WO2001060959A1 - Antioxidant additive composition for lubricating oils - Google Patents

Antioxidant additive composition for lubricating oils Download PDF

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Publication number
WO2001060959A1
WO2001060959A1 PCT/US2001/009730 US0109730W WO0160959A1 WO 2001060959 A1 WO2001060959 A1 WO 2001060959A1 US 0109730 W US0109730 W US 0109730W WO 0160959 A1 WO0160959 A1 WO 0160959A1
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Prior art keywords
compound
composition
cst
phenolic
aminic
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PCT/US2001/009730
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English (en)
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WO2001060959A8 (fr
Inventor
Jason Gao
Christopher John May
Jeffrey Robert Torkelson
Paul S. Woolley
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Exxonmobil Research And Engineering Company
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Application filed by Exxonmobil Research And Engineering Company filed Critical Exxonmobil Research And Engineering Company
Priority to AU2001245992A priority Critical patent/AU2001245992A1/en
Priority to BR0108330-9A priority patent/BR0108330A/pt
Priority to CA002397885A priority patent/CA2397885C/fr
Priority to EP01918980A priority patent/EP1280873A1/fr
Priority to US10/181,860 priority patent/US6734150B2/en
Priority to JP2001560331A priority patent/JP2003523456A/ja
Publication of WO2001060959A1 publication Critical patent/WO2001060959A1/fr
Publication of WO2001060959A8 publication Critical patent/WO2001060959A8/fr

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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/18—Complexes with metals
    • 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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • 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
    • 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
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/084—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/085—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/086—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing sulfur atoms bound to carbon atoms of six-membered aromatic rings
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/09—Complexes with metals
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/065—Saturated Compounds
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/50—Emission or smoke controlling properties
    • C—CHEMISTRY; METALLURGY
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • This invention relates to lubricating oil compositions, especially lubricants used in internal combustion engines, comprising base oils high in saturates which are resistant to oxidation.
  • Lubricating oil compositions are used for the smooth operation of internal combustion engines, power transmission components including automatic transmissions, shock absorbers and power steering devices and gears.
  • the engine oils for internal combustion engines in particular serve to (i) lubricate various sliding interfaces eg between the piston ring and cylinder liner, in bearings of the crank shaft and the connecting rod, and in the valve driving mechanism including cams and valve lifters, (ii) cool the engine, (iii) clean and disperse the combustion products and (iv) prevent corrosion and consequent rust formation.
  • the stringent requirements for high performance engines in recent years has meant greater demand from lubricants used in such engines.
  • Lubricating oils used in such engines usually deteriorate due to oxidation by oxygen and nitrogen oxides (NOx) formed during combustion of fuels and lubricants and that contained in blow-by gas in turn formed by leakage of combustion gases into the crankcase via the piston and cylinder interface.
  • NOx oxygen and nitrogen oxides
  • the concentration of NOx increases in the blow-by gas with increasing demand in performance of the engine.
  • the deleterious effects of oxidation can be and have been mitigated by the use of various additives including antioxidants, anti-wear agents, ash-free detergent dispersants, friction modifiers and the like.
  • the present invention is a lubricating oil composition
  • a base stock and an antioxidant comprising an oil soluble trinuclear organomolybdenum compound of the generic formula: Mo 3 S x -(Q) (I) wherein x is from 4 to 10, preferably 7, and Q is a core group, which may be a ligand, and at least one other compound selected from a phenolic and an aminic compound characterised in that the base stock has a kinematic viscosity at 100°C (KNioo) from about 2 cSt to 20 cSt (2 x 10 "6 to 20 x 10 "6 m 2 /sec) and a saturates content of at least 85%.
  • KNioo kinematic viscosity at 100°C
  • the lubricating oil compositions of the present invention are those that comprise a major amount of a Group II or Group III base stock which may be a natural or synthetic lubricating oil having a KNioo of 2-20 cSt, preferably from 2-12 cSt and a saturates content of at least 85%, preferably at least 88%.
  • Specific examples of Group II basestock high in saturates include inter alia RLOP 500R and Mobil Jurong 500 ⁇ (with > 97% saturates), and MXT 5 (with 92% saturates); and examples of Group III basestock include inter alia Yubase 4 (with saturate contents of 99.5%) and Yubase 6 (with saturate contents of 97.5%).
  • the present invention is a method of stabilizing a lubricant composition against oxidative degradation, said composition comprising a base stock which has a kinematic viscosity at 100°C (KNioo) from about 2 cSt to 20 cSt (2 x 10 "6 to 20 x 10 "6 m 2 /sec) and a saturates content of at least 85% said method comprising adding to the basestock an effective amount of an antioxidant comprising an oil soluble trinuclear organomolybdenum compound of the generic formula:
  • the trinuclear molybdenum compounds are of formula (I)
  • x is from 4 to 10, preferably 7, and Q is a core group.
  • the core group (Q) may be a ligand capable of rendering the organomolybdenum compound of formula (I) oil soluble and ensuring that said molybdenum compound is substantially charge neutral.
  • the core group (Q) is generally associated with suitable ligands such as L y wherein L is the ligand and y is of a sufficient number, type and charge to render the compound of formula (I) oil soluble and to neutralise the charge on the compound of formula (I) as a whole.
  • suitable ligands such as L y wherein L is the ligand and y is of a sufficient number, type and charge to render the compound of formula (I) oil soluble and to neutralise the charge on the compound of formula (I) as a whole.
  • the trinuclear molybdenum compound used in the compositions of the present invention may be represented by the formula (II):
  • the ligands "L” are suitably dihydrocarbyl dithiocarbamates of the structure (-S CNR 2 ) wherein the dihydrocarbyl groups, R 2 impart oil solubility to the molybdenum compound.
  • hydrocarbyl denotes a substituent having carbon atoms directly attached to the remainder of the ligand and is predominantly hydrocarbyl in character within the context of this invention.
  • substituents include the following:
  • hydrocarbon substituents ie, aliphatic (for example alkyl or alkenyl), alicyclic (for example cycloalkyl or cycloalkenyl), aromatic-, aliphatic- and alicyclic-substituted aromatic nuclei and the like, as well as cyclic substituents wherein the ring is completed through another portion of the ligand (that is, any two indicated substituents may together form an alicyclic group);
  • hetero substituents ie, substituents which, while predominantly hydrocarbon in character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms.
  • the hydrocarbyl groups are preferably alkyl (e.g, in which the carbon atom attached to the remainder of the ligand "L" is primary, secondary or tertiary), aryl, substituted aryl and/or ether groups.
  • the hydrocarbyl groups of the ligands should be such that they have a sufficient number of carbon atoms to render the compound (I) soluble or dispersible in the oil to which the trinuclear organomolybdenum compound containing the ligand is added.
  • the total number of carbon atoms present among all of the hydrocarbyl groups of the organomolybdenum compounds' ligands is suitably at least 21, preferably at least 25, more preferably at least 30 and even more preferably at least 35, typically e.g., 21 to 800.
  • the number of carbon atoms in each hydrocarbyl group will generally range from 1 to 100, preferably from 1 to 40 and more preferably from 3 to 20.
  • the antioxidant in the compositions of the present invention suitably also include at least one other compound selected from a phenolic compound and an aminic compound.
  • phenolic compounds hindered phenols are preferred. Examples of such phenolic compounds include ter alia:
  • antioxidants which are preferred as the antioxidants may be represented by the generic formulae (III) - (IN) below in which R l5 R 2 , and R 3 are the same or different alkyl groups from 3-9 carbon atoms and x and y are integers from 1 to 4.
  • Suitable aminic compounds for use in the compositions of the present invention are diaryl amines, aryl naphthyl amines and alkyl derivatives of diaryl amines and the aryl naphthyl amines.
  • Preferred aminic antioxidants are represented by the formulae (VII) and (VIII) wherein each of ⁇ and R 5 is a hydrogen atom or represents the same or different alkyl groups from 1-8 carbon atoms.
  • Monoalkyldiphenyl amines such as eg monooctyldiphenyl amine and monononyl diphenyl amine; dialkyldiphenyl amines such as eg 4,4'-dibutyldiphenyl amine, 4,4'- dipentyldiphenyl amine, 4,4'-dihexyldiphenyl amine, 4,4'-diheptyldiphenyl amine, 4,4'- dioctyldiphenyl amine and 4,4'-dinonyldiphenyl amine; polyalkyldiphenyl amines such as eg tetra-butyldiphenyl amine, tetra-hexyldiphenyl amine, tetra-octyldiphenyl amine and tetra- nonyldiphenyl amine; the naphthylamines such as eg ⁇ -naphthy
  • the antioxidant which comprises the organomolybdenum compound in combination with a phenolic and/or an aminic compound will form a minor component of the total lubricant composition.
  • the organomolybdenum compound typically will comprise about 0.05 to about 5.00 wt % of the total composition, preferably from 0.05 to 2.0 wt%, and more preferably from 0.1 to 0.7 wt%, i.e., the molybdenum metal is suitably present in an amount of from about 25 to 2500 ppm, preferably from about 50 to 1000 ppm, and more preferably from 100 to 700 ppm, and the phenolic and/or aminic compounds about 0.10 to about 3.0 wt % of the total composition.
  • the antioxidant comprises in addition to the organo molybdenum compound, a mixture of the phenols (III)-(VI) above and the diaryl amines (VII)-(VIII) in a weight ratio ranging from about 80: 10: 10 to about 10:30:60 respectively, preferably typically 50:15:35 respectively.
  • the antioxidants may be combined with a carrier liquid in the form of a concentrate.
  • concentration of the combined antioxidants in the concentrate may vary from 1 to 80% by weight, and will preferably be in the range of 5 to 50% by weight.
  • the antioxidant combination of the present invention can be used with any of the conventional dispersants used hitherto in the lubricating compositions.
  • dispersants include mter alia the polyalkylene succinimides, Mannich condensation products of polylalkylphenol-formaldehyde polyamine and boronated derivatives thereof.
  • ashless dispersants such as the ashless succinimides, especially the polyisobutenyl succinimides of a polyamine such as eg tetraethylenepentamine or its homologues, benzylamine ashless dispersants, and ester ashless dispersants.
  • the dispersants are generally used in the compositions of the present invention in an amount ranging from about 2-10% by weight based on the total weight of the lubricant composition, preferably from about 4-8% by weight.
  • a feature of the present invention is that the compositions of the present invention the presence of a trinuclear organo molybdenum compound facilitates the control of deposit formation from engine oils. More specifically, formulations containing eg a contribution of 200- 750 ppm, preferably from 450-550 ppm of Mo metal from the trimer and an additional contribution of from 80-100 ppm from a detergent inhibitor package enables the amount of deposit formed to be significantly reduced.
  • This reduction in deposit formation has been monitored by the so-called TEOST-MHT-2 test which test is similar to the conventionally used TEOST-33 test method except that it is run at a relatively lower temperature and for a longer time. These tests are especially designed to test the formulations for a GF-3 specification.
  • the TEOST-33 test is carried out at temperature cycles which fluctuate from 200-500°C and last for about 2 hours and results in bulk oxidation of the oil (about 100 g).
  • the TEOST-MHT-2 test relates to high temperature engine deposits as measured in tests such as TU3HT and is carried out at about 285°C over 24 hours and is a thin-film test on about 8 g of oil.
  • the TEOST-MHT-2 test measures deposits produced on a heated rod or in the oil itself (filtered residue) and the GF-3 specification is envisioned to specify a limit of 40 mg deposit. From the results in the Examples below it will be seen that the presence of a trinuclear organo molybdenum compound in such oils results in about 66% reduction in the total weight of the deposits formed which satisfies the GF-3 specification.
  • these lubricating compositions may include additives commonly used in lubricating oils especially crankcase lubricants, such as antiwear agents, detergents, dispersants, rust inhibitors, viscosity index improvers, extreme-pressure agents, friction modifiers, corrosion inhibitors, emulsifying aids, pour point depressants, anti-foams and the like.
  • crankcase lubricants such as antiwear agents, detergents, dispersants, rust inhibitors, viscosity index improvers, extreme-pressure agents, friction modifiers, corrosion inhibitors, emulsifying aids, pour point depressants, anti-foams and the like.
  • a feature of the present invention is that lubricant compositions comprising high saturates base oils and trinuclear organomolybdenum compounds in combination with a phenolic and/or an aminic compound as antioxidant provide unexpected improvement in oxidation control and significant benefits in fuel economy.
  • the present invention confers the added benefits of viscosity increase control and dispersancy retention over compositions which contain only one of these antioxidants used alone.
  • Test oils were prepared. These oils were then tested in a bench oxidation test which was conducted at 165°C under a mixed nitrogen/air flow, with 40 ppm iron from added ferric acetylacetonate as catalyst. The flow rates of air and nitrogen were controlled at 500 ml/min and 350ml/min respectively.
  • Irganox® L57 is an octylated/butylated diphenylamine (ex Ciba Geigy)
  • Irganox® LI 01 is a high molecular weight phenolic antioxidant (ex Ciba Geigy)
  • Irganox® LI 15 and Irganox® L 1035 are high molecular weight phenolic antioxidants with a thioether group (ex Ciba Geigy)
  • Irganox® L06 is an alkylated phenyl- ⁇ -naphthylamine (ex Ciba Geigy)
  • Irganox® LI 35 is a high molecular weight phenolic antioxidant (ex Ciba Geigy)
  • Irganox® LI 50 is a mixture of alkylated diphenylamine, a phenolic antioxidant and a phenolic antioxidant with a thioether group (ex Ciba Geigy)
  • Paranox® 106 is a polyisobutenylsuccinimide dispersant (ex Infenium, Linden, NJ)
  • Molyvan® 822 is a dinuclear molybdenum dithiocarbamate containing 5 % wt molybdenum (ex R T Vanderbilt Co)
  • PDN5203 is an experimental sample of trinucler molybdenum dithiocarbamate containing 5% wt molybdenum
  • Paratone 8451 is a viscosity index improver (ex Oronite)
  • Paraflow®390 is a pour point depressant (ex Oronite)
  • DI is a conventional detergent inhibitor package which is free of a friction modifier package
  • compositions of the test oils in these used in these Examples and their changes m respective viscosities after a 48 hour oxidation test are given m Table 1 below
  • compositions of the test oils in Examples J-Q and their respective changes in viscosity data after a 48-hour oxidation test on each are shown in Table 2 below TABLE 2
  • Examples J-Q show that the trinuclear molybdnum dithiocarbamate gives better performance than conventional dinuclear molybdenum dithiocarbamate in oxidation control.
  • the performance of the trinuclear molybdenum compound is further enhanced in base oils high in saturates.
  • Examples R-U demonstrate that mixtures of aminic and phenolic antioxidants give equivalent performance to an aminic antioxidant.
  • Base oils high in saturates provide additional benefit in viscosity control.
  • Fuel economy is measured in different types of engine tests including the Sequence VIA, Sequence VIB and the Ml 11 tests. Sequence VIA and the Ml 11 tests evaluate initial fuel economy while Sequence VIB test determines initial and retained fuel economy after 96 hours.
  • a 5W-20 formulation comprising a Group II base oil is shown in Table 4 below:
  • the fuel economy and fuel economy retention data were collected using a gasoline passenger car Ml 11 fuel economy test (CES-L54-X-94) and a Ml 11 fuel economy retention test.
  • Ml 11 fuel economy retention test the duration of the test is extended by repeating the standard test cycles 21 times. Each test cycle is followed by a period of steady state aging. The aging is equivalent to 500 miles. The total test is thus equivalent to about 10,000 miles, and takes about 185 hours. Fuel consumptions are measured at every cycle, hence every 500 miles. The fuel consumption reference RL191 is measured both at the beginning and end of the test, thereby allowing uninterrupted aging of the test oil.
  • Example V shows that addition of molybdenum compounds leads to better fuel economy retention in a European gasoline passenger car engine.
  • the use of trinuclear molybdenum dithiocarbamate provides significant improvement in initial fuel economy and fuel economy retention over the conventional dinuclear molybdenum dithiocarbamate.
  • a 5W-20 engine oil formulation comprising a Group III base oil is shown in Table 6 below:
  • Example W further demonstrates the benefit of trinuclear molybdenum dithiocarbamate in fuel economy improvement in a North American gasoline engine.
  • the TEOST-MHT-2 test was performed in a manner very similar to the conventional TEOST-33 test for a GF-2 specification by running at a lower temperature (285°C) but for a longer period of time ie 24 hours on an 8 g sample of oil.
  • the test is set to measure deposits produced on a heated rod or in the oil itself (filtered residue) and it was expected to match the currently given GF-3 specification limit of 40 mg of deposit.
  • Table 8 The results are tabulated in Table 8 below:

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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)
  • Lubricants (AREA)

Abstract

L'invention concerne une composition d'huile lubrifiante qui comprend une huile de base et un antioxydant renfermant un composé d'organomolybdène trinucléaire soluble dans l'huile de formule générale (I) Mo3Sx-(Q). Dans ladite formule, x vaut de 4 à 10 et Q est un groupe central, qui peut être un ligand. Il existe au moins un autre composé pouvant être un composé phénolique ou aminofonctionnel. L'huile de base a une viscosité cinématique, à 100 °C (KV100), comprise entre environ 2 cSt et 20 cSt (2 x 10-6 à 20 x 10-6 m2/sec) et une teneur en produits saturés d'au moins 85 %. La composition présente une stabilité élevée à l'oxydation, une formation de dépôts réduite, permettant par ailleurs d'améliorer de manière satisfaisante les économies de carburant.
PCT/US2001/009730 2000-02-14 2001-02-08 Antioxidant additive composition for lubricating oils WO2001060959A1 (fr)

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AU2001245992A AU2001245992A1 (en) 2000-02-14 2001-02-08 Antioxidant additive composition for lubricating oils
BR0108330-9A BR0108330A (pt) 2000-02-14 2001-02-08 Composição de óleo lubrificante, e métodos de estabilização de uma composição lubrificante contra a degradação oxidativa, e, de melhoria da economia de combustìvel de uma composição lubrificante
CA002397885A CA2397885C (fr) 2000-02-14 2001-02-08 Compositions d'huile lubrifiante
EP01918980A EP1280873A1 (fr) 2000-02-14 2001-02-08 Composition d'additifs antioxidants pour huiles lubrifiantes
US10/181,860 US6734150B2 (en) 2000-02-14 2001-02-08 Lubricating oil compositions
JP2001560331A JP2003523456A (ja) 2000-02-14 2001-02-08 潤滑油組成物

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GB0003388A GB2359093A (en) 2000-02-14 2000-02-14 Lubricating oil compositions

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Cited By (5)

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EP1451275A1 (fr) * 2001-11-29 2004-09-01 Chevron Oronite Company LLC Systeme d'additif d'huile de lubrification contenant du soufre particulierement utile pour des moteurs fonctionnant au gaz naturel
EP1451274A1 (fr) * 2001-11-29 2004-09-01 Chevron Oronite Company LLC Systeme d'additif d'huile de lubrification particulierement utile pour des moteurs fonctionnant au gaz naturel
EP1479887A1 (fr) * 2003-05-22 2004-11-24 Ethyl Corporation Transport d'un composé organique de molybdène de lubrifiant aux système de combustion de carburant
WO2005021693A1 (fr) * 2003-08-22 2005-03-10 Exxonmobil Research And Engineering Company Huiles de moteur zero phosphore, sans zinc a performance elevee destinees aux moteurs thermiques
WO2005078054A1 (fr) * 2004-02-03 2005-08-25 Chemtura Corporation Compositions lubrifiantes comportant un melange antioxydant

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US6852679B2 (en) 2002-02-20 2005-02-08 Infineum International Ltd. Lubricating oil composition
EP2123739B1 (fr) * 2008-05-20 2017-09-27 Infineum International Limited Lubrification de moteur marin
EP2123740B1 (fr) 2008-05-20 2017-08-23 Infineum International Limited Lubrification de moteur marin
EP2135926A1 (fr) 2008-05-20 2009-12-23 Infineum International Limited Lubrification de moteur marin
CN102365352A (zh) * 2009-04-07 2012-02-29 英菲诺姆国际有限公司 船用发动机润滑

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JP4528439B2 (ja) * 1997-12-12 2010-08-18 インフィニューム ユーエスエイ リミテッド パートナーシップ 三核モリブデン−イオウ化合物の製造方法及びそれらの潤滑剤用添加剤としての使用
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WO1998026030A1 (fr) * 1996-12-13 1998-06-18 Exxon Research And Engineering Company Compositions d'huile lubrifiante contenant des complexes de molybdene organiques
US5906968A (en) * 1997-12-12 1999-05-25 Exxon Research & Engineering Company Method of synthesizing Mo3 Sx containing compounds
WO1999047629A1 (fr) * 1998-03-13 1999-09-23 Infineum Usa L.P. Huile lubrifiante presentant des proprietes ameliorees de maintien d'economie de carburant
WO2001030948A1 (fr) * 1999-10-25 2001-05-03 Infineum International Limited Composition d'huile lubrifiante contenant deux additifs au molybdene

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1451275A1 (fr) * 2001-11-29 2004-09-01 Chevron Oronite Company LLC Systeme d'additif d'huile de lubrification contenant du soufre particulierement utile pour des moteurs fonctionnant au gaz naturel
EP1451274A1 (fr) * 2001-11-29 2004-09-01 Chevron Oronite Company LLC Systeme d'additif d'huile de lubrification particulierement utile pour des moteurs fonctionnant au gaz naturel
EP1451274A4 (fr) * 2001-11-29 2005-03-16 Chevron Oronite Co Systeme d'additif d'huile de lubrification particulierement utile pour des moteurs fonctionnant au gaz naturel
EP1451275A4 (fr) * 2001-11-29 2005-03-16 Chevron Oronite Co Systeme d'additif d'huile de lubrification contenant du soufre particulierement utile pour des moteurs fonctionnant au gaz naturel
EP1479887A1 (fr) * 2003-05-22 2004-11-24 Ethyl Corporation Transport d'un composé organique de molybdène de lubrifiant aux système de combustion de carburant
US7134427B2 (en) 2003-05-22 2006-11-14 Afton Chemical Intangibles Llc Delivery of organomolybdenum via vapor phase from a lubricant source into a fuel combustion system
WO2005021693A1 (fr) * 2003-08-22 2005-03-10 Exxonmobil Research And Engineering Company Huiles de moteur zero phosphore, sans zinc a performance elevee destinees aux moteurs thermiques
WO2005078054A1 (fr) * 2004-02-03 2005-08-25 Chemtura Corporation Compositions lubrifiantes comportant un melange antioxydant
US7494960B2 (en) 2004-02-03 2009-02-24 Crompton Corporation Lubricant compositions comprising an antioxidant blend

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AU2001245992A1 (en) 2001-08-27
BR0108330A (pt) 2003-03-11
AR031551A1 (es) 2003-09-24
WO2001060959A8 (fr) 2001-12-06
CA2397885A1 (fr) 2001-08-23
EP1280873A1 (fr) 2003-02-05

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