EP0264842B1 - Use of carboxylic-acid esters in completely or partially synthetic lubricants, and lubricants containing them - Google Patents

Use of carboxylic-acid esters in completely or partially synthetic lubricants, and lubricants containing them Download PDF

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Publication number
EP0264842B1
EP0264842B1 EP87115127A EP87115127A EP0264842B1 EP 0264842 B1 EP0264842 B1 EP 0264842B1 EP 87115127 A EP87115127 A EP 87115127A EP 87115127 A EP87115127 A EP 87115127A EP 0264842 B1 EP0264842 B1 EP 0264842B1
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Prior art keywords
formula
lubricants
esters
acid esters
radical
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German (de)
French (fr)
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EP0264842A2 (en
EP0264842A3 (en
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Helmut Dr. Mach
Hans-Henning Dr. Vogel
Juergen Dr. Jahn
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BASF SE
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BASF SE
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    • 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
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • 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
    • C10M105/36—Esters of polycarboxylic 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
    • C10M2207/2825—Esters of (cyclo)aliphatic oolycarboxylic acids used as base material
    • 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
    • C10M2207/285—Esters of aromatic polycarboxylic acids
    • C10M2207/2855—Esters of aromatic polycarboxylic acids used as base material
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron

Definitions

  • the invention relates to the use of aliphatic or aromatic polycarboxylic acid esters in fully or partially synthetic lubricants and lubricants which contain these esters.
  • the HD (Heavy Duty) oils to which additives were added for their additional tasks, such as aging and corrosion protection, high pressure resistance, and as "dirt carriers" - were followed by the multigrade oils with flat viscosity curves and suitable for summer and winter operation, for longer oil change intervals and already reduced fuel consumption, especially in winter and short-haul operations.
  • a flat viscosity curve means a reduced temperature dependence of the lubricating oil.
  • the viscosity index (VI) is a measure of the temperature dependence.
  • US-A-4 130 494 relates to the use of amine salts of phosphate esters as additives to synthetic lubricating oil compositions. This is intended to reduce unwanted deposits in the engines, especially in turbine engines.
  • US-A-4 155 861 relates to a lubricant which comprises a mixture of a monomeric ester of a branched dicarboxylic acid with an aliphatic primary monoalcohol and a complex ester of a dicarboxylic acid and hexanediol or trimethylhexanediol.
  • the monomeric diester is always a mixed diester (column 6, lines 1 and 2), with octyl trimethyladipate being mentioned in particular.
  • the described lubricant combination should be characterized by universal applicability.
  • the known polycarboxylic acid esters are produced, for example, on an industrial scale using oxo alcohols as esterification components.
  • Oxo alcohols which are particularly suitable for esters as synthetic lubricants, are made from oligo-olefins.
  • Table 1 shows examples of known oligo-olefins and the alcohols which can be prepared therefrom by oxo reaction.
  • Polycarboxylic esters have already been produced from these industrially available oxo alcohols, which are also used as synthetic lubricants, cf. R.C. Gunderson and A.W. Hunt, Synthetic Lubricants, Reinhold Publishing Company, 1962, pp. 151ff.
  • the invention has for its object to provide polycarboxylic acid esters for use in synthetic lubricants which, compared to the known polycarboxylic acid esters, have improved temperature-viscosity behavior, expressed by a higher viscosity index and improved low-temperature properties, as well as a lower evaporation loss and a higher flash point.
  • aliphatic or aromatic polycarboxylic esters of the general formula in which X represents a straight-chain or branched alkylene radical or an arylene radical, R represents a radical originating from the oxidation of an n-butene oligomer and y represents 1 or 2, individually or as a mixture in fully or partially synthetic lubricants.
  • the invention also relates to a lubricant which contains at least one polycarboxylic acid ester of the general formula (1).
  • the radical X in the general formula (I) represents an arylene radical of the formulas
  • the radical R in the general formula (I) has 9, 13 or 17 carbon atoms, it being particularly preferred if the mixtures are ester mixtures in which the radicals R have the meanings mentioned.
  • the radical R in the general formula (I) particularly advantageously stems from the oxidation of a largely linearly oligomerized n-butene oligomer with a degree of oligomerization of 2 to 4.
  • the polycarboxylic acid esters of the general formula (I) are particularly preferably phthalic acid esters or adipic acid esters with C 9 and / or C 13 oxo alcohols.
  • the lubricants according to the invention contain at least one compound of the general formula (I).
  • the lubricant may also contain other components, for example common components, e.g. Mineral oil-based base oils or other synthetic lubricant components, for example poly-a-olefins.
  • esters of the general formula I can be used either individually or as a mixture with one another.
  • the polycarboxylic acid esters of the general formula I preferably have the nonyl and tridecyl radical as the monoalcohol component.
  • the alcohols R-OH (nonyl or tridecyl alcohol) used in the esterification are mixtures of isomers as are obtained in the oxo synthesis of corresponding butene oligomers, namely octene and dodecene (butene dimer or butene trimer).
  • lubricants for the engines of motor vehicles, compressor oils, hydraulic fluids, insulating fluids for electrical devices, electrical contact oils, lubricating greases, chain lubricants, heat transfer fluids, vacuum pump oils, synthetic fiber lubricants, instrument oils, rust protection oils and rolling oils . All applications in lubricants that have a lubricating function are the subject of the invention.
  • the polycarboxylic esters according to the invention have a significantly better temperature-viscosity behavior than conventional esters, expressed by a significantly higher viscosity index.
  • An essential requirement criterion for lubricating oils is the viscosity at low temperatures, eg at 0 to -30 ° C, as required in the lubricating oil specifications according to SAE J 300 (April 1984).
  • DIN 51 377 ASSE J 2606
  • the results from viscosity measurements for the esters according to the invention also show serious application advantages over conventional esters.
  • esters according to the invention have a significantly higher flash point than esters which have been prepared from the oxo alcohols previously used.
  • esters are chemically more uniform than e.g. Ester from oxo alcohols, based on conventional propylene tetramer (isododecene).
  • the esters according to the invention have lower evaporation losses (DIN 51 581) than conventional esters.
  • the evaporation loss measured according to DIN 51 581 is a further essential quality criterion for the suitability as a lubricant component in addition to the other basic technical data.
  • olefin oligomers suitable for the oxo reaction are prepared by known processes. So you get e.g. n-butene dimers or n-butene trimers according to the teaching in EP-A-143 703, EP-A-012 685, EP-A-00 24 971 and DE-A-31 17 864.
  • the invention is further illustrated by the examples below.
  • the lubrication data of conventional esters are compared in each case with the data of the esters refined in the lubricant according to the invention.
  • the di-isononyl adipate based on dimerbutene used according to the invention has a comparable flash point and evaporation loss, although it has two CH 2 groups less.
  • it has a significantly higher viscosity index and a significantly lower low-temperature viscosity than the well-known di-isodecyl adipate.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

This invention relates to aliphatic or aromatic polycarboxylic acid esters as defined herein which are useful as base oils alone in lubricating oil compositions or in admixture with completely synthetic, partially synthetic, or mineral oil-based lubricant compositions.

Description

Die Erfindung betrifft die Verwendung von aliphatischen oder aromatischen Polycarbonsäureestern in voll- oder teilsynthetischen Schmiermitteln sowie Schmiermittel, welche diese Ester enthalten.The invention relates to the use of aliphatic or aromatic polycarboxylic acid esters in fully or partially synthetic lubricants and lubricants which contain these esters.

Moderne Schmiermittel, insbesondere Leichtlauf-Motoröle, sind nicht mehr allein durch Mineralölkomponenten herstellbar, die Zumischung von Synthesekomponenten ist erforderlich. Insbesondere bei Schmierölen für Kraftfahrzeugmotoren werden ständig steigende Anforderungen gestellt, da Drehzahlen, Arbeitsdrücke und Leistungen bei gleichzeitiger Forderung nach hoher Lebensdauer und Zuverlässigkeit im Motorenbau ständig ansteigen.Modern lubricants, especially low-friction motor oils, can no longer be produced using mineral oil components alone, the addition of synthetic components is necessary. In particular, lubricating oils for motor vehicle engines are subject to ever increasing demands, since speeds, working pressures and outputs are constantly increasing while at the same time demanding a long service life and reliability in engine construction.

Den HD(Heavy Duty)Ölen, denen für ihre zusätzlichen Aufgaben, wie Alterungs- und Korrosionsschutz, Hochdruckbeständigkeit, sowie als "Schmutzträger" Additive zugesetzt wurden - folgten die Mehrbereichsöle mit flachen Viskositätskurven und einer Eignung für Sommer- und Winterbetrieb, für längere Olwechselintervalle und auch bereits verminderten Kraftstoffverbrauch, insbesondere im Winter- und Kurzstreckenbetrieb. Eine flache Viskositätskurve bedeutet eine verminderte Temperaturabhängigkeit des Schmieröls. Ein Maß für die Temperaturabhängigkeit ist der Viskositätsindex (VI).The HD (Heavy Duty) oils, to which additives were added for their additional tasks, such as aging and corrosion protection, high pressure resistance, and as "dirt carriers" - were followed by the multigrade oils with flat viscosity curves and suitable for summer and winter operation, for longer oil change intervals and already reduced fuel consumption, especially in winter and short-haul operations. A flat viscosity curve means a reduced temperature dependence of the lubricating oil. The viscosity index (VI) is a measure of the temperature dependence.

Die Verwendung einer Vielzahl unterschiedlichster Ester in synthetischen Schmiermittelzusetzungen ist im Stand der Technik bekannt. So betrifft beispielsweise die US-A-4 130 494 die Verwendung von Aminsalzen von Phosphatestern als Additive zu synthetischen Schmierölzusammensetzungen. Hierdurch sollen unerwünschte Ablagerungen in den Motoren, insbesondere in Turbinenmotoren, verringert werden.The use of a large number of very different esters in synthetic lubricant additives is known in the prior art. For example, US-A-4 130 494 relates to the use of amine salts of phosphate esters as additives to synthetic lubricating oil compositions. This is intended to reduce unwanted deposits in the engines, especially in turbine engines.

Die US-A-4 155 861 betrifft ein Schmiermittel, welches eine Mischung aus einem monomeren Ester einer verzweigten Dicarbonsäure mit einem aliphatischen primären Monoalkohol und einem Komplexester einer Dicarbonsäure und Hexandiol oder Trimethylhexandiol umfaßt. Beim monomeren Diester handelt es sich stets um einen gemischten Diester (Spalte 6, Zeilen 1 und 2), wobei namentlich der Trimethyladipinsäureoctyldecylester genannt ist. Die beschriebene Schmiermittelkombination soll sich durch universelle Anwendbarkeit auszeichnen.US-A-4 155 861 relates to a lubricant which comprises a mixture of a monomeric ester of a branched dicarboxylic acid with an aliphatic primary monoalcohol and a complex ester of a dicarboxylic acid and hexanediol or trimethylhexanediol. The monomeric diester is always a mixed diester (column 6, lines 1 and 2), with octyl trimethyladipate being mentioned in particular. The described lubricant combination should be characterized by universal applicability.

Die bekannten Polycarbonsäureester werden beispielsweise großtechnisch unter Verwendung von Oxoalkoholen als Veresterungskomponenten hergestellt. Oxoalkohole, die für Ester als synthetische Schmiermittel besonders geeignet sind, werden aus Oligoolefinen hergestellt.The known polycarboxylic acid esters are produced, for example, on an industrial scale using oxo alcohols as esterification components. Oxo alcohols, which are particularly suitable for esters as synthetic lubricants, are made from oligo-olefins.

In Tabelle 1 sind beispielhaft bekannte Oligoolefine und die daraus durch Oxoreaktion herstellbaren Alkohole zusammengestellt.

Figure imgb0001
Table 1 shows examples of known oligo-olefins and the alcohols which can be prepared therefrom by oxo reaction.
Figure imgb0001

Aus diesen großtechnisch verfügbaren Oxoalkoholen wurden bereits Polycarbonsäureester hergestellt, welche auch als synthetische Schmiermittel Verwendung finden, vgl. R.C. Gunderson und A.W. Hunt, Synthetic Lubricants, Reinhold Publishing Company, 1962, S. 151ff.Polycarboxylic esters have already been produced from these industrially available oxo alcohols, which are also used as synthetic lubricants, cf. R.C. Gunderson and A.W. Hunt, Synthetic Lubricants, Reinhold Publishing Company, 1962, pp. 151ff.

Der Erfindung liegt die Aufgabe zugrunde, Polycarbonsäureester zur Verwendung in synthetischen Schmiermitteln zur Verfügung zu stellen, welche gegenüber den bekannten Polycarbonsäureestern ein verbessertes TemperaturNiskositätsverhalten, ausgedrückt durch einen höheren Viskositätsindex und verbesserte Tieftemperatureigenschaften, sowie einen niedrigeren Vedampfungsverlust und einen höheren Flammpunkt aufweisen.The invention has for its object to provide polycarboxylic acid esters for use in synthetic lubricants which, compared to the known polycarboxylic acid esters, have improved temperature-viscosity behavior, expressed by a higher viscosity index and improved low-temperature properties, as well as a lower evaporation loss and a higher flash point.

Diese Aufgabe wird gelöst durch die Verwendung von aliphatischen oder aromatischen Polycarbonsäureestern der allgemeinen Formel

Figure imgb0002
worin X einen geradkettigen oder verzweigten Alkylenrest oder einen Arylenrest darstellt, R einen von der Oxierung eines n-Buten-Oligomers herrührenden Rest bedeutet und y für 1 oder 2 steht,
einzeln oder in Mischung in voll- oder teilsynthetischen Schmiermitteln.This object is achieved by using aliphatic or aromatic polycarboxylic esters of the general formula
Figure imgb0002
 in which X represents a straight-chain or branched alkylene radical or an arylene radical, R represents a radical originating from the oxidation of an n-butene oligomer and y represents 1 or 2,
individually or as a mixture in fully or partially synthetic lubricants.

Gegenstand der Erfindung ist auch ein Schmiermittel, welches mindestens einen Polycarbonsäureester der allgemeinen Formel (1) enthält.The invention also relates to a lubricant which contains at least one polycarboxylic acid ester of the general formula (1).

Nach einer bevorzugten Ausführungsform der Erfindung steht der Rest X in der allgemeinen Formel (I) für einen Arylenrest der Formeln

Figure imgb0003
According to a preferred embodiment of the invention, the radical X in the general formula (I) represents an arylene radical of the formulas
Figure imgb0003

Nach einer weiteren bevorzugten Ausfürungsform der Erfindung steht der Rest X für einen Rest der Formel

Figure imgb0004
worin Ri und R2 unabhängig voneinander für Wasserstoff oder CI-CS-Alkylreste stehen und n die Bedeutungen 2 bis 12 besitzt, z.B. für einen - (CH2)n-Rest (R1 = R2 = H).According to a further preferred embodiment of the invention, the radical X represents a radical of the formula
Figure imgb0004
 wherein R i and R2 independently of one another are hydrogen or C I -C S alkyl radicals and n has the meanings 2 to 12, for example for a - (CH 2 ) n radical (R 1 = R 2 = H).

Nach einer weiteren bevorzugten Ausführungsform weist der Rest R in der allgemeinen Formel (I) 9, 13 oder 17 Kohlenstoffatome auf, wobei es besonders bevorzugt ist, wenn es sich um Estergemische handelt, in denen die Reste R die genannten Bedeutungen besitzen.According to a further preferred embodiment, the radical R in the general formula (I) has 9, 13 or 17 carbon atoms, it being particularly preferred if the mixtures are ester mixtures in which the radicals R have the meanings mentioned.

Besonders zweckmäßig rührt der Rest R in der allgemeinen Formel (I) von der Oxierung eines weitgehend linear oligomerisierten n-Buten-Oligomeren mit einem Oligomerisationsgrad von 2 bis 4 her.The radical R in the general formula (I) particularly advantageously stems from the oxidation of a largely linearly oligomerized n-butene oligomer with a degree of oligomerization of 2 to 4.

Besonders bevorzugt handelt es sich bei den Polycarbonsäureestern der allgemeinen Formel (I) um Phthalsäureester oder Adipinsäureester mit C9- und/oder C13-Oxoalkoholen.The polycarboxylic acid esters of the general formula (I) are particularly preferably phthalic acid esters or adipic acid esters with C 9 and / or C 13 oxo alcohols.

Die erfindungsgemäßen Schmiermittel enthalten mindestens eine Verbindung der allgemeinen Formel (I). Das Schmiermittel kann auch andere Komponenten enthalten, beispielsweise übliche Komponenten, z.B. Grundöle auf Mineralölbasis oder andere synthetische Schmiermittelkomponenten, beispielsweise Poly-a-olefine.The lubricants according to the invention contain at least one compound of the general formula (I). The lubricant may also contain other components, for example common components, e.g. Mineral oil-based base oils or other synthetic lubricant components, for example poly-a-olefins.

Die Ester der allgemeinen Formel I können entweder einzeln oder in Mischung untereinander eingesetzt werden.The esters of the general formula I can be used either individually or as a mixture with one another.

Als Monoalkoholkomponente weisen die Polycarbonsäureester der allgemeinen Formel I bevorzugt den Nonyl- und Tridecylrest auf.The polycarboxylic acid esters of the general formula I preferably have the nonyl and tridecyl radical as the monoalcohol component.

Die bei der Veresterung benutzten Alkohole R-OH (Nonyl- bzw. Tridecylalkohol), sind Isomerengemische, wie sie bei der Oxosynthese von entsprechenden Buten-Oligomeren, nämlich Octen und Dodecen (Buten-Dimer bzw. Buten-Trimer) anfallen.The alcohols R-OH (nonyl or tridecyl alcohol) used in the esterification are mixtures of isomers as are obtained in the oxo synthesis of corresponding butene oligomers, namely octene and dodecene (butene dimer or butene trimer).

Die Verwendung der Polycarbonsäureester der allgemeinen Formel I ist vorgesehen in Schmiermitteln. Hierbei kann es sich beispielsweise um Schmierstoffe (Schmieröle) für Triebwerke der Kfz-Motoren, um Kompressorenöle, hydraulische Flüssigkeiten, Isolierflüssigkeiten für elektrische Geräte, elektrische Kontaktöle, Schmierfette, Kettenschmierstoffe, Wärmeübertragungs-Flüssigkeiten, Vakuumpumpenöle, synthetische Faserschmierstoffe, Instrumentenöle, Rostschutzöle und Walzöle handeln. Sämtliche Anwendungen in Schmiermitteln, welche eine Schmierfunktion haben sind Gegenstand der Erfindung.The use of the polycarboxylic acid esters of the general formula I is intended in lubricants. These can be, for example, lubricants (lubricating oils) for the engines of motor vehicles, compressor oils, hydraulic fluids, insulating fluids for electrical devices, electrical contact oils, lubricating greases, chain lubricants, heat transfer fluids, vacuum pump oils, synthetic fiber lubricants, instrument oils, rust protection oils and rolling oils . All applications in lubricants that have a lubricating function are the subject of the invention.

Die erfindungsgemäßen Polycarbonsäureester weisen gegenüber herkömmlichen Estern ein deutlich besseres Temperatur-Viskositätsverhalten, ausgedrückt durch einen deutlich höheren Viskositätsindex, auf. Ein wesentliches Anforderungskriterium an Schmieröle ist die Viskosität bei tiefen Temperaturen, d.h. z.B. bei 0 bis -30°C, wie sie in den Schmieröl-Spezifikationen gemäß SAE J 300 (April 1984) gefordert wird. Als Meßmethode für die Tieftemperaturviskosität dient die Methode aus DIN 51 377 (ASTM D 2606). Die Ergebnisse aus Viskositätsmessungen bei den erfindungsgemäßen Estern zeigen auch hier gegenüber herkömmlichen Estern gravierende anwendungstechnische Vorteile.The polycarboxylic esters according to the invention have a significantly better temperature-viscosity behavior than conventional esters, expressed by a significantly higher viscosity index. An essential requirement criterion for lubricating oils is the viscosity at low temperatures, eg at 0 to -30 ° C, as required in the lubricating oil specifications according to SAE J 300 (April 1984). The method from DIN 51 377 (ASTM D 2606) serves as the measuring method for the low-temperature viscosity. The results from viscosity measurements for the esters according to the invention also show serious application advantages over conventional esters.

Außerdem haben die erfindungsgemäßen Ester einen wesentlich höheren Flammpunkt als Ester, die aus den bisher verwendeten Oxoalkoholen hergestellt wurden.In addition, the esters according to the invention have a significantly higher flash point than esters which have been prepared from the oxo alcohols previously used.

Auf Grund ihrer für den Anwendungszweck neuartigen chemischen Struktur und der Möglichkeit einer besseren destillativen Trennung der einzelnen Buten-Oligomeren (z.B. Abtrennung des Butendimer von Butentrimer bzw. Butentetramer) sind die Ester chemisch einheitlicher als z.B. Ester aus Oxoalkoholen, basierend auf herkömmlichem Propylentetramer (Isododecen).Due to their new chemical structure for the intended use and the possibility of a better separation of the individual butene oligomers by distillation (e.g. separation of the butene dimer from butene trimer or butene tetramer), the esters are chemically more uniform than e.g. Ester from oxo alcohols, based on conventional propylene tetramer (isododecene).

Als Folge dessen weisen die erfindungsgemäßen Ester geringere Verdampfungsverluste (DIN 51 581) als herkömmliche Ester auf. Der nach DIN 51 581 gemessene Verdampfungsverlust ist neben den anderen anwendungstechnischen Grunddaten ein weiteres wesentliches Qualitätskriterium für die Eignung als Schmiermittelkomponente.As a result, the esters according to the invention have lower evaporation losses (DIN 51 581) than conventional esters. The evaporation loss measured according to DIN 51 581 is a further essential quality criterion for the suitability as a lubricant component in addition to the other basic technical data.

Die für die Oxoreaktion geeigneten Olefinoligomeren werden nach bekannten Verfahren hergestellt. So erhält man z.B. n-Buten-Dimere bzw. n-Buten-Trimere nach der Lehre in EP-A-143 703, EP-A-012 685, EP-A- 00 24 971 und DE-A-31 17 864.The olefin oligomers suitable for the oxo reaction are prepared by known processes. So you get e.g. n-butene dimers or n-butene trimers according to the teaching in EP-A-143 703, EP-A-012 685, EP-A-00 24 971 and DE-A-31 17 864.

Dabei wird jeweils z.B. ein technisches Gemisch aus C4-Kohlenwasserstoffen (Raffinat-II, enthaltend 60 bis 80 % n-Butene) katalytisch olgiomerisiert. Die Ausbeute ist je nach Verfahrensbedingungen steuerbar. Man erhält z.B. ein Buten-Oligomerisat, welches zu 60 bis 90 % aus Buten-Dimer (Octen), zu 10 bis 30 % aus Buten-Trimer (Dodecen) und einen entsprechenden Rest an C12+-0Iigomeren besteht. Durch destillative Trennung des Roholigomerisats erhält man z.B. folgende Olgiomerfraktionen, die sich zur Herstellung von Oxoalkoholen für eine Veresterung zu den erfindungsgemäßen Estern eignen:

  • 1. Fraktion: Siedelage 118-122°C (Octenfraktion)
  • 2. Fraktion: Siedelage 200-220°C (Dodecenfraktion)
In each case, for example, a technical mixture of C 4 hydrocarbons (raffinate II, containing 60 to 80% n-butenes) is catalytically oligomerized. The yield can be controlled depending on the process conditions. For example, a butene oligomer is obtained which consists of 60 to 90% butene dimer (octene), 10 to 30% butene trimer (dodecene) and a corresponding residue of C 12+ oligomers. Separation of the crude oligomer by distillation gives, for example, the following olgiomer fractions which are suitable for the preparation of oxoalcohols for esterification to the esters according to the invention:
  • 1st fraction: boiling point 118-122 ° C (octene fraction)
  • 2nd fraction: boiling point 200-220 ° C (dodecene fraction)

Rückstand: Siedelage über 230°C.Residue: boiling point above 230 ° C.

Die analytische Untersuchung der Oligomeren zeigt, daß z.B. die Octenfraktion wie folgt zusammengesetzt ist:

  • 55 bis 60 % Methylheptene
  • 5 bis 7 % n-Octene
  • Rest Dimethylhexene.
The analytical examination of the oligomers shows that, for example, the octene fraction is composed as follows:
  • 55 to 60% methylheptene
  • 5 to 7% n-octenes
  • Balance dimethylhexenes.

Die Erfindung wird durch die nachstehenden Beispiele weiter erläutert. Es werden jeweils die schmiertechnischen Daten von herkömmlichen Estern mit den Daten der im erfindungsgemäßen Schmiermittel veredelten Estern verglichen.The invention is further illustrated by the examples below. The lubrication data of conventional esters are compared in each case with the data of the esters refined in the lubricant according to the invention.

Die erhaltenen Ergebnisse sind in der nachstehenden Tabelle 2 zusammengefaßt:

Figure imgb0005
The results obtained are summarized in Table 2 below:
Figure imgb0005

Den Daten ist zu entnehmen, daß im Vergleich zu herkömmlichem Di-Isodecyladipat auf der Basis Trimerpropylen das erfindungsgemäß verwendete Di-Isononyladipat auf der Basis Dimerbuten einen vergleichbaren Flammpunkt und Verdampfungsverlust aufweist, obgleich es zwei CH2-Gruppen weniger aufweist. Darüber hinaus besitzt es einen deutlich höheren Viskositätsindex und eine erheblich niedrigere Tieftemperaturviskosität als das bekannte Di-Isodecyladipat.The data show that compared to conventional di-isodecyl adipate based on trimer propylene, the di-isononyl adipate based on dimerbutene used according to the invention has a comparable flash point and evaporation loss, although it has two CH 2 groups less. In addition, it has a significantly higher viscosity index and a significantly lower low-temperature viscosity than the well-known di-isodecyl adipate.

Claims (8)

1. Use of aliphatic or aromatic polycarboxylates of the formula I
Figure imgb0009
where X is straight-chain or branched alkylene or is arylene, R is a radical obtained by subjecting an n-butene oligomer to an oxo reaction and y is 1 or 2, individually or as a mixture in fully or partly synthetic lubricants.
2. Use as claimed in claim 1, wherein X is aryl of the formula
Figure imgb0010
3. Use as claimed in claim 1, wherein X is a radical of the formula
Figure imgb0011
where R1 and R2 independently of one another are each hydrogen or C1-C5-alkyl and n is from 2 to 12.
4. Use as claimed in any of claims 1 to 3, wherein R in formula I is of 9, 13 or 17 carbon atoms.
5. Use as claimed in any of claims 1 to 4, wherein R in formula I is obtained by subjecting a substantially linear n-butene oligomer having a degree of oligomerization of from 2 to 4 to an oxo reaction.
6. Use as claimed in any of claims 1 to 5, wherein the polycarboxylates of the formula I are phthalates or adipates of C9- and/or C13-oxo alcohols.
7. A lubricant containing one or more polycarboxylates of the formula I as claimed in any of claims 1 to 6.
8. A lubricant as claimed in claim 7, additionally containing base oils based on mineral oil, and other, conventional lubricant components.
EP87115127A 1986-10-18 1987-10-16 Use of carboxylic-acid esters in completely or partially synthetic lubricants, and lubricants containing them Expired - Lifetime EP0264842B1 (en)

Priority Applications (1)

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AT87115127T ATE59202T1 (en) 1986-10-18 1987-10-16 USE OF CARBON ACID ESTERS IN FULLY OR PARTIALLY SYNTHETIC LUBRICANTS AND LUBRICANTS CONTAINING THESE ESTERS.

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DE19863635490 DE3635490A1 (en) 1986-10-18 1986-10-18 USE OF POLYCARBONIC ACID ESTERS IN FULL OR PART SYNTHETIC LUBRICANTS AND LUBRICANTS CONTAINING THESE ESTERS
DE3635490 1986-10-18

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US5372736A (en) * 1993-10-27 1994-12-13 Nalco Chemical Company Synthetic hot mill lubricant for high temperature applications
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CA1276649C (en) 1990-11-20
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ATE59202T1 (en) 1991-01-15
DE3766793D1 (en) 1991-01-31
EP0264842A3 (en) 1989-03-22

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