and with the linear side chain R₂ = alkyl with 4 to 8 C atoms preferably 4 to 6 C atoms. They are known under the name Guerbet alcohols and are accessible in technical processes.

Um im Einzelfall spezifische Eigenschaften der Hydraulikflüssigkeiten zu verbessern, werden den Veresterungsprodukten übliche Additive zugefügt, und zwar insbesondere bis zu 5 Gew.% ökologisch verträgliche Additive bezogen auf die Gesamthydraulikflüssigkeit, u.a. Alterungsschutz, Verschleißschutz-, Korrosionsschutz- und Antischaum-Komponenten. Die Auswahl dieser Komponenten erfolgt nach den Vorgaben des betreffenden Einsatzgebietes, wie z.B. in Dämpfungssystemen für PKW, Nutzfahrzeuge, Eisenbahnen.In order to improve specific properties of the hydraulic fluids in individual cases, the esterification products are added with customary additives, in particular up to 5% by weight of ecologically compatible additives based on the total hydraulic fluid, i.a. Protection against aging, wear protection, corrosion protection and anti-foam components. These components are selected according to the requirements of the relevant area of application, e.g. in damping systems for cars, commercial vehicles, railways.

BeispieleExamples

Alle Beispiele wurden jeweils mit ökotoxikologisch akzeptablen Additiven (WGK = 1 max) nämlich 1% Antioxidant, einem kommerziellen Gemisch aus hydroxylierten aromatischen Kohlenwasserstoffen, und 1% Verschleißschutz, einem kommerziellen Phosphorsäureester additiviert.All examples were made with ecotoxicologically acceptable additives (WGK = 1 max), namely 1% antioxidant, a commercial mixture of hydroxylated aromatic hydrocarbons, and 1% wear protection, a commercial phosphoric acid ester.

Die eingesetzten Ester und die Ergebnisse der Vergleichsversuche sind den Tabellen 1 und 2 zu entnehmen, wobei die folgenden Prüfmethoden zur Anwendung kamen:

  • Alle Viskositätsmessungen entsprechend DIN 51562
  • Viskositätsindex entsprechend DIN-ISO 2909
  • Pourpoint (PP) entsprechend DIN-ISO 3016
  • Verdampfung nach Noack entsprechend DIN 51581
  • Standard-Referenzelastomer NBR-1, Volumenquellung für 168h/100° C
  • Bestimmung der Verschleißkennwerte im Vierkugelapparat (VKA) entsprechend DIN 51350 T5
  • Bestimmung der biologischen Abbaubarkeit nach 21 Tagen entsprechend Norm CEC L-33-T-82
  • Künstliche Alterung von Schmierölen bei 120° C in Gegenwart von Eisenspänen.
The esters used and the results of the comparative tests can be found in Tables 1 and 2, the following test methods being used:
  • All viscosity measurements according to DIN 51562
  • Viscosity index according to DIN ISO 2909
  • Pourpoint (PP) according to DIN ISO 3016
  • Evaporation according to Noack according to DIN 51581
  • Standard reference elastomer NBR-1, volume swelling for 168h / 100 ° C
  • Determination of the wear parameters in the four-ball device (VKA) according to DIN 51350 T5
  • Determination of biodegradability after 21 days according to standard CEC L-33-T-82
  • Artificial aging of lubricating oils at 120 ° C in the presence of iron filings.

Beispiel 1 (Vergleich)Example 1 (comparison)

Im Vergleich zu den erfindungsgemäßen Hydraulikflüssigkeiten zeigte raffiniertes Rapsöl ein hervorragendes VT-Verhalten (VI), jedoch waren die Kälteeigenschaften (Tabelle 1) nicht akzeptabel für den Außeneinsatz.Compared to the hydraulic fluids according to the invention, refined rapeseed oil showed excellent VT behavior (VI), but the cold properties (Table 1) were not acceptable for outdoor use.

Beispiel 2 (Vergleich)Example 2 (comparison)

Ein synthetisches, kommerzielles Polyoleat auf Basis eines Polyol-Ölsäureesters mit einer Jodzahl von 48 und einer Verseifungszahl von 265 (Oleatester A) verfehlte dagegen nur knapp die Viskositätslage und Kälteanforderungen (Tabelle 1). Allerdings waren sehr deutliche Alterungserscheinungen sowie eine überhöhte Quellneigung (Tabelle 2) nachweisbar.In contrast, a synthetic, commercial polyoleate based on a polyol oleic acid ester with an iodine number of 48 and a saponification number of 265 (oleate ester A) only just missed the viscosity position and cold requirements (Table 1). However, very clear signs of aging and an excessive tendency to swell (Table 2) were detectable.

Beispiel 3 (erfindungsgemäß)Example 3

Der synthetische Oleatester B hat die folgende Zusammensetzung: 2-Butyloctanol-oleat 15 % 2-Butyldecanol-oleat 50 % 2-Hexyldecanol-oleat 35 % Die biologische Abbaurate beträgt nahezu 100 %.The synthetic oleatester B has the following composition: 2-butyl octanol oleate 15% 2-butyl decanol oleate 50% 2-hexyl decanol oleate 35% The biodegradation rate is almost 100%.

Die Meßdaten zeigten Ergebnisse, die den technischen Anforderungen gerecht wurden. In Tabelle 3 ist hierzu der VT-Verlauf zwischen -40 °C und +120 °C im Vergleich zu einem konventionellen Stoßdämpferöl (Serienöl) aufgezeigt.The measurement data showed results that met the technical requirements. Table 3 shows the VT curve between -40 ° C and +120 ° C compared to a conventional shock absorber oil (standard oil).

Darüber hinaus wurden mit den erfindungsgemäßen Hydraulikflüssigkeiten Stoßdämpfer-Dauerlaufversuche bei 85 °C (1 Mill. Hübe) durchgeführt, die eine nur sehr geringe Ölalterung ergeben haben. In einem 3-fach-Versuch wurden folgende Daten erhalten:

  • a. Kältefunktions-/Dichtungstest
    Befüllte Stoßdämpfer wurden bei -40 °C 24 Stunden gelagert und mit max. 0,52 m/s auf +120 °C gefahren. Test bestanden b. Reibungs-/Graunztest
    Befüllte Stoßdämpfer wurden durch langsames, kurzhubiges Ein- und Ausfahren der Kolbenstange auf Reibungsgeräusche untersucht. Test bestanden c. Dämpfungscharakteristik
    Befüllte Stoßdämpfer wurden im Bereich von -40 °C bis 180 °C mit Hubgeschwindigkeiten zwischen 0,01 bis 0,52 m/s Dämpfkraftmessungen unterworfen. Test bestanden d. Dauerprüflauf Befüllte Stoßdämpfer wurden im Dauerlaufprüfstand über 500 h mit einer Überlagerungsfrequenz von 1/12 Hz belastet. Beurteilt wurden mechanischer Verschleiß, Veränderung der Dämpfkraft und mögliche Ölverluste.

1 x 10⁶ Hübe bei 85 °C
Ölverlust 1 %
Viskositätszunahme +4,5 % bei 40 °C.In addition, shock absorber endurance tests were carried out at 85 ° C. (1 million strokes) with the hydraulic fluids according to the invention, which resulted in very little oil aging. The following data were obtained in a triple test:
  • a. Cold function / seal test
    Filled shock absorbers were stored at -40 ° C for 24 hours and with a max. 0.52 m / s to +120 ° C. Passed the test b. Friction / grunt test
    Filled shock absorbers were checked for friction noises by slowly moving the piston rod in and out. Passed the test c. Damping characteristics
    Filled shock absorbers were subjected to damping force measurements in the range from -40 ° C to 180 ° C with stroke speeds between 0.01 and 0.52 m / s. Test passed d. Endurance test run Filled shock absorbers were subjected to a superimposition frequency of 1/12 Hz in the endurance test stand for 500 h. Mechanical wear, changes in damping force and possible oil losses were assessed.

1 x 10⁶ strokes at 85 ° C
Oil loss 1%
Viscosity increase +4.5% at 40 ° C.

Die übrigen Vergleichsbeispiele wurden mit den folgenden kommerziell erhältlichen Flüssigkeiten durchgeführt:

  • Beispiel 4 (Vergleich) Diisodecylazelainsäureester
  • Beispiel 5 (Vergleich) Diethylhexylsebacat
  • Beispiel 6 (Vergleich) Dialkylazelainsäureester
  • Beispiel 7 (Vergleich) Trimethylolpropan-Komplexester
  • Beispiel 8 (Vergleich) Polyethylenglykol
    Figure imgb0002
    Figure imgb0003
    Figure imgb0004
The remaining comparative examples were carried out with the following commercially available liquids:
  • Example 4 (comparison) diisodecylazelaic acid ester
  • Example 5 (comparison) Diethylhexyl sebacate
  • Example 6 (comparison) Dialkylazelainic acid ester
  • Example 7 (Comparison) Trimethylolpropane complex ester
  • Example 8 (comparison) polyethylene glycol
    Figure imgb0002
    Figure imgb0003
    Figure imgb0004

Claims (5)

  1. Use of esterification products of oleic acid and 2-alkyl-1-alkanols with 12 to 20 carbon atoms as biologically degradable base fluids for employing with ecologically compatible additives as hydraulic fluids, particularly for shock absorption and level controlling in vehicles.
  2. Use according to claim 1,
       whereby the alkanol components of the esterification products contain 12 to 16 carbon atoms.
  3. Use according to claim 1 or claim 2,
       whereby the alkanol components of the esterification products are mixtures.
  4. Use according to any of the claims 1 to 3,
       whereby besides one or more of the claimed base fluids known base fluids are contained.
  5. Use according to any of the claims 1 to 4,
       whereby the claimed base fluids contain 0.1 to 5 weight per cent of ecologically compatible additives, related to the total composition.
EP93902039A 1992-01-25 1993-01-19 Use as hydraulic fluids of esterification products of oleic acid with 2-alkyl-1-alkanols Expired - Lifetime EP0623164B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4202034 1992-01-25
DE4202034A DE4202034A1 (en) 1992-01-25 1992-01-25 hydraulic fluids
PCT/DE1993/000049 WO1993015167A1 (en) 1992-01-25 1993-01-19 Hydraulic fluids

Publications (2)

Publication Number Publication Date
EP0623164A1 EP0623164A1 (en) 1994-11-09
EP0623164B1 true EP0623164B1 (en) 1996-01-03

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Publication number Priority date Publication date Assignee Title
FR2808534B1 (en) * 2000-05-03 2002-08-02 Total Raffinage Distribution BIODEGRADABLE LUBRICANT COMPOSITION AND USES THEREOF, ESPECIALLY IN A DRILLING FLUID
DE102006001768A1 (en) * 2006-01-12 2007-07-19 Cognis Ip Management Gmbh Use of esters with branched alkyl groups as lubricants
EP1889640A1 (en) * 2006-08-18 2008-02-20 Cognis IP Management GmbH Cosmetic compositions containing ester obtained from 2-butyl-1-octanol
EP2192105A1 (en) 2008-11-25 2010-06-02 Dako Ag Lubricant and method of its production
EP2228425A1 (en) * 2009-02-27 2010-09-15 Dako Ag Lubricant

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US2757139A (en) * 1953-11-30 1956-07-31 Exxon Research Engineering Co Synthetic lubricating composition
DE3521711A1 (en) * 1985-06-18 1986-12-18 Henkel KGaA, 4000 Düsseldorf Ester oils and their use
AU1227388A (en) * 1987-01-28 1988-08-24 Raision Tehtaat Oy Ab Hydraulic fluids
WO1988005809A1 (en) * 1987-02-06 1988-08-11 Gaf Corporation Propoxylated guerbet alcohols and esters thereof
US4957648A (en) * 1987-08-06 1990-09-18 The Lubrizol Corporation Spin fiber lubricant compositions
JP2649951B2 (en) * 1988-07-21 1997-09-03 富士写真フイルム株式会社 Magnetic recording media
DE3929069A1 (en) * 1989-09-01 1991-03-07 Henkel Kgaa NEW BASE OIL FOR THE LUBRICANT INDUSTRY

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AU3343493A (en) 1993-09-01
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US5474714A (en) 1995-12-12
WO1993015167A1 (en) 1993-08-05

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