EP0272575A2 - High viscosity, neutral polyolesters - Google Patents

High viscosity, neutral polyolesters Download PDF

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Publication number
EP0272575A2
EP0272575A2 EP87118481A EP87118481A EP0272575A2 EP 0272575 A2 EP0272575 A2 EP 0272575A2 EP 87118481 A EP87118481 A EP 87118481A EP 87118481 A EP87118481 A EP 87118481A EP 0272575 A2 EP0272575 A2 EP 0272575A2
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EP
European Patent Office
Prior art keywords
acids
class
acid
fatty acids
range
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EP87118481A
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German (de)
French (fr)
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EP0272575B2 (en
EP0272575A3 (en
EP0272575B1 (en
Inventor
Karl-Heinz Dr. Schmid
Uwe Dr. Ploog
Alfred Dr. Meffert
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BASF Personal Care and Nutrition GmbH
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Henkel AG and Co KGaA
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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
    • C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic 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
    • 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
    • C10M105/38—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
    • 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
    • C10M105/40—Esters containing free hydroxy or carboxyl groups
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • 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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • 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

  • esters so-called ester oils
  • ester oils have found increasing use as high-quality lubricating oils in recent years.
  • diesters of dibasic carboxylic acids with monohydric alcohols for example dioctyl sebacate
  • esters of polyols with monobasic acids such as trimethylolpropane tripelargonate
  • polyols e.g. uses trimethylolpropane, neopentyl glycol and / or pentaerythritol.
  • the good suitability of the synthetic esters as lubricants results from the fact that they have a more favorable viscosity-temperature behavior than conventional lubricating oils based on mineral oil and that the setting points are significantly lower when comparable viscosities are set.
  • the invention has for its object to provide new synthetic polyol esters, which are particularly suitable for are suitable for use in the field of temperature-resistant lubricating oils such as gear and hydraulic oils as well as lubricating oil dispersions or lubricating greases and can also be optimally adapted to the aforementioned selection criteria.
  • the technical solution to this problem according to the invention is based on the selection of a specific polyol component as the hydroxyl group function for the production of the polyol esters and combines this selection on the side of the hydroxyl group components with a specific selection of mono- and optionally polyfunctional carboxylic acids on the acid side for the production of the new synthetic polyol ester.
  • Class C acids di- and / or tricarboxylic acids in the range from C6 to C54
  • Class D acids difunctional fatty acids which have been prepared by adding acrylic acid to the double bonds of oleic, linoleic and / or linolenic acid,
  • Class E acids Aromatic and / or paraffinic cyclic polycarboxylic acids with 2 to 6 acid functions.
  • the invention relates to the use of the new synthetic polyol esters for the production of temperature-resistant transmission and hydraulic oils as well as lubricating oil dispersions and / or lubricating greases.
  • the selection of the monofunctional carboxylic acid components used for the esterification and, if desired, also used in minor amounts is of crucial importance.
  • the fatty acids used for the esterification can be divided into the classes A to E listed below, the fatty acid classes A and B relating to monocarboxylic acids, while the acid classes C, D and E contain higher-functional carboxylic acids. The following details apply here:
  • Class A acids Branched fatty acids in the C chain range from C8 to C16
  • Class B acids linear fatty acids in the C chain range from C8 to C14, preferably in the range from C8 to C10.
  • the new synthetic polyol esters of the invention can contain exclusively branched fatty acids from class A or else mixtures of branched fatty acids of class A with linear fatty acids from class B as fatty acid components. Details of the preferred mixing ratios are given below.
  • the multifunctional carboxylic acids used together with the branched fatty acids (class A) or with the mixtures of branched and linear fatty acids (classes A + D) can be classified in the following classes:
  • Class C acids di- and / or tricarboxylic acids in the C number range from C6 to C54. Adipic acid, trimethyladipic acid, azelaic acid and / or sebacic acid are particularly preferred here. Further suitable and particularly preferred polyfunctional acids of this class are di- or trimer fatty acids from the polymerization of mono- and / or polyunsaturated fatty acids in the C range from C16 to C22.
  • Class D acids This covers difunctional fatty acids obtained by adding acrylic acids to the double bonds of oleic acid, linoleic acid and / or linolenic acid. Corresponding addition products to the mixtures of the three unsaturated acids mentioned which are obtained in practice are particularly suitable. The preparation of such difunctional acids of this class D is described for example in DE-OS 24 06 401 and DE-OS 22 53 930.
  • Class E acids Cyclic polycarboxylic acids of aromatic and / or paraffinic nature with 2 to 6 acid functions. Particularly preferred here are terephthalic acid, trimellitic acid, pyromellitic acid and / or cyclohexane carboxylic acid, which can be used as such or in the form of their anhydrides for the preparation of the new synthetic polyol esters.
  • synthetic polyol esters of the type mentioned with the lowest possible acid numbers are preferred, neutral esters or those with a limited excess of free hydroxyl groups are particularly affected.
  • 6.0 to 7.2 equivalents (corresponding to 1 to 1.2 mol) of dipentaerythritol are used in the preparation of the esters per 6 equivalents of the acids or acid mixtures used.
  • Preferred polyol esters of this type show hydroxyl numbers in the range from 0 to about 25.
  • Esters preferred according to the invention furthermore have viscosity values at 40 ° C. in the range from 50 to 1000 mm 2 / s and have pour points in the range from approximately 0 to -30 ° C.
  • branched fatty acids (acid class A) - especially when using 2-ethyl-hexanoic acid, isononanoic acid, isodecanoic acid and / or isotridecanoic acid - esters in the viscosity class range (definition according to ISO 3448 or DIN 51 519) ISO VG 320 to 460.
  • the viscosity of the polyol esters produced is reduced to the viscosity class range ISO VG 46 to ISO VG 220. If you want to increase the viscosity of the esters, the use of dibasic and polybasic acids from the acid classes C, D and / or E indispensable.
  • the new polyol esters according to the invention are suitable carrier oils for temperature-resistant lubricating oil dispersions and greases and are also due to their good tribological properties - for example an excellent pressure absorption capacity - also as an addition components or used alone for hydraulic and gear oils.
  • Usual additives such as oxidation and corrosion inhibitors, dispersants, high pressure additives, anti-foaming agents, metal deactivators and other additives can be added in the usual effective amounts.
  • Dipentaerythritol and the selected fatty acid mixture are esterified in the presence of 0.5% tin grinding at 240 ° C. for 6 to 8 hours while distilling off the water formed in the reaction. Towards the end of the reaction, esterification continues at the same temperature but under reduced pressure. After cooling to 120 ° C., 1 percent by weight of activated bleaching earth is added, the mixture is heated again to 200 ° C. and excess monocarboxylic acid is distilled off in vacuo. After cooling, the reaction mixture is filtered.
  • Viscosity index approx. 90
  • the temperature / weight analysis gives the mass loss of the substance in percent, which occurs when heated with a continuous temperature rise of 20 ° C per minute.
  • Viscosity index approx. 120 Pour point: approx. - 30 ° C

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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)
  • Polyesters Or Polycarbonates (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

Die Erfindung betrifft synthetische Polyolester mit Schmieröleigenschaften auf Basis im wesentlichen neutraler Veresterungsprodukte eines polyfunktionellen Alkohols mit ausgewählten Monocarbonsäuren und gewünschtenfalls mehrfunktionellen Carbonsäuren, wobei die polyfunktionelle Alkoholkomponente Dipentaerythrit ist, der mit

  • I verzweigten Fettsäuren im C-Kettenbereich von C₈ bis C₁₆ (Säuren der Klasse A) oder mit
  • II Gemischen von linearen Fettsäuren in C-Kettenbereich von C₈ bis C₁₄ (Säuren der Klasse B) in Abmischung mit verzweigten Fettsäuren der Klasse A
verestert ist und dabei gewünschtenfalls zusätzlich beschränkte Mengen an mehrfunktionellen Carbonsäuren der nachfolgenden Klassen C, D und/oder E in das Polyolestermolekül einkonden­siert, enthält:The invention relates to synthetic polyol esters with lubricating oil properties based on essentially neutral esterification products of a polyfunctional alcohol with selected monocarboxylic acids and, if desired, polyfunctional carboxylic acids, the polyfunctional alcohol component being dipentaerythritol which is associated with
  • I branched fatty acids in the C chain range from C₈ to C₁₆ (acids of class A) or with
  • II Mixtures of linear fatty acids in the C chain range from C₈ to C₁₄ (acids of class B) in admixture with branched fatty acids of class A.
is esterified and, if desired, additionally condensed limited amounts of polyfunctional carboxylic acids of the following classes C, D and / or E into the polyol ester molecule contains:

Säuren der Klasse C: Di-und/oder Tricarbonsäuren im Bereich von C₆ bis C₅₄,Class C acids: di- and / or tricarboxylic acids in the range from C₆ to C₅₄,

Säuren der Klasse D: Difunktionelle Fettsäuren, die durch Anlagerung von Acrylsäure an die Doppelbindungen von Öl- Linol- und/oder Linolensäure hergestellt worden sind,Class D acids: difunctional fatty acids which have been produced by adding acrylic acid to the double bonds of oleic, linoleic and / or linolenic acid,

Säuren der Klasse E: Aromatische und/oder paraffinische, cyclische Polycarbonsäuren mit 1 bis 6 Säurefunktionen. Class E acids: Aromatic and / or paraffinic, cyclic polycarboxylic acids with 1 to 6 acid functions.

Description

Synthetische Ester, sogenannte Esteröle, haben in den letzten Jahren als hockwertige Schmieröle eine immer größer werdende Anwendung gefunden. So wurden zum Beispiel Diester von zwei­basischen Carbonsäuren mit einwertigen Alkoholen, zum Beispiel Dioctylsebacat, oder auch Ester von Polyolen mit einbasischen Säuren wie Trimethylolpropantripelargonat als Schmiermittel für Flugzeugturbinen vorgeschlagen. Als Polyole werden dabei z.B. verwendet Trimethylolpropan, Neopentylglykol und/oder Penta­erythrit.Synthetic esters, so-called ester oils, have found increasing use as high-quality lubricating oils in recent years. For example, diesters of dibasic carboxylic acids with monohydric alcohols, for example dioctyl sebacate, or also esters of polyols with monobasic acids such as trimethylolpropane tripelargonate have been proposed as lubricants for aircraft turbines. As polyols, e.g. uses trimethylolpropane, neopentyl glycol and / or pentaerythritol.

Die gute Eignung der synthetischen Ester als Schmiermittel ergibt sich daraus, daß sie gegenüber herkömmlichen Schmierölen auf Mineralölbasis ein günstigeres Viskositätstemperaturverhalten aufweisen und daß bei Einstellung vergleichbarer Viskositäten die Stockpunkte deutlich niedriger liegen.The good suitability of the synthetic esters as lubricants results from the fact that they have a more favorable viscosity-temperature behavior than conventional lubricating oils based on mineral oil and that the setting points are significantly lower when comparable viscosities are set.

Es besteht gleichwohl weiterhin ausgesprochenes Interesse an neuen synthetischen Esterkomponenten, die einen tiefliegenden Stockpunkt mit hoher Viskosität, einem guten Viskositätstempera­turverhalten, hoher Temperaturbeständigkeit, hohem Flammpunkt sowie bei hohen Temperaturen möglichst geringen Verdampfungs­verlusten verbinden.Nevertheless, there is still great interest in new synthetic ester components that combine a low pour point with high viscosity, good viscosity temperature behavior, high temperature resistance, high flash point and low evaporation losses at high temperatures.

Die Erfindung geht von der Aufgabe aus, neue synthetische Polyolester zur Verfügung zu stellen, die sich insbesondere für den Einsatz auf dem Gebiet der temperaturbelastbaren Schmieröle wie Getriebe- und Hydraulikölen sowie der Schmieröldispersionen beziehungsweise Schmierfette eignen und dabei auch den zuvor genannten Auswahlkriterien optimal angepaßt werden können.The invention has for its object to provide new synthetic polyol esters, which are particularly suitable for are suitable for use in the field of temperature-resistant lubricating oils such as gear and hydraulic oils as well as lubricating oil dispersions or lubricating greases and can also be optimally adapted to the aforementioned selection criteria.

Die technische Lösung dieser erfindungsgemäßen Aufgabenstellung geht von der Auswahl einer bestimmten Polyolkomponente als Hydroxylgruppen - Funktion für die Herstellung der Polyolester aus und verbindet dabei diese Auswahl auf der Seite der Hydroxyl­gruppenkomponete mit einer bestimmten Auswahl von ein- und gegebenenfalls mehrfunktionellen Carbonsäuren auf der Säureseite zur Herstellung der neuen synthetischen Polyolester.The technical solution to this problem according to the invention is based on the selection of a specific polyol component as the hydroxyl group function for the production of the polyol esters and combines this selection on the side of the hydroxyl group components with a specific selection of mono- and optionally polyfunctional carboxylic acids on the acid side for the production of the new synthetic polyol ester.

Gegenstand der Erfindung sind dementsprechend in einer ersten Ausführungsform synthetische Polyolester mit Schmieröleigen­schaften aus Basis im wesentlichen neutraler Veresterungs­produkte eines polyfunktionellen Alkohols mit ausgewählten Monocarbonsäuren und gewünschtenfalls mehrfunktionellen Carbonsäuren. Das Kennzeichen der Erfindung liegt dabei darin, daß die polyfunktionelle Alkoholkomponente Dipentaerythrit ist, der mit

  • I verzweigten Fettsäuren im C-Kettenbereich von C₈ bis C₁₆ (Säuren der Klasse A) oder mit
  • II Gemischen von linearen Fettsäuren im C-Kettenbereich C₈ bis C₁₄ (Säuren der Klasse B) in Abmischung mit verzweigten Fettsäuren der Klasse A
verestert ist und dabei gewünschtenfalls zusätzlich beschränkte Mengen an mehrfunktionellen Carbonsäuren der nachfolgenden Klassen C, D und/oder E in das Polyolestermolekül einkondensiert, enthält.Accordingly, the invention relates in a first embodiment to synthetic polyol esters with lubricating oil properties based on essentially neutral esterification products of a polyfunctional alcohol with selected monocarboxylic acids and, if desired, polyfunctional carboxylic acids. The characteristic of the invention is that the polyfunctional alcohol component is dipentaerythritol, which with
  • I branched fatty acids in the C chain range from C₈ to C₁₆ (acids of class A) or with
  • II Mixtures of linear fatty acids in the C chain range C₈ to C₁₄ (acids of class B) in admixture with branched fatty acids of class A.
is esterified and, if desired, additional limited amounts of polyfunctional carboxylic acids of the following classes C, D and / or E are condensed into the polyol ester molecule.

Säuren der Klasse C: Di- und/oder Tricarbonsäuren im Bereich von C₆ bis C₅₄Class C acids: di- and / or tricarboxylic acids in the range from C₆ to C₅₄

Säuren der Klasse D: Difunktionelle Fettsäuren, die durch Anlagerung von Acrylsäure an die Doppelbindungen von Öl-, Linol- und/oder Linolensäure hergestellt worden sind,Class D acids: difunctional fatty acids which have been prepared by adding acrylic acid to the double bonds of oleic, linoleic and / or linolenic acid,

Säuren der Klasse E: Aromatische und/oder paraffinische cyclische Polycarbonsäuren mit 2 bis 6 Säurefunktionen.Class E acids: Aromatic and / or paraffinic cyclic polycarboxylic acids with 2 to 6 acid functions.

Die Erfindung betrifft in einer weiteren Ausgestaltung die Verwendung der neuen synthetischen Polyolester zur Herstellung von temperaturbelastbaren Getriebe- und Hydraulikölen sowie Schmieröldispersionen und/oder Schmierfetten.In a further embodiment, the invention relates to the use of the new synthetic polyol esters for the production of temperature-resistant transmission and hydraulic oils as well as lubricating oil dispersions and / or lubricating greases.

Neben der erfindungsgemäßen Auswahl des Dipentaerythrits als zentrale Polyolkomponente für die Herstellung der erfindungs­gemäßen neuen synthetischen Pololyester ist die Auswahl der zur Veresterung eingesetzten monofunktionellen und gewünschtenfalls in untergeordneten Mengen mitverwendeten polyfunktionellen Carbonsäurekomponenten von entscheidender Bedeutung. Die zur Veresterung eingesetzten Fettsäuren lassen sich in die nach­folgend aufgezählten Klassen A bis E unterteilen, wobei die Fettsäureklassen A und B Monocarbonsäuren betreffen, während die Säureklassen C, D und E höherfunktionelle Carbonsäuren beinhalten. Im einzelnen gelten hier die folgenden Angaben:In addition to the selection according to the invention of dipentaerythritol as the central polyol component for the preparation of the new synthetic pololyesters according to the invention, the selection of the monofunctional carboxylic acid components used for the esterification and, if desired, also used in minor amounts is of crucial importance. The fatty acids used for the esterification can be divided into the classes A to E listed below, the fatty acid classes A and B relating to monocarboxylic acids, while the acid classes C, D and E contain higher-functional carboxylic acids. The following details apply here:

Säuren der Klasse A: Verzweigte Fettsäuren im C-Kettenbereich von C₈ bis C₁₆Class A acids: Branched fatty acids in the C chain range from C₈ to C₁₆

Säuren der Klasse B: Lineare Fettsäuren im C-Kettenbereich von C₈ bis C₁₄, bevorzugt im Bereich von C₈ bis C₁₀.Class B acids: linear fatty acids in the C chain range from C₈ to C₁₄, preferably in the range from C₈ to C₁₀.

Die neuen synthetischen Polyolester der Erfindung können als Fettsäurekomponenten ausschließlich verzweigte Fettsäuren aus der Klasse A oder aber auch Gemische aus verzweigten Fettsäuren der Klasse A mit linearen Fettsäuren aus der Klasse B enthalten. Einzelheiten zu den dabei bevorzugten Mischungsverhältnissen werden im nachfolgenden noch angegeben.The new synthetic polyol esters of the invention can contain exclusively branched fatty acids from class A or else mixtures of branched fatty acids of class A with linear fatty acids from class B as fatty acid components. Details of the preferred mixing ratios are given below.

Die gewünschtenfalls zusammen mit den verzweigten Fettsäuren (Klasse A) oder mit den Gemischen aus verzweigten und linearen Fettsäuren (Klassen A + D) eingesetzten mehrfunktionellen Carbonsäuren sind in die nachfolgenden Klassen einzuordnen:If desired, the multifunctional carboxylic acids used together with the branched fatty acids (class A) or with the mixtures of branched and linear fatty acids (classes A + D) can be classified in the following classes:

Säuren der Klasse C: Di- und/oder Tricarbonsäuren im C- Zahlbereich von C₆ bis C₅₄. Besonders bevorzugt sind hier die Adipinsäure, die Trimethyladipinsäure, die Azelainsäure und/oder die Sebacinsäure. Weitere geeignete und besonders bevorzugte polyfunktionelle Säuren dieser Klasse sind Di- beziehungsweise Trimerfettsäuren aus der Polymerisation von ein- und/oder mehr­fach ungesättigten Fettsäuren im C-Bereich C₁₆ bis C₂₂.Class C acids: di- and / or tricarboxylic acids in the C number range from C₆ to C₅₄. Adipic acid, trimethyladipic acid, azelaic acid and / or sebacic acid are particularly preferred here. Further suitable and particularly preferred polyfunctional acids of this class are di- or trimer fatty acids from the polymerization of mono- and / or polyunsaturated fatty acids in the C range from C₁₆ to C₂₂.

Säuren der Klasse D: Erfasst sind hier difunktionelle Fettsäuren, die durch Anlagerung von Acrylsäuren an die Doppelbindungen von Ölsäure, Linolsäure und/oder Linolensäure erhalten werden. Insbesondere geeignet sind entsprechende Anlagerungsprodukte an die in der Praxis anfallenden Gemische der drei genannten ungesättigten Säuren. Die Her­stellung solcher difunktionellen Säuren dieser Klasse D ist beispielsweise beschrieben in den DE-OS 24 06 401 und DE-OS 22 53 930.Class D acids: This covers difunctional fatty acids obtained by adding acrylic acids to the double bonds of oleic acid, linoleic acid and / or linolenic acid. Corresponding addition products to the mixtures of the three unsaturated acids mentioned which are obtained in practice are particularly suitable. The preparation of such difunctional acids of this class D is described for example in DE-OS 24 06 401 and DE-OS 22 53 930.

Säuren der Klasse E: Cyclische Polycarbonsäuren von aromatischer und/oder paraffinischer Natur mit 2 bis 6 Säurefunktionen. Besonders bevorzugt sind hier Terephthalsäure, Trimellithsäure, Pyromellithsäure und/oder Cyclohexancarbonsäure, die zur Herstellung der neuen synthetischen Polyolester als solche oder auch in Form ihrer Anhydride zum Einsatz kommen können.Class E acids: Cyclic polycarboxylic acids of aromatic and / or paraffinic nature with 2 to 6 acid functions. Particularly preferred here are terephthalic acid, trimellitic acid, pyromellitic acid and / or cyclohexane carboxylic acid, which can be used as such or in the form of their anhydrides for the preparation of the new synthetic polyol esters.

Erfindungsgemäße synthetische Polyolester der genannten Art ent­sprechen bezüglich ihrer mengenmäßigen Definition an die Polyol­ester bildenden Reaktanten - insbesondere bezüglich der einge­setzten Carbonsäurekomponenten - den folgenden Definitionen, wobei sich die in folgenden angeführten Äquivalente an Säure­komponenten jeweils auf 1 Mol Dipentaerythrit - das heißt 6 Hydroxyl-Äquivalente - beziehen:

  • 1. 6 Äquivalente einer oder mehrerer Fettsäuren aus der Klasse A
  • 2. Gemische aus 1 bis 4 Äquivalenten von verzweigten Fettsäuren der Klasse A und 2 bis 5 Äquivalente von linearen Fettsäuren der Klasse B
  • 3. 4 bis 5,8 Äquivalente eines Gemisches von Säuren gemäß I mit o,2 bis 2 Äquivalenten von Fettsäuren aus den Klassen C und/oder D und/oder E sowie
  • 4. 4 bis 5,8 Äquivalente eines Gemisches gemäß II mit 0,2 bis 2 Äquivalenten von Fettsäuren aus den Klassen C und/oder D und/oder E.
Synthetic polyol esters according to the invention of the type mentioned correspond to the following definitions with regard to their quantitative definition of the reactants forming the polyol esters - in particular with regard to the carboxylic acid components used, the equivalents of acid components listed below each referring to 1 mol of dipentaerythritol - that is to say 6 hydroxyl equivalents :
  • 1. 6 equivalents of one or more fatty acids from class A
  • 2. Mixtures of 1 to 4 equivalents of class A branched fatty acids and 2 to 5 equivalents of class B linear fatty acids
  • 3. 4 to 5.8 equivalents of a mixture of acids according to I with o, 2 to 2 equivalents of fatty acids from classes C and / or D and / or E as well
  • 4. 4 to 5.8 equivalents of a mixture according to II with 0.2 to 2 equivalents of fatty acids from classes C and / or D and / or E.

Im Sinne der Erfindung sind synthetische Polyolester der genannten Art mit möglichst geringen Säurezahlen bevorzugt, wobei insbesondere neutrale Ester oder solche mit einem be­schränkten Überschuß an freien Hydroxylgruppen betroffen sind.For the purposes of the invention, synthetic polyol esters of the type mentioned with the lowest possible acid numbers are preferred, neutral esters or those with a limited excess of free hydroxyl groups are particularly affected.

In einer besonders bevorzugten Ausführungsform der Erfindung werden bei der Herstellung der Ester auf 6 Äquivalente der ein­gesetzten Säuren beziehungsweise Säuregemische 6,0 bis 7,2 Äquivalente (entsprechend 1 bis 1,2 Mol) Dipentaerythrit verwendet. Bevorzugte Polyolester dieser Art zeigen Hydroxyl­zahlen im Bereich von 0 bis etwa 25. In a particularly preferred embodiment of the invention, 6.0 to 7.2 equivalents (corresponding to 1 to 1.2 mol) of dipentaerythritol are used in the preparation of the esters per 6 equivalents of the acids or acid mixtures used. Preferred polyol esters of this type show hydroxyl numbers in the range from 0 to about 25.

Erfindungsgemäß bevorzugte Ester haben weiterhin Viskositäts­werte bei 40 °C im Bereich von 50 bis 1000 mm²/s und besitzen Stockpunkte im Bereich von etwa 0 bis -30 °C.Esters preferred according to the invention furthermore have viscosity values at 40 ° C. in the range from 50 to 1000 mm 2 / s and have pour points in the range from approximately 0 to -30 ° C.

Bei ausschließlicher Verwendung von verzweigten Fettsäuren (Säureklasse A) - insbesondere beim Einsatz von 2-Ethyl-hexan­säure, Isononansäure, Isodecansäure und/oder Isotridecansäure - erhält man Ester im Viskositätsklassenbereich (Definition nach ISO 3448 beziehungsweise DIN 51 519) ISO VG 320 bis 460.With the exclusive use of branched fatty acids (acid class A) - especially when using 2-ethyl-hexanoic acid, isononanoic acid, isodecanoic acid and / or isotridecanoic acid - esters in the viscosity class range (definition according to ISO 3448 or DIN 51 519) ISO VG 320 to 460.

Durch Mitverwendung von linearen Fettsäuren wird die Viskosität der hergestellten Polyolester erniedrigt auf den Viskositäts­klassenbereich ISO VG 46 bis ISO VG 220. Will man die Viskosität der Ester erhöhen, so ist die Mitverwendung von zwei- und mehrbasischen Säuren aus den zuvor aufgezählten Säureklassen C, D und/oder E unabdingbar.By using linear fatty acids, the viscosity of the polyol esters produced is reduced to the viscosity class range ISO VG 46 to ISO VG 220. If you want to increase the viscosity of the esters, the use of dibasic and polybasic acids from the acid classes C, D and / or E indispensable.

Aufgrund ihrer hohen termischen Stabilität, geringsten Ver­dampfungsverlusten bei 250 °C und höher sowie Flammpunkten von ca. 300 °C stellen die erfindungsgemäßen neuen Polyolester geeignete Trägeröle für temperaturbelastbare Schmieröldis­persionen und Schmierfette dar und sind darüber hinaus wegen ihrer guten tribologischen Eigenschaften - z.B. einem ausgezeichneten Druckaufnahmevermögen - auch als Zusatz­ komponenten oder im Alleineinsatz für Hydraulik- und Getriebeöle geeignet. Übliche Zusatzstoffe wie Oxidations- und Korrosionsinhibitoren, Dispergiermittel, Hochdruckzusätze Antischaummittel, Metalldesaktivatoren und andere Zusatzstoffe können in den üblichen wirksamen Mengen zugesetzt werden.Due to their high thermal stability, lowest evaporation losses at 250 ° C and higher and flash points of approx. 300 ° C, the new polyol esters according to the invention are suitable carrier oils for temperature-resistant lubricating oil dispersions and greases and are also due to their good tribological properties - for example an excellent pressure absorption capacity - also as an addition components or used alone for hydraulic and gear oils. Usual additives such as oxidation and corrosion inhibitors, dispersants, high pressure additives, anti-foaming agents, metal deactivators and other additives can be added in the usual effective amounts.

BeispieleExamples Allgemeine Arbeitsanweisungen zur Herstellung der PolyesterGeneral working instructions for the production of the polyester HerstellungsweiseProduction method

Dipentaerythrit und das gewählte Fettsäuregemisch werden in Gegenwart von 0,5 % Zinnschliff bei 240 °C 6 bis 8 Stunden lang unter Abdestillation des bei der Reaktion gebildeten Wassers verestert. Gegen Ende der Reaktion wird bei gleicher Tempera­tur, aber vermindertem Druck, weiterverestert. Nach dem Abkühlen auf 120 °C werden 1 Gewichtsprozent aktivierte Bleicherde zugesetzt, nochmals auf 200 °C erwärmt und über­schüssige Monocarbonsäure im Vakuum abdestilliert. Nach Abkühlen wird das Reaktionsgemisch filtriert.

Figure imgb0001
Figure imgb0002
 Dipentaerythritol and the selected fatty acid mixture are esterified in the presence of 0.5% tin grinding at 240 ° C. for 6 to 8 hours while distilling off the water formed in the reaction. Towards the end of the reaction, esterification continues at the same temperature but under reduced pressure. After cooling to 120 ° C., 1 percent by weight of activated bleaching earth is added, the mixture is heated again to 200 ° C. and excess monocarboxylic acid is distilled off in vacuo. After cooling, the reaction mixture is filtered.
Figure imgb0001
Figure imgb0002

Nähere Einzelheiten zu den Produkteigenschaften der Polyolester gemäß Beispiel 1 und Beispiel 5 sind im nachfolgenden zusammengefaßt.Further details on the product properties of the polyol esters according to Example 1 and Example 5 are summarized below.

Beispiel 1example 1

Kinematische Viskosität bei 20 °C: ca. 1816 mm²/s
bei 40°C: ca. 361 mm²/s
bei 100°C: ca. 25 mm²/sKinematic viscosity at 20 ° C: approx. 1816 mm² / s
at 40 ° C: approx. 361 mm² / s
at 100 ° C: approx. 25 mm² / s

Viskositätsindex : ca. 90

Figure imgb0003
Viscosity index: approx. 90
Figure imgb0003

Thermogravimetrische Analyse (Flüchtigkeit)Thermogravimetric analysis (volatility)

Die Temperatur-/Gewichtsanalyse gibt den Massenverlust der Substanz in Prozent an, der bei einer Erwärmung mit einem kontinuierlichen Temperaturanstieg von 20 °C pro Minute auftritt.The temperature / weight analysis gives the mass loss of the substance in percent, which occurs when heated with a continuous temperature rise of 20 ° C per minute.

Beispiel 5Example 5

Kinematische Viskosität bei 20 °C: ca. 1800 mm²/s
bei 40 °C: ca 440 mm²/s
bei 100 °C: ca. 35 mm²/sKinematic viscosity at 20 ° C: approx. 1800 mm² / s
at 40 ° C: approx. 440 mm² / s
at 100 ° C: approx. 35 mm² / s

Viskositätsindex : ca. 120
Stockpunkt : ca. - 30 °C

Figure imgb0004
Viscosity index: approx. 120
Pour point: approx. - 30 ° C
Figure imgb0004

SRV-Methode:SRV method:

R. Schumann, ant. "Antriebstechnik" 19 (1980) Nr. 1 -2R. Schumann, ant. "Drive Technology" 19 (1980) No. 1 -2

Claims (7)

1. Synthetische Polyolester mit Schmieröleigenschaften auf Basis im wesentlichen neutraler Veresterungsprodukte eines polyfunktionellen Alkohols mit ausgewählten Monocarbonsäuren und gewünschtenfalls mehrfunktionellen Carbonsäuren, dadurch gekennzeichnet, daß die polyfunktionelle Alkoholkomponente Dipentaerythrit ist, der mit
I verzweigten Fettsäuren im C-Kettenbereich von C₈ bis C₁₆ (Säuren der Klasse A) oder mit
II Gemischen von linearen Fettsäuren im C-Kettenbereich von C₈ bis C₁₄ (Säuren der Klasse B) in Abmischung mit verzweigten Fettsäuren der Klasse A
verestert ist und dabei gewünschtenfalls zusätzlich beschränkte Mengen an mehrfunktionellen Carbonsäuren der nachfolgenden Klassen C, D und/oder E in das Polyolestermolekül einkonden­siert, enthält:
Säuren der Klasse C: Di-und/oder Tricarbonsäuren im Bereich von C₆ bis C₅₄,
Säuren der Klasse D: Difunktionelle Fettsäuren, die durch Anlagerung von Acrylsäure an die Doppelbindungen von Öl-, Linol- und/oder Linolensäure hergestellt worden sind,
Säuren der Klasse E: Aromatische und/oder paraffinische, cyclische Polycarbonsäuren mit 2 bis 6 Säurefunktionen.1. Synthetic polyol esters with lubricating oil properties based on essentially neutral esterification products of a polyfunctional alcohol with selected monocarboxylic acids and, if desired, polyfunctional carboxylic acids, characterized in that the polyfunctional alcohol component is dipentaerythritol, which with
I branched fatty acids in the C chain range from C₈ to C₁₆ (acids of class A) or with
II Mixtures of linear fatty acids in the C chain range from C₈ to C₁₄ (acids of class B) in admixture with branched fatty acids of class A.
is esterified and, if desired, additionally condensed limited amounts of polyfunctional carboxylic acids of the following classes C, D and / or E into the polyol ester molecule contains:
Class C acids: di- and / or tricarboxylic acids in the range from C₆ to C₅₄,
Class D acids: difunctional fatty acids which have been prepared by adding acrylic acid to the double bonds of oleic, linoleic and / or linolenic acid,
Class E acids: Aromatic and / or paraffinic, cyclic polycarboxylic acids with 2 to 6 acid functions. 2. Synthetische Polyolester nach Anspruch 1, dadurch gekenn­zeichnet, daß beim gemeinsamen Einsatz von Resten der Säuren aus den Klassen A und B im Polyolester Äquivalentverhältnisse von 1 bis 4 Äquivalenten an Säureresten der Klasse A auf 2 bis 5 Äquivalente an Säureresten der Klasse B bei insgesamt wenigstens stöchiometrischen Mengen - bezogen auf die 6 Hydroxyl-Äquivalente des Dipentaerythrits - zugegen sind.2. Synthetic polyol esters according to claim 1, characterized in that when residues of the acids from classes A and B are used together in the polyol ester, equivalent ratios of 1 to 4 equivalents of acid residues of class A to 2 to 5 equivalents of acid residues of class B in total at least stoichiometric amounts - based on the 6 hydroxyl equivalents of dipentaerythritol - are present. 3. Synthetische Polyolester nach Ansprüchen 1 und 2, dadurch gekennzeichnet, daß bei Mitverwendung von Säuren der Klassen C, D und/oder E die Säurereste im Polyester in den folgenden Äquivalentverhältnissen vorliegen - jeweils bezogen wieder auf die 6 Hydroxyläquivalente des Dipentaerythrits bei wenigstens stöchiometrischen Verhältnissen von Hydroxyl-/Säuregruppen -
4 bis 5,8 Äquivalente von Säuren der Klasse A beziehungsweise des Gemisches von Säuren der Klassen A und B mit
0,2 bis 2 Äquivalenten von Säuren der Klassen C, D und/oder E.3. Synthetic polyol esters according to Claims 1 and 2, characterized in that when acids of classes C, D and / or E are used, the acid residues in the polyester are present in the following equivalent ratios - in each case again based on the 6 hydroxyl equivalents of dipentaerythritol in at least stoichiometric ratios of hydroxyl / acid groups -
4 to 5.8 equivalents of Class A acids or the mixture of Class A and B acids with
0.2 to 2 equivalents of Class C, D and / or E acids. 4. Synthetische Polyester nach Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß als Säuren der Klassen B, C und/oder E wenigstens anteilsweise die folgenden Komponenten ausgewählt sind. Klasse B: Lineare Fettsäuren des C-Kettenbereichs von C₈ bis C₁₀, Klasse C: Adipinsäure, Trimethyladipinsäure, Azelainsäure und/oder Sebacinsäure sowie Di- beziehungsweise Trimerfettsäuren aus der Polymerisation von ein- oder mehrfach ungesättigten Fettsäuren im C-Bereich C₁₆ bis C₂₂, Klasse E: Terephthalsäure, Trimellithsäure, Pyromellithsäure und/oder Cyclohexancarbonsäure beziehungsweise deren Anhydride. 4. Synthetic polyester according to claims 1 to 3, characterized in that the following components are selected at least in part as acids of classes B, C and / or E. Class B: linear fatty acids of the C chain range from C₈ to C₁₀, Class C: adipic acid, trimethyladipic acid, azelaic acid and / or sebacic acid and di- or trimer fatty acids from the polymerization of mono- or polyunsaturated fatty acids in the C range from C₁₆ to C₂₂, Class E: terephthalic acid, trimellitic acid, pyromellitic acid and / or cyclohexane carboxylic acid or their anhydrides. 5. Synthetische Polyolester nach Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß sie eine OH-Zahl bis etwa 25 bei einem Dipentaerythrit-Überschuß bis etwa 0,2 Mol/Mol vollverestertem Dipentaerythrit aufweisen.5. Synthetic polyol esters according to Claims 1 to 4, characterized in that they have an OH number of up to about 25 with an excess of dipentaerythritol up to about 0.2 mol / mol of fully esterified dipentaerythritol. 6. Synthetische Polyolester nach Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß sie Viskositätswerte bei 40°C im Bereich von 50 bis 1000 mm²/s und Stockpunkte im Temperaturbereich von 0 bis minus 30 °C aufweisen.6. Synthetic polyol esters according to Claims 1 to 5, characterized in that they have viscosity values at 40 ° C in the range from 50 to 1000 mm² / s and pour points in the temperature range from 0 to minus 30 ° C. 7. Verwendung der synthetischen Polyolester nach Anprüchen 1 bis 6 zur Herstellung von temperaturbelastbaren Schmieröl­dispersionen und/oder Schmierfetten.7. Use of the synthetic polyol esters according to claims 1 to 6 for the production of temperature-resistant lubricating oil dispersions and / or greases.
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JPS5651433A (en) * 1979-10-04 1981-05-09 Nippon Kayaku Co Ltd Preparation of mixture of dipentaerythritol esters
US4477383A (en) * 1982-05-05 1984-10-16 National Distillers And Chemical Corporation Di- and tripentaerythritol esters of isostearic acid
US4589900A (en) * 1983-03-17 1986-05-20 United Technologies Corporation High-strength thermally stable magnesium aluminosilicate glass-ceramic matrix sic fiber composite
US4589990A (en) * 1985-06-21 1986-05-20 National Distillers And Chemical Corporation Mist lubricant compositions
US4645615A (en) * 1986-02-27 1987-02-24 Fmc Corporation Fire-resistant hydraulic fluid

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0406479A1 (en) * 1989-07-05 1991-01-09 Japan Energy Corporation Refrigeration lubricants
EP0480479A3 (en) * 1989-07-05 1992-06-17 Kyodo Oil Technical Research Center Co., Ltd. Refrigeration lubricants
EP0536814A1 (en) * 1989-07-05 1993-04-14 Japan Energy Corporation use of a lubricant for compressors using a hydrofluorocarbon refrigerant containing no chlorine.
US6029459A (en) * 1990-11-16 2000-02-29 Hitachi, Ltd. Refrigeration cycle
EP0518567A1 (en) * 1991-06-07 1992-12-16 Hatco Corporation Synthetic lubricant base stock formed from high content branched chain acid mixtures
US5833876A (en) * 1992-06-03 1998-11-10 Henkel Corporation Polyol ester lubricants for refrigerating compressors operating at high temperatures
US5853609A (en) * 1993-03-10 1998-12-29 Henkel Corporation Polyol ester lubricants for hermetically sealed refrigerating compressors
WO1994021581A1 (en) * 1993-03-15 1994-09-29 Henkel Kommanditgesellschaft Auf Aktien Alkylene-bridged polyol ethers and their esters
WO1996017909A1 (en) * 1994-12-08 1996-06-13 Exxon Chemical Patents Inc. Biodegradable branched synthetic ester base stocks and lubricants formed therefrom
US5817607A (en) * 1994-12-08 1998-10-06 Exxon Chemical Patents Inc. Biodegradable branched synthetic ester base stocks and lubricants formed therefrom
EP0890634A1 (en) * 1997-07-09 1999-01-13 Voith Turbo GmbH & Co. KG Working fluid for hydrodynamic machine

Also Published As

Publication number Publication date
JP2661927B2 (en) 1997-10-08
EP0272575B2 (en) 1995-12-13
JPS63170337A (en) 1988-07-14
BR8706979A (en) 1988-07-26
DE3643935C2 (en) 1995-07-06
ES2052537T3 (en) 1994-07-16
EP0272575A3 (en) 1989-08-09
CA1317974C (en) 1993-05-18
EP0272575B1 (en) 1992-09-16
US5057247A (en) 1991-10-15
MX169267B (en) 1993-06-28
DE3781782D1 (en) 1992-10-22
ES2052537T5 (en) 1996-03-01
DE3643935A1 (en) 1988-06-23
ATE80607T1 (en) 1992-10-15

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