USRE37363E1 - Lubricant containing molybdenum compound and secondary diarylamine - Google Patents

Lubricant containing molybdenum compound and secondary diarylamine Download PDF

Info

Publication number
USRE37363E1
USRE37363E1 US09/359,770 US35977099A USRE37363E US RE37363 E1 USRE37363 E1 US RE37363E1 US 35977099 A US35977099 A US 35977099A US RE37363 E USRE37363 E US RE37363E
Authority
US
United States
Prior art keywords
molybdenum
acid
carbon atoms
oil
amine
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
US09/359,770
Inventor
Vincent James Gatto
Mark Thomas Devlin
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.)
Afton Chemical Intangibles LLC
Original Assignee
Ethyl Corp
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
Priority to US09/359,770 priority Critical patent/USRE37363E1/en
Application filed by Ethyl Corp filed Critical Ethyl Corp
Priority to US09/604,285 priority patent/USRE38929E1/en
Assigned to BANK OF AMERICA, N.A., AS COLLATERAL AGENT reassignment BANK OF AMERICA, N.A., AS COLLATERAL AGENT NOTICE OF GRANT SECURITY INTEREST Assignors: ETHYL CORPORATION
Application granted granted Critical
Publication of USRE37363E1 publication Critical patent/USRE37363E1/en
Assigned to ETHLYL CORPORATION reassignment ETHLYL CORPORATION RELEASE OF SECURITY INTEREST Assignors: BANK OF AMERICA, N.A.
Assigned to CREDIT SUISSE FIRST BOSTON, CAYMAN ISLANDS BRANCH reassignment CREDIT SUISSE FIRST BOSTON, CAYMAN ISLANDS BRANCH GRANT OF PATENT SECURITY INTEREST Assignors: ETHYL CORPORATION
Assigned to SUNTRUST BANK, AS ADMINISTRATIVE AGENT reassignment SUNTRUST BANK, AS ADMINISTRATIVE AGENT SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ETHYL CORPORATION
Assigned to SUNTRUST BANK, AS ADMINISTRATIVE AGENT reassignment SUNTRUST BANK, AS ADMINISTRATIVE AGENT ASSIGNMT. OF SECURITY INTEREST Assignors: CREDIT SUISSE FIRST BOSTON, CAYMAN ISLANDS BRANCH
Assigned to AFTON CHEMICAL INTANGIBLES LLC reassignment AFTON CHEMICAL INTANGIBLES LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ETHYL CORPORATION
Priority to US11/133,442 priority patent/USRE40595E1/en
Assigned to SUNTRUST BANK reassignment SUNTRUST BANK SECURITY AGREEMENT Assignors: AFTON CHEMICAL INTANGIBLES LLC
Assigned to AFTON CHEMICAL INTANGIBLES LLC reassignment AFTON CHEMICAL INTANGIBLES LLC RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: SUNTRUST BANK
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/06Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26Carboxylic acids; Salts thereof
    • C10M129/28Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/30Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms
    • C10M129/32Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms monocarboxylic
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26Carboxylic acids; Salts thereof
    • C10M129/28Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/40Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26Carboxylic acids; Salts thereof
    • C10M129/56Acids of unknown or incompletely defined constitution
    • C10M129/58Naphthenic acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04Phosphate esters
    • C10M137/10Thio derivatives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M139/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • C10M139/06Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00 having a metal-to-carbon bond
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/12Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M143/00Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/04Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing propene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M143/00Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/06Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing butene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M143/00Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/12Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing conjugated diene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/16Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate polycarboxylic
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12Reaction products
    • C10M159/18Complexes with metals
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12Reaction products
    • C10M159/20Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12Reaction products
    • C10M159/20Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12Reaction products
    • C10M159/20Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00Lubricating 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M167/00Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024Propene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026Butene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/06Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/024Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028Overbased salts thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/09Metal enolates, i.e. keto-enol metal complexes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/122Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix 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
    • C10M2207/126Carboxylix 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/14Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/14Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/142Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings polycarboxylic
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/16Naphthenic acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26Overbased carboxylic acid salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26Overbased carboxylic acid salts
    • C10M2207/262Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/287Partial esters
    • C10M2207/289Partial esters containing free hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064Di- and triaryl amines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064Di- and triaryl amines
    • C10M2215/065Phenyl-Naphthyl amines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/066Arylene diamines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/067Polyaryl amine alkanes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/068Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings having amino groups bound to polycyclic aromatic ring systems, i.e. systems with three or more condensed rings
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/221Six-membered rings containing nitrogen and carbon only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/225Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/225Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226Morpholines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/24Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26Amines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/30Heterocyclic compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046Overbasedsulfonic acid salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066Thiocarbamic type compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066Thiocarbamic type compounds
    • C10M2219/068Thiocarbamate metal salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088Neutral salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089Overbased salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/108Phenothiazine
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/045Metal containing thio derivatives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/065Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds containing sulfur
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00Organic 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
    • C10M2227/08Organic 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 having metal-to-carbon bonds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00Organic 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
    • C10M2227/08Organic 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 having metal-to-carbon bonds
    • C10M2227/081Organic 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 having metal-to-carbon bonds with a metal carbon bond belonging to a ring, e.g. ferocene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00Organic 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
    • C10M2227/08Organic 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 having metal-to-carbon bonds
    • C10M2227/082Pb compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00Organic 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
    • C10M2227/08Organic 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 having metal-to-carbon bonds
    • C10M2227/083Sn compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00Organic 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
    • C10M2227/09Complexes with metals
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/04Groups 2 or 12
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/12Groups 6 or 16
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/08Hydraulic fluids, e.g. brake-fluids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • C10N2040/251Alcohol-fuelled engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • C10N2040/252Diesel engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • C10N2040/252Diesel engines
    • C10N2040/253Small diesel engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • C10N2040/255Gasoline engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • C10N2040/255Gasoline engines
    • C10N2040/28Rotary engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00Specific manufacturing methods for lubricant compositions
    • C10N2070/02Concentrating of additives

Definitions

  • This invention relates to lubricating oil compositions, their method of preparation, and use. More specifically this invention relates to lubricating oil compositions which contain a molybdenum compound and a secondary diarylamine wherein the molybdenum compound is substantially free of active sulfur. The use of both the molybdenum and amine within certain concentrations provide improved oxidation control and friction modifier performance to lubricating oil compositions.
  • the lubricating oil compositions of this invention are particularly useful as crankcase lubricants.
  • Lubricating oils as used in the internal combustion engines of automobiles or trucks are subjected to a demanding environment during use. This environment results in the oil suffering oxidation which is catalyzed by the presence of impurities in the oil such as iron compounds and is also promoted by the elevated temperatures of the oil during use. This oxidation of lubrication oils during use is usually controlled to some extent by the use of antioxidant additives which may extend the useful life of the oil, particularly by reducing or preventing unacceptable viscosity increases.
  • molybdenum acts synergistically with secondary diarylamines to provide significant improvement in oxidation control.
  • the molybdenum compounds also act as friction modifiers to provide substantial fuel economy performance.
  • Lubricant compositions containing various molybdenum compounds and aromatic amines have been used in lubricating oils.
  • Such compositions include active sulfur or phosphorus as part of the molybdenum compound, use additional metallic additives, various amine additives which are different from those used in this invention, and/or have concentrations of molybdenum and amine which do not show the synergistic results obtained by this invention.
  • U.S. Pat. No. 4,394,279 of Jul. 19, 1983 to L. de Vries et al. discloses an antioxidant additive combination for lubrication oils prepared by combining (a) an active sulfur containing molybdenum compound prepared by reacting an acidic molybdenum compound, a basic nitrogen compound and carbon disulfide with (b) an aromatic amine compound.
  • U.S. Pat. No. 4,832,857 of May 23, 1989 to Amoco Corp discloses a process for preparation of overbased molybdenum alkaline earth metal and alkali metal dispersions for use in lubricating oil compositions.
  • WO95/07962 of Mar. 23, 1995 to A. Richie et al. discloses a crankcase lubricant composition for use in automobile or truck engines which contains copper, molybdenum, and aromatic amines.
  • this publication recites a very broad range of concentrations for the molybdenum and the amine whereas the concentrations of amine used with the molybdenum in the examples of that publication is well outside the range which this invention has found to be synergistic.
  • molybdenum compounds of this reference contain active sulphur, phosphorus, and other elements and the amines include compounds such as primary amines which were not found synergistic with the molybdenum carboxylates of this invention.
  • WO95/07963 of 23 Mar. 1995 to H. Shaub discloses highly sulfurized molybdenum compounds and various secondary aromatic amines having at least one aromatic group for producing a synergistic antioxidant effect when used as an antioxidant additive for lubricating oils. Again the molybdenum compounds contain active sulfur.
  • WO95/07966 of 23 Mar. 1995 to J. Atherton et al. discloses engine oil lubricants of various molybdenum compounds including that of some with active sulfur, certain organo-phosphorus compounds, an aminic antioxidant and a phenolic antioxidant within certain proportions.
  • this invention is directed to a lubricating composition
  • a lubricating composition comprising (a) a major amount of lubrication oil, (b) an oil soluble molybdenum compound substantially free of active sulfur which provides about 100 to 450 parts per million of molybdenum, and (c) about 750 to 5,000 parts per million (ppm) of an oil soluble secondary diarylamine.
  • the invention is directed to a method for improving the antioxidant and friction properties of a lubricant by incorporating in the lubricant a molybdenum compound which is substantially free of active sulfur and a secondary diarylamine in the above described concentrations.
  • the invention is directed to a lubrication oil concentrate comprising a solvent and a combination of from about 2.5 to 90 percent by weight of an oil soluble molybdenum compound which is substantially free of active sulfur and an oil soluble secondary diarylamine wherein the weight ratio of molybdenum from the molybdenum compound to the diarylamine in the concentrate is from about 0.020 to 0.60 parts of molybdenum for each part of amine.
  • the invention is directed to a lubricating composition prepared by mixing 100 to 450 parts per million of oil soluble molybdenum compound substantially free of active sulfur and 750 to 5,000 parts of a secondary diaryl amine in a lubricating composition.
  • the invention is directed to a lubrication oil concentrate prepared by dissolving in about 10 to 97.5 parts of a solvent a total of 2.5 to 90 parts of an oil soluble molybdenum compound substantially free of active sulfur and an oil soluble secondary diaryl amine.
  • the molybdenum compound used in the various compositions and methods of this invention is substantially free of sulfur.
  • compositions of this invention have various uses as lubricants such as for automotive and truck crankcase lubricants as well as transmission lubricants.
  • a key advantage of this invention is the multifunctional nature of the molybdenum/diarylamine combination and the relatively low treat levels required for a performance benefit.
  • This additive combination provides both oxidation control and friction control to the oil. This reduces the need for supplemental oxidation protection and frictional properties and should reduce the overall cost of the entire additive package. Further cost reduction is gained by the low treat levels employed.
  • the molybdenum compound used in this invention can be any molybdenum compound which is soluble in the lubricant of formulated lubricant package and is substantially free of active sulfur.
  • soluble or “oil soluble” is meant that the compound is oil soluble or solubilized under normal blending conditions into the lubrication oil or concentrate thereof.
  • Active sulfur is sulfur which is not fully oxidized. Active sulfur further oxidizes and becomes more acidic in the oil upon use.
  • sulfur such as divalent sulfur is active sulfur whereas the sulfur in a sulfonate group is fully oxidized and thus non-active sulfur. It is preferred however that the molybdenum compound be substantially free of all sulfur.
  • the molybdenum compound contains less than about 0.5% by weight of the material in question, e.g., active sulfur which is generally an insufficient amount to add significantly to corrosion.
  • the sulfur content of some commercially available molybdenum compounds can often have as much as about 1,000 ppm of sulfur as a contaminant and occasionally there can be as much as 2,000 ppm of the active sulfur. Such small amounts often come from contamination in processing the various ingredients involved.
  • alkphenyl or “alkaryl” we mean a phenyl or aryl group, respectively, which contains an alkyl substituent.
  • a molybdenum source such as ammonium molybdates, alkali and alkaline earth metal molybdates, molybdenum trioxide, and molybdenum acetylacetonates and an active hydrogen compound such as alcohols and polyols, primary and secondary amines and polyamines, phenols, ketones, anilines, etc.
  • an active hydrogen compound such as alcohols and polyols, primary and secondary amines and polyamines, phenols, ketones, anilines,
  • the main purpose for adding the molybdenum-free overbased sulfonates is to provide detergency.
  • the overbased molybdenum sulfonates such as those described by Hunt et al are expected to provide synergistic antioxidant protection to lubricants.
  • the molybdenum containing overbased alkaline earth metal and alkali metal sulfonates, phenates, and salicylates are prepared by a process which comprises:
  • Molybdenum complexes prepared by reacting a fatty oil, a diethanolamine and a molybdenum source as described by Rowan et al in U.S. Pat. No. 4,889,647 of Dec. 26, 1989;
  • Molybdenum salts such as the carboxylates are a preferred group of molybdenum compounds.
  • the molybdenum salts used in this invention may be completely dehydrated (complete removal of water during preparation), or partially dehydrated. They may be salts of the same anion or mixed salts, meaning that they are formed from more than one type of acid.
  • suitable anions there can be mentioned chloride, carboxylate, nitrate, sulfonate, or any other anion.
  • the molybdenum carboxylates may be derived from any organic carboxylic acid.
  • the molybdenum carboxylate is preferably that of a monocarboxylic acid such a that having from about 4 to 30 carbon atoms.
  • Such acids can be hydrocarbon aliphatic, alicyclic, or aromatic carboxylic acids.
  • Monocarboxylic acids such as those of aliphatic acids having about 4 to 18 carbon atoms are preferred, particularly those having an alkyl group of about 6 to 18 carbon atoms.
  • the alicyclic acids may generally contain from 4 to 12 carbon atoms.
  • the aromatic acids may generally contain one or two fused rings and contain from 7 to 14 carbon atoms wherein the carboxyl group may or may not be attached to the ring.
  • the carboxylic acid can be a saturated or unsaturated fatty acid having from about 4 to 18 carbon atoms.
  • carboxylic acids that may be used to prepare the molybdenum carboxylates include: butyric acid; valeric acid; caproic acid heptanoic acid; cyclohexanecarboxylic acid; cyclodecanoic acid; naphthenic acid; phenyl acetic acid; 2- methylhexanoic acid; 2-ethylhexanoic acid; suberic acid; octanoic acid; nonanoic acid; decanoic acid; undecanoic acid; lauric acid, tridecanoic acid; myristic acid; pentadecanoic acid; palmitic acid; linolenic acid; heptadecanoic acid; stearic acid; oleic acid; nonadecanoic acid; eicosanoic acid; heneicosanoic acid; do
  • 3,578,690 prepares its molybdenum carboxylates by reacting molybdenum oxide, molybdenum halide, alkali earth molybdate, alkaline earth molybdate, ammonium molybdate or mixtures of molybdenum sources with carboxylic acids at elevated temperatures and with removal of water.
  • composition of the oil soluble molybdenum carboxylates can vary. Most of the literature refers to these compounds as molybdenum carboxylates. They have also been referred to as molybdenum carboxylate salts, molybdenyl (Mo O 2 2+ ) carboxylates and molybdenyl carboxylate salts, molybdenum carboxylic acid salts, and molybdenum salts of carboxylic acids.
  • the concentration of the molybdenum from the molybdenum compound in the lubricant composition can vary depending upon the customer's requirements and applications.
  • the actual amount of molybdenum added is based on the desired final molybdenum level in the lubricating composition. From about 100 to 450 parts per million of molybdenum are used in this invention based on the weight of the lubricating oil composition which may be formulated to contain additional additives and preferably about 100 to 250 parts per million of molybdenum and particularly 125 to 250 ppm are used based on the weight of the lubricating oil composition.
  • the quantity of additive e.g., molybdenum carboxylate to provide molybdenum, is based on the total weight of the formulated or unformulated lubricating oil composition.
  • the secondary diarylamines are well known antioxidants and there is no particular restriction on the type of secondary diarylamine used in the invention.
  • the secondary diarylamine antioxidant has the general formula:
  • R 1 and R 2 each independently represents a substituted or unsubstituted aryl group having from 6 to 30 carbon atoms.
  • substituents for the aryl there can be mentioned aliphatic hydrocarbon groups such as alkyl having from about 1 to 20 carbon atoms, hydroxy, carboxyl or nitro, e.g., an alkaryl group having from 7 to 20 carbon atoms in the alkyl group.
  • the aryl is preferably substituted or unsubstituted phenyl or naphthyl, particularly wherein one or both of the aryl groups are substituted with an alkyl such as one having from 4 to 18 carbon atoms. It is further preferred that both aryl groups be substituted, e.g. alkyl substituted phenyl.
  • the secondary diarylamines used in this invention can be of a structure other than that shown in the above formula which shows but one nitrogen atom in the molecule.
  • the secondary diarylamine can be of a different structure provided that at least one nitrogen has 2 aryl groups attached thereto, e.g., as in the case of various diamines having a secondary nitrogen atom as well as two aryls on one of the nitrogens.
  • the secondary diarylamines used in this invention preferably have antioxidant properties in lubricating oils, even in the absence of the molybdenum compound.
  • the secondary diarylamines used in this invention should be soluble in the formulated crankcase oil package.
  • examples of some secondary diarylamines that may be used in this invention include: diphenyl amine; various alkylated diphenylamines, 3-hydroxydiphenylamine; N-phenyl-1,2-phenylenediamine; N-phenyl-1,4-phenylenediamine; dibutyldiphenylamine; dioctyldiphenylamine; dinonyldiphenylamine; phenyl-alipha-naphthylamine; phenyl-beta-naphthylamine; diheptyldiphenylamine; and p-oriented styrenated diphenylamine.
  • the concentration of the secondary diarylamine in the lubricating composition can vary depending upon the customer's requirements and applications.
  • a practical diarylamine use range in the lubricating composition is from about 750 parts per million to 5,000 parts per million (i.e. 0.075 to 0.5 wt %), preferably the concentration is from 1,000 to 4,000 parts per million (ppm) and particularly from about 1,200 to 3,000 ppm by weight. Quantities of less than 750 ppm have little or minimal effectiveness whereas quantities larger than 5,000 ppm are not economical.
  • the quantity of molybdenum in relation to the quantity of the secondary amine should be within a certain ratio.
  • the quantity of molybdenum should be about 0.020 to 0.6 parts by weight for each part by weight of the amine in the lubricating oil composition.
  • this ratio will be from about 0.040 to 0.40 parts of the molybdenum per part of the amine and particularly about 0.05 to 0.3 parts of the molybdenum per part of the amine.
  • the total quantity of molybdenum and amine can be provided by one or more than one molybdenum or amine compound.
  • the composition of the lubricant oil can vary significantly based on the customer and specific application.
  • the oil is a formulated oil which is composed of between 75 and 95 wt % of a mineral lubrication oil, between 0 and 10 wt % of a polymeric viscosity index improver, and between about 5 and 15 wt % (weight percent) of an additive package.
  • the additive package generally contains the following components:
  • the dispersants are nonmetallic additives containing nitrogen or oxygen polar groups attached to a high molecular weight hydrocarbon chain.
  • the hydrocarbon chain provides solubility on the hydrocarbon base stocks.
  • the dispersant functions to keep oil degradation products suspended in the oil.
  • Examples of commonly used dispersants include copolymers such as polymethacrylates and styrenemaleinic ester copolymers, substituted succinamides, polyamine succinamides, polyhydroxy succinic esters, substituted mannich bases, and substituted triazoles.
  • the dispersant is present in the finished oil between about 4.0 and8.5 wt %.
  • the detergents are metallic additives containing charged polar groups, such as sulfonates or carboxylates, with aliphatic, cycloaliphatic, or alkylaromatic chains, and several metal ions.
  • the detergents function by lifting deposits from the various surfaces of the engine. Examples of commonly used detergents include neutral and overbased alkali and alkaline earth metal sulfonates, neutral and overbased alkali and alkaline earth metal phenates, sulfurized phenates, overbased alkaline earth salicylates, phosphonates, thiopyrophosphonate, and thiophosphonates.
  • the detergents are present in the finished oil between about 1.0 and 2.5 wt %.
  • ZDDP's The ZDDP's (zinc dihydrocarbyl dithiophosphates) are the most commonly used antiwear additives in formulated lubricants. These additives function by reaction with the metal surface to form a new surface active compound which itself is deformed and thus protects the original engine surface. Other examples of anti-wear additives include tricresol phosphate, dilauryl phosphate, sulfurized terpenes and sulfurized fats.
  • the ZDDP's also function as antioxidants. Generally, the ZDDP is present in the finished oil between about 1.0 and 1.5 wt %, although when used, they can be used at substantially lower concentrations, e.g., 0.5 wt %. It is desirable from environmental concerns to have lower levels of ZDDP.
  • antioxidants in molybdenum-free oils other antioxidants in addition to the zinc dihydrocarbyl dithiophosphates are used to protect the oil from oxidative degradation.
  • the amount of supplemental antioxidant will vary depending on the oxidative stability of the base stock. Typical treat levels in finished oils can vary from about 1.0 to 2.5 wt %.
  • the supplementary antioxidants that are generally used include hindered phenols, hindered bisphenols, sulfurized phenols, alkylated diphenylamines, sulfurized olefins, alkyl sulfides and disulfides, dialkyl dithiocarbamates,and phenothiazines.
  • molybdenum carboxylates with diphenylamines removes the need for these supplementary antioxidatives.
  • a supplementary antioxidant may be included in oils that are less oxidatively stable or in oils that are subjected to unusually severe conditions.
  • the lubrication oil component of this invention may be selected from any of the synthetic or natural oils used as lubricants such as that for crankcase lubrication oils for spark-ignited and compression-ignited internal combustion engines, for example automobiles and truck engines, marine, and a railroad diesel engines.
  • Synthetic base oils include alkyl esters of dicarboxylic acids, polyglycols and alcohols, poly-alpha-olefins, including polybutenes, alkyl benzenes, organic esters of phosphoric acids, and polysilicone oils.
  • Natural base oils include mineral lubrication oils which may vary widely as to their crude source, e.g., as to whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic.
  • the lubrication oil base stock conveniently has a viscosity of about 2.5 to about 15 cSt or mm 2/ s and preferably about 2.5 to about 11 cSt or mm 2/ s at 100° C.
  • a polymeric viscosity index improver (VII) component may be used in this invention and such component may be selected from any of the known viscosity index improvers.
  • the function of the VII is to reduce the rate of change of viscosity with temperature, i.e. they cause minimal increase in engine oil viscosity at low temperature but considerable increase at high temperature.
  • examples of viscosity index improvers include polyisobutylenes, polymethacrylates, ethylene/propylene copolymers, polyacrylates, styrene/maleic ester copolymers, and hydrogenated styrene/butadiene copolymers.
  • supplemental additives that perform specific functions not provided by the main components.
  • additional additives include, pour point depressants, corrosion inhibitors, rust inhibitors, foam inhibitors and supplemental friction modifiers.
  • the lubricating oil compositions of this invention can be made by adding the molybdenum additive and the secondary diarylamine additive in a lubricant oil composition.
  • the composition can also contain additional additives such as dispersants, detergents, zinc dihydrocarbyl dithiophsophates, and still additional antioxidants.
  • additional additives such as dispersants, detergents, zinc dihydrocarbyl dithiophsophates, and still additional antioxidants.
  • the method or order of component addition is not critical.
  • the combination of molybdenum and amine additives can be added to the lubrication oil as a concentrate with or without such concentrate containing the remaining additives.
  • the lubricating oil concentrate will comprise a solvent and from about 2.5 to 90 weight percent (wt %) and preferably 5 to 75 wt % of the combination of the molybdenum additive and amine additive of this invention.
  • the solvent may be that of hydrocarbon oils, e.g., mineral lubrication oil or a synthetic oil.
  • the ratio of molybdenum to amine in the concentrate composition is from about 0.02 to 0.6 parts of molybdenum per part of amine and preferably from about 0.04 to 0.4 parts of molybdenum for each part of the amine by weight.
  • the concentrate may contain additional additives as is conventional in the art, e.g., dispersants, detergents, and zinc dihydrocarbyl dithiophosphates.
  • the molybdenum compound in this invention is preferably substantially free of phosphorus and substantially free of active sulfur and it is particularly preferred to have the molybdenum compound substantially free of sulfur whether active or otherwise.
  • the following example shows the antioxidant synergism that exist,; when molybdenum naphthenate and a diphenylamine are formulated into an ADE Grade 5W-30 type motor oil.
  • the example also shows that this antioxidant behavior is unique when compared to other metals.
  • the DSC cell was pressurized with 500 psi air and programmed with the following heating sequence: (1) jump from ambient to 165° C., (2) jump from 165° C. to 175° C. at 2 C/min, (3) isothermal at 175° C.
  • the oil samples were held at 175° C. until an exothermic release of heat was observed.
  • the exothermic release of heat marks the oxidation reaction.
  • the time from the start of the experiment to the exothermic release of heat is called the oxidation induction time and is a measure of the oxidative stability of the oil (i.e. the longer the oxidation induction time the greater the oxidative stability of the oil). All oils are evaluated in duplicate and the results averaged.
  • the improved oxidative stability of the oil is predominantly due to the presence of molybdenum naphthenate and diphenylamine.
  • the other metals show very little effect, or a negative effect, on the oxidative stability of the oil.
  • the other metals show no interaction effect, or a negative interaction effect, with the diphenylamine.
  • Ce Nap is cesium naphthenate
  • Co Nap is cobalt naphthenate
  • Ni Oct is nickel octanoate
  • Mo Nap is molybdenum naphthenate.
  • concentration of metallic additives is expressed in parts per million of the metal.
  • DPA is dinonyldiphenylamine which is expressed in percent by weight, e.g. 0.1 wt % being 1,000 ppm;
  • Induction Time is the DSC Induction Time in minutes as an average.
  • Molybdenum naphthenate and a variety of amines were blended into an SAE Grade 5W-30 type motor oil (formulated crankcase oil as described in Example 2) as shown in Table III and as further described below.
  • the only additional antioxidant in these blends was the zinc dialkyl dithiophosphate.
  • the oxidation stability of these oils was measured by pressurized differential scanning calorimetry (PDSC) as described in Example 1. These oils were also subjected to the hot oil oxidation test described in Example 2.
  • Example 3 The results of the tests of Example 3 are shown in Table III.
  • Table III the first column is the test number involved.
  • the column headed “A” shows the concentration of molybdenum naphthenate expressed in ppm of molybdenum.
  • the remaining columns “B” through “J” show concentrations in weight percent wherein column “B” is that of dinonyl diphenylamine; column “C” is an alkylated diphenylamine trade named Naugalube 680, from Uniroyal Chemical Company; “D” is phenyl-alpha-naphthylamine; “E” is disecbutyl phenylenediamine; “F” is 4-tetradecylaniline; “G” is 2,5-di-t-butylaniline; “H” is 2,6-diisopropyl aniline; “T” is di-n-decylamine; and “J” is that of process oil.
  • Table IIIA wherein for each of the
  • Molybdenum octoate and alkylated diphenylamine were blended into an SAE grade 5W-30 type motor oil as shown in Table IV. The only additional antioxidant in these blends was the zinc dialkyldithiophosphate. The frictional properties of these oils were measured using the High Frequency Reciprocating Rig. In this instrument 1-2 mls (milliliters) of a sample oil are placed in a temperature controlled steel pan. A steel ball attached to a moveable arm is lowered into the pan. A load of 400 g is applied to the steel ball/arm assembly. The steel/ball arm assembly is oscillated at 20 Hz over a 1 mm (millimeter) path length.
  • Mo-Oct is molybdenum octoate
  • N-680 is alkylated diphenylamine
  • t-Bu is t-butylphenols
  • PO is process oil.
  • Molybdenum 2-ethylhexanoate containing 13.0 wt % molybdenum and alkylated diphenylamine, Naugalube 680, from Uniroyal Chemical Company, were blended into an SAE grade 5W-30 motor oil as shown in Table V below.
  • the control 5W-30 motor oil contained the following additives:
  • the oxidative stability of these oils was measured by using the following Hot Oil Oxidation Test: Into 25 g of each motor oil was blended 0.8 g of catalyst mixture containing 5.55 wt % Iron (III) Naphthenate (6 wt % Fe content) and 94.45 wt % xylenes. Dry air was blown through the oil at a rate of 10 L/h (liters per hour) while maintaining the temperature at 160° C. for a period of 64 hours. The oil was cooled and the percent change in viscosity between the new oil and the oxidized oil was determined at 40° C. The lower percent change in viscosity for an oil is an indication of less oil degradation and thus better oxidation control by the additives.
  • the abbreviation “% visc Incr” in Table V relates to percent viscosity increase. All oils were evaluated in duplicate and the results averaged. The results are found in Table IV.
  • a sample of molybdenum octoate was diluted with paraffin oil, blended at 50° C. for 1 hour and filtered using a pressure filtration apparatus.
  • the molybdenum content of the filtered oil was determined to be 2.91 wt %
  • a series of lubrication formulations in accordance with this invention were tested in the Sequence IIIE engine test.
  • the IIIE test uses a 231 CID (3.8 liter) Buick V-6 engine at high speed (3,000 pm) and a very high oil temperature of 149° C. for 64 hours. This test is used to evaluate an engine oil's ability to minimize oxidation, thickening, sludge, varnish, deposits, and wear.
  • the formulations contained 7.0 wt % viscosity index improver, 7.0 wt % ashless dispersant, 1.1 wt % ZDDP, 1.4 wt % detergents, 0.5 wt % supplemental additives, with the remainder being mineral oil.
  • supplemental antioxidants are indicated in Table VII along with the engine test results.
  • Hindered, mixed t-butylphenol antioxidant, referred to as “Phenolic” in Table VII below and a secondary alkylated diphenylamine, referred to as “Amine” in Table VII below disclosed for use in this invention are commercially available.
  • Formulation A also simply referred to in the table as “A” contained no molybdenum.
  • the molybdenum source in formulation B simply referred to as “B” in the table is molybdenum octoate available from Shepherd Chemical Company.
  • the molybdenum source in formulation C simply referred to as “C” in the table, is molybdenum 2-ethylhexanoate available from OM Group.
  • the following example shows antioxidant synergism between molybdenum and a diarylamine wherein the molybdenum compound is not a carboxylate.
  • Molyvan855 a sulfur and phosphorus free organic amide molybdenum complex supplied by R. T. Vanderbilt Company, Inc. (CAS Reg. No. 64742-52-5), alkylated diphenylamine Naugalube 680, from Uniroyal Chemical Company, and process oil were blended into an SAE Grade 5W-30 type motor oil as shown in Table IX below.
  • the formulated oil used in this example was the same as that used in Example 1.
  • the only additional antioxidant in these blends was the zinc dialkyldithiophosphate.
  • the oxidation stability of these oils was measured by pressurized differential scanning calorimetry (PDSC) as described in Example 1.
  • the expected values are what one would observe if there were no synergism between the Molyvan 855 and the alkylated diphenylamine, i.e., the additives act independently of each other.
  • the much larger measured OIT values versus the expected values clearly show the organic amide molybdenum complex/diphenylamine synergism.

Landscapes

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

Abstract

There is disclosed a lubricating oil composition which contains from about 100 to 450 parts per million of molybdenum from a molybdenum compound which is substantially free of active sulfur and about 750 to 5,000 parts per million of a secondary diarylamine. This combination of ingredients provides improved oxidation control and friction modifier performance to the lubricating oil. The composition is particularly suited for use as a crankcase lubricant.

Description

Application Ser. No. 09/359,770, filed Jul. 22, 1990, and copending application Ser. No. 09/604,285, filed Jun. 26, 2000 are each reissues of U.S. Pat. No. 5,650,381 (application Ser. No. 08/559,879 ), filed Nov. 20, 1995.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to lubricating oil compositions, their method of preparation, and use. More specifically this invention relates to lubricating oil compositions which contain a molybdenum compound and a secondary diarylamine wherein the molybdenum compound is substantially free of active sulfur. The use of both the molybdenum and amine within certain concentrations provide improved oxidation control and friction modifier performance to lubricating oil compositions. The lubricating oil compositions of this invention are particularly useful as crankcase lubricants.
2. Description of the Related Art
Lubricating oils as used in the internal combustion engines of automobiles or trucks are subjected to a demanding environment during use. This environment results in the oil suffering oxidation which is catalyzed by the presence of impurities in the oil such as iron compounds and is also promoted by the elevated temperatures of the oil during use. This oxidation of lubrication oils during use is usually controlled to some extent by the use of antioxidant additives which may extend the useful life of the oil, particularly by reducing or preventing unacceptable viscosity increases.
We have now discovered that a combination of about 100 to 450 parts per million (ppm) of molybdenum from an oil soluble molybdenum compound which is substantially free of active sulfur and about 750 to 5,000 ppm of an oil soluble secondary diarylamine is highly effective in inhibiting oxidation in lubricant compositions and that this antioxidant performance is supplemented by improved friction modifier performance. The molybdenum acts synergistically with secondary diarylamines to provide significant improvement in oxidation control. In addition to excellent oxidation control, the molybdenum compounds also act as friction modifiers to provide substantial fuel economy performance.
Lubricant compositions containing various molybdenum compounds and aromatic amines have been used in lubricating oils. Such compositions include active sulfur or phosphorus as part of the molybdenum compound, use additional metallic additives, various amine additives which are different from those used in this invention, and/or have concentrations of molybdenum and amine which do not show the synergistic results obtained by this invention.
U.S. Pat. No. 3,285,942 of Nov. 15, 1966 to Esso discloses the preparation of glycol molybdate complexes which have utility in lubrication oils.
U.S. Pat. No. 4,394,279 of Jul. 19, 1983 to L. de Vries et al. discloses an antioxidant additive combination for lubrication oils prepared by combining (a) an active sulfur containing molybdenum compound prepared by reacting an acidic molybdenum compound, a basic nitrogen compound and carbon disulfide with (b) an aromatic amine compound.
U.S. Pat. No. 4,832,857 of May 23, 1989 to Amoco Corp discloses a process for preparation of overbased molybdenum alkaline earth metal and alkali metal dispersions for use in lubricating oil compositions.
U.S. Pat. No. 4,846,983 of Jul. 11, 1989 W. C. Ward discloses molybdenum containing hydrocarbyl dithiocarbamates prepared from primary amines that impart anti-wear, antioxidant, extreme pressure, and friction properties to lubricating oils. Again, among other shortcomings, these molybdenum compounds contain substantial quantities of active sulfur.
U.S. Pat. No. 4,889,647 of Dec. 26, 1989 to R. T. Vanderbilt Co. discloses organic molybdenum complexes for use in lubrication oil compositions.
U.S. Pat. No. 5,137,647 of Aug. 11, 1992 to R. T. Venderbilt Co. discloses molybdenum complexes for use in fuels and lubricating oil compositions.
U.S. Pat. No. 5,143,633 of Sept. 1, 1992 to Gallo et al discloses superbasic additives for lubricant oils containing an organic molybdenum complex.
WO95/07962 of Mar. 23, 1995 to A. Richie et al. discloses a crankcase lubricant composition for use in automobile or truck engines which contains copper, molybdenum, and aromatic amines. In addition to the requirement for use of copper, this publication recites a very broad range of concentrations for the molybdenum and the amine whereas the concentrations of amine used with the molybdenum in the examples of that publication is well outside the range which this invention has found to be synergistic. Also, many of the molybdenum compounds of this reference contain active sulphur, phosphorus, and other elements and the amines include compounds such as primary amines which were not found synergistic with the molybdenum carboxylates of this invention.
WO95/07963 of 23 Mar. 1995 to H. Shaub discloses highly sulfurized molybdenum compounds and various secondary aromatic amines having at least one aromatic group for producing a synergistic antioxidant effect when used as an antioxidant additive for lubricating oils. Again the molybdenum compounds contain active sulfur.
WO95/07966 of 23 Mar. 1995 to J. Atherton et al. discloses engine oil lubricants of various molybdenum compounds including that of some with active sulfur, certain organo-phosphorus compounds, an aminic antioxidant and a phenolic antioxidant within certain proportions.
SUMMARY OF THE INVENTION
In one aspect, this invention is directed to a lubricating composition comprising (a) a major amount of lubrication oil, (b) an oil soluble molybdenum compound substantially free of active sulfur which provides about 100 to 450 parts per million of molybdenum, and (c) about 750 to 5,000 parts per million (ppm) of an oil soluble secondary diarylamine.
In another aspect, the invention is directed to a method for improving the antioxidant and friction properties of a lubricant by incorporating in the lubricant a molybdenum compound which is substantially free of active sulfur and a secondary diarylamine in the above described concentrations.
In still another aspect, the invention is directed to a lubrication oil concentrate comprising a solvent and a combination of from about 2.5 to 90 percent by weight of an oil soluble molybdenum compound which is substantially free of active sulfur and an oil soluble secondary diarylamine wherein the weight ratio of molybdenum from the molybdenum compound to the diarylamine in the concentrate is from about 0.020 to 0.60 parts of molybdenum for each part of amine.
In yet another aspect the invention is directed to a lubricating composition prepared by mixing 100 to 450 parts per million of oil soluble molybdenum compound substantially free of active sulfur and 750 to 5,000 parts of a secondary diaryl amine in a lubricating composition.
In yet further aspect, the invention is directed to a lubrication oil concentrate prepared by dissolving in about 10 to 97.5 parts of a solvent a total of 2.5 to 90 parts of an oil soluble molybdenum compound substantially free of active sulfur and an oil soluble secondary diaryl amine.
In yet a still further aspect, the molybdenum compound used in the various compositions and methods of this invention is substantially free of sulfur.
The compositions of this invention have various uses as lubricants such as for automotive and truck crankcase lubricants as well as transmission lubricants.
A key advantage of this invention is the multifunctional nature of the molybdenum/diarylamine combination and the relatively low treat levels required for a performance benefit. This additive combination provides both oxidation control and friction control to the oil. This reduces the need for supplemental oxidation protection and frictional properties and should reduce the overall cost of the entire additive package. Further cost reduction is gained by the low treat levels employed.
DETAILED DESCRIPTION OF THE INVENTION
The molybdenum compound used in this invention can be any molybdenum compound which is soluble in the lubricant of formulated lubricant package and is substantially free of active sulfur. By “soluble” or “oil soluble” is meant that the compound is oil soluble or solubilized under normal blending conditions into the lubrication oil or concentrate thereof. “Active” sulfur is sulfur which is not fully oxidized. Active sulfur further oxidizes and becomes more acidic in the oil upon use. Illustratively, sulfur such as divalent sulfur is active sulfur whereas the sulfur in a sulfonate group is fully oxidized and thus non-active sulfur. It is preferred however that the molybdenum compound be substantially free of all sulfur. By “substantially free” we mean that the molybdenum compound contains less than about 0.5% by weight of the material in question, e.g., active sulfur which is generally an insufficient amount to add significantly to corrosion. The sulfur content of some commercially available molybdenum compounds can often have as much as about 1,000 ppm of sulfur as a contaminant and occasionally there can be as much as 2,000 ppm of the active sulfur. Such small amounts often come from contamination in processing the various ingredients involved. By “alkphenyl” or “alkaryl” we mean a phenyl or aryl group, respectively, which contains an alkyl substituent.
Oil soluble molybdenum compounds prepared from a molybdenum source such as ammonium molybdates, alkali and alkaline earth metal molybdates, molybdenum trioxide, and molybdenum acetylacetonates and an active hydrogen compound such as alcohols and polyols, primary and secondary amines and polyamines, phenols, ketones, anilines, etc. can be used in combination with the diarylamines in this invention. The following listing provides examples of some molybdenum compounds which are substantially free of active sulfur and that may be used in combination with diarylamines in this invention:
1. Glycol molybdate complexes as described by Price et al in U.S. Pat. No. 3,285,942 of Nov. 15, 1966;
2. Overbased alkali metal and alkaline earth metal sulfonates, phenates and salicylate compositions containing molybdenum such as those disclosed and claimed by Hunt et al in U.S. Pat. No. 4,832,857 of May 23, 1988 which is incorporated herein by reference in its entirety. The sulfur in the compounds of Hunt et al does not provide antioxidant protection in the oil, i.e., the activity of the sulfur is deactivated by the overbased nature of these additives. Indeed, it is generally known that the molybdenum-free sulfonates act as pro-degradants in the oil (Atmospheric Oxidation and Stabilization” by T. Colclough page 49). The main purpose for adding the molybdenum-free overbased sulfonates is to provide detergency. When used in combination with diarylamines, the overbased molybdenum sulfonates such as those described by Hunt et al are expected to provide synergistic antioxidant protection to lubricants. The molybdenum containing overbased alkaline earth metal and alkali metal sulfonates, phenates, and salicylates are prepared by a process which comprises:
(a) introducing into a reaction zone a compound selected from the group consisting of a sulfonate, a phenate, and a salicylate wherein said compound is an overbased alkaline earth or alkali metal compound; (b) adding to said reaction zone a solvent to solubilize said compound and to form a mixture A; (c) heating said mixture A to an elevated temperature of 120° F. or less; (d) preparing an aqueous solution of a molybdenum compound at a temperature of 120° F. or less; (e) adding said aqueous solution of said molybdenum compound to said mixture A with stirring during a period of about 15 minutes or less to form a mixture B; (f) adding said mixture B containing said molybdenum compound to a non-polar compound at a temperature of 220° F. or greater within a period of up to 40 minutes wherein resulting mixture C during said addition is at a temperature of a least 220° F.; (g) driving off said water and said non-polar compound as overhead by increasing temperature of said mixture C containing said molybdenum compound to about 240° F. to about 300° F. to obtain a water-free composition; (h) adding additional quantity of a non-polar compound to said water-free composition to dilute said composition to clarify said composition by filtration or centrifugation; (i) heating said clarified composition to a temperature of from about 300° F. to about 400° F. to remove solvent and said non-polar compound and to recover product comprising an overbased molybdenum-containing alkaline earth metal or alkali metal compound.
3. Molybdenum complexes prepared by reacting a fatty oil, a diethanolamine and a molybdenum source as described by Rowan et al in U.S. Pat. No. 4,889,647 of Dec. 26, 1989;
4. Molybdenum containing compounds prepared from fatty acids and 2-(2-aminoethyl)aminoethanol as described by Karol in U.S. Pat. No. 5,137,647 of Aug. 11, 1992;
5. Overbased molybdenum complexes prepared from amines, diamines, alkoxylated amines, glycols and polyols as described by Gallo et al in U.S. Pat. No. 5,143,633 of Sep. 1, 1992; and
6. 2,4-Heteroatom substituted-molybdena-3,3-dioxacycloalkanes as described by Karol in U.S. Pat. No. 5,412,130 of May 2, 1995.
Molybdenum salts such as the carboxylates are a preferred group of molybdenum compounds. The molybdenum salts used in this invention may be completely dehydrated (complete removal of water during preparation), or partially dehydrated. They may be salts of the same anion or mixed salts, meaning that they are formed from more than one type of acid. Illustrative of suitable anions there can be mentioned chloride, carboxylate, nitrate, sulfonate, or any other anion.
The molybdenum carboxylates may be derived from any organic carboxylic acid. The molybdenum carboxylate is preferably that of a monocarboxylic acid such a that having from about 4 to 30 carbon atoms. Such acids can be hydrocarbon aliphatic, alicyclic, or aromatic carboxylic acids. Monocarboxylic acids such as those of aliphatic acids having about 4 to 18 carbon atoms are preferred, particularly those having an alkyl group of about 6 to 18 carbon atoms. The alicyclic acids may generally contain from 4 to 12 carbon atoms. The aromatic acids may generally contain one or two fused rings and contain from 7 to 14 carbon atoms wherein the carboxyl group may or may not be attached to the ring. The carboxylic acid can be a saturated or unsaturated fatty acid having from about 4 to 18 carbon atoms. Examples of some carboxylic acids that may be used to prepare the molybdenum carboxylates include: butyric acid; valeric acid; caproic acid heptanoic acid; cyclohexanecarboxylic acid; cyclodecanoic acid; naphthenic acid; phenyl acetic acid; 2- methylhexanoic acid; 2-ethylhexanoic acid; suberic acid; octanoic acid; nonanoic acid; decanoic acid; undecanoic acid; lauric acid, tridecanoic acid; myristic acid; pentadecanoic acid; palmitic acid; linolenic acid; heptadecanoic acid; stearic acid; oleic acid; nonadecanoic acid; eicosanoic acid; heneicosanoic acid; docosanoic acid; and erucic acid.
A number of methods have been reported in the literature for preparing the molybdenum carboxylates, e.g., U.S. Pat. No. 4,593,012 of Jun. 3, 1986 to Usui and U.S. Pat. No. 3,758,690 of May 11, 1971 to Becker, both of which are incorporated herein by reference in their entirety. The Usui patent describes the production of hydrocarbon soluble salts (molybdenyl carboxylates) by reaction of an ammonium molybdate with a carboxylic acid in the presence of an organic amine at specified elevated temperatures while removing water. U.S. Pat. No. 3,578,690 prepares its molybdenum carboxylates by reacting molybdenum oxide, molybdenum halide, alkali earth molybdate, alkaline earth molybdate, ammonium molybdate or mixtures of molybdenum sources with carboxylic acids at elevated temperatures and with removal of water.
The exact composition of the oil soluble molybdenum carboxylates can vary. Most of the literature refers to these compounds as molybdenum carboxylates. They have also been referred to as molybdenum carboxylate salts, molybdenyl (Mo O2 2+) carboxylates and molybdenyl carboxylate salts, molybdenum carboxylic acid salts, and molybdenum salts of carboxylic acids.
The concentration of the molybdenum from the molybdenum compound in the lubricant composition can vary depending upon the customer's requirements and applications. The actual amount of molybdenum added is based on the desired final molybdenum level in the lubricating composition. From about 100 to 450 parts per million of molybdenum are used in this invention based on the weight of the lubricating oil composition which may be formulated to contain additional additives and preferably about 100 to 250 parts per million of molybdenum and particularly 125 to 250 ppm are used based on the weight of the lubricating oil composition. The quantity of additive, e.g., molybdenum carboxylate to provide molybdenum, is based on the total weight of the formulated or unformulated lubricating oil composition.
The secondary diarylamines are well known antioxidants and there is no particular restriction on the type of secondary diarylamine used in the invention. Preferably, the secondary diarylamine antioxidant has the general formula:
Figure USRE037363-20010911-C00001
wherein R1 and R2 each independently represents a substituted or unsubstituted aryl group having from 6 to 30 carbon atoms. Illustrative of substituents for the aryl there can be mentioned aliphatic hydrocarbon groups such as alkyl having from about 1 to 20 carbon atoms, hydroxy, carboxyl or nitro, e.g., an alkaryl group having from 7 to 20 carbon atoms in the alkyl group. The aryl is preferably substituted or unsubstituted phenyl or naphthyl, particularly wherein one or both of the aryl groups are substituted with an alkyl such as one having from 4 to 18 carbon atoms. It is further preferred that both aryl groups be substituted, e.g. alkyl substituted phenyl.
The secondary diarylamines used in this invention can be of a structure other than that shown in the above formula which shows but one nitrogen atom in the molecule. Thus, the secondary diarylamine can be of a different structure provided that at least one nitrogen has 2 aryl groups attached thereto, e.g., as in the case of various diamines having a secondary nitrogen atom as well as two aryls on one of the nitrogens. The secondary diarylamines used in this invention preferably have antioxidant properties in lubricating oils, even in the absence of the molybdenum compound.
The secondary diarylamines used in this invention should be soluble in the formulated crankcase oil package. Examples of some secondary diarylamines that may be used in this invention include: diphenyl amine; various alkylated diphenylamines, 3-hydroxydiphenylamine; N-phenyl-1,2-phenylenediamine; N-phenyl-1,4-phenylenediamine; dibutyldiphenylamine; dioctyldiphenylamine; dinonyldiphenylamine; phenyl-alipha-naphthylamine; phenyl-beta-naphthylamine; diheptyldiphenylamine; and p-oriented styrenated diphenylamine.
The concentration of the secondary diarylamine in the lubricating composition can vary depending upon the customer's requirements and applications. A practical diarylamine use range in the lubricating composition is from about 750 parts per million to 5,000 parts per million (i.e. 0.075 to 0.5 wt %), preferably the concentration is from 1,000 to 4,000 parts per million (ppm) and particularly from about 1,200 to 3,000 ppm by weight. Quantities of less than 750 ppm have little or minimal effectiveness whereas quantities larger than 5,000 ppm are not economical.
Preferably, the quantity of molybdenum in relation to the quantity of the secondary amine should be within a certain ratio. The quantity of molybdenum should be about 0.020 to 0.6 parts by weight for each part by weight of the amine in the lubricating oil composition. Preferably, this ratio will be from about 0.040 to 0.40 parts of the molybdenum per part of the amine and particularly about 0.05 to 0.3 parts of the molybdenum per part of the amine. The total quantity of molybdenum and amine can be provided by one or more than one molybdenum or amine compound.
The composition of the lubricant oil can vary significantly based on the customer and specific application. In general, the oil is a formulated oil which is composed of between 75 and 95 wt % of a mineral lubrication oil, between 0 and 10 wt % of a polymeric viscosity index improver, and between about 5 and 15 wt % (weight percent) of an additive package. The additive package generally contains the following components:
(a) Dispersants. The dispersants are nonmetallic additives containing nitrogen or oxygen polar groups attached to a high molecular weight hydrocarbon chain. The hydrocarbon chain provides solubility on the hydrocarbon base stocks. The dispersant functions to keep oil degradation products suspended in the oil. Examples of commonly used dispersants include copolymers such as polymethacrylates and styrenemaleinic ester copolymers, substituted succinamides, polyamine succinamides, polyhydroxy succinic esters, substituted mannich bases, and substituted triazoles. Generally, the dispersant is present in the finished oil between about 4.0 and8.5 wt %.
(b) Detergents. The detergents are metallic additives containing charged polar groups, such as sulfonates or carboxylates, with aliphatic, cycloaliphatic, or alkylaromatic chains, and several metal ions. The detergents function by lifting deposits from the various surfaces of the engine. Examples of commonly used detergents include neutral and overbased alkali and alkaline earth metal sulfonates, neutral and overbased alkali and alkaline earth metal phenates, sulfurized phenates, overbased alkaline earth salicylates, phosphonates, thiopyrophosphonate, and thiophosphonates. Generally, the detergents are present in the finished oil between about 1.0 and 2.5 wt %.
(c). ZDDP's. The ZDDP's (zinc dihydrocarbyl dithiophosphates) are the most commonly used antiwear additives in formulated lubricants. These additives function by reaction with the metal surface to form a new surface active compound which itself is deformed and thus protects the original engine surface. Other examples of anti-wear additives include tricresol phosphate, dilauryl phosphate, sulfurized terpenes and sulfurized fats. The ZDDP's also function as antioxidants. Generally, the ZDDP is present in the finished oil between about 1.0 and 1.5 wt %, although when used, they can be used at substantially lower concentrations, e.g., 0.5 wt %. It is desirable from environmental concerns to have lower levels of ZDDP.
(d). Antioxidants. In molybdenum-free oils other antioxidants in addition to the zinc dihydrocarbyl dithiophosphates are used to protect the oil from oxidative degradation. The amount of supplemental antioxidant will vary depending on the oxidative stability of the base stock. Typical treat levels in finished oils can vary from about 1.0 to 2.5 wt %. The supplementary antioxidants that are generally used include hindered phenols, hindered bisphenols, sulfurized phenols, alkylated diphenylamines, sulfurized olefins, alkyl sulfides and disulfides, dialkyl dithiocarbamates,and phenothiazines. The inclusion of molybdenum carboxylates with diphenylamines removes the need for these supplementary antioxidatives. However, a supplementary antioxidant may be included in oils that are less oxidatively stable or in oils that are subjected to unusually severe conditions.
The lubrication oil component of this invention may be selected from any of the synthetic or natural oils used as lubricants such as that for crankcase lubrication oils for spark-ignited and compression-ignited internal combustion engines, for example automobiles and truck engines, marine, and a railroad diesel engines. Synthetic base oils include alkyl esters of dicarboxylic acids, polyglycols and alcohols, poly-alpha-olefins, including polybutenes, alkyl benzenes, organic esters of phosphoric acids, and polysilicone oils.
Natural base oils include mineral lubrication oils which may vary widely as to their crude source, e.g., as to whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic.
The lubrication oil base stock conveniently has a viscosity of about 2.5 to about 15 cSt or mm2/s and preferably about 2.5 to about 11 cSt or mm2/s at 100° C.
A polymeric viscosity index improver (VII) component may be used in this invention and such component may be selected from any of the known viscosity index improvers. The function of the VII is to reduce the rate of change of viscosity with temperature, i.e. they cause minimal increase in engine oil viscosity at low temperature but considerable increase at high temperature. Examples of viscosity index improvers include polyisobutylenes, polymethacrylates, ethylene/propylene copolymers, polyacrylates, styrene/maleic ester copolymers, and hydrogenated styrene/butadiene copolymers.
In addition to the lubricant additives mentioned thus far, there is sometimes a need for other supplemental additives that perform specific functions not provided by the main components. These additional additives include, pour point depressants, corrosion inhibitors, rust inhibitors, foam inhibitors and supplemental friction modifiers.
The lubricating oil compositions of this invention can be made by adding the molybdenum additive and the secondary diarylamine additive in a lubricant oil composition. In the case of a formulated oil, the composition can also contain additional additives such as dispersants, detergents, zinc dihydrocarbyl dithiophsophates, and still additional antioxidants. The method or order of component addition is not critical. Alternatively, the combination of molybdenum and amine additives can be added to the lubrication oil as a concentrate with or without such concentrate containing the remaining additives.
The lubricating oil concentrate will comprise a solvent and from about 2.5 to 90 weight percent (wt %) and preferably 5 to 75 wt % of the combination of the molybdenum additive and amine additive of this invention. The solvent may be that of hydrocarbon oils, e.g., mineral lubrication oil or a synthetic oil. The ratio of molybdenum to amine in the concentrate composition is from about 0.02 to 0.6 parts of molybdenum per part of amine and preferably from about 0.04 to 0.4 parts of molybdenum for each part of the amine by weight. In addition to the molybdenum and amine additives of this invention, the concentrate may contain additional additives as is conventional in the art, e.g., dispersants, detergents, and zinc dihydrocarbyl dithiophosphates.
There are a number of recent trends in the petroleum additive industry that may restrict, and/or limit, the use of certain additives in formulated crankcase oils. The key trends are the move to lower phosphorus levels in the oil, the new fuel economy requirements and the move to more severe engine test conditions for qualifying oils. Such changes may show that certain currently used antioxidant additives are no longer effective in protecting the oil against oxidation. The molybdenum/diarylamine based antioxidant mixture disclosed herein provides a solution to this need. Furthermore, there is concern that phosphorus from the lubricant tends to poison catalyst used in catalytic converters, thereby preventing them from functioning to full effect. Also, active sulfur containing antioxidants, including active sulfur containing molybdenum compounds are known to cause copper corrosion. This is generally known and has been disclosed by T. Colelough in Atmospheric oxidation and Antioxidants, Volume II, chapter 1, Lubrication Oil Oxidation and Stabilization, G. Scott, editor, 1993 Elsevier Science Publishers.
The molybdenum compound in this invention is preferably substantially free of phosphorus and substantially free of active sulfur and it is particularly preferred to have the molybdenum compound substantially free of sulfur whether active or otherwise.
The following examples are illustrative of the invention and its advantageous properties. In these examples as well as elsewhere in this application, all parts and percentages are by weight unless otherwise indicated.
EXAMPLE 1
The following example shows the antioxidant synergism that exist,; when molybdenum naphthenate and a diphenylamine are formulated into an ADE Grade 5W-30 type motor oil. The example also shows that this antioxidant behavior is unique when compared to other metals.
A variety of oil soluble metals and one diphenylamine type antioxidant were blended into an ADE Grade 5W-30 type motor oil as shown in Table 1. The only additional antioxidant in these blends were the zinc dialkyldithiophosphate. The oxidation stability of these oils was measured by pressurized differential scanning calorimetry (PDSC) as described by J. A. Walker and W. Tsang in “Characterization of Lubrication Oils by Differential Scanning Calorimetry”, SAE Technical Paper Series, 801383 (Oct. 20-23, 1980). Oil samples were treated with an iron (III) acetylacetonate catalyst (55 ppm Fe) and 2 milligrams (mg) were analyzed in an open aluminum hermetic pan. The DSC cell was pressurized with 500 psi air and programmed with the following heating sequence: (1) jump from ambient to 165° C., (2) jump from 165° C. to 175° C. at 2 C/min, (3) isothermal at 175° C. The oil samples were held at 175° C. until an exothermic release of heat was observed. The exothermic release of heat marks the oxidation reaction. The time from the start of the experiment to the exothermic release of heat is called the oxidation induction time and is a measure of the oxidative stability of the oil (i.e. the longer the oxidation induction time the greater the oxidative stability of the oil). All oils are evaluated in duplicate and the results averaged. As shown in Table 1 the oil samples containing both molybdenum naphthenate and diphenylamine had the longest oxidation induction times. These oil samples also contain other metals. In order to rule out the possibility of the other metal contributing to the improved oxidative stability of the oils, the oxidation induction time data were analyzed for main and interaction effects as described by G. E. P. Box, W. G. Hunter, and J. S. Hunter in “Statistics for Experiments”, 1978, John Wiley & Sons. The results are provided in Table IA. The results show the following:
1. The improved oxidative stability of the oil is predominantly due to the presence of molybdenum naphthenate and diphenylamine.
2. There is a strong interaction effect, i.e. synergism, between molybdenum naphthenate and the diphenylamine.
The other metals show very little effect, or a negative effect, on the oxidative stability of the oil. In addition, the other metals show no interaction effect, or a negative interaction effect, with the diphenylamine.
In the below Tables I and IA: Ce Nap is cesium naphthenate; Co Nap is cobalt naphthenate; Ni Oct is nickel octanoate; and Mo Nap is molybdenum naphthenate. The concentration of metallic additives is expressed in parts per million of the metal. DPA is dinonyldiphenylamine which is expressed in percent by weight, e.g. 0.1 wt % being 1,000 ppm; Induction Time is the DSC Induction Time in minutes as an average.
TABLE I
PDSC Induction Times for Motor Oi1 Blends
Concentration of Additives In SAE Grade 5W-30 Type Motor Oil*
Oil Ce Co Ni Mo Process Induction
No. Nap Nap Oct Nap DPA Oil Wt. % Time
1 0 0 0 0 0.10 1.50 41.8
2 200 0 0 0 0.00 1.27 16.5
3 0 200 0 0 0.00 1.27 26.4
4 200 200 0 0 0.10 0.83 26.5
5 0 0 200 0 0.00 1.35 16.1
6 200 0 200 0 0.10 0.92 28.1
7 0 200 200 0 0.10 0.92 33.5
8 200 200 200 0 0.00 0.68 22.7
9 0 0 0 200 0.00 1.27 24.7
10 200 0 0 200 0.10 0.83 60.1
11 0 200 0 200 0.10 0.83 62.5
12 200 200 0 200 0.00 0.60 34.6
13 0 0 200 200 0.10 0.92 72.4
14 200 0 200 200 0.00 0.68 26.0
15 0 200 200 200 0.00 0.68 40.9
16 200 200 200 200 0.10 0.25 54.2
*A formulated crankcase oil containing 83.2 wt % base oil, 6.2 wt % polymeric viscosity index improver, 6.9 wt % ashless dispersant, 2.1 wt % calcium, sodium & magnesium overbased & neutral detergents, and 1.2 wt % zinc dialkyldithiophosphate.
TABLE I
PDSC Induction Times for Motor Oi1 Blends
Concentration of Additives In SAE Grade 5W-30 Type Motor Oil*
Oil Ce Co Ni Mo Process Induction
No. Nap Nap Oct Nap DPA Oil Wt. % Time
1 0 0 0 0 0.10 1.50 41.8
2 200 0 0 0 0.00 1.27 16.5
3 0 200 0 0 0.00 1.27 26.4
4 200 200 0 0 0.10 0.83 26.5
5 0 0 200 0 0.00 1.35 16.1
6 200 0 200 0 0.10 0.92 28.1
7 0 200 200 0 0.10 0.92 33.5
8 200 200 200 0 0.00 0.68 22.7
9 0 0 0 200 0.00 1.27 24.7
10 200 0 0 200 0.10 0.83 60.1
11 0 200 0 200 0.10 0.83 62.5
12 200 200 0 200 0.00 0.60 34.6
13 0 0 200 200 0.10 0.92 72.4
14 200 0 200 200 0.00 0.68 26.0
15 0 200 200 200 0.00 0.68 40.9
16 200 200 200 200 0.10 0.25 54.2
*A formulated crankcase oil containing 83.2 wt % base oil, 6.2 wt % polymeric viscosity index improver, 6.9 wt % ashless dispersant, 2.1 wt % calcium, sodium & magnesium overbased & neutral detergents, and 1.2 wt % zinc dialkyldithiophosphate.
EXAMPLE 2
Molybdenum naphthenate and alkylated diphenylamine, Naugalube 680, from Uniroyal Chemical Company; were blended into an SAE Grade 5W-30 type motor oil as shown in Table II. The only additional antioxidant in these blends was the zinc dialkyldithiophosphate. The oxidation stability of these oils was measured by pressurized differential scanning calorimetry (PDSC) as described in Example 1. These oils were also subjected to the following hot oil oxidation test: Into 25 grams (g) of each motor oil was blended 0.8 g of a catalyst mixture containing 5.55 wt % iron (III) naphthenate (6 wt % Fe content) and 94.45 wt % xylenes. Dry air was blown through the oil at rates of 10 Liters (L)/hour (h) while maintaining the temperature at 160° C. for a period of 72 hours. The oil was cooled and the percent change in viscosity between the new oil and the oxidized oil wad determined at 40° C. A lower percent change in viscosity for an oil is an indication of less oil degradation and thus better oxidation control by the additives. All oils were evaluated in duplicate and the results averaged. Results from the PDSC and the hot oil oxidation test are found in Table II. Both the PDSC results and the hot oil oxidation test results show that the combination of molybdenum naphthenate (Mo-Nap) and alkylated diphenylamine (N-680) provides superior oxidation control versus use of these additives separately. Note that for the samples containing a combination of molybdenum naphthenate and the diphenylamine the measured oxidation induction time values are significantly larger than the expected values. The expected values are what one would observe if there was no synergism between the molybdenum naphthenate and the diphenylamine, i.e. the additives act independently of each other. Expected values are calculated by adding the increase in induction time due to the individual additives. The much larger measured induction time values versus the expected values clearly show the molybdenum naphthenate/diphenylamine synergism. In the following Table II, the concentration of the molybdenum naphthenate is expressed in ppm of molybdenum whereas the concentration of the N-680 Amine is expressed in weight percent, i.e. 0.1 wt % is equal to 1,000 ppm. The oxidation induction time by PDSC in minutes is in the column headed as “Induction Time”, The OIT expected response in minutes is in the column under “Expected Time”; the viscosity increase from 72 hour HOOT (%) is an average of duplicate runs and is under the column headed “Viscosity Increase”.
TABLE II
Oxidative Stability of Motor oil Blends*
by PDSC and the Hot Oil Oxidation Test
Concentration
of Additives Process Induc-
Oil Mo Nap N-680 Oil tion Expected Viscosity
# (As ppm Mo) Wt % Wt % Time Time Increase
1 0 0.000 1.25 28.4 28.4 303.18
2 125 0.000 1.04 35.1 35.1 671.48
3 250 0.000 0.83 33.0 33.0 362.22
4 0 0.075 1.18 44.9 44.9 44.64
5 125 0.075 0.97 63.5 51.6 36.93
6 250 0.075 0.76 73.0 49.5 66.10
7 0 0.150 1.10 62.5 62.5 31.61
8 125 0.150 0.89 107.8 69.2 11.93
9 250 0.150 0.68 108.7 67.1 10.02
*A formulated crankcase oil containing 83.2 wt % base oil, 6.2 wt % polymeric viscosity index improver, 6.9 wt % ashless dispersant, 2.1 wt % calcium, sodium, and magnesium overbased and neutral detergents, and 1.2 wt % zinc dialkyldithiophosphate.
EXAMPLE 3
The following example shows that other classes of amines, e.g., certain substituted amines, disubstituted phenylene diamines, and alkyl amines, are not effective or minimally effective at controlling oxidation when used in combination with molybdenum carboxylates.
Molybdenum naphthenate and a variety of amines, were blended into an SAE Grade 5W-30 type motor oil (formulated crankcase oil as described in Example 2) as shown in Table III and as further described below. The only additional antioxidant in these blends was the zinc dialkyl dithiophosphate. The oxidation stability of these oils was measured by pressurized differential scanning calorimetry (PDSC) as described in Example 1. These oils were also subjected to the hot oil oxidation test described in Example 2.
Both the hot oil oxidation test results (small percentage changes in viscosity) and the PDSC test results (prolonged oxidation induction times) show that the combination of molybdenum naphthenate and alkylated diarylamines is more effective than the individual additives. Phenylnaphthyl amines show some effectiveness when used in combination with molybdenum naphthenate. The substituted anilines, substituted phenylene diamines, and alkyl amines, were much less effective when used in combination with molybdenum naphthenate. In fact, the hot oil oxidation test results show that many of these other amines show a prodegradant effect (large percent changes in viscosity versus oil #0) when used in combination with molybdenum naphthenate.
The results of the tests of Example 3 are shown in Table III. In Table III, the first column is the test number involved. The column headed “A” shows the concentration of molybdenum naphthenate expressed in ppm of molybdenum. The remaining columns “B” through “J” show concentrations in weight percent wherein column “B” is that of dinonyl diphenylamine; column “C” is an alkylated diphenylamine trade named Naugalube 680, from Uniroyal Chemical Company; “D” is phenyl-alpha-naphthylamine; “E” is disecbutyl phenylenediamine; “F” is 4-tetradecylaniline; “G” is 2,5-di-t-butylaniline; “H” is 2,6-diisopropyl aniline; “T” is di-n-decylamine; and “J” is that of process oil. The results of these tests are shown in Table IIIA wherein for each of the numbered oil samples there is shown the results of the tests of Table III.
TABLE III
Oxidation of Motor Oil Containing Molybdenum Naphthenates and Amines
Concentration of additives in SAE Grade 5W-30 Type Motor Oil*
Oil A B C D E F G H I J
0 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.25
1 200 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.92
2 0 0.10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.15
3 200 0.10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.82
4 0 0.00 0.10 0.00 0.00 0.00 0.00 0.00 0.00 1.15
5 200 0.00 0.10 0.00 0.00 0.00 0.00 0.00 0.00 0.82
6 0 0.00 0.00 0.10 0.00 0.00 0.00 0.00 0.00 1.15
7 200 0.00 0.00 0.10 0.00 0.00 0.00 0.00 0.00 0.82
8 0 0.00 0.00 0.00 0.10 0.00 0.00 0.00 0.00 1.15
9 200 0.00 0.00 0.00 0.10 0.00 0.00 0.00 0.00 0.82
10 0 0.00 0.00 0.00 0.00 0.10 0.00 0.00 0.00 1.15
11 200 0.00 0.00 0.00 0.00 0.10 0.00 0.00 0.00 0.82
12 0 0.00 0.00 0.00 0.00 0.00 0.10 0.00 0.00 1.15
13 200 0.00 0.00 0.00 0.00 0.00 0.10 0.00 0.00 0.82
14 0 0.00 0.00 0.00 0.00 0.00 0.00 0.10 0.00 1.15
15 200 0.00 0.00 0.00 0.00 0.00 0.00 0.10 0.00 0.82
16 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.10 1.15
17 200 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.10 0.82
*A formulated crankcase oil containing 83.2 wt % base oil, 6.2 wt % polymeric viscosity index improver, 6.9 ashless dispersant, 2.1 wt % calcium, sodium and magnesium overbased & neutral detergents, and 1.2 wt % zinc dialkyldithiophosphate.
TABLE IIIA
Oxidation Induction Time Viscosity Increase
By PDSC (min) From 72 h HOOT (%)
Oil # Avg From Duplicate Runs Avg From Duplicate Runs
0 41.8 510.6
1 54.0 1650.2
2 72.9 89.3
3 111.2 59.5
4 81.8 68.3
5 102.8 48.8
6 66.8 129.1
7 74.3 102.2
8 61.3 150.6
9 62.6 417.3
10 40.8 728.1
11 41.8 1387.4
12 40.3 534.2
13 48.2 1058.8
14 34.2 463.2
15 46.2 561.7
16 39.9 305.0
17 39.7 905.8
EXAMPLE 4
Molybdenum octoate and alkylated diphenylamine. Naugalube 680, from Uniroyal Chemical Company, were blended into an SAE grade 5W-30 type motor oil as shown in Table IV. The only additional antioxidant in these blends was the zinc dialkyldithiophosphate. The frictional properties of these oils were measured using the High Frequency Reciprocating Rig. In this instrument 1-2 mls (milliliters) of a sample oil are placed in a temperature controlled steel pan. A steel ball attached to a moveable arm is lowered into the pan. A load of 400 g is applied to the steel ball/arm assembly. The steel/ball arm assembly is oscillated at 20 Hz over a 1 mm (millimeter) path length. As the arm is oscillated, a friction coefficient is determined every 5 seconds. The test lasts 3 minutes so approximately 30 data points are averaged to determine the friction coefficient of an oil in a given test. A reduction in the friction coefficient corresponds to improved friction properties of the oil. Duplicate tests were performed on each oil at 70° C., 100° C., and 130° C. The average friction coefficient and standard deviation (SD) for each sample are shown in Table IV.
It can be seen from Table IV that an improvement in friction properties (lower coefficient of friction) results when the concentration of molybdenum octoate is increased in the oil. Reference oil 5 (R5) shows that a conventional antioxidant is not as effective as a friction modifier compared to molybdenum octanoate.
In Table IV: “Mo-Oct.” is molybdenum octoate; “N-680” is alkylated diphenylamine; “t-Bu” is t-butylphenols; and “PO” is process oil.
TABLE IV
Frictional Properties Of Motor Oil Blends using the High Frequency Reciprocating Rig Test
Concentration of additives in
SAE GRADE 5W-30 TYPE
MOTOR OIL
Mo-Oct A-N-680 t-Bu P.O. FRICTION COEFFICIENT
Oil ppm wt % wt % wt % 70 C SD 100 C SD 130 C SD
R1 0 0 0 0 0.117 0.001 0.116 0.001 0.116 0.001
2 204 0.125 0 0.375 0.117 0.001 0.113 0.002 0.113 0.001
3 319 0.125 0 0 0.110 0.001 0.104 0.004 0.106 0.004
4 432 0.125 0 0 0.105 0.001 0.095 0.001 0.092 0.001
Rs 0 0.125 0.70 0.375 0.125 0.001 0.128 0.002 0.127 0.003
EXAMPLE 5
This example shows that the benefit of the molybdenum/diphenylamine combination requires using at least 100 ppm of the molybdenum. As shown in Example 6, this enhanced oxidation performance starts to break down at extremely high levels( greater than 400 ppm) of molybdenum.
Molybdenum 2-ethylhexanoate, containing 13.0 wt % molybdenum and alkylated diphenylamine, Naugalube 680, from Uniroyal Chemical Company, were blended into an SAE grade 5W-30 motor oil as shown in Table V below. The control 5W-30 motor oil contained the following additives:
Formulated Motor Oil Components Weight %
ZDDP 1.1
Ashless dispersant 7.0
Viscosity Index Improver 7.0
Neutral & Overbased Detergents 1.4
Pour Point Depressant 0.5
Diluent Oil 83.0
The oxidative stability of these oils was measured by using the following Hot Oil Oxidation Test: Into 25 g of each motor oil was blended 0.8 g of catalyst mixture containing 5.55 wt % Iron (III) Naphthenate (6 wt % Fe content) and 94.45 wt % xylenes. Dry air was blown through the oil at a rate of 10 L/h (liters per hour) while maintaining the temperature at 160° C. for a period of 64 hours. The oil was cooled and the percent change in viscosity between the new oil and the oxidized oil was determined at 40° C. The lower percent change in viscosity for an oil is an indication of less oil degradation and thus better oxidation control by the additives. The abbreviation “% visc Incr” in Table V relates to percent viscosity increase. All oils were evaluated in duplicate and the results averaged. The results are found in Table IV.
TABLE V
Oxidative Stability of Motor Oil Blends By the Hot Oil Oxidation Test
Amine Molybdenum % Viscosity Increase Change
N-680 2-ethylhexanoate After 74 h % Visc
Sample wt % ppm Mo in the HOOT Incr
0 0.15 0 70 0
1 0.15 52 69 −1
2 0.15 104 68 −2
3 0.15 156 49 −21
4 0.15 208 43 −27
5 0.15 260 46 −24
6 0.15 312 35 −35
7 0.15 364 32 −38
8 0.15 416 27 −43
9 0.15 468 23 −47
The viscosity results in the above table clearly show that at molybdenum level of 104 ppm, the molybdenum/diarylamine combination showed but a small improvement for the oxidative stability of the oil. However, at molybdenum levels greater than 104 such as 156 ppm, a significant improvement in oxidation control is seen. The largest improvement occurs between 104 ppm and 156 ppm molybdenum content.
EXAMPLE 6
A sample of molybdenum octoate was diluted with paraffin oil, blended at 50° C. for 1 hour and filtered using a pressure filtration apparatus. The molybdenum content of the filtered oil was determined to be 2.91 wt %
The diluted and filtered molybdenum octoate sample described above, and alkylated diphenylamine, Naugalube 680, from Uniroyal Chemical Company, were blended into an SAE grade 5W-30 type motor oil as shown in Table VI. The control 5W-30 motor oil contained the components specified in Example 5 above. The oxidative stability of these oils was measured using the Hot Oil Oxidation Test described in Example 5. All oils were evaluated in duplicate and the results averaged. The results are found in Table VI.
TABLE VI
Oxidative Stability of Motor Oil Blends By the Hot Oil Oxidation Test
Amine % Viscosity Change %
Sample Wt % PPM Mo Increase Viscosity
1 0.125  0 55 0
2 0.125 204 35 −20
3 0.125 318 27 −28
4 0.125 432 133 78
The viscosity results of the above Table VI clearly show that if a sufficient amount of amine is not present, a high molybdenum content becomes detrimental to the oxidative stability of the oil. In this example 0.125% amine with 318 ppm molybdenum provides good antioxidant protection. Increasing the molybdenum level to 432 ppm is not as effective as the lower concentrations to the oxidative stability of the oil (large increase in viscosity).
EXAMPLE 7
A series of lubrication formulations in accordance with this invention were tested in the Sequence IIIE engine test. The IIIE test uses a 231 CID (3.8 liter) Buick V-6 engine at high speed (3,000 pm) and a very high oil temperature of 149° C. for 64 hours. This test is used to evaluate an engine oil's ability to minimize oxidation, thickening, sludge, varnish, deposits, and wear. The formulations contained 7.0 wt % viscosity index improver, 7.0 wt % ashless dispersant, 1.1 wt % ZDDP, 1.4 wt % detergents, 0.5 wt % supplemental additives, with the remainder being mineral oil. The addition of supplemental antioxidants are indicated in Table VII along with the engine test results. Hindered, mixed t-butylphenol antioxidant, referred to as “Phenolic” in Table VII below and a secondary alkylated diphenylamine, referred to as “Amine” in Table VII below disclosed for use in this invention are commercially available. Formulation A, also simply referred to in the table as “A” contained no molybdenum. The molybdenum source in formulation B, simply referred to as “B” in the table is molybdenum octoate available from Shepherd Chemical Company. The molybdenum source in formulation C, simply referred to as “C” in the table, is molybdenum 2-ethylhexanoate available from OM Group. TVTM indicates that the oils viscosity was too viscous to measure and represents a severe failing result in the IIIE engine. Some of the abbreviations used in the below Table VII are as follows: “% Visc. Inc.@ 64 h” means percent viscosity increase in 64 hours; “AE Sludge” is average engine sludge rating; “APS Varnish” is average piston skirt varnish; “ORL Deposit” is oil ring land deposit; “AC Wear” is average cam wear; MC Wear is maximum cam wear; and “L” is liters.
TABLE VII
Sequence IIIE Evaluation of
Molybdenum/Secondary Diphenylamine Antioxidants
Passing
Result Limits A B C
Phenolic Content (wt %) 0.7 0 0
Amine Content (wt %) 0.1 0.125 0.2
Molybdenum Content 0 458 115
(ppm Mo)
% Vis. Inc. @ 64 h 375 Max.  TVTM 152 300
AE Sludge 9.2 Min. 9 9.54 9.56
APS Varnish 8.9 Min. 7.96 9.1 9.38
ORL Deposit 3.5 Min. 2.53 4.38 4.8
Stuck Ring 2 2 1
AC Wear 30 Max. 7.2 7.8 6.5
MC Wear 64 Max. 15.0 12.00 11.00
Oil Consumption in Liters 5.1 Max  4.35 3.32 3.35
The results of the above Table VII clearly show that the conventional phenolic antioxidant in Formulation A is ineffective in combination with the diphenylamine at controlling viscosity and passing the IIIE engine test. The molybdenum/diphenylamine combination in formulations B and C is very effective at both controlling viscosity and passing the engine test.
EXAMPLE 8
This example shows that the molybdenum carboxylate/diphenylamine combination is also effective in lubricants that do not contain additional additives. Alkylated diphenylamine, Naugalube 680, from Uniroyal Chemical Company, and molybdenum HEX-CEM, from OM Group, were blended into Petro Canada Paraflex HT100 (650N) base oil as described in Tabe VIII. These samples were subjected to the hot oil oxidation test described in Example 2 with the only change being that the heating period was reduced from 72 hours to 40 hours. The oils were cooled and the percent change in viscosity between the new oil and the oxidized oil was determined at 40° C. The results were shown in Table VIII below.
TABLE VIII
Hot Oil Oxidation Unadditized Base Oil
In the Presence and Absence of Molybdenum.
Base Oil N-680 Mo HEX-CEM % Change Visc.
Oil # (wt %) (wt %) (ppm Mo) After 40 h
1 99.75 0.25  0 318
2 99.65 0.25 130 −2
3 99.55 0.25 260 1
It can be seen from the above Table VIII that significant improvement in oxidative stability of unadditized base oil occurs when a molybdenum carboxylate is combined with a secondary diarylamine.
EXAMPLE 19
The following example shows antioxidant synergism between molybdenum and a diarylamine wherein the molybdenum compound is not a carboxylate.
Molyvan855, a sulfur and phosphorus free organic amide molybdenum complex supplied by R. T. Vanderbilt Company, Inc. (CAS Reg. No. 64742-52-5), alkylated diphenylamine Naugalube 680, from Uniroyal Chemical Company, and process oil were blended into an SAE Grade 5W-30 type motor oil as shown in Table IX below. The formulated oil used in this example was the same as that used in Example 1. The only additional antioxidant in these blends was the zinc dialkyldithiophosphate. The oxidation stability of these oils was measured by pressurized differential scanning calorimetry (PDSC) as described in Example 1. These oils were also subjected to the hot oil oxidation test described in Example 2 with the only change being that the heating period was reduced from 72 hours to 64 hours. All oils were evaluated in duplicate or triplicate and the results averaged. The results are found in Table IX below. Both the PDSC results and the hot oil oxidation test results show that the combination of the organic amide molybdenum complex and the alkylated diphenylamine provides superior oxidation control versus use of these additives separately. Note that for samples containing a combination of Molyvan 855 and alkylated diphenylamine the measured values are significantly larger than the expected value. The expected values are what one would observe if there were no synergism between the Molyvan 855 and the alkylated diphenylamine, i.e., the additives act independently of each other. The much larger measured OIT values versus the expected values clearly show the organic amide molybdenum complex/diphenylamine synergism.
TABLE IX
Molyvan 855 Process
Added N-680 Oil Induction Expected Viscosity
Wt % Added Added Time OIT Increase
Oil (ppm Mo) Wt % Wt % (min) (min) (%)
A 0 0 1.25 26.6 201
B 0 0.1 1.15 59.4 42
C 0.272 (200) 0 0.98 50.8 548
D 0.272 (200) 0.1 0.88 106.2 83.6 25

Claims (22)

What is claimed is:
1. A lubricating composition comprising a major amount of lubricating oil, an oil soluble molybdenum compound providing about 100 to 450 parts per million of molybdenum, said molybdenum compound selected from the group consisting of a sulfur and phosphorus free organic amide molybdenum complex and a molybdenum carboxylate wherein the carboxylate anion has from about 4 to 30 carbon atoms and about 750 to 5,000 parts per million of an oil soluble secondary diarylamine.
2. The composition of claim 1 wherein the carboxylate is that of a monocarboxylic aliphatic acid having from about 4 to 18 carbon atoms or an alicyclic acid having from about 4 to 12 carbon atoms.
3. The composition of claim 1 wherein the diarylamine has from about 6 to 30 carbon atoms in each of the aryl groups.
4. The composition of claim 3 wherein at least one of the aryl groups is alkaryl having from 7 to 20 carbon atoms in the alkyl group.
5. The composition of claim 1 wherein the secondary diarylamine is of the formula:
Figure USRE037363-20010911-C00002
wherein R1 and R2 each independently represent an aryl group having from about 6 to 30 carbon atoms.
6. The composition of claim 1 wherein: the molybdenum carboxylate is that of an aliphatic acid having from about 4 to 18 carbon atoms or an alicyclic acid having from 4 to 12 carbon atoms; each of the aryl groups of the amine is a member selected from the group consisting of phenyl, naphthyl, alkphenyl wherein the alkyl portion has from about 4 to 18 carbon atoms and alknaphthyl wherein the alkyl portion has about 4 to 18 carbon atoms; the quantity of molybdenum is from about 100 to 250 parts per million; and the quantity of amine is from about 1,000 to 4,000 parts per million.
7. A method for improving the antioxidancy and friction properties of a lubricant which comprises including in the lubricant, a molybdenum compound which provides about 100 to 450 part per million of molybdenum said molybdenum compound selected from the group consisting of a sulfur and phosphorus free organic amide molybdenum complex and a molybdenum carboxylate wherein the carboxylate anion has from about 4 to 30 carbon atoms and about 750 to 5,000 parts per million of an oil soluble secondary diarylamine.
8. The method of claim 7, wherein the amine is of the formula
Figure USRE037363-20010911-C00003
wherein each of R1 and R2 is alkylphenyl having from about 4 to 18 carbon atoms in each alkyl group.
9. The method of claim 8 wherein the molybdenum carboxylate is prepared from an acid having from 4 to 18 carbon atoms and the quantity of molybdenum from the molybdenum carboxylate is from about 100 to 250 parts per million and the quantity of the amine is from about 1,200 to 3,000 parts per million.
10. The method of claim 9 wherein the acid is a monocarboxylic saturated fatty acid.
11. The method of claim 8 wherein the molybdenum carboxylate is molybdenum 2-ethylhexanonate.
12. The method of claim 7 wherein the molybdenum compound is a sulfur and phosphorus free organic amide molybdenum complex.
13. A lubricating oil concentrate prepared by dissolving a total of from about 2.5 to 90 parts by weight of an oil soluble molybdenum compound selected from the group consisting of a sulfur and phosphorus free organic amide molybdenum complex and a molybdenum carboxylate derived from an organic carboxylic acid having about 4 to 30 carbon atoms and an oil soluble secondary diarylamine dissolved in 10 to 97.5 parts of a solvent wherein the weight ratio of molybdenum to amine is from about 0.02 to 0.06 parts of molybdenum for each part of amine.
14. The concentrate of claim 13 wherein the solvent is a mineral oil or synthetic oil and the ratio of molybdenum to amine is from about 0.04 to 0.4 parts of the molybdenum for each part of the amine, the molybdenum carboxylate is that of a monocarboxylic aliphatic acid having from about 4 to 18 carbon atoms or an alicyclic acid having from 4 to 12 carbon atoms, and at least one of the aryl groups of the amine is alkaryl having from 7 to 20 carbon atoms in the alkyl group.
15. The concentrate of claim 13 wherein one or more of the following additives are further present: a dispersant; a detergent; and a zinc dihydrocarbyl dithiophosphate.
16. A lubricating oil composition prepared by mixing an oil soluble molybdenum compound selected from the group consisting of a sulfur and phosphorus free organic amide molybdenum complex and a molybdenum carboxylate derived from monocarboxylic acids selected from the group consisting of aliphatic acids having about 4 to 18 carbon atoms, alicyclic acids containing from 4 to 12 carbon atoms and aromatic acids containing from 7 to 14 carbon atoms and an oil soluble secondary diaryl amine in a lubricating oil wherein the concentration of the molybdenum in the oil is from about 100 to 450 parts per million and the concentration of the amine in the oil is from about 750 to 5,000 parts per million based n said composition.
17. The lubrication composition of claim 16 wherein:
A. the molybdenum compound is a molybdenum carboxylate of an aliphatic acid having from 4 to 18 carbon atoms and the concentration thereof is from about 100 to 250 parts per million of the composition; and
B. the diaryl amine is of the formula:
Figure USRE037363-20010911-C00004
wherein R1 and R2 each independently represent an aryl group having from about 6 to 30 carbon atoms and the concentration thereof is from about 1,000 to 4,000 parts per million of the composition.
18. The lubrication composition of claim 17 wherein the molybdenum carboxylate is that of a fatty acid having from about 4 to 18 carbon atoms and each of R1 and R2 of the amine is a member selected from the group consisting of phenyl, naphthyl, alkphenyl having from about 4 to 18 carbon atoms in the alkyl group and alknaphthyl having from about 4 to 18 carbon atoms in the alkyl group.
19. A method for improving the antioxidant and friction properties of a lubricant which comprises adding to the lubricant an oil soluble molybdenum carboxylate derived from an organic carboxylic acid having from about 4 to 30 carbon atoms and wherein said molybdenum carboxylate provides about 100 to 450 parts per million of molybdenum and about 750 to 5,000 parts per million of an oil soluble secondary diarylamine.
20. The method of claim 19 wherein the carboxylate is derived from a carboxylic acid selected from the group consisting of: butyric acid; valeric acid; caproic acid heptanoic acid; cyclohexanecarboxylic acid; cyclodecanoic acid; naphthenic acid; phenyl acetic acid; 2-methylhexanoic acid; 2-ethylhexanoic acid; suberic acid; octanoic acid; nonanoic acid; decanoic acid; undecanoic acid; lauric acid, tridecanoic acid; myristic acid; pentadecanoic acid; palmitic acid; linolenic acid; heptadecanoic acid; stearic acid; oleic acid; nonadecanoic acid; eicosanoic acid; heneicosanoic acid; docosanoic acid; and eurcic acid.
21. The method of claim 20 wherein: the molybdenum carboxylate provides about 100 to 250 parts per million of molybdenum; about 1,000 to 4,000 parts per million of the oil soluble secondary diarylamine are added to the lubricant and said amine is of the formula
Figure USRE037363-20010911-C00005
wherein each of R1 and R2 is alkphenyl having from about 4 to 18 carbon atoms in each alkyl group.
22. A method for lubricating an automotive or truck crankcase or transmission comprising adding the lubricating composition according to claim 1 to said crankcase or transmission.
US09/359,770 1995-11-20 1999-07-22 Lubricant containing molybdenum compound and secondary diarylamine Expired - Lifetime USRE37363E1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US09/359,770 USRE37363E1 (en) 1995-11-20 1999-07-22 Lubricant containing molybdenum compound and secondary diarylamine
US09/604,285 USRE38929E1 (en) 1995-11-20 2000-06-26 Lubricant containing molybdenum compound and secondary diarylamine
US11/133,442 USRE40595E1 (en) 1995-11-20 2005-05-20 Lubricant containing molybdenum compound and secondary diarylamine

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/559,879 US5650381A (en) 1995-11-20 1995-11-20 Lubricant containing molybdenum compound and secondary diarylamine
US09/359,770 USRE37363E1 (en) 1995-11-20 1999-07-22 Lubricant containing molybdenum compound and secondary diarylamine

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US08/559,879 Reissue US5650381A (en) 1995-11-20 1995-11-20 Lubricant containing molybdenum compound and secondary diarylamine

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US08/559,879 Continuation US5650381A (en) 1995-11-20 1995-11-20 Lubricant containing molybdenum compound and secondary diarylamine
US09/604,285 Continuation USRE38929E1 (en) 1995-11-20 2000-06-26 Lubricant containing molybdenum compound and secondary diarylamine

Publications (1)

Publication Number Publication Date
USRE37363E1 true USRE37363E1 (en) 2001-09-11

Family

ID=24235439

Family Applications (2)

Application Number Title Priority Date Filing Date
US08/559,879 Ceased US5650381A (en) 1995-11-20 1995-11-20 Lubricant containing molybdenum compound and secondary diarylamine
US09/359,770 Expired - Lifetime USRE37363E1 (en) 1995-11-20 1999-07-22 Lubricant containing molybdenum compound and secondary diarylamine

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US08/559,879 Ceased US5650381A (en) 1995-11-20 1995-11-20 Lubricant containing molybdenum compound and secondary diarylamine

Country Status (4)

Country Link
US (2) US5650381A (en)
JP (1) JP3758259B2 (en)
CA (1) CA2189387C (en)
GB (1) GB2307245B (en)

Cited By (77)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6645921B2 (en) 2002-02-08 2003-11-11 Ethyl Corporation Molybdenum-containing lubricant additive compositions, and processes for making and using same
US6723685B2 (en) * 2002-04-05 2004-04-20 Infineum International Ltd. Lubricating oil composition
US20040198616A1 (en) * 2003-03-27 2004-10-07 Keiji Hirao Lubricating base stock for internal combustion engine oil and composition containing the same
USRE38929E1 (en) * 1995-11-20 2006-01-03 Afton Chemical Intangibles Llc Lubricant containing molybdenum compound and secondary diarylamine
US20060084584A1 (en) * 2004-10-20 2006-04-20 Gatto Vincent J Oil-soluble molybdenum derivatives derived from hydroxyethyl-substituted mannich bases
US20070254821A1 (en) * 2006-04-26 2007-11-01 R. T. Vanderbilt Company, Inc. Antioxidant Synergist for Lubricating Compositions
WO2007131027A2 (en) 2006-05-05 2007-11-15 R.T. Vanderbilt Company, Inc. Lubricant antioxidant compositions employing synergistic organotungstate component
US20080312112A1 (en) * 2004-08-09 2008-12-18 Rountree Philip L Lubricating formulations for dispersancy and temperature, friction, and wear reduction
EP2746374A2 (en) 2012-12-21 2014-06-25 Afton Chemical Corporation Additive compositions with a friction modifier and a detergent
EP2746371A1 (en) 2012-12-21 2014-06-25 Afton Chemical Corporation Additive compositions with a friction modifier and a metal dialkyl dithio phosphate salt
EP2746372A1 (en) 2012-12-21 2014-06-25 Afton Chemical Corporation Additive compositions with plural friction modifiers
EP2746370A1 (en) 2012-12-21 2014-06-25 Afton Chemical Corporation Friction modifiers for lubricating oils
EP2746373A2 (en) 2012-12-21 2014-06-25 Afton Chemical Corporation Friction modifiers for use in lubricating oil compositions
EP2767577A1 (en) 2012-12-21 2014-08-20 Afton Chemical Corporation Additive compositions with a friction modifier and a dispersant
EP2826843A1 (en) 2013-07-18 2015-01-21 Afton Chemical Corporation Amide alcohol friction modifiers for lubricating oils
EP2826842A1 (en) 2013-07-18 2015-01-21 Afton Chemical Corporation Friction modifiers for lubricating oils
EP2826841A1 (en) 2013-07-18 2015-01-21 Afton Chemical Corporation Friction modifiers for engine oils
EP2933320A1 (en) 2014-04-17 2015-10-21 Afton Chemical Corporation Lubricant additives and lubricant compositions having improved frictional characteristics
EP2957624A1 (en) 2014-06-19 2015-12-23 Afton Chemical Corporation Novel phosphorus anti-wear compounds for use in lubricant compositions
EP2990469A1 (en) 2014-08-27 2016-03-02 Afton Chemical Corporation Lubricant composition suitable for use in gasoline direct injection engines
WO2017011689A1 (en) 2015-07-16 2017-01-19 Afton Chemical Corporation Lubricants with titanium and/or tungsten and their use for improving low speed pre-ignition
US9677026B1 (en) 2016-04-08 2017-06-13 Afton Chemical Corporation Lubricant additives and lubricant compositions having improved frictional characteristics
US9701921B1 (en) 2016-04-08 2017-07-11 Afton Chemical Corporation Lubricant additives and lubricant compositions having improved frictional characteristics
WO2017146867A1 (en) 2016-02-25 2017-08-31 Afton Chemical Corporation Lubricants for use in boosted engines
WO2017189277A1 (en) 2016-04-26 2017-11-02 Afton Chemical Corporation Random copolymers of acrylates as polymeric friction modifiers, and lubricants containing same
WO2017192217A1 (en) 2016-05-05 2017-11-09 Afton Chemical Corporation Lubricants for use in boosted engines
WO2017192202A1 (en) 2016-05-05 2017-11-09 Afton Chemical Corporaion Lubricant compositions for reducing timing chain stretch
EP3246383A1 (en) 2016-05-17 2017-11-22 Afton Chemical Corporation Synergistic dispersants
EP3336163A1 (en) 2016-12-13 2018-06-20 Afton Chemical Corporation Polyolefin-derived dispersants
WO2018111726A1 (en) 2016-12-16 2018-06-21 Afton Chemical Corporation Multi-functional olefin copolymers and lubricating compositions containing same
WO2018136138A1 (en) 2017-01-18 2018-07-26 Afton Chemical Corporation Lubricants with overbased calcium and overbased magnesium detergents and method for improving low-speed pre-ignition
WO2018136136A1 (en) 2017-01-18 2018-07-26 Afton Chemical Corporation Lubricants with calcium-containing detergents and their use for improving low-speed pre-ignition
WO2018136137A1 (en) 2017-01-18 2018-07-26 Afton Chemical Corporation Lubricants with calcium and magnesium-containing detergents and their use for improving low-speed pre-ignition and for corrosion resistance
WO2018226277A1 (en) 2017-06-05 2018-12-13 Afton Chemical Company Methods for improving resistance to timing chain wear with a multi-component detergent system
US10174272B2 (en) 2016-07-14 2019-01-08 Afton Chemical Corporation Dispersant viscosity index improver-containing lubricant compositions and methods of use thereof
US10214703B2 (en) 2015-07-16 2019-02-26 Afton Chemical Corporation Lubricants with zinc dialkyl dithiophosphate and their use in boosted internal combustion engines
EP3476923A1 (en) 2017-10-25 2019-05-01 Afton Chemical Corporation Dispersant viscosity index improvers to enhance wear protection in engine oils
US10280383B2 (en) 2015-07-16 2019-05-07 Afton Chemical Corporation Lubricants with molybdenum and their use for improving low speed pre-ignition
US10336959B2 (en) 2015-07-16 2019-07-02 Afton Chemical Corporation Lubricants with calcium-containing detergent and their use for improving low speed pre-ignition
US10377963B2 (en) 2016-02-25 2019-08-13 Afton Chemical Corporation Lubricants for use in boosted engines
US10421922B2 (en) 2015-07-16 2019-09-24 Afton Chemical Corporation Lubricants with magnesium and their use for improving low speed pre-ignition
EP3560966A2 (en) 2018-04-25 2019-10-30 Afton Chemical Corporation Multifunctional branched polymers with improved low-temperature performance
EP3578625A1 (en) 2018-06-05 2019-12-11 Afton Chemical Corporation Lubricant composition and dispersants therefor having a beneficial effect on oxidation stability
EP3680312A1 (en) 2019-01-11 2020-07-15 Afton Chemical Corporation Oxazoline modified dispersants
WO2020149958A1 (en) 2019-01-18 2020-07-23 Afton Chemical Corporation Engine oils for soot handling and friction reduction
WO2020174454A1 (en) 2019-02-28 2020-09-03 Afton Chemical Corporation Lubricating compositions for diesel particulate filter performance
US10836976B2 (en) 2018-07-18 2020-11-17 Afton Chemical Corporation Polymeric viscosity modifiers for use in lubricants
WO2021138285A1 (en) 2020-01-03 2021-07-08 Afton Chemical Corporation Silicone functionlized viscosity index improver
EP3858954A1 (en) 2020-01-29 2021-08-04 Afton Chemical Corporation Lubricant formulations with silicon-containing compounds
EP3954753A1 (en) 2020-08-12 2022-02-16 Afton Chemical Corporation Polymeric surfactants for improved emulsion and flow properties at low temperatures
WO2022094557A1 (en) 2020-10-30 2022-05-05 Afton Chemical Corporation Engine oils with low temperature pump ability
WO2022112899A1 (en) 2020-11-25 2022-06-02 Chevron Japan Ltd. Lubricating oil compositions
EP4067463A1 (en) 2021-03-30 2022-10-05 Afton Chemical Corporation Engine oils with improved viscometric performance
US11479736B1 (en) 2021-06-04 2022-10-25 Afton Chemical Corporation Lubricant composition for reduced engine sludge
EP4098723A1 (en) 2021-06-04 2022-12-07 Afton Chemical Corporation Lubricating compositions for a hybrid engine
WO2023004265A1 (en) 2021-07-21 2023-01-26 Afton Chemical Corporation Methods of reducing lead corrosion in an internal combustion engine
EP4124648A1 (en) 2021-07-31 2023-02-01 Afton Chemical Corporation Engine oil formulations for low timing chain stretch
US11572523B1 (en) 2022-01-26 2023-02-07 Afton Chemical Corporation Sulfurized additives with low levels of alkyl phenols
EP4202023A1 (en) 2021-12-21 2023-06-28 Afton Chemical Corporation Mixed fleet capable lubricating compositions
WO2023141399A1 (en) 2022-01-18 2023-07-27 Afton Chemical Corporation Lubricating compositions for reduced high temperature deposits
WO2023159095A1 (en) 2022-02-21 2023-08-24 Afton Chemical Corporation Polyalphaolefin phenols with high para-position selectivity
US11773343B2 (en) 2021-11-17 2023-10-03 Afton Chemical Corporation Engine oil formulation with improved Sequence VIII performance
US11788027B2 (en) 2022-02-18 2023-10-17 Afton Chemical Corporation Engine oil formulation with improved sequence VIII performance
WO2023212165A1 (en) 2022-04-27 2023-11-02 Afton Chemical Corporation Additives with high sulfurization for lubricating oil compositions
EP4282937A1 (en) 2022-05-26 2023-11-29 Afton Chemical Corporation Engine oil formluation for controlling particulate emissions
US11851628B2 (en) 2021-12-21 2023-12-26 Afton Chemical Corporation Lubricating oil composition having resistance to engine deposits
EP4306624A1 (en) 2022-07-14 2024-01-17 Afton Chemical Corporation Transmission lubricants containing molybdenum
EP4310162A1 (en) 2022-07-15 2024-01-24 Afton Chemical Corporation Detergent systems for oxidation resistance in lubricants
EP4317369A1 (en) 2022-08-02 2024-02-07 Afton Chemical Corporation Detergent systems for improved piston cleanliness
US11898119B2 (en) 2022-01-25 2024-02-13 Afton Chemical Corporation Lubricating oil compositions with resistance to engine deposit and varnish formation
WO2024073304A1 (en) 2022-09-27 2024-04-04 Afton Chemical Corporation Lubricating composition for motorcycle applications
EP4357442A1 (en) 2022-09-21 2024-04-24 Afton Chemical Corporation Lubricating composition for fuel efficient motorcycle applications
EP4361235A1 (en) 2022-10-28 2024-05-01 Afton Chemical Corporation Lubricating compositions for reduced low temperature valve train wear
EP4389859A2 (en) 2022-12-20 2024-06-26 Afton Chemical Corporation Low ash lubricating compositions for controlling steel corrosion
EP4410934A1 (en) 2023-01-31 2024-08-07 Afton Chemical Corporation Dispersant and detergent systems for improved motor oil performance
EP4435077A1 (en) 2023-03-22 2024-09-25 Afton Chemical Corporation Antiwear systems for medium and/or heavy duty diesel engines
EP4446398A1 (en) 2023-04-13 2024-10-16 Afton Chemical Corporation Lubricating composition for durability and enhanced fuel economy

Families Citing this family (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2171536C (en) * 1993-09-13 2001-02-06 Andrew James Dalziel Ritchie Lubricating compositions with improved antioxidancy
US5880073A (en) * 1995-05-24 1999-03-09 Tonen Corporation Lubricating oil composition
US5736491A (en) * 1997-01-30 1998-04-07 Texaco Inc. Method of improving the fuel economy characteristics of a lubricant by friction reduction and compositions useful therein
US5840672A (en) * 1997-07-17 1998-11-24 Ethyl Corporation Antioxidant system for lubrication base oils
GB9807843D0 (en) 1998-04-09 1998-06-10 Ethyl Petroleum Additives Ltd Lubricating compositions
US6150309A (en) * 1998-08-04 2000-11-21 Exxon Research And Engineering Co. Lubricant formulations with dispersancy retention capability (law684)
US6179978B1 (en) 1999-02-12 2001-01-30 Eastman Kodak Company Mandrel for forming a nozzle plate having a non-wetting surface of uniform thickness and an orifice wall of tapered contour, and method of making the mandrel
US6103674A (en) * 1999-03-15 2000-08-15 Uniroyal Chemical Company, Inc. Oil-soluble molybdenum multifunctional friction modifier additives for lubricant compositions
US6174842B1 (en) 1999-03-30 2001-01-16 Ethyl Corporation Lubricants containing molybdenum compounds, phenates and diarylamines
US6184186B1 (en) * 1999-04-09 2001-02-06 Ethyl Petroleum Additives, Ltd Lubricating compositions
US6300291B1 (en) 1999-05-19 2001-10-09 Infineum Usa L.P. Lubricating oil composition
US6528461B1 (en) 2000-11-28 2003-03-04 Bank Of America, N.A. Lubricant containing molybdenum and polymeric dispersant
BR0208479B1 (en) * 2001-03-22 2013-02-05 composition and method for inhibiting oxidation on high sulfur api group i basic stocks.
KR100416067B1 (en) * 2001-06-14 2004-01-24 한국화학연구원 A engine treatment for gasoline engine oil
US7112558B2 (en) * 2002-02-08 2006-09-26 Afton Chemical Intangibles Llc Lubricant composition containing phosphorous, molybdenum, and hydroxy-substituted dithiocarbamates
US6962896B2 (en) * 2002-05-31 2005-11-08 Chevron Oronite Company Llc Reduced color molybdenum-containing composition and a method of making same
US20070213235A1 (en) * 2002-07-29 2007-09-13 Saini Mandeep S Lubricant and additive formulation
US20050043191A1 (en) * 2003-08-22 2005-02-24 Farng L. Oscar High performance non-zinc, zero phosphorus engine oils for internal combustion engines
JP5258143B2 (en) * 2004-10-19 2013-08-07 Jx日鉱日石エネルギー株式会社 Lubricating oil composition
US8709989B2 (en) 2004-10-19 2014-04-29 Nippon Oil Corporation Lubricant composition and antioxident composition
US8202829B2 (en) * 2004-11-04 2012-06-19 Afton Chemical Corporation Lubricating composition
US8703872B2 (en) * 2005-03-11 2014-04-22 Castrol Limited Multiple function graft polymer
US20060223724A1 (en) * 2005-03-29 2006-10-05 Gatto Vincent J Lubricating oil composition with reduced phosphorus levels
US8030257B2 (en) * 2005-05-13 2011-10-04 Exxonmobil Research And Engineering Company Catalytic antioxidants
JP5114428B2 (en) * 2006-05-05 2013-01-09 アール.ティー. ヴァンダービルト カンパニー インコーポレーティッド Antioxidant additives for lubricant compositions comprising organotungstate, diarylamine and organomolybdenum compounds
US20080090742A1 (en) * 2006-10-12 2008-04-17 Mathur Naresh C Compound and method of making the compound
US20080090743A1 (en) * 2006-10-17 2008-04-17 Mathur Naresh C Compounds and methods of making the compounds
DE112011103822T5 (en) 2010-11-19 2013-08-22 Chevron U.S.A. Inc. Lubricant for percussion equipment
FR2981728B1 (en) * 2011-10-21 2014-07-04 Hydromecanique & Frottement FRICTION PIECE OPERATING IN A LUBRICATED ENVIRONMENT
KR102209010B1 (en) 2013-11-22 2021-01-27 가부시키가이샤 아데카 Lubricant agent composition and lubricant oil composition containing same
FR3014898B1 (en) * 2013-12-17 2016-01-29 Total Marketing Services LUBRICATING COMPOSITION BASED ON FATTY TRIAMINES
JP6480324B2 (en) * 2015-12-28 2019-03-06 Jxtgエネルギー株式会社 Lubricating oil composition
WO2020194125A1 (en) * 2019-03-22 2020-10-01 Chevron Oronite Company Llc Antioxidants with high mono-alkylated diphenylamine content
CN111979012A (en) * 2020-09-01 2020-11-24 力能石油科技有限公司 Antioxidant lubricating oil and preparation method thereof
EP4225878B1 (en) 2020-10-05 2024-07-03 Chevron Japan Ltd. Friction modifier system
JP2024518127A (en) 2021-05-20 2024-04-24 シェブロンジャパン株式会社 Low ash lubricating oil composition
US20240336862A1 (en) 2023-04-06 2024-10-10 Afton Chemical Corporation Methods of improving the performance of combustion engine after-treatment devices

Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3285942A (en) 1962-03-06 1966-11-15 Exxon Research Engineering Co Preparation of glycol molybdate complexes
US4095963A (en) 1977-02-17 1978-06-20 Chemetron Corporation Stabilization of deodorized edible oils
US4175043A (en) 1978-09-21 1979-11-20 Mobil Oil Corporation Metal salts of sulfurized olefin adducts of phosphorodithioic acids and organic compositions containing same
GB2097422A (en) 1981-04-27 1982-11-03 Chevron Res Lubricating oil additive comprising a molybdenum complex and an aromatic amine compound
US4394279A (en) 1981-08-07 1983-07-19 Chevron Research Company Antioxidant combinations of sulfur containing molybdenum complexes and aromatic amine compounds for lubricating oils
US4428848A (en) 1981-11-09 1984-01-31 Texaco Inc. Molybdenum derivatives and lubricants containing same
US4479883A (en) * 1982-01-06 1984-10-30 Exxon Research & Engineering Co. Lubricant composition with improved friction reducing properties containing a mixture of dithiocarbamates
US4593012A (en) 1984-03-09 1986-06-03 Atlantic Richfield Company Production of hydrocarbon-soluble salts of molybdenum for epoxidation of olefins
US4648985A (en) * 1984-11-15 1987-03-10 The Whitmore Manufacturing Company Extreme pressure additives for lubricants
US4812246A (en) 1987-03-12 1989-03-14 Idemitsu Kosan Co., Ltd. Base oil for lubricating oil and lubricating oil composition containing said base oil
US4832857A (en) 1988-08-18 1989-05-23 Amoco Corporation Process for the preparation of overbased molybdenum alkaline earth metal and alkali metal dispersions
US4846983A (en) 1986-02-21 1989-07-11 The Lubrizol Corp. Novel carbamate additives for functional fluids
US4889647A (en) 1985-11-14 1989-12-26 R. T. Vanderbilt Company, Inc. Organic molybdenum complexes
US5137647A (en) 1991-12-09 1992-08-11 R. T. Vanderbilt Company, Inc. Organic molybdenum complexes
US5143633A (en) 1989-06-19 1992-09-01 Societe Nationale Elf Aquitaine Overbased additives for lubricant oils containing a molybdenum complex, process for preparing them and compositions containing the said additives
US5232614A (en) * 1989-02-23 1993-08-03 Exxon Chemical Patents Inc. Lubricating oil compositions and additives for use therein
WO1995007962A1 (en) 1993-09-13 1995-03-23 Exxon Chemical Patents Inc. Lubricating compositions with improved antioxidancy
WO1995007966A1 (en) 1993-09-13 1995-03-23 Exxon Research And Engineering Company Lubricant composition containing combination of antiwear and antioxidant additives
WO1995007963A1 (en) 1993-09-13 1995-03-23 Exxon Chemical Patents Inc. Mixed antioxidant composition
WO1995027022A1 (en) 1994-03-31 1995-10-12 Exxon Research & Engineering Company Lubrication oil composition
EP0696636A1 (en) 1993-04-30 1996-02-14 Tonen Corporation Lubricating oil composition

Patent Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3285942A (en) 1962-03-06 1966-11-15 Exxon Research Engineering Co Preparation of glycol molybdate complexes
US4095963A (en) 1977-02-17 1978-06-20 Chemetron Corporation Stabilization of deodorized edible oils
US4175043A (en) 1978-09-21 1979-11-20 Mobil Oil Corporation Metal salts of sulfurized olefin adducts of phosphorodithioic acids and organic compositions containing same
GB2097422A (en) 1981-04-27 1982-11-03 Chevron Res Lubricating oil additive comprising a molybdenum complex and an aromatic amine compound
US4394279A (en) 1981-08-07 1983-07-19 Chevron Research Company Antioxidant combinations of sulfur containing molybdenum complexes and aromatic amine compounds for lubricating oils
US4428848A (en) 1981-11-09 1984-01-31 Texaco Inc. Molybdenum derivatives and lubricants containing same
US4479883A (en) * 1982-01-06 1984-10-30 Exxon Research & Engineering Co. Lubricant composition with improved friction reducing properties containing a mixture of dithiocarbamates
US4593012A (en) 1984-03-09 1986-06-03 Atlantic Richfield Company Production of hydrocarbon-soluble salts of molybdenum for epoxidation of olefins
US4648985A (en) * 1984-11-15 1987-03-10 The Whitmore Manufacturing Company Extreme pressure additives for lubricants
US4889647A (en) 1985-11-14 1989-12-26 R. T. Vanderbilt Company, Inc. Organic molybdenum complexes
US4846983A (en) 1986-02-21 1989-07-11 The Lubrizol Corp. Novel carbamate additives for functional fluids
US4812246A (en) 1987-03-12 1989-03-14 Idemitsu Kosan Co., Ltd. Base oil for lubricating oil and lubricating oil composition containing said base oil
US4832857A (en) 1988-08-18 1989-05-23 Amoco Corporation Process for the preparation of overbased molybdenum alkaline earth metal and alkali metal dispersions
US5232614A (en) * 1989-02-23 1993-08-03 Exxon Chemical Patents Inc. Lubricating oil compositions and additives for use therein
US5143633A (en) 1989-06-19 1992-09-01 Societe Nationale Elf Aquitaine Overbased additives for lubricant oils containing a molybdenum complex, process for preparing them and compositions containing the said additives
US5137647A (en) 1991-12-09 1992-08-11 R. T. Vanderbilt Company, Inc. Organic molybdenum complexes
EP0696636A1 (en) 1993-04-30 1996-02-14 Tonen Corporation Lubricating oil composition
WO1995007962A1 (en) 1993-09-13 1995-03-23 Exxon Chemical Patents Inc. Lubricating compositions with improved antioxidancy
WO1995007966A1 (en) 1993-09-13 1995-03-23 Exxon Research And Engineering Company Lubricant composition containing combination of antiwear and antioxidant additives
WO1995007963A1 (en) 1993-09-13 1995-03-23 Exxon Chemical Patents Inc. Mixed antioxidant composition
WO1995027022A1 (en) 1994-03-31 1995-10-12 Exxon Research & Engineering Company Lubrication oil composition

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Vanderbilt Lubricant Additives", R.T. Vanderbilt Company, Inc. (date?) Not provided.
MOLYVAN(R)822 Oil Soluble Molybdenum-Sulfur Lubricant Additive Non-Phosphorus Friction Reducer Antioxidant, Technical Data, MV-822-1A/8604 (8203), R.T. Vanderbilt Company, Inc., (Apr. 1986).
MOLYVAN®822 Oil Soluble Molybdenum-Sulfur Lubricant Additive Non-Phosphorus Friction Reducer Antioxidant, Technical Data, MV-822-1A/8604 (8203), R.T. Vanderbilt Company, Inc., (Apr. 1986).
Vanderbilt Lubricant Additives Technical Bulletin 941, R.T. Vanderbilt Company, Inc., (Jun. 1994).

Cited By (113)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE40595E1 (en) * 1995-11-20 2008-12-02 Afton Chemical Intangibles Llc Lubricant containing molybdenum compound and secondary diarylamine
USRE38929E1 (en) * 1995-11-20 2006-01-03 Afton Chemical Intangibles Llc Lubricant containing molybdenum compound and secondary diarylamine
US20040082486A1 (en) * 2002-02-08 2004-04-29 Ethyl Corporation Molybdenum-containing lubricant additive compositions and processes for making and using same
US6914037B2 (en) 2002-02-08 2005-07-05 Ethyl Corporation Molybdenum-containing lubricant additive compositions and processes for making and using same
US6645921B2 (en) 2002-02-08 2003-11-11 Ethyl Corporation Molybdenum-containing lubricant additive compositions, and processes for making and using same
US6723685B2 (en) * 2002-04-05 2004-04-20 Infineum International Ltd. Lubricating oil composition
US20040198616A1 (en) * 2003-03-27 2004-10-07 Keiji Hirao Lubricating base stock for internal combustion engine oil and composition containing the same
US20080312112A1 (en) * 2004-08-09 2008-12-18 Rountree Philip L Lubricating formulations for dispersancy and temperature, friction, and wear reduction
US20090075849A1 (en) * 2004-10-20 2009-03-19 Afton Chemical Corporation Oil-soluble molybdenum derivatives derived from hydroxyethyl-substituted mannich bases
US20060084584A1 (en) * 2004-10-20 2006-04-20 Gatto Vincent J Oil-soluble molybdenum derivatives derived from hydroxyethyl-substituted mannich bases
US7884059B2 (en) 2004-10-20 2011-02-08 Afton Chemical Corporation Oil-soluble molybdenum derivatives derived from hydroxyethyl-substituted Mannich bases
US7960321B2 (en) 2004-10-20 2011-06-14 Afton Chemical Corporation Oil-soluble molybdenum derivatives derived from hydroxyethyl-substituted Mannich bases
US20070254821A1 (en) * 2006-04-26 2007-11-01 R. T. Vanderbilt Company, Inc. Antioxidant Synergist for Lubricating Compositions
US7902131B2 (en) 2006-04-26 2011-03-08 R.T. Vanderbilt Company, Inc. Antioxidant synergist for lubricating compositions
WO2007131027A2 (en) 2006-05-05 2007-11-15 R.T. Vanderbilt Company, Inc. Lubricant antioxidant compositions employing synergistic organotungstate component
EP2021441A2 (en) * 2006-05-05 2009-02-11 R.T. Vanderbilt Company, Inc. Lubricant antioxidant compositions employing synergistic organotungstate component
EP2021441A4 (en) * 2006-05-05 2011-07-06 Vanderbilt Co R T Lubricant antioxidant compositions employing synergistic organotungstate component
EP2746371A1 (en) 2012-12-21 2014-06-25 Afton Chemical Corporation Additive compositions with a friction modifier and a metal dialkyl dithio phosphate salt
EP2746372A1 (en) 2012-12-21 2014-06-25 Afton Chemical Corporation Additive compositions with plural friction modifiers
EP2746370A1 (en) 2012-12-21 2014-06-25 Afton Chemical Corporation Friction modifiers for lubricating oils
EP2746373A2 (en) 2012-12-21 2014-06-25 Afton Chemical Corporation Friction modifiers for use in lubricating oil compositions
EP2767577A1 (en) 2012-12-21 2014-08-20 Afton Chemical Corporation Additive compositions with a friction modifier and a dispersant
EP2746374A2 (en) 2012-12-21 2014-06-25 Afton Chemical Corporation Additive compositions with a friction modifier and a detergent
EP2826843A1 (en) 2013-07-18 2015-01-21 Afton Chemical Corporation Amide alcohol friction modifiers for lubricating oils
EP2826842A1 (en) 2013-07-18 2015-01-21 Afton Chemical Corporation Friction modifiers for lubricating oils
EP2826841A1 (en) 2013-07-18 2015-01-21 Afton Chemical Corporation Friction modifiers for engine oils
EP2993220A1 (en) 2013-07-18 2016-03-09 Afton Chemical Corporation Friction modifiers for lubricating oils
US9657252B2 (en) 2014-04-17 2017-05-23 Afton Chemical Corporation Lubricant additives and lubricant compositions having improved frictional characteristics
EP2933320A1 (en) 2014-04-17 2015-10-21 Afton Chemical Corporation Lubricant additives and lubricant compositions having improved frictional characteristics
EP2957624A1 (en) 2014-06-19 2015-12-23 Afton Chemical Corporation Novel phosphorus anti-wear compounds for use in lubricant compositions
EP2990469A1 (en) 2014-08-27 2016-03-02 Afton Chemical Corporation Lubricant composition suitable for use in gasoline direct injection engines
WO2017011689A1 (en) 2015-07-16 2017-01-19 Afton Chemical Corporation Lubricants with titanium and/or tungsten and their use for improving low speed pre-ignition
EP3943581A1 (en) 2015-07-16 2022-01-26 Afton Chemical Corporation Lubricants with tungsten and their use for improving low speed pre-ignition
US10550349B2 (en) 2015-07-16 2020-02-04 Afton Chemical Corporation Lubricants with titanium and/or tungsten and their use for improving low speed pre-ignition
US10421922B2 (en) 2015-07-16 2019-09-24 Afton Chemical Corporation Lubricants with magnesium and their use for improving low speed pre-ignition
US10214703B2 (en) 2015-07-16 2019-02-26 Afton Chemical Corporation Lubricants with zinc dialkyl dithiophosphate and their use in boosted internal combustion engines
US10336959B2 (en) 2015-07-16 2019-07-02 Afton Chemical Corporation Lubricants with calcium-containing detergent and their use for improving low speed pre-ignition
US10280383B2 (en) 2015-07-16 2019-05-07 Afton Chemical Corporation Lubricants with molybdenum and their use for improving low speed pre-ignition
US10377963B2 (en) 2016-02-25 2019-08-13 Afton Chemical Corporation Lubricants for use in boosted engines
WO2017146867A1 (en) 2016-02-25 2017-08-31 Afton Chemical Corporation Lubricants for use in boosted engines
EP3613831A1 (en) 2016-02-25 2020-02-26 Afton Chemical Corporation Lubricants for use in boosted engines
EP3228684A1 (en) 2016-04-08 2017-10-11 Afton Chemical Corporation Lubricant compositions having improved frictional characteristics and methods of use thereof
US9677026B1 (en) 2016-04-08 2017-06-13 Afton Chemical Corporation Lubricant additives and lubricant compositions having improved frictional characteristics
EP3243892A1 (en) 2016-04-08 2017-11-15 Afton Chemical Corporation Lubricant compositions having improved frictional characteristics and methods of use thereof
US9701921B1 (en) 2016-04-08 2017-07-11 Afton Chemical Corporation Lubricant additives and lubricant compositions having improved frictional characteristics
WO2017189277A1 (en) 2016-04-26 2017-11-02 Afton Chemical Corporation Random copolymers of acrylates as polymeric friction modifiers, and lubricants containing same
WO2017192202A1 (en) 2016-05-05 2017-11-09 Afton Chemical Corporaion Lubricant compositions for reducing timing chain stretch
US11155764B2 (en) 2016-05-05 2021-10-26 Afton Chemical Corporation Lubricants for use in boosted engines
WO2017192217A1 (en) 2016-05-05 2017-11-09 Afton Chemical Corporation Lubricants for use in boosted engines
US10323205B2 (en) 2016-05-05 2019-06-18 Afton Chemical Corporation Lubricant compositions for reducing timing chain stretch
US10494583B2 (en) 2016-05-17 2019-12-03 Afton Chemical Corporation Synergistic dispersants
EP3246383A1 (en) 2016-05-17 2017-11-22 Afton Chemical Corporation Synergistic dispersants
US10179886B2 (en) 2016-05-17 2019-01-15 Afton Chemical Corporation Synergistic dispersants
US10174272B2 (en) 2016-07-14 2019-01-08 Afton Chemical Corporation Dispersant viscosity index improver-containing lubricant compositions and methods of use thereof
US10584297B2 (en) 2016-12-13 2020-03-10 Afton Chemical Corporation Polyolefin-derived dispersants
WO2019117992A1 (en) 2016-12-13 2019-06-20 Afton Chemical Corporation Polyolefin-derived dispersants
WO2018111846A1 (en) 2016-12-13 2018-06-21 Afton Chemical Corporation Polyolefin-derived dispersants
EP3336163A1 (en) 2016-12-13 2018-06-20 Afton Chemical Corporation Polyolefin-derived dispersants
WO2018111726A1 (en) 2016-12-16 2018-06-21 Afton Chemical Corporation Multi-functional olefin copolymers and lubricating compositions containing same
WO2018136137A1 (en) 2017-01-18 2018-07-26 Afton Chemical Corporation Lubricants with calcium and magnesium-containing detergents and their use for improving low-speed pre-ignition and for corrosion resistance
US10443558B2 (en) 2017-01-18 2019-10-15 Afton Chemical Corporation Lubricants with calcium and magnesium-containing detergents and their use for improving low-speed pre-ignition and for corrosion resistance
US10443011B2 (en) 2017-01-18 2019-10-15 Afton Chemical Corporation Lubricants with overbased calcium and overbased magnesium detergents and method for improving low-speed pre-ignition
US10370615B2 (en) 2017-01-18 2019-08-06 Afton Chemical Corporation Lubricants with calcium-containing detergents and their use for improving low-speed pre-ignition
WO2018136136A1 (en) 2017-01-18 2018-07-26 Afton Chemical Corporation Lubricants with calcium-containing detergents and their use for improving low-speed pre-ignition
WO2018136138A1 (en) 2017-01-18 2018-07-26 Afton Chemical Corporation Lubricants with overbased calcium and overbased magnesium detergents and method for improving low-speed pre-ignition
WO2018226277A1 (en) 2017-06-05 2018-12-13 Afton Chemical Company Methods for improving resistance to timing chain wear with a multi-component detergent system
EP3476923A1 (en) 2017-10-25 2019-05-01 Afton Chemical Corporation Dispersant viscosity index improvers to enhance wear protection in engine oils
US10513668B2 (en) 2017-10-25 2019-12-24 Afton Chemical Corporation Dispersant viscosity index improvers to enhance wear protection in engine oils
US11098262B2 (en) 2018-04-25 2021-08-24 Afton Chemical Corporation Multifunctional branched polymers with improved low-temperature performance
EP3560966A2 (en) 2018-04-25 2019-10-30 Afton Chemical Corporation Multifunctional branched polymers with improved low-temperature performance
US11760953B2 (en) 2018-04-25 2023-09-19 Afton Chemical Corporation Multifunctional branched polymers with improved low-temperature performance
EP3578625A1 (en) 2018-06-05 2019-12-11 Afton Chemical Corporation Lubricant composition and dispersants therefor having a beneficial effect on oxidation stability
US10836976B2 (en) 2018-07-18 2020-11-17 Afton Chemical Corporation Polymeric viscosity modifiers for use in lubricants
EP3680312A1 (en) 2019-01-11 2020-07-15 Afton Chemical Corporation Oxazoline modified dispersants
WO2020149958A1 (en) 2019-01-18 2020-07-23 Afton Chemical Corporation Engine oils for soot handling and friction reduction
WO2020174454A1 (en) 2019-02-28 2020-09-03 Afton Chemical Corporation Lubricating compositions for diesel particulate filter performance
WO2021138285A1 (en) 2020-01-03 2021-07-08 Afton Chemical Corporation Silicone functionlized viscosity index improver
US11214753B2 (en) 2020-01-03 2022-01-04 Afton Chemical Corporation Silicone functionalized viscosity index improver
EP3858954A1 (en) 2020-01-29 2021-08-04 Afton Chemical Corporation Lubricant formulations with silicon-containing compounds
EP3954753A1 (en) 2020-08-12 2022-02-16 Afton Chemical Corporation Polymeric surfactants for improved emulsion and flow properties at low temperatures
EP4368689A1 (en) 2020-08-12 2024-05-15 Afton Chemical Corporation Polymeric surfactants for improved emulsion and flow properties at low temperatures
WO2022094557A1 (en) 2020-10-30 2022-05-05 Afton Chemical Corporation Engine oils with low temperature pump ability
WO2022112899A1 (en) 2020-11-25 2022-06-02 Chevron Japan Ltd. Lubricating oil compositions
EP4067463A1 (en) 2021-03-30 2022-10-05 Afton Chemical Corporation Engine oils with improved viscometric performance
EP4098723A1 (en) 2021-06-04 2022-12-07 Afton Chemical Corporation Lubricating compositions for a hybrid engine
US11479736B1 (en) 2021-06-04 2022-10-25 Afton Chemical Corporation Lubricant composition for reduced engine sludge
US11753599B2 (en) 2021-06-04 2023-09-12 Afton Chemical Corporation Lubricating compositions for a hybrid engine
WO2023004265A1 (en) 2021-07-21 2023-01-26 Afton Chemical Corporation Methods of reducing lead corrosion in an internal combustion engine
EP4124648A1 (en) 2021-07-31 2023-02-01 Afton Chemical Corporation Engine oil formulations for low timing chain stretch
US11608477B1 (en) 2021-07-31 2023-03-21 Afton Chemical Corporation Engine oil formulations for low timing chain stretch
US11773343B2 (en) 2021-11-17 2023-10-03 Afton Chemical Corporation Engine oil formulation with improved Sequence VIII performance
EP4202023A1 (en) 2021-12-21 2023-06-28 Afton Chemical Corporation Mixed fleet capable lubricating compositions
US11851628B2 (en) 2021-12-21 2023-12-26 Afton Chemical Corporation Lubricating oil composition having resistance to engine deposits
WO2023141399A1 (en) 2022-01-18 2023-07-27 Afton Chemical Corporation Lubricating compositions for reduced high temperature deposits
US11898119B2 (en) 2022-01-25 2024-02-13 Afton Chemical Corporation Lubricating oil compositions with resistance to engine deposit and varnish formation
US11572523B1 (en) 2022-01-26 2023-02-07 Afton Chemical Corporation Sulfurized additives with low levels of alkyl phenols
US11976250B2 (en) 2022-01-26 2024-05-07 Afton Chemical Corporation Sulfurized additives with low levels of alkyl phenols
WO2023147258A1 (en) 2022-01-26 2023-08-03 Afton Chemical Corporation Sulfurized additives with low levels of alkyl phenols
US11788027B2 (en) 2022-02-18 2023-10-17 Afton Chemical Corporation Engine oil formulation with improved sequence VIII performance
US11976252B2 (en) 2022-02-21 2024-05-07 Afton Chemical Corporation Polyalphaolefin phenols with high para-position selectivity
WO2023159095A1 (en) 2022-02-21 2023-08-24 Afton Chemical Corporation Polyalphaolefin phenols with high para-position selectivity
WO2023212165A1 (en) 2022-04-27 2023-11-02 Afton Chemical Corporation Additives with high sulfurization for lubricating oil compositions
EP4282937A1 (en) 2022-05-26 2023-11-29 Afton Chemical Corporation Engine oil formluation for controlling particulate emissions
EP4306624A1 (en) 2022-07-14 2024-01-17 Afton Chemical Corporation Transmission lubricants containing molybdenum
EP4310162A1 (en) 2022-07-15 2024-01-24 Afton Chemical Corporation Detergent systems for oxidation resistance in lubricants
EP4317369A1 (en) 2022-08-02 2024-02-07 Afton Chemical Corporation Detergent systems for improved piston cleanliness
EP4357442A1 (en) 2022-09-21 2024-04-24 Afton Chemical Corporation Lubricating composition for fuel efficient motorcycle applications
WO2024073304A1 (en) 2022-09-27 2024-04-04 Afton Chemical Corporation Lubricating composition for motorcycle applications
EP4361235A1 (en) 2022-10-28 2024-05-01 Afton Chemical Corporation Lubricating compositions for reduced low temperature valve train wear
EP4389859A2 (en) 2022-12-20 2024-06-26 Afton Chemical Corporation Low ash lubricating compositions for controlling steel corrosion
EP4410934A1 (en) 2023-01-31 2024-08-07 Afton Chemical Corporation Dispersant and detergent systems for improved motor oil performance
EP4435077A1 (en) 2023-03-22 2024-09-25 Afton Chemical Corporation Antiwear systems for medium and/or heavy duty diesel engines
EP4446398A1 (en) 2023-04-13 2024-10-16 Afton Chemical Corporation Lubricating composition for durability and enhanced fuel economy

Also Published As

Publication number Publication date
CA2189387A1 (en) 1997-05-21
GB2307245B (en) 2000-07-12
CA2189387C (en) 2001-03-13
GB9624118D0 (en) 1997-01-08
GB2307245A (en) 1997-05-21
JPH09151387A (en) 1997-06-10
JP3758259B2 (en) 2006-03-22
US5650381A (en) 1997-07-22

Similar Documents

Publication Publication Date Title
USRE37363E1 (en) Lubricant containing molybdenum compound and secondary diarylamine
USRE40595E1 (en) Lubricant containing molybdenum compound and secondary diarylamine
US6174842B1 (en) Lubricants containing molybdenum compounds, phenates and diarylamines
EP0892037B1 (en) Improved antioxidant system for lubrication base oils
US6528463B1 (en) Oil soluble molybdenum compositions
US4192757A (en) Alkyl phenol solutions of organo molybdenum complexes as friction reducing antiwear additives
KR960014934B1 (en) Low phosphorus and zinc lubricants
US4201683A (en) Alkanol solutions of organo molybdenum complexes as friction reducing antiwear additives
CA1125735A (en) Molybdenum complexes of ashless nitrogen dispersants as friction reducing antiwear additives for lubricating oils
KR960014933B1 (en) Low phosphorus lubricants
EP0389237B1 (en) Friction modifier
EP0737675B1 (en) Basic metal salt of dithiocarbamic acid and lubricating oil composition containing said salt
US6528461B1 (en) Lubricant containing molybdenum and polymeric dispersant
EP0556404A1 (en) Lubricating oil composition
EP0384720B1 (en) Crankcase lubricating oil compositions and additives for use therein
US11697785B2 (en) Lubricant composition for a gas engine
EP0444830A1 (en) Succinimide composition

Legal Events

Date Code Title Description
AS Assignment

Owner name: BANK OF AMERICA, N.A., AS COLLATERAL AGENT, CALIFO

Free format text: NOTICE OF GRANT SECURITY INTEREST;ASSIGNOR:ETHYL CORPORATION;REEL/FRAME:011712/0298

Effective date: 20010410

AS Assignment

Owner name: CREDIT SUISSE FIRST BOSTON, CAYMAN ISLANDS BRANCH,

Free format text: GRANT OF PATENT SECURITY INTEREST;ASSIGNOR:ETHYL CORPORATION;REEL/FRAME:014146/0832

Effective date: 20030430

Owner name: ETHLYL CORPORATION, VIRGINIA

Free format text: RELEASE OF SECURITY INTEREST;ASSIGNOR:BANK OF AMERICA, N.A.;REEL/FRAME:014146/0783

Effective date: 20030430

AS Assignment

Owner name: SUNTRUST BANK, AS ADMINISTRATIVE AGENT, GEORGIA

Free format text: ASSIGNMT. OF SECURITY INTEREST;ASSIGNOR:CREDIT SUISSE FIRST BOSTON, CAYMAN ISLANDS BRANCH;REEL/FRAME:014788/0105

Effective date: 20040618

Owner name: SUNTRUST BANK, AS ADMINISTRATIVE AGENT, GEORGIA

Free format text: SECURITY INTEREST;ASSIGNOR:ETHYL CORPORATION;REEL/FRAME:014782/0348

Effective date: 20040618

AS Assignment

Owner name: AFTON CHEMICAL INTANGIBLES LLC, VIRGINIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ETHYL CORPORATION;REEL/FRAME:016301/0175

Effective date: 20040630

FEPP Fee payment procedure

Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

CC Certificate of correction
FPAY Fee payment

Year of fee payment: 8

SULP Surcharge for late payment

Year of fee payment: 7

AS Assignment

Owner name: SUNTRUST BANK, VIRGINIA

Free format text: SECURITY AGREEMENT;ASSIGNOR:AFTON CHEMICAL INTANGIBLES LLC;REEL/FRAME:018883/0902

Effective date: 20061221

AS Assignment

Owner name: AFTON CHEMICAL INTANGIBLES LLC, VIRGINIA

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:SUNTRUST BANK;REEL/FRAME:026761/0050

Effective date: 20110513