EP0272575B1 - High viscosity, neutral polyolesters - Google Patents

High viscosity, neutral polyolesters Download PDF

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Publication number
EP0272575B1
EP0272575B1 EP87118481A EP87118481A EP0272575B1 EP 0272575 B1 EP0272575 B1 EP 0272575B1 EP 87118481 A EP87118481 A EP 87118481A EP 87118481 A EP87118481 A EP 87118481A EP 0272575 B1 EP0272575 B1 EP 0272575B1
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EP
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Prior art keywords
acids
class
acid
fatty acids
dipentaerythritol
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EP87118481A
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German (de)
French (fr)
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EP0272575A2 (en
EP0272575B2 (en
EP0272575A3 (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.
  • US Pat. No. 4,234,497 describes polyol esters based on one or more polyhydric alcohols with 2 to 8 hydroxyl groups, isopalmitic acid and one or more monocarboxylic acids with 5 to 11 carbon atoms, which serve as the basis for synthetic lubricants. Dipentaerythritol is also mentioned as a polyhydric alcohol; Both straight-chain and branched can be used as monocarboxylic acids. These polyol esters are characterized, among other things, by good viscosity properties and by low pour points.
  • the present invention is based on the object of providing new synthetic polyol esters which are particularly suitable for use in the field of temperature-resistant lubricating oils such as gear and hydraulic oils and lubricating oil dispersions or lubricating greases and which are also optimally adapted to the aforementioned selection criteria can be.
  • the technical solution to this problem according to the invention is based on the selection of a specific polyol component as a hydroxyl group function for the production of the polyol esters and combines this selection on the side of the hydroxyl group component with a specific selection of mono- and polyfunctional carboxylic acids on the acid side for the production of the new ones synthetic polyol esters.
  • 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 new synthetic polyol esters of the invention can be branched as fatty acid components Contain fatty acids from class A or mixtures of branched fatty acids of class A with linear fatty acids from class B. Details of the preferred mixing ratios are given below.
  • 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 being 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 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.
  • the nice polyol esters according to the invention are suitable carrier oils for temperature-resistant lubricating oil dispersions and lubricating greases and are moreover due to their good tribological properties - e.g. excellent pressure absorption capacity - also suitable as additional 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 in the presence of 0.5% tin grinding at 240 ° C esterified 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.
  • 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.

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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

Synthetic polyol esters with lubricating oil properties based on substantially neutral esterification products of a polyhydric alcohol with selected monocarboxylic acids and, optionally, polybasic carboxylic acids, wherein the polyfunctional alcohol component is dipentaerythritol which is esterified with I-branched C8-C16 fatty acids (class A acids) or with II-mixtures of linear C8-C14 fatty acids (class B acids) with branched fatty acids of class A and, optionally, limited quantities of polybasic carboxylic acids of the following classes C, D and/or E incorporated in the polyester molecular by condensation: class C acids: di- and/or tricarboxylic acids in the range from C6 to C54 class D acids: difunctional fatty acids which have been obtained by addition of acrylic acid onto the double bonds of oleic acid, linoleic acid and/or linolenic acid class E acids: aromatic and/or paraffinic, cyclic polycarboxylic acids containing from 2 to 6 acid functions.

Description

Synthetische Ester, sogenannte Esteröle, haben in den letzten Jahren als hochwertige 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 US-A-4 234 497 beschreibt Polyolester auf Basis von einem oder mehreren mehrwertigen Alkoholen mit 2 bis 8 Hydroxylgruppen, Isopalmitinsäure und einer oder mehreren Monocarbonsäuren mit 5 bis 11 C-Atomen, die als Grundstock für synthetische Schmiermittel dienen. Als mehrwertiger Alkohol wird neben anderen auch Dipentaerythrit genannt; als Monocarbonsäuren kommen sowohl geradkettige als auch verzweigte in Frage. Diese Polyolester zeichnen sich unter anderem durch gute Viskositätseigenschaften sowie durch niedere Stockpunkte aus.US Pat. No. 4,234,497 describes polyol esters based on one or more polyhydric alcohols with 2 to 8 hydroxyl groups, isopalmitic acid and one or more monocarboxylic acids with 5 to 11 carbon atoms, which serve as the basis for synthetic lubricants. Dipentaerythritol is also mentioned as a polyhydric alcohol; Both straight-chain and branched can be used as monocarboxylic acids. These polyol esters are characterized, among other things, by good viscosity properties and by low pour points.

Demgegenüber geht die vorliegende Erfindung 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.In contrast, the present invention is based on the object of providing new synthetic polyol esters which are particularly suitable for use in the field of temperature-resistant lubricating oils such as gear and hydraulic oils and lubricating oil dispersions or lubricating greases and which are also optimally adapted to the aforementioned selection criteria can be.

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 Hydroxylgruppenkomponente mit einer bestimmten Auswahl von ein- und 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 a hydroxyl group function for the production of the polyol esters and combines this selection on the side of the hydroxyl group component with a specific selection of mono- and polyfunctional carboxylic acids on the acid side for the production of the new ones synthetic polyol esters.

Gegenstand der Erfindung sind dementsprechend in einer ersten Ausführungsform synthetische Polyolester mit Schmieröleigenschaften auf Basis im wesentlichen neutraler Veresterungsprodukte von Dipentaerythrit mit verzweigten Monocarbonsäuren und ausgewählten Carbonsäuren, dadurch gekennzeichnet, daß Dipentaerythrit mit

  • I verzweigten Fettsäuren im C-Kettenbereich von C8 bis C16 6 (Säuren der Klasse A) oder mit
  • 11 Gemischen von linearen Fettsäuren im C-Kettenbereich C8 bis C14 (Säuren der Klasse B) in
Accordingly, the invention relates in a first embodiment to synthetic polyol esters with lubricating oil properties based on essentially neutral esterification products of dipentaerythritol with branched monocarboxylic acids and selected carboxylic acids, characterized in that dipentaerythritol with
  • I branched fatty acids in the C chain range from C 8 to C16 6 (acids of class A) or with
  • 11 Mixtures of linear fatty acids in the C chain range C 8 to C 14 (acids of class B) in

Abmischung mit verzweigten Fettsäuren der Klasse A verestert ist und dabei 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 CS4,
  • 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
Mixture is esterified with branched fatty acids of class A and additionally contains limited amounts of polyfunctional carboxylic acids of the following classes C, D and / or E condensed into the polyol ester molecule:
  • Class C acids: di- and / or tricarboxylic acids in the range from C 6 to C S4 ,
  • 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

Säurefunktionen.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 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:

  • Säuren der Klasse A: Verzweigte Fettsäuren im C-Kettenbereich von C8 bis C,6, insbesondere 2-Ethyl-hexansäure, Isononansäure, Isodecansäure und/ oder Isotridecansäure,
  • Säuren der Klasse B: Lineare Fettsäuren im C-Kettenbereich von C8 bis C14, bevorzugt im Bereich
In addition to the selection of dipentaerythritol according to the invention as the central polyol component for the production of the new synthetic pololyesters according to the invention, the selection of the monofunctional carboxylic acid components used for the esterification and in minor amounts also used 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 C 8 to C, 6 , in particular 2-ethyl-hexanoic acid, isononanoic acid, isodecanoic acid and / or isotridecanoic acid,
  • Class B acids: linear fatty acids in the C chain range from C 8 to C 14 , preferably in the range

von C8 bis C, o.from C 8 to C, o.

Die neuen synthetischen Polyolester der Erfindung können als Fettsäurekomponenten 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 be branched as fatty acid components Contain fatty acids from class A or mixtures of branched fatty acids of class A with linear fatty acids from class B. Details of the preferred mixing ratios are given below.

Die zusammen mit den verzweigten Fettsäuren (Klasse A) oder mit den Gemischen aus verzweigten und linearen Fettsäuren (Klassen A + B) eingesetzten mehrfunktionellen Carbonsäuren sind in die nachfolgenden Klassen einzuordnen:

  • 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- oder Trimerfettsäuren aus der Polymerisation von ein- und/oder mehrfach ungesättigten Fettsäuren im C-Bereich C16 bis 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-A-24 06 401 und DE-A-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.
The polyfunctional carboxylic acids used together with the branched fatty acids (class A) or with the mixtures of branched and linear fatty acids (classes A + B) can be classified into the following classes:
  • Class C acids: di- and / or tricarboxylic acids in the C number range from C 6 to C 54 . 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 C 16 to C 22 .
  • Class D acids: This covers difunctional fatty acids which are obtained by the addition of 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-A-24 06 401 and DE-A-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.

Erfindungsgemäße synthetische Polyolester der genannten Art entsprechen bezüglich ihrer mengenmä- ßigen 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. 4 bis 5,8 Äquivalente eines Gemisches von Säuren gemäß I mit 0,2 bis 2 Äquivalenten von Fettsäuren aus den Klassen C und/oder D und/oder E sowie
  • 2. 4 bis 5,8 Äquivalente eines Gemisches gemäß 11 mit 0,2 bis 2 Äquivalenten von Fettsäuren aus den Klassen C und/oder D und/oder E,
    wobei beim Einsatz eines Gemisches gemäß II
In terms of their quantitative definition of the reactants forming the polyol esters - in particular with regard to the carboxylic acid components used - synthetic polyol esters of the type mentioned according to the invention correspond to the following definitions, the equivalents of acid components given below being based on 1 mol of dipentaerythritol - that is to say 6 hydroxyl equivalents - Respectively:
  • 1. 4 to 5.8 equivalents of a mixture of acids according to I with 0.2 to 2 equivalents of fatty acids from classes C and / or D and / or E as well
  • 2. 4 to 5.8 equivalents of a mixture according to 11 with 0.2 to 2 equivalents of fatty acids from classes C and / or D and / or E,
    where when using a mixture according to II

Gemische aus 1 bis 4 Äquivalenten von verzweigten Fettsäuren der Klasse A und 2 bis 5 Äquivalente von linearen Fettsäuren der Klasse B Verwendung finden.Mixtures of 1 to 4 equivalents of branched fatty acids of class A and 2 to 5 equivalents of linear fatty acids of class B are used.

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 being 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 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 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.

Aufgrund ihrer hohen termischen Stabilität, geringsten Verdampfungsverlusten bei 250 ° C und höher sowie Flammpunkten von ca. 300 ° C stellen die erfindungsgemäßen netten Polyolester geeignete Träger- öle für temperaturbelastbare Schmieröldispersionen und Schmierfette dar und sind darüber hinaus wegen ihrer guten tribologischen Eigenschaften - z.B. einem ausgezeichneten Druckaufnahmevermögen - auch als Zusatzkomponenten 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 nice polyol esters according to the invention are suitable carrier oils for temperature-resistant lubricating oil dispersions and lubricating greases and are moreover due to their good tribological properties - e.g. excellent pressure absorption capacity - also suitable as additional 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 in the presence of 0.5% tin grinding at 240 ° C esterified 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 3 sind im nachfolgenden zusammengefaßt.Further details on the product properties of the polyol esters according to Example 3 are summarized below.

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 3Example 3

Figure imgb0003
Verschleißkennwerte

  • a) Shell-Vierkugel-Apparat
  • VKA-Schweißkraft (DIN 51 350) Teil 2
  • ca. 1500 N
  • Kalottendurchmesser (DIN 51 350, Teil 3)
  • ca. 1,05 mm bei 600 N Belastung
  • b) Optimol "SRV-Gerät"
  • Schweißkraft: ca. 400 N bei 100 ° C
  • Reibungskoeffizient (µ) bei 100 ° C und 100 N
  • min.: ca. 0,105
  • max.: ca. 0,129
Figure imgb0003
 Wear parameters
  • a) Shell four-ball apparatus
  • VKA welding force (DIN 51 350) part 2
  • approx. 1500 N
  • Calotte diameter (DIN 51 350, part 3)
  • 1.05 mm at 600 N load
  • b) Optimol "SRV device"
  • Welding force: approx. 400 N at 100 ° C
  • Friction coefficient (µ) at 100 ° C and 100 N.
  • min .: approx. 0.105
  • max .: approx. 0.129

SRV-Methode:

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

Claims (6)

1. Synthetic polyol esters with lubricating oil properties based on substantially neutral esterification products of dipentaerythritol with branched monocarboxylic acids and selected carboxylic acids,
characterized in that dipentaerythritol is esterified with
I branched C8 -16 fatty acids (class A acids) or with
II mixtures of linear C8-14 fatty acids (class B acids) in admixture with branched class A fatty acids and additionally contains limited quantities of polybasic carboxlic acids of the following classes C, D and/or E incorporated in the polyester molecule by condensation:
class C acids: di- and/or tricarboxylic acids in the range from C6 to C54
class D acids: difunctional fatty acids which have been obtained by addition of acrylic acid onto the double bonds of oleic acid, linoleic acid and/or linolenic acid
class E acids: aromatic and/or paraffinic, cyclic polycarboxylic acids containing from 2 to 6 acid functions.
2. Synthetic polyol esters as claimed in claim 1, characterized in that the acid residues are present in the polyester in the following equivalent ratios based on the 6 hydroxyl equivalents of the dipentaerythritol for at least stoichiometric ratios of hydroxyl to acid groups:
from 4 to 5.8 equivalents of class A acids or of the mixture of class A and class B acids with 0.2 to 2 equivalents of class C, class D and/or class E acids; where residues of the class A and B acids are used together, equivalent ratios of
1 to 4 equivalents of class A acid residues to 2 to 5 equivalents of class B acid residues are present in the polyester.
3. Synthetic polyesters as claimed in claims 1 and 2, characterized in that the following components are selected as class B, class C and/or class E acids:
class B: linear C8 -1 fatty acids
class C: adipic acid, trimethyl adipic acid, azelaic acid and/or sebacic acid and also di- and trimer fatty acids from the polymerization of mono- or polyunsaturated C16-22 fatty acids, class E: terephthalic acid, trimellitic acid, pyromellitic acid and/or cyclohexane carboxylic acid or their anhydrides.
4. Synthetic polyol esters as claimed in claims 1 to 3, characterized in that they have an OH value of up to 25 for a dipentaerythritol excess of up to 0.2 mol/mol fully esterified dipentaerythritol.
5. Synthetic polyol esters as claimed in claims 1 to 4, characterized in that they have viscosity values at 40 °C of from 50 to 1000 mm2/s and pour points of from 0 to -30 C.
6. The use of the synthetic polyol esters claimed in claims 1 to 5 for the production of temperature-stable lubricating oil dispersions and/or lubricating greases.
EP87118481A 1986-12-22 1987-12-14 High viscosity, neutral polyolesters Expired - Lifetime EP0272575B2 (en)

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DE3643935A DE3643935C2 (en) 1986-12-22 1986-12-22 Synthetic polyol esters
DE3643935 1986-12-22

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Families Citing this family (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR950005694B1 (en) * 1989-07-05 1995-05-29 가부시끼가이샤 교오세끼 세이힝기주쓰 겡뀨쇼 Refrigeration lubricants
DE3927155A1 (en) * 1989-08-17 1991-02-21 Henkel Kgaa ENVIRONMENTALLY FRIENDLY BASIC OIL FOR THE FORMULATION OF HYDRAULIC OILS
JP2967574B2 (en) * 1990-11-16 1999-10-25 株式会社日立製作所 Refrigeration equipment
EP0518567B1 (en) * 1991-06-07 2000-09-13 Hatco Corporation Synthetic lubricant base stock formed from high content branched chain acid mixtures
US20030104956A1 (en) * 1994-04-28 2003-06-05 Schaefer Thomas G. Synthetic lubricant base stock formed from high content branched chain acid mixtures
JP3001679B2 (en) * 1991-07-19 2000-01-24 出光興産株式会社 Lubricating oil composition for two-stroke engine or rotary engine
DE4214653A1 (en) * 1992-05-02 1993-11-04 Henkel Kgaa ENGINE BASE OIL WITH IMPROVED SEALING COMPATIBILITY
US5976399A (en) 1992-06-03 1999-11-02 Henkel Corporation Blended polyol ester lubricants for refrigerant heat transfer fluids
US6183662B1 (en) 1992-06-03 2001-02-06 Henkel Corporation Polyol ester lubricants, especially those compatible with mineral oils, for refrigerating compressors operating at high temperatures
ATE184310T1 (en) * 1992-06-03 1999-09-15 Henkel Corp POLYOL/ESTER MIXTURE AS A LUBRICANT FOR HEAT TRANSFER FLUIDS IN REFRIGERANT SYSTEMS
ATE194641T1 (en) * 1992-06-03 2000-07-15 Henkel Corp POLYOLESTER AS A LUBRICANT FOR HIGH TEMPERATURE REFRIGERANT COMPRESSORS
BR9207136A (en) * 1992-06-03 1995-08-29 Henkel Corp Refrigerant working fluid, and, process to operate a mechanical refrigerant system
JP2613526B2 (en) * 1992-07-04 1997-05-28 花王株式会社 Composition for working fluid of refrigerator
WO1994005745A1 (en) * 1992-08-28 1994-03-17 Henkel Corporation Biodegradable two-cycle engine oil compositions and ester base stocks
US6656888B1 (en) * 1992-08-28 2003-12-02 Cognis Corporation Biodegradable two-cycle engine oil compositions, grease compositions, and ester base stocks use therein
US5853609A (en) * 1993-03-10 1998-12-29 Henkel Corporation Polyol ester lubricants for hermetically sealed refrigerating compressors
DE4308102A1 (en) * 1993-03-15 1994-09-22 Henkel Kgaa Alkylene-bridged polyol ethers and their esters
US5458794A (en) * 1993-09-30 1995-10-17 The Lubrizol Corporation Lubricants containing carboxylic esters from polyhydroxy compounds, suitable for ceramic-containing engines
JPH10500719A (en) * 1994-05-23 1998-01-20 ヘンケル・コーポレイション Methods for increasing the resistivity of ester lubricants, especially for use with hydrofluorocarbon refrigerants
ES2165440T3 (en) * 1994-12-08 2002-03-16 Exxonmobil Chem Patents Inc BASED MATERIAL OF BIODEGRADABLE AND LUBRICANT BRANCHED SYNTHETIC ESTERS FORMED FROM THEMSELVES.
US5665686A (en) * 1995-03-14 1997-09-09 Exxon Chemical Patents Inc. Polyol ester compositions with unconverted hydroxyl groups
TW349119B (en) * 1996-04-09 1999-01-01 Mitsubishi Gas Chemical Co Polyol ester based-lubricant
DE19616733C2 (en) * 1996-04-26 2000-07-13 Stockhausen Chem Fab Gmbh Process for the thermal-mechanical surface treatment of sheet-like material webs, in particular made of paper and cardboard, using adhesive agents
US5728658A (en) * 1996-05-21 1998-03-17 Exxon Chemical Patents Inc Biodegradable synthetic ester base stocks formed from branched oxo acids
US5798322A (en) * 1996-08-30 1998-08-25 Gateway Additive Company Friction-modifying additives for slideway lubricants
US5922658A (en) * 1996-09-06 1999-07-13 Exxon Chemical Patents Inc. Two-cycle engine oil formed from a blend of a complex alcohol ester and other basestocks
US5942475A (en) * 1996-09-06 1999-08-24 Exxon Chemical Patents Inc. Engine oil lubricants formed from complex alcohol esters
US5698502A (en) * 1996-09-11 1997-12-16 Exxon Chemical Patents Inc Polyol ester compositions with unconverted hydroxyl groups for use as lubricant base stocks
EP0890634A1 (en) * 1997-07-09 1999-01-13 Voith Turbo GmbH & Co. KG Working fluid for hydrodynamic machine
EP1019465B1 (en) * 1997-10-01 2003-07-30 Unichema Chemie B.V. Complex esters, formulations comprising these esters and use thereof
US20060229409A1 (en) * 2005-04-08 2006-10-12 Ilmenev Pavel E Method for preparing polyurethane dispersions
DE102006027602A1 (en) * 2006-06-13 2007-12-20 Cognis Ip Management Gmbh Lubricant compositions containing complex esters
US9481852B2 (en) * 2008-01-24 2016-11-01 The Lubrizol Corporation High viscosity synthetic ester lubricant base stock blends
US10336958B2 (en) 2016-08-30 2019-07-02 Resinate Materials Group, Inc. Sustainable base oils for lubricants
JP2018095840A (en) 2016-12-13 2018-06-21 花王株式会社 Lubricant base oil, and lubricant composition including the same
CN110036095B (en) 2016-12-13 2022-01-04 花王株式会社 Lubricant base oil and lubricant composition containing the same
JP6928445B2 (en) 2016-12-21 2021-09-01 花王株式会社 Lubricating oil base oil, lubricating oil composition containing the lubricating oil base oil, and a method for producing the same.
JP7216563B2 (en) * 2019-02-12 2023-02-01 花王株式会社 Grease base oil and grease composition containing the grease base oil

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB644597A (en) * 1946-08-17 1950-10-11 Bakelite Corp Mixed esters
GB663566A (en) * 1948-12-01 1951-12-27 George Bruce Ingram Improvements in or relating to the production of organic carboxylic esters of polyhydric alcohols
US3000917A (en) * 1957-03-15 1961-09-19 Drew & Co Inc E F Linear mixed ester lubricants
BE596980A (en) * 1959-11-11
BE649019A (en) * 1963-06-12
GB1122466A (en) * 1966-01-12 1968-08-07 Exxon Research Engineering Co Complex esters
IL32628A0 (en) * 1968-07-18 1969-09-25 Stauffer Chemical Co Pentaerythritol ester lubricants
US3708522A (en) * 1969-12-29 1973-01-02 Lubrizol Corp Reaction products of high molecular weight carboxylic acid esters and certain carboxylic acid acylating reactants
US3753968A (en) * 1971-07-01 1973-08-21 Westvaco Corp Selective reaction of fatty acids and their separation
CA1016539A (en) * 1973-02-12 1977-08-30 Benjamin F. Ward Process for producing a dicarboxylic acid from linoleic acid containing fatty acid mixture
US4049563A (en) * 1973-06-18 1977-09-20 Chevron Research Company Jet engine oils containing extreme pressure additive
JPS5321068B2 (en) * 1973-10-22 1978-06-30
DE2538232C2 (en) * 1975-08-28 1982-03-11 Dynamit Nobel Ag, 5210 Troisdorf Surface-active, liquid, hydroxyl-containing ester mixtures
GB1481270A (en) * 1975-12-31 1977-07-27 Hercules Inc Synthetic oil lubricant
JPS536350A (en) * 1976-07-08 1978-01-20 Riken Vitamin Co Ltd Lubricants and compositions for molding plastics
JPS5421806A (en) * 1977-07-20 1979-02-19 Fuji Photo Film Co Ltd Magnetic recording medium
SU739083A1 (en) * 1978-02-22 1980-06-05 Предприятие П/Я Р-6711 Lubricating composition
US4175045A (en) * 1978-02-27 1979-11-20 Stauffer Chemical Company Compressor lubrication
JPS552659A (en) * 1978-06-22 1980-01-10 Lion Corp Continuous preparation of polyhydric alcohol complete ester
US4277417A (en) * 1978-12-29 1981-07-07 Exxon Research & Engineering Co. Hydrocarbon soluble sulfonated polyols, esters of hydrocarbon substituted C4 -C10 dicarboxylic acids with polyols and sulfonic acid, processes therefor, and lubricating compositions thereof
US4234497A (en) * 1979-04-30 1980-11-18 Standard Lubricants, Inc. Iso-palmitate polyol ester lubricants
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

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

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