EP0788535B1 - Kobalt enthaltende additive zur kontrolle von ablagerungen - Google Patents

Kobalt enthaltende additive zur kontrolle von ablagerungen Download PDF

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Publication number
EP0788535B1
EP0788535B1 EP95938911A EP95938911A EP0788535B1 EP 0788535 B1 EP0788535 B1 EP 0788535B1 EP 95938911 A EP95938911 A EP 95938911A EP 95938911 A EP95938911 A EP 95938911A EP 0788535 B1 EP0788535 B1 EP 0788535B1
Authority
EP
European Patent Office
Prior art keywords
cobalt
oil
composition
formulated
copper
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
Application number
EP95938911A
Other languages
English (en)
French (fr)
Other versions
EP0788535A1 (de
Inventor
David G. L. Holt
Manuel A. Francisco
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Publication of EP0788535A1 publication Critical patent/EP0788535A1/de
Application granted granted Critical
Publication of EP0788535B1 publication Critical patent/EP0788535B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • 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
    • C10M129/24—Aldehydes; Ketones
    • 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
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
    • 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
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/56—Acids of unknown or incompletely defined constitution
    • C10M129/58—Naphthenic 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/86—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
    • C10M129/92—Carboxylic acids
    • C10M129/93—Carboxylic acids having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • 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
    • C10M2207/08—Aldehydes; Ketones
    • 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/16—Naphthenic acids

Definitions

  • the present invention relates to novel lube oil base stock compositions containing deposit control additives.
  • Copper is a common lube oil antioxidant additive. However, it forms deposits at higher temperatures. As a result additives and methods for increasing the lifetime of copper antioxidants and for retarding their degradation and resulting deposit formation would be desirable. The present invention addresses these needs.
  • FR-A-2 372 222 and GB-A-772 029 disclose the use of copper and cobalt as lubricating oil additives.
  • the present invention provides for formulated lubricating oil compositions, comprising a base stock of lubricating viscosity, a copper containing antioxidant and a deposit control enhancing amount of an oil soluble or oil dispersible cobalt containing compound.
  • the present invention also provides for a method of controlling deposit formation in an engine lubricating system, comprising adding a deposit control enhancing amount of an oil soluble or oil dispersible cobalt containing compound to a base oil of lubricating viscosity formulated with a copper containing antioxidant.
  • the present invention may suitably comprise, consist or consist essentially of the elements disclosed herein and may be practiced in the absence of any element not disclosed herein as required.
  • the present invention provides for a method of controlling deposits, i.e. retarding deposit formation and buildup, in internal combustion engines by enhancing the performance of a certain base stocks containing copper containing antioxidants, with the addition of cobalt containing compounds as disclosed in claim 1.
  • the invention also provides for novel formulated oil and additive compositions related thereto. As a benefit the life of the copper containing antioxidant and the formulated oil can be extended, as disclosed in claim 7 and the use of cobalt and copper soluble compound to enhance the control of deposit formation disclosed in claim 8.
  • the starting materials disclosed herein may be made by methods known in the art or obtained from commercial sources.
  • copper containing compounds and the cobalt containing compounds are individually present in a minor amount by weight percent of the compound to a major amount of the oil.
  • minor amount as used herein is intended to mean that amount is less than 50% by weight of the composition.
  • major amount is intended to mean that amount is more than 50% by weight of the composition.
  • the copper antioxidant should be present in a hydrocarbon, preferably oil soluble or dispersible form. These antioxidants are of the type and are present in amounts typically used as lube additives for internal combustion engines as these represent an economical and readily available source of the materials. Suitable examples include copper naphthenates, oleates and polyisobutylene succinic anhydride (“PIBSA”) compounds. Thus, these amounts may vary with the particular formulation without affecting the present invention.
  • PIBSA polyisobutylene succinic anhydride
  • cobalt containing compounds that produce the synergistic effect of enhancing deposit control in formulated oils having copper containing antioxidants therein should be present in a hydrocarbon, preferably oil soluble or dispersible form.
  • any source of cobalt is acceptable provided that it is oil soluble or dispersible.
  • oil soluble cobalt salts such as cobalt naphthenates, or cobalt stearates and inorganic cobalt salts in combination with suitable dispersants or surfactants, for example cobalt PIBSA or cobalt acetylacetonate ("acac").
  • the cobalt containing compound be compatible with the copper containing compound as well as the base stock or formulated oil to which it is added in order to achieve the synergistic effect of retarding deposit formation and extending the life of the copper antioxidant and formulated oil.
  • the cobalt is present in an amount sufficient to enhance deposit control performance, i.e., to retard deposit formation and, thus, extend the life of the lube oil containing the copper antioxidant.
  • This amount typically is a minor amount of cobalt metal, from about 10-1000 ppm, preferably about 50-500 ppm, more preferably about 75-200 ppm, as determined on the basis of the amount of the metal present in the formulated compositions.
  • hydrocarbon or oil “soluble” and “dispersible” means that the material is soluble or stably dispersible in hydrocarbons, preferably oils of lubricating viscosity, that are liquid at temperatures found in the environments at which the formulated oils are typically used.
  • stably dispersible means that the material is capable of being dispersed in the hydrocarbon or oil to an extent that allows it to function in its intended manner.
  • a copper antioxidant or the cobalt antioxidant is hydrocarbon or oil soluble or dispersible if it is capable of being dissolved, dispersed or otherwise suspended in the oil in a manner sufficient to allow the oil to function as a lubricant.
  • Detergents such as neutral and/or overbased blends of calcium sulfonated detergents and dispersants such as borated PIBSA-PAM may be used to achieve oil solubility or dispersibility.
  • the base oils employed in the lubricant compositions according to the invention may be any base oil suitable for the intended use of the lubricant.
  • the base oil may be, for example, a conventionally refined mineral oil, an oil derived from coal tar or shale, a vegetable oil, an animal oil, a hydrocracked oil, or a synthetic oil, or a mixture of two or more of these types of oils.
  • synthetic oils include hydroisomerised paraffins, polyalpha-olefins, polybutenes, alkylbenzenes, polyglycols, esters such as polyol esters or dibasic carboxylic acid esters, alkylene oxide polymers, and silicone oils.
  • the viscosity of the base oil depends upon the intended use, but generally is in the range of from 3 to 20cSt at 100°C.
  • the present invention also permits the use of other additives in the oil compositions.
  • additives include such conventional additive types as viscosity modifiers, extreme pressure agents, corrosion-inhibiting agents, pour point depressants, color stabilizing agents, anti-foam agents, and other such additive materials known generally to those skilled in the art of formulating lubricants.
  • IPDT Inclined Panel Deposit Test
  • the IPDT is a bench test that simulates piston deposit formation during engine operation. 35 ml of oil was heated to 150°C and run down a metal panel heated to 308°C at a 2 degree angle. The oil was then pumped through a sump back onto the panel. The oil was exposed to a synthetic blow-by gas throughout the 2 hour duration of the test. The panel was cooled and washed with heptane. The rating figure (demerit) value indicates the amount of deposition on the plate. A higher number (greater demerit) indicates greater deposit formation, with 10 being the highest and zero the lowest.
  • Table 1 shows the results of the IPDT using a commercially available mineral oil base stock formulated with commercially available additive package containing copper PIBSA and a monofunctional olefin copolymer VI improver, borated PIBSA pour point depressant, calcium sulfonate overbased detergent, neutral calcium sulfonate detergent, nonyl phenyl sulfide antioxidant, ZDDP antiwear, molybdenum dithiocarbonate antiwear additive alone (Run 1) and in the presence of cobalt additive (Run 2) demonstrating the synergistic effect of adding cobalt in copper antioxidant systems.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (8)

  1. Formulierte Schmierölzusammensetzung für Verbrennungsmotoren, die Basismotoröl mit Schmierviskosität, kupferhaltiges Antioxidans und eine die Kontrolle von Ablagerungen erhöhende Menge öllösliche oder öldispergierbare kobalthaltige Verbindung umfaßt, die 10 bis 1000 Gew.ppm Kobaltmetall in der formulierten Schmierstoffzusammensetzung liefert.
  2. Zusammensetzung nach Anspruch 1, bei der die Menge an kobalthaltiger Verbindung 50 bis 500 Gew.ppm beträgt, bezogen auf die Menge an Kobaltmetall in der formulierten Schmierstoffzusammensetzung.
  3. Zusammensetzung nach Anspruch 1 oder 2, bei der die kobalthaltige Verbindung ausgewählt ist aus Kobaltnaphthenaten, Kobaltstearaten, Kobalt-Polyisobutylenbernsteinsäureanhydriden und Kobaltacetylacetonaten.
  4. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei der das kupferhaltige Antioxidans ausgewählt ist aus Kupfernaphthenaten, -oleaten, -stearaten und -Polyisobutylenbernsteinsäureanhydriden.
  5. Zusammensetzung nach einem der vorhergehenden Ansprüche, die ferner mindestens ein Mittel ausgewählt aus Dispergiermittel und Detergens umfaßt.
  6. Zusammensetzung nach einem der vorhergehenden Ansprüche, die ferner mindestens ein Additiv ausgewählt aus Antiverschleißmitteln, Viskositätsmodifizierungsmitteln, Extremdruckmitteln, Antischaummitteln, Stockpunktsenkungsmitteln und Farbstabilisierungsmitteln umfaßt.
  7. Verfahren zur Kontrolle der Bildung von Ablagerungen im Schmiersystem eines Verbrennungsmotors, bei dem eine die Kontrolle von Ablagerungen erhöhende Menge von 10 bis 1000 Gew.ppm, bezogen auf die Menge an Kobaltmetall in der formulierten Schmierstoffzusammensetzung, einer öllöslichen oder öldispergierbaren kobalthaltigen Verbindung mit einem Basismotoröl mit Schmierviskosität kombiniert wird, das mit kupferhaltigem Antioxidans formuliert ist.
  8. Verwendung von öllöslicher oder öldispergierbarer kobalthaltiger Verbindung zur Erhöhung der Kontrolle der Bildung von Ablagerungen im Schmiersystem eines Verbrennungsmotors, wobei das Schmiersystem Basismotoröl mit Schmierviskosität und kupferhaltiges Antioxidans umfaßt.
EP95938911A 1994-10-25 1995-10-25 Kobalt enthaltende additive zur kontrolle von ablagerungen Expired - Lifetime EP0788535B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US328209 1981-12-07
US32820994A 1994-10-25 1994-10-25
PCT/US1995/013840 WO1996012779A1 (en) 1994-10-25 1995-10-25 Novel cobalt containing deposit control additives

Publications (2)

Publication Number Publication Date
EP0788535A1 EP0788535A1 (de) 1997-08-13
EP0788535B1 true EP0788535B1 (de) 2000-05-03

Family

ID=23279994

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95938911A Expired - Lifetime EP0788535B1 (de) 1994-10-25 1995-10-25 Kobalt enthaltende additive zur kontrolle von ablagerungen

Country Status (5)

Country Link
EP (1) EP0788535B1 (de)
JP (1) JPH10508053A (de)
CA (1) CA2201960A1 (de)
DE (1) DE69516710T2 (de)
WO (1) WO1996012779A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7648949B2 (en) 2005-01-27 2010-01-19 The Lubrizol Corporation Low phosphorus cobalt complex-containing engine oil lubricant
US10000721B2 (en) 2014-12-30 2018-06-19 Exxonmobil Research And Engineering Company Lubricating oil compositions with engine wear protection
US10781397B2 (en) 2014-12-30 2020-09-22 Exxonmobil Research And Engineering Company Lubricating oil compositions with engine wear protection
WO2016184842A1 (en) * 2015-05-18 2016-11-24 Shell Internationale Research Maatschappij B.V. Lubricating composition
JP6480324B2 (ja) * 2015-12-28 2019-03-06 Ｊｘｔｇエネルギー株式会社 潤滑油組成物

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB772029A (en) * 1954-12-07 1957-04-10 Shell Res Ltd Lubricating oil compositions
US3360467A (en) * 1965-03-29 1967-12-26 Monsanto Res Corp Functional fluid
US3412028A (en) * 1966-12-13 1968-11-19 Texaco Inc Synthetic ester base lubricating composition containing a copper or cobalt acetylacetonate
US4122033A (en) * 1976-11-26 1978-10-24 Black James F Oxidation inhibitor and compositions containing the same
EP0444830A1 (de) * 1990-02-26 1991-09-04 Ethyl Petroleum Additives Limited Succinimid-Zusammensetzung

Also Published As

Publication number Publication date
DE69516710T2 (de) 2000-08-31
JPH10508053A (ja) 1998-08-04
EP0788535A1 (de) 1997-08-13
DE69516710D1 (de) 2000-06-08
CA2201960A1 (en) 1996-05-02
WO1996012779A1 (en) 1996-05-02

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