EP0272575B1 - High viscosity, neutral polyolesters - Google Patents
High viscosity, neutral polyolesters Download PDFInfo
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- 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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- acids
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- fatty acids
- dipentaerythritol
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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
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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
- C10M105/38—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
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
- 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
- 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
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
- 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
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.
- 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
- 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.
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.
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.
- 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
- 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
- R. Schumann, ant. "Drive Technology" 19 (1980) No. 1 - 2
Claims (6)
characterized in that dipentaerythritol is esterified with
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3643935A DE3643935C2 (en) | 1986-12-22 | 1986-12-22 | Synthetic polyol esters |
DE3643935 | 1986-12-22 |
Publications (4)
Publication Number | Publication Date |
---|---|
EP0272575A2 EP0272575A2 (en) | 1988-06-29 |
EP0272575A3 EP0272575A3 (en) | 1989-08-09 |
EP0272575B1 true EP0272575B1 (en) | 1992-09-16 |
EP0272575B2 EP0272575B2 (en) | 1995-12-13 |
Family
ID=6316900
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87118481A Expired - Lifetime EP0272575B2 (en) | 1986-12-22 | 1987-12-14 | High viscosity, neutral polyolesters |
Country Status (9)
Country | Link |
---|---|
US (1) | US5057247A (en) |
EP (1) | EP0272575B2 (en) |
JP (1) | JP2661927B2 (en) |
AT (1) | ATE80607T1 (en) |
BR (1) | BR8706979A (en) |
CA (1) | CA1317974C (en) |
DE (2) | DE3643935C2 (en) |
ES (1) | ES2052537T5 (en) |
MX (1) | MX169267B (en) |
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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 |
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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 |
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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 |
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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 |
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-
1986
- 1986-12-22 DE DE3643935A patent/DE3643935C2/en not_active Expired - Fee Related
-
1987
- 1987-12-14 MX MX009736A patent/MX169267B/en unknown
- 1987-12-14 ES ES87118481T patent/ES2052537T5/en not_active Expired - Lifetime
- 1987-12-14 AT AT87118481T patent/ATE80607T1/en not_active IP Right Cessation
- 1987-12-14 DE DE8787118481T patent/DE3781782D1/en not_active Expired - Lifetime
- 1987-12-14 EP EP87118481A patent/EP0272575B2/en not_active Expired - Lifetime
- 1987-12-21 US US07/136,037 patent/US5057247A/en not_active Expired - Fee Related
- 1987-12-21 BR BR8706979A patent/BR8706979A/en not_active IP Right Cessation
- 1987-12-22 JP JP62326635A patent/JP2661927B2/en not_active Expired - Lifetime
- 1987-12-22 CA CA000555085A patent/CA1317974C/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
EP0272575A2 (en) | 1988-06-29 |
US5057247A (en) | 1991-10-15 |
JP2661927B2 (en) | 1997-10-08 |
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 |
DE3643935A1 (en) | 1988-06-23 |
BR8706979A (en) | 1988-07-26 |
ATE80607T1 (en) | 1992-10-15 |
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