EP0489809B1 - New base oil for the lubricant industry - Google Patents
New base oil for the lubricant industry Download PDFInfo
- Publication number
- EP0489809B1 EP0489809B1 EP90913144A EP90913144A EP0489809B1 EP 0489809 B1 EP0489809 B1 EP 0489809B1 EP 90913144 A EP90913144 A EP 90913144A EP 90913144 A EP90913144 A EP 90913144A EP 0489809 B1 EP0489809 B1 EP 0489809B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lubricant compositions
- ester oils
- viscosity
- carbon atoms
- dicarboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000314 lubricant Substances 0.000 title claims abstract description 16
- 239000002199 base oil Substances 0.000 title 1
- 239000010696 ester oil Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 6
- -1 aliphatic dicarboxylic acids Chemical class 0.000 claims description 5
- XULHFMYCBKQGEE-UHFFFAOYSA-N 2-hexyl-1-Decanol Chemical compound CCCCCCCCC(CO)CCCCCC XULHFMYCBKQGEE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- LOIMOHMWAXGSLR-UHFFFAOYSA-N 2-hexyldodecan-1-ol Chemical compound CCCCCCCCCCC(CO)CCCCCC LOIMOHMWAXGSLR-UHFFFAOYSA-N 0.000 claims description 2
- JYZLSYFPFQTNNO-UHFFFAOYSA-N 2-octyldecan-1-ol Chemical compound CCCCCCCCC(CO)CCCCCCCC JYZLSYFPFQTNNO-UHFFFAOYSA-N 0.000 claims description 2
- LEACJMVNYZDSKR-UHFFFAOYSA-N 2-octyldodecan-1-ol Chemical compound CCCCCCCCCCC(CO)CCCCCCCC LEACJMVNYZDSKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005068 cooling lubricant Substances 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 230000001050 lubricating effect Effects 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010722 industrial gear oil Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000010723 turbine oil Substances 0.000 description 1
Classifications
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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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/72—Esters of polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/36—Esters of polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
-
- 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
- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
-
- 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
-
- 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
-
- 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
- C10N2040/20—Metal working
-
- 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
- C10N2040/30—Refrigerators lubricants or compressors lubricants
-
- 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
- C10N2040/32—Wires, ropes or cables lubricants
-
- 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
- C10N2040/34—Lubricating-sealants
-
- 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
- C10N2040/36—Release agents or mold release agents
-
- 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
- C10N2040/38—Conveyors or chain belts
-
- 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
- C10N2040/40—Generators or electric motors in oil or gas winning field
-
- 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
- C10N2040/42—Flashing oils or marking oils
-
- 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
- C10N2040/44—Super vacuum or supercritical use
-
- 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
- C10N2040/50—Medical uses
Definitions
- the invention relates to a high and low temperature stable, low viscosity ester oil based on an aliphatic dicarboxylic acid and an appropriately selected Guerbet alcohol.
- ester oils go back more than 50 years, in which ever more powerful ester oils have developed due to the special requirements of the lubricant industry.
- synthetic aviation turbine oils based on diesters of adipic, azelaic and sebacic acid with aliphatic alcohols played an important role (see: M. Wildersohn, Tribologie und Schm michtechnik, Volume 32, page 70 to 75, 1985 and Ullmann, volume 20, pages 457 to 671, 1984).
- ester oils are characterized by better viscosity / temperature behavior, a significantly better load-bearing capacity at high temperatures coupled with a lower vaporizability and in particular by significantly lower pour points.
- the invention is based on the object of providing new synthetic diesters of dibasic carboxylic acids with monohydric alcohols which, compared with the known ester oils, have improved temperature / viscosity behavior, expressed by a higher viscosity index and improved low-temperature properties, as well as a lower evaporation loss and a higher one Flash point, mark.
- the technical solution to this problem according to the invention is based on the selection of a specific alcohol component and combines this selection of the hydroxyl group component with the selection of a specific dicarboxylic acid on the acid side to produce a new ester oil with surprising properties.
- the present invention now relates to high and low temperature stable, low-viscosity lubricant compositions based on ester oils, produced from the known esterification of a dicarboxylic acid with a fatty alcohol, characterized in that the ester oils are the esterification product of aliphatic dicarboxylic acids with 8 and / or 9 carbon atoms and branched Guerbet alcohols or Guerbet alcohol mixtures containing at least 12 to 20 carbon atoms.
- ester oils which are composed of aliphatic dicarboxylic acid components are already known from the prior art, so that the selection according to the invention of suberic acid and / or azelaic acid, preferably of azelaic acid, can be described as known per se.
- the core of the action according to the invention turns out to be the selection of the alcohol component which is derived from a Guerbet alcohol or a Guerbet alcohol mixture with at least 12 to 20 carbon atoms.
- the trivial name Guerbet alcohol means 2-alkyl-substituted 1-alkanols, their technical synthesis, for example, in H. Machemer, Angewandte Chemie, Volume 64, pages 213-220 (1952) and in G. Dieckelmann and HJ Heinz in "The Basics of Industrial Oleochemistry ", Pages 145-146 (1988) is described in detail.
- the Guerbet alcohol content of the ester oils is derived at least in part from 2-hexyldecanol, 2-hexyldodecanol, 2-octyldecanol and / or 2-octyldodecanol, with the use of 2-hexyldecanol being particularly preferred.
- the actual esterification reaction is carried out according to a known method by reacting a one-molar amount of dicarboxylic acid with at least 2 moles of Guerbet alcohol in the presence of an esterification catalyst while distilling off the water formed in the reaction.
- Ester oils preferred according to the invention have a kinematic viscosity in the range from about 7 to 50 mm 2 / s, preferably from about 15 to 40 mm 2 / s, at 40 ° C. according to DIN 51 562. These low Viscosity values are somewhat surprising in view of the relatively high molecular weight, since comparable polyol esters with a lower molecular weight, such as, for example, trimethylolpropane esterified with adipic acid, give significantly more viscous ester oils.
- the ester oils according to the invention have excellent viscosity / temperature behavior, which is also found in the pour points determined according to DIN ISO 3016 of about -40 down to -65 ° C, preferably from below -55 ° C.
- the high-temperature behavior in addition to the low-temperature behavior, the high-temperature behavior also plays an important role.
- the new ester oils according to the invention are particularly suitable for temperature-resistant applications.
- the evaporation losses determined by thermogravimetric analysis at a heating rate of 1 ° C./min are also 0% by weight at 200 ° C., approximately 1% by weight at 250 ° C. and approximately 5 to 10% by weight. important at 300 ° C.
- the dicarboxylic acid ester oils according to the invention are particularly suitable as lubricant compositions in industrial gear oil, hydraulic and / or cooling lubricants in metal, plastic and textile processing, and as additives with lubricant properties in one of the areas mentioned.
- additives such as oxidation and Corrosion inhibitors, dispersants, high-pressure additives, anti-foaming agents, metal deactivators are used in the usual effective amounts.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Lubricants (AREA)
- Lenses (AREA)
- Studio Devices (AREA)
- Arc Welding Control (AREA)
Abstract
Description
Die Erfindung betrifft ein hoch- und tieftemperaturstabiles, niedrigviskoses Esteröl auf der Basis einer aliphatischen Dicarbonsäure und eines entsprechend ausgesuchten Guerbetalkoholes.The invention relates to a high and low temperature stable, low viscosity ester oil based on an aliphatic dicarboxylic acid and an appropriately selected Guerbet alcohol.
Die Geschichte der Esteröle reicht mittlerweile schon über 50 Jahre zurück, in denen sich infolge der besonderen Anforderungen der Schmierstoffindustrie immer leistungsfähigere Esteröle entwickelt haben. Insbesondere in der zivilen und militärischen Luftfahrt spielte die erste Generation synthetischer Flugturbinenöle auf der Basis von Diestern der Adipin-, Azelain- und Sebacinsäure mit aliphatischen Alkoholen eine bedeutende Rolle (siehe dazu: M. Wildersohn, Tribologie und Schmierungstechnik, Band 32, Seite 70 bis 75, 1985 und Ullmann, Band 20, Seite 457 bis 671, 1984).The history of ester oils goes back more than 50 years, in which ever more powerful ester oils have developed due to the special requirements of the lubricant industry. In civil and military aviation in particular, the first generation of synthetic aviation turbine oils based on diesters of adipic, azelaic and sebacic acid with aliphatic alcohols played an important role (see: M. Wildersohn, Tribologie und Schmierungstechnik, Volume 32, page 70 to 75, 1985 and Ullmann, volume 20, pages 457 to 671, 1984).
Im Vergleich zu den billigeren, aber umweltgefährdenden Mineralölen zeichnen sich die Esteröle durch ein besseres Viskositäts/Temperatur-Verhalten, ein deutlich besseres Lasttragevermögen bei hohen Temperaturen gekoppelt mit einer geringeren Verdampfbarkeit und insbesondere durch deutlich niedrigere Pour-points, aus.Compared to the cheaper, but environmentally hazardous mineral oils, the ester oils are characterized by better viscosity / temperature behavior, a significantly better load-bearing capacity at high temperatures coupled with a lower vaporizability and in particular by significantly lower pour points.
Es besteht gleichwohl weiterhin ausgesprochenes Interesse an neuen synthetischen Esterölen, deren Einsatz im Bereich der Kraftfahrzeugöle und Industrieschmierstoffe gerade dann besonders gefragt ist, wenn die Belastbarkeitsgrenze der bisher bekannten Ester- und Mineralöle überschritten ist.Nevertheless, there is still a pronounced interest in new synthetic ester oils, the use of which is particularly in demand in the field of motor vehicle oils and industrial lubricants when the load limit of the previously known ester and mineral oils has been exceeded.
Die Erfindung geht dementsprechend von der Aufgabe aus, neue synthetische Diester zweibasischer Carbonsäuren mit einwertigen Alkoholen zur Verfügung zu stellen, die sich gegenüber den bekannten Esterölen durch ein verbessertes Temperatur/Viskositätsverhalten, ausgedrückt durch einen höheren Viskositätsindex und verbesserten Tieftemperatureigenschaften sowie einen niedrigeren Verdampfungsverlust und einen höheren Flammpunkt, auszeichnen.Accordingly, the invention is based on the object of providing new synthetic diesters of dibasic carboxylic acids with monohydric alcohols which, compared with the known ester oils, have improved temperature / viscosity behavior, expressed by a higher viscosity index and improved low-temperature properties, as well as a lower evaporation loss and a higher one Flash point, mark.
Die technische Lösung dieser erfindungsgemäßen Aufgabenstellung geht von der Auswahl einer bestimmten Alkoholkomponente aus und verbindet diese Auswahl der Hydroxylgruppenkomponente mit der Auswahl einer bestimmten Dicarbonsäure auf der Säureseite zur Herstellung eines neuen Esteröles mit überraschenden Eigenschaften.The technical solution to this problem according to the invention is based on the selection of a specific alcohol component and combines this selection of the hydroxyl group component with the selection of a specific dicarboxylic acid on the acid side to produce a new ester oil with surprising properties.
Gegenstand der vorliegenden Erfindung sind nunmehr hoch- und tieftemperaturstabile, niedrigviskose Schmiermittelzusammensetzungen auf der Basis von Esterölen, hergestellt aus der bekannten Veresterung einer Dicarbonsäure mit einem Fettalkohol, dadurch gekennzeichnet, daß die Esteröle das Veresterungsprodukt von aliphatischen Dicarbonsäuren mit 8 und/oder 9 C-Atomen und verzweigten Guerbetalkoholen oder Guerbetalkoholgemischen mit wenigstens 12 bis 20 C-Atomen enthalten.The present invention now relates to high and low temperature stable, low-viscosity lubricant compositions based on ester oils, produced from the known esterification of a dicarboxylic acid with a fatty alcohol, characterized in that the ester oils are the esterification product of aliphatic dicarboxylic acids with 8 and / or 9 carbon atoms and branched Guerbet alcohols or Guerbet alcohol mixtures containing at least 12 to 20 carbon atoms.
Aus dem Stand der Technik sind bereits zahlreiche Beispiele für Esteröle, die sich aus aliphatischen Dicarbonsäureanteilen zusammensetzen, bekannt, so daß die erfindungsgemäße Auswahl von Korksäure und/oder Azelainsäure, vorzugsweise von Azelainsäure, an sich als bekannt zu bezeichnen ist.Numerous examples of ester oils which are composed of aliphatic dicarboxylic acid components are already known from the prior art, so that the selection according to the invention of suberic acid and / or azelaic acid, preferably of azelaic acid, can be described as known per se.
Als Kern des erfindungsgemäßen Handelns erweist sich im folgenden jedoch die Auswahl der Alkoholkomponente, die sich von einem Guerbetalkohol oder einem Guerbetalkoholgemisch mit wenigstens 12 bis 20 C-Atomen ableitet. Unter dem Trivialnamen Guerbetalkohol versteht man 2-alkylsubstituierte 1-Alkanole, deren technische Synthese beispielsweise in H. Machemer, Angewandte Chemie, Band 64, Seite 213 - 220 (1952) und in G. Dieckelmann und H. J. Heinz in "The Basics of Industrial Oleochemistry", Seite 145 - 146 (1988) ausführlich beschrieben ist.In the following, however, the core of the action according to the invention turns out to be the selection of the alcohol component which is derived from a Guerbet alcohol or a Guerbet alcohol mixture with at least 12 to 20 carbon atoms. The trivial name Guerbet alcohol means 2-alkyl-substituted 1-alkanols, their technical synthesis, for example, in H. Machemer, Angewandte Chemie, Volume 64, pages 213-220 (1952) and in G. Dieckelmann and HJ Heinz in "The Basics of Industrial Oleochemistry ", Pages 145-146 (1988) is described in detail.
In einer bevorzugten Ausführungsform dieser Erfindung leitet sich der Guerbetalkoholanteil der Esteröle wenigstens anteilsweise von 2-Hexyldecanol, 2-Hexyldodecanol, 2-Octyldecanol und/oder 2-Octyldodecanol ab, wobei insbesondere der Einsatz von 2-Hexyldecanol bevorzugt wird.In a preferred embodiment of this invention, the Guerbet alcohol content of the ester oils is derived at least in part from 2-hexyldecanol, 2-hexyldodecanol, 2-octyldecanol and / or 2-octyldodecanol, with the use of 2-hexyldecanol being particularly preferred.
Die eigentliche Veresterungsreaktion erfolgt nach bekannter Methode durch die Reaktion einer einmolaren Menge an Dicarbonsäure mit wenigstens 2 Mol Guerbetalkohol in Gegenwart eines Veresterungskatalysators unter Abdestillation des bei der Reaktion gebildeten Wassers.The actual esterification reaction is carried out according to a known method by reacting a one-molar amount of dicarboxylic acid with at least 2 moles of Guerbet alcohol in the presence of an esterification catalyst while distilling off the water formed in the reaction.
Erfindungsgemäß bevorzugte Esteröle haben nach DIN 51 562 bei 40 °C eine kinematische Viskosität im Bereich von etwa 7 bis 50 mm²/s, vorzugsweise von etwa 15 bis 40 mm²/s. Diese niedrigen Viskositätswerte sind angesichts des relativ hohen Molekulargewichts einigermaßen überraschend, da vergleichbare Polyolester mit geringerem Molekulargewicht, wie beispielsweise Trimethylolpropan verestert mit Adipinsäure, wesentlich hochviskosere Esteröle ergeben.Ester oils preferred according to the invention have a kinematic viscosity in the range from about 7 to 50 mm 2 / s, preferably from about 15 to 40 mm 2 / s, at 40 ° C. according to DIN 51 562. These low Viscosity values are somewhat surprising in view of the relatively high molecular weight, since comparable polyol esters with a lower molecular weight, such as, for example, trimethylolpropane esterified with adipic acid, give significantly more viscous ester oils.
Mit einem Viskositätsindex (nach DIN ISO 2909) von wenigstens etwa 150, vorzugsweise von wenigstens 160, weisen die erfindungsgemäßen Esteröle ein ausgezeichnetes Viskositäts-/Temperatur-Verhalten auf, das sich auch in den nach DIN ISO 3016 bestimmten Pour-Points von etwa -40 bis -65 °C, vorzugsweise von unterhalb -55 °C, widerspiegelt.With a viscosity index (according to DIN ISO 2909) of at least about 150, preferably at least 160, the ester oils according to the invention have excellent viscosity / temperature behavior, which is also found in the pour points determined according to DIN ISO 3016 of about -40 down to -65 ° C, preferably from below -55 ° C.
Im Sinne dieser Erfindung spielt neben dem Tieftemperaturverhalten auch das Hochtemperaturverhalten eine bedeutende Rolle. Infolge der nach DIN ISO 2592 bestimmten Flammpunkte von wenigstens 250 bis etwa 300 °C, vorzugsweise von oberhalb 270 °C, eignen sich die erfindungsgemäßen neuen Esteröle besonders gut für temperaturbelastbare Anwendungen. In diesem Sinne sind auch die bei einer Aufheizrate von 1 °C/Min durch thermogravimetrische Analyse bestimmten Verdampfungsverluste von 0 Gew.-% bei 200 °C, etwa 1 Gew.-% bei 250 °C und etwa 5 bis 10 Gew.-% bei 300 °C von Bedeutung.In the sense of this invention, in addition to the low-temperature behavior, the high-temperature behavior also plays an important role. As a result of the flash points of at least 250 to approximately 300 ° C., preferably above 270 ° C., determined according to DIN ISO 2592, the new ester oils according to the invention are particularly suitable for temperature-resistant applications. In this sense, the evaporation losses determined by thermogravimetric analysis at a heating rate of 1 ° C./min are also 0% by weight at 200 ° C., approximately 1% by weight at 250 ° C. and approximately 5 to 10% by weight. important at 300 ° C.
Aufgrund ihrer guten tribologischen Eigenschaften sind die erfindungsgemäßen Dicarbonsäureesteröle als Schmiermittelzusammensetzungen in Industriegetriebeöl-, Hydraulik- und/oder Kühlschmierflüssigkeiten bei der Metall-, Kunststoff- und Textilbearbeitung sowie als Additive mit Schmierstoffeigenschaften in einem der genannten Bereiche besonders gut geeignet. Zur Verbesserung des Schmiercharakters können auch Zusatzstoffe wie Oxidations- und Korrosionsinhibitoren, Dispergiermittel, Hochdruckzusätze, Antischaummittel, Metalldesaktivatoren in den üblichen wirksamen Mengen eingesezt werden.Because of their good tribological properties, the dicarboxylic acid ester oils according to the invention are particularly suitable as lubricant compositions in industrial gear oil, hydraulic and / or cooling lubricants in metal, plastic and textile processing, and as additives with lubricant properties in one of the areas mentioned. To improve the lubricating character, additives such as oxidation and Corrosion inhibitors, dispersants, high-pressure additives, anti-foaming agents, metal deactivators are used in the usual effective amounts.
Die entsprechende Dicarbonsäure und der ausgewählte Guerbetalkohol (im geringen Überschuß) wurden in Gegenwart von 0,1 Gew.-% Zinn(II)oxalat bei etwa 160 bis 240 °C 6 bis 8 Stunden unter Abdestillation des bei der Reaktion gebildeten Wassers verestert. Gegen Ende der Reaktion wurde bei gleicher Temperatur unter vermindertem Druck weiterverestert. Nach dem Abkühlen auf 90 °C wurden zur Naßbleichung etwa 0,5 bis 1 % Bleicherde zugesetzt und das Reaktionsprodukt nach dem Abkühlen abfiltriert.The corresponding dicarboxylic acid and the selected Guerbet alcohol (in slight excess) were esterified in the presence of 0.1% by weight of tin (II) oxalate at about 160 to 240 ° C. for 6 to 8 hours while the water formed in the reaction was distilled off. Towards the end of the reaction, esterification was continued at the same temperature under reduced pressure. After cooling to 90 ° C., about 0.5 to 1% bleaching earth was added for wet bleaching and the reaction product was filtered off after cooling.
Nähere Einzelheiten zu den Produkteigenschaften A-F kinematische Viskosität, Viskositätsindex, Cloud-Point, Pour-point und Flammpunkt der Diacarbonsäureester sind in Tabelle 1 zusammengefaßt. Um einen Vergleich mit aus dem Stand der Technik bekannten Schmierstoffen zu ermöglichen, sind in Tabelle 2 dieselben Produkteigenschaften A-F für vergleichbare Schmiermittel zusammengefaßt.
Die in Tabelle 1 beschriebenen, erfindungsgemäßen Esteröle besitzen nun überraschenderweise, gegenüber den viskositätskonformen Vergleichsbindungen, insbesondere den Mineralölen, wesentlich höhere Flammpunkte bei ausgezeichneten Kälteeigenschaften. Auch vergleichbare Esteröle mit gleichen oder größeren Molekulargewichten auf der Basis aliphatischer Dicarbonsäuren, wie Adipin- oder Sebacinsäure, erreichen die Kälteeigenschaften der erfindungsgemäßen Esteröle bei weitem nicht.Further details on the product properties AF kinematic viscosity, viscosity index, cloud point, pour point and flash point of the diacarboxylic acid esters are summarized in Table 1. In order to enable a comparison with lubricants known from the prior art, the same product properties AF for comparable lubricants are summarized in Table 2.
The ester oils according to the invention described in Table 1 now surprisingly have, compared to the viscosity-compliant comparative bonds, in particular the mineral oils, significantly higher flash points with excellent low-temperature properties. Comparable ester oils with the same or greater molecular weights based on aliphatic dicarboxylic acids, such as adipic or sebacic acid, also by no means achieve the low-temperature properties of the ester oils according to the invention.
Claims (7)
- Low-viscosity lubricant compositions stable to high and low temperatures based on ester oils prepared by the known esterification of a dicarboxylic acid with a fatty alcohol, characterized in that the ester oils contain the esterification product of aliphatic dicarboxylic acids containing 8 and/or 9 carbon atoms and branched Guerbet alcohols or mixtures of Guerbet alcohols containing at least 12 to 20 carbon atoms.
- Lubricant compositions as claimed in claim 1, characterized in that the aliphatic dicarboxylic acid component of the ester oils is derived from suberic acid and/or azelaic acid.
- Lubricant compositions as claimed in claims 1 and 2, characterized in that the Guerbet alcohol component of the ester oils is derived at leastly partly from 2-hexyl decanol, 2-hexyl dodecanol, 2-octyl decanol and/or 2-octyl dodecanol, the use of 2-hexyl decanol being particularly preferred.
- Lubricant compositions as claimed in claims 1 to 3, characterized in that they have a kinematic viscosity (DIN 51 562) at 40°C in the range from 7 to 50 mm²/s and preferably in the range from about 15 to 40 mm²/s and a viscosity index (DIN ISO 2909) of at least about 150 and preferably of at least 160.
- Lubricant compositions as claimed in claims 1 to 4, characterized in that they have a pour point (DIN ISO 3016) of about -40 to -65°C and preferably below about -55°C.
- Lubricant compositions as claimed in claims 1 to 5, characterized in that they have a flash point (DIN ISO 2592) of at least 250 to about 300°C and preferably above 270°C.
- The use of the lubricant compositions described in claims 1 to 6 as industrial transmission oils, hydraulic fluids and/or cooling lubricants in the processing of metals, plastics and textiles and as a lubricating additive in any of the fields mentioned.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3929069A DE3929069A1 (en) | 1989-09-01 | 1989-09-01 | NEW BASE OIL FOR THE LUBRICANT INDUSTRY |
| DE3929069 | 1989-09-01 | ||
| PCT/EP1990/001404 WO1991003531A1 (en) | 1989-09-01 | 1990-08-23 | New base oil for the lubricant industry |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0489809A1 EP0489809A1 (en) | 1992-06-17 |
| EP0489809B1 true EP0489809B1 (en) | 1994-12-07 |
Family
ID=6388435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90913144A Expired - Lifetime EP0489809B1 (en) | 1989-09-01 | 1990-08-23 | New base oil for the lubricant industry |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5286397A (en) |
| EP (1) | EP0489809B1 (en) |
| JP (1) | JP2848702B2 (en) |
| AT (1) | ATE115175T1 (en) |
| AU (1) | AU6298490A (en) |
| CA (1) | CA2066444A1 (en) |
| DE (2) | DE3929069A1 (en) |
| ES (1) | ES2064758T3 (en) |
| WO (1) | WO1991003531A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015036293A1 (en) * | 2013-09-16 | 2015-03-19 | Basf Se | Polyester and use of polyester in lubricants |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993007240A1 (en) * | 1991-10-03 | 1993-04-15 | Exxon Chemical Patents Inc. | Process for producing fluids of enhanced thermal stability |
| DE4202034A1 (en) * | 1992-01-25 | 1993-07-29 | Rwe Dea Ag | hydraulic fluids |
| DE4313948A1 (en) * | 1993-04-28 | 1994-11-03 | Henkel Kgaa | Hydraulic oils with improved seal compatibility |
| US5578642A (en) * | 1994-08-17 | 1996-11-26 | Henkel Corporation | Self-emulsifying and/or emollient agents |
| DE4436764A1 (en) * | 1994-10-14 | 1996-04-18 | Henkel Kgaa | Use of guanidinium salts of unsaturated fatty acids as an anti-corrosion agent |
| US5998340A (en) * | 1997-03-07 | 1999-12-07 | Hitachi Maxell, Ltd. | Lubricant and magnetic recording medium using the same |
| EP0890634A1 (en) * | 1997-07-09 | 1999-01-13 | Voith Turbo GmbH & Co. KG | Working fluid for hydrodynamic machine |
| DE19830240C1 (en) * | 1998-07-07 | 2000-02-17 | Chemtec Leuna Ges Fuer Chemie | Wax esters with a vaseline-like consistency, process and use |
| US6362265B1 (en) * | 1998-12-04 | 2002-03-26 | Rhodia Inc | Additives with reduced residual tin content and thermoplastic compositions containing the same |
| JP4028982B2 (en) * | 2001-12-27 | 2008-01-09 | 新日鐵化学株式会社 | Fluid bearing unit and lubricating oil composition for bearing |
| CA2537311C (en) * | 2003-09-13 | 2010-11-30 | Exxonmobil Chemical Patents Inc. | Lubricating compositions for automotive gears |
| DE102006001768A1 (en) * | 2006-01-12 | 2007-07-19 | Cognis Ip Management Gmbh | Use of esters with branched alkyl groups as lubricants |
| EP1958932A1 (en) * | 2007-02-16 | 2008-08-20 | Cognis IP Management GmbH | Esters and mixtures thereof and their application as lubricants or in hydraulic oils |
| EP2009289A1 (en) * | 2007-06-25 | 2008-12-31 | Siemens Aktiengesellschaft | Winterproof turbo compressor unit and method for winterproofing the turbo compressor unit |
| JP5334421B2 (en) * | 2008-02-07 | 2013-11-06 | コスモ石油ルブリカンツ株式会社 | Ester base oil and lubricating oil for lubricating oil |
| JP5334432B2 (en) * | 2008-03-17 | 2013-11-06 | コスモ石油ルブリカンツ株式会社 | Grease composition |
| WO2011080991A1 (en) * | 2009-12-28 | 2011-07-07 | 出光興産株式会社 | Base oil for cooling of device, device-cooling oil containing the base oil, device to be cooled by the cooling oil, and device cooling method using the cooling oil |
| GB201508971D0 (en) * | 2015-05-26 | 2015-07-01 | Croda Int Plc | Hair care formulation |
| WO2018063602A1 (en) * | 2016-09-27 | 2018-04-05 | Exxonmobil Research And Engineering Company | Processes for preparing vinylidene dimer derivatives |
| SG11201908484PA (en) * | 2017-03-28 | 2019-10-30 | Exxonmobil Chemical Patents Inc | Cold cranking simulator viscosity reducing base stocks and lubricating oil formulations containing the same |
| JP2019119838A (en) * | 2018-01-11 | 2019-07-22 | Ｅｍｇルブリカンツ合同会社 | Lubricant composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2921089A (en) * | 1957-11-27 | 1960-01-12 | Eastman Kodak Co | 2-propylheptanol and its esters |
| US4425458A (en) * | 1982-04-09 | 1984-01-10 | Henkel Corporation | Polyguerbet alcohol esters |
| US4830769A (en) * | 1987-02-06 | 1989-05-16 | Gaf Corporation | Propoxylated guerbet alcohols and esters thereof |
| US4731190A (en) * | 1987-02-06 | 1988-03-15 | Alkaril Chemicals Inc. | Alkoxylated guerbet alcohols and esters as metal working lubricants |
| AU2785789A (en) * | 1987-10-28 | 1989-05-23 | Gaf Corporation | Polycarbonate internal lubricants |
-
1989
- 1989-09-01 DE DE3929069A patent/DE3929069A1/en not_active Withdrawn
-
1990
- 1990-08-23 AU AU62984/90A patent/AU6298490A/en not_active Abandoned
- 1990-08-23 DE DE59007953T patent/DE59007953D1/en not_active Expired - Lifetime
- 1990-08-23 AT AT90913144T patent/ATE115175T1/en not_active IP Right Cessation
- 1990-08-23 US US07/836,333 patent/US5286397A/en not_active Expired - Lifetime
- 1990-08-23 CA CA002066444A patent/CA2066444A1/en not_active Abandoned
- 1990-08-23 EP EP90913144A patent/EP0489809B1/en not_active Expired - Lifetime
- 1990-08-23 WO PCT/EP1990/001404 patent/WO1991003531A1/en active IP Right Grant
- 1990-08-23 JP JP2512143A patent/JP2848702B2/en not_active Expired - Fee Related
- 1990-08-23 ES ES90913144T patent/ES2064758T3/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015036293A1 (en) * | 2013-09-16 | 2015-03-19 | Basf Se | Polyester and use of polyester in lubricants |
| KR20160058864A (en) * | 2013-09-16 | 2016-05-25 | 바스프 에스이 | Polyester and use of polyester in lubricants |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1991003531A1 (en) | 1991-03-21 |
| US5286397A (en) | 1994-02-15 |
| DE59007953D1 (en) | 1995-01-19 |
| JP2848702B2 (en) | 1999-01-20 |
| JPH05500382A (en) | 1993-01-28 |
| EP0489809A1 (en) | 1992-06-17 |
| ES2064758T3 (en) | 1995-02-01 |
| ATE115175T1 (en) | 1994-12-15 |
| CA2066444A1 (en) | 1991-03-02 |
| DE3929069A1 (en) | 1991-03-07 |
| AU6298490A (en) | 1991-04-08 |
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