EP0272575B2 - High viscosity, neutral polyolesters - Google Patents

High viscosity, neutral polyolesters Download PDF

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Publication number
EP0272575B2
EP0272575B2 EP87118481A EP87118481A EP0272575B2 EP 0272575 B2 EP0272575 B2 EP 0272575B2 EP 87118481 A EP87118481 A EP 87118481A EP 87118481 A EP87118481 A EP 87118481A EP 0272575 B2 EP0272575 B2 EP 0272575B2
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Prior art keywords
acids
class
acid
dipentaerythritol
polyol esters
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German (de)
French (fr)
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EP0272575A3 (en
EP0272575B1 (en
EP0272575A2 (en
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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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    • 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

  • the invention relates to the use of the new synthetic polyol esters for the production of temperature-resistant gear and hydraulic oils as well as lubricating oil dispersions and / or lubricating greases.

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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, neopentylglycol 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 which combine a low pour point with high viscosity, good viscosity temperature behavior, high temperature resistance, high flash point and, at high temperatures, the lowest possible evaporation losses.

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-A-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 C 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.

Die US-A-3 790 481 betrifft Ester oder Komplexester von Polyolen mit aliphatischen Monocarbonsäuren und/oder Polycarbonsäuren.US-A-3 790 481 relates to esters or complex esters of polyols with aliphatic monocarboxylic acids and / or polycarboxylic acids.

Die GB-A1-915 161 beschreibt Komplexester aus neo-Glykolen, linearen Carbonsäuren und Dicarbonsäuren und ihre Verwendung als Schmiermittel.GB-A1-915 161 describes complex esters of neo-glycols, linear carboxylic acids and dicarboxylic acids and their use as lubricants.

Die JP-A-53/108917 und JP-A-53/102307 betreffen komplexe Ester, die durch Umesterung von Pentaerythrit mit Fettsäuremethylester und Veresterung mit Dicarbonsäuren erhältlich sind und ihre Verwendung als Schmiermittel.JP-A-53/108917 and JP-A-53/102307 relate to complex esters which are obtainable by transesterification of pentaerythritol with fatty acid methyl ester and esterification with dicarboxylic acids and their use as lubricants.

Die US-A-3 000 917 betrifft komplexe Ester aus Polyolen, Dicarbonsäuren und linearen Carbonsäuren.US-A-3,000,917 relates to complex esters of polyols, dicarboxylic acids and linear carboxylic acids.

In Tribologie + Schmierstofftechnik, 32, 75 (1985) werden komplexe Ester aus Pentaerythrit, Dicarbonsäuren und Monocarbonsäuren referiert.Complex esters of pentaerythritol, dicarboxylic acids and monocarboxylic acids are reported in Tribologie + Schmierstofftechnik, 32 , 75 (1985).

Ein Hinweis, daß Komplexester des Dipentaerythrits ein ausgewogenes Eigenschaftsbild zeigen und insbesondere geringe Verdampfungsverluste bei hohen Temperaturen aufweisen, ist den genannten Schriften nicht zu entnehmen.The documents mentioned do not indicate that complex esters of dipentaerythritol have a balanced property profile and in particular have low evaporation losses at high temperatures.

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 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 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 the 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

  • a) verzweigten Fettsäuren im C-Kettenbereich von C₈ bis C₁₆ (Säuren der Klasse A) und
  • b) linearen Fettsäuren im C-Kettenbereich von C₈ bis C₁₄ (Säuren der Klasse B)
verestert ist und dabei zusätzlich beschränkte Mengen an Di- und/oder Tricarbonsäuren im C-Kettenbereich von C₆ bis C₅₄ (Säuren der Klasse C) enthält.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
  • a) branched fatty acids in the C chain range from C₈ to C₁₆ (acids of class A) and
  • b) linear fatty acids in the C chain range from C₈ to C₁₄ (acids of class B)
is esterified and additionally contains limited amounts of di- and / or tricarboxylic acids in the C chain range from C₆ to C₅₄ (acids of class C).

Unter Säuren der Klasse C sind Di- und/oder Tricarbonsäuren im C-Kettenbereich von C₆ bis C₅₄ unter Einschluß aromatischer und/oder paraffinischer cyclischer Carbonsäuren mit 2 bis 3 Säurefunktionen zu verstehen.Acids of class C are to be understood as meaning di- and / or tricarboxylic acids in the C chain range from C₆ to C₅₄ including aromatic and / or paraffinic cyclic carboxylic acids with 2 to 3 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 gear 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 C unterteilen, wobei die Fettsäureklassen A und B Monocarbonsäuren betreffen, während die Säureklasse C, höherfunktionelle Carbonsäuren beinhaltet. Im einzelnen gelten hier die folgenden Angaben:

Säuren der Klasse A:
Verzweigte Fettsäuren im C-Kettenbereich von C₈ bis C₁₆, 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 von C₈ bis C₁₀.
In addition to the selection according to the invention of dipentaerythritol as the central polyol component for the production of the novel synthetic pololyesters according to the invention, the selection of the monofunctional carboxylic acid components used for the esterification and also used in minor amounts is of crucial importance. The fatty acids used for the esterification can be divided into the classes A to C listed below, the fatty acid classes A and B relating to monocarboxylic acids, while the acid class C contains higher-functional carboxylic acids. The following details apply here:
Class A acids:
Branched fatty acids in the C chain range from C₈ to C₁₆, 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 C₈ to C₁₄, preferably in the range from C₈ to C₁₀.

Die neuen synthetischen Polyolester der Erfindung enthalten als Fettsäurekomponenten verzweigte Fettsäuren aus der Klasse A und lineare Fettsäuren aus der Klasse B. Einzelheiten zu den dabei bevorzugten Mischungsverhältnissen werden im nachfolgenden noch angegeben.The new synthetic polyol esters of the invention contain, as fatty acid components, branched fatty acids from class A and linear fatty acids from class B. Details of the preferred mixing ratios are given below.

Die zusammen mit den verzweigten (Klasse A) und linearen Fettsäuren (Klasse B) eingesetzten mehrfunktionellen Carbonsäuren sind in die Säureklasse C einzuordnen:

Säuren der Klasse C:
Di- und/oder Tricarbonsäuren im C-Zahlbereich von C₆ bis C₅₄. unter Einschluß aromatischer und/oder paraffinischer cyclischer Carbonsäuren mit 2 bis 3 Säurefunktionen 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. Weitere bevorzugte säuren sind die Terephthalsäure, Trimellithsäure, und/oder Cyclohexancarbonsäure, die zur Herstellung der neuen synthetischen Polyolester als solche oder auch in Form ihrer Anhydride zum Einsatz kommen können.
The multifunctional carboxylic acids used together with the branched (class A) and linear fatty acids (class B) are classified in acid class C:
Class C acids:
Di- and / or tricarboxylic acids in the C number range from C₆ to C₅₄. including aromatic and / or paraffinic cyclic carboxylic acids with 2 to 3 acid functions 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. Other preferred acids are Terephthalic acid, trimellitic 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. 4 bis 5,8 Äquivalente eines Gemisches von Säuren gemäß a) und b) mit 0,2 bis 2 Äquivalenten von Fettsäuren der Klasse C,

wobei
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.Synthetic polyol esters according to the invention of the type mentioned correspond to the following definitions in terms of 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. 4 to 5.8 equivalents of a mixture of acids according to a) and b) with 0.2 to 2 equivalents of fatty acids of class C,

in which
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, preference is given to synthetic polyol esters of the type mentioned with the lowest possible acid numbers, 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 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 Trägeröle 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 furthermore due to their good tribological properties - for example an excellent pressure absorption capacity - also as additional components or suitable for hydraulic and gear oils on its own. 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 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

Kinematische ViskositätKinematic viscosity bei 20 °C:at 20 ° C: ca. 1800 mm²/sapprox. 1800 mm² / s bei 40 °C:at 40 ° C: ca. 440 mm²/sapprox. 440 mm² / s bei 100 °C:at 100 ° C: ca. 35 mm²/sapprox. 35 mm² / s ViskositätsindexViscosity index ca. 120approx. 120 StockpunktPour point ca. - 30 °Capprox. - 30 ° C Thermogravimetrische Analyse (Substanzverlust bei kontinuierlicher Erwärmung mit 20 °C pro Minute)Thermogravimetric analysis (loss of substance with continuous heating at 20 ° C per minute) bei 200 °C:at 200 ° C: 0 %0% bei 250 °C:at 250 ° C: 0 %0% bei 300 °C:at 300 ° C: 1 %1 %

Flammpunkt (DIN ISO 2592): ca. 300 °CFlash point (DIN ISO 2592): approx. 300 ° C

VerschleißkennwerteWear parameters

  • 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    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-Gerät"
    Schweißkraft: ca. 400 N bei 100 °C
    Reibungskoeffizient (») bei 100 °C und 100 N
    min.: ca. 0,105
    max.: ca. 0,129    b) Optimol "SRV device"
    Welding force: approx. 400 N at 100 ° C
    Friction coefficient (») at 100 ° C and 100 N
    min .: approx. 0.105
    max .: approx. 0.129
SRV-Methode:SRV method:

R. Schumann, ant. "Antriebstechnik"
19 (1980) Nr. 1 - 2R. 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
    a) branched C₈₋₁₆ fatty acids (class A acids) and
    b) linear C₈₋₁₄ fatty acids (class B acids)
    and additionally contains limited quantities of C₆₋₅₄ di- and/or tricarboxylic acids (class C acids) incorporated by condensation.
  2. Synthetic polyol esters as claimed in claim 1, characterized in that adipic acid and/or di- or trimer fatty acids are used as the di- and/or tricarboxylic acids.
  3. Synthetic polyol esters as claimed in claims 1 and 2, 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 mixtures of class A and class B acids with 0.2 to 2 equivalents of class C acids, equivalent ratios of 1 to 4 equivalents of class A acid residues to 2 to 5 equivalents of class B acid residues being present in the polyester.
  4. Synthetic polyesters 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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DE3643935 1986-12-22
DE3643935A DE3643935C2 (en) 1986-12-22 1986-12-22 Synthetic polyol esters

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ES2052537T3 (en) 1994-07-16
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CA1317974C (en) 1993-05-18
EP0272575B1 (en) 1992-09-16
DE3781782D1 (en) 1992-10-22
ES2052537T5 (en) 1996-03-01
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JPS63170337A (en) 1988-07-14
DE3643935C2 (en) 1995-07-06
EP0272575A2 (en) 1988-06-29
BR8706979A (en) 1988-07-26
US5057247A (en) 1991-10-15

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