Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
  • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
  • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
  • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
  • C10M133/38—Heterocyclic nitrogen compounds
  • C10M133/44—Five-membered ring containing nitrogen and carbon only
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M141/00—Lubricating 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
  • C10M141/06—Lubricating 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M141/00—Lubricating 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
  • C10M141/08—Lubricating 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 sulfur-, selenium- or tellurium-containing compound
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
  • C10M2215/064—Di- and triaryl amines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/22—Heterocyclic nitrogen compounds
  • C10M2215/223—Five-membered rings containing nitrogen and carbon only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
  • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
  • C10M2219/108—Phenothiazine
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/02—Groups 1 or 11
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/08—Groups 4 or 14
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/04—Detergent property or dispersant property
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/04—Detergent property or dispersant property
  • C10N2030/041—Soot induced viscosity control
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/52—Base number [TBN]
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines
  • C10N2040/253—Small diesel engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/255—Gasoline engines

Definitions

• the present disclosure is directed to additive and lubricant compositions and methods for use thereof.
• Lubricating oils as used in the internal combustion engines and transmissions of automobiles or trucks are subjected to a demanding environment during use. This environment results in oxidation of the oil which is catalyzed by the presence of impurities in the oil, and is also promoted by the elevated temperatures of the oil during use.
• the oxidation of lubricating oils contributes to the formation of sludge in oils and the breakdown of viscosity characteristics of the lubricant.
• the oxidation is often controlled to some extent by selecting the proper antioxidant additives thereby significantly improving the life of the lubricating oils.
• Antioxidant additives can extend the useful life of the lubricating oil by, for example, reducing or preventing unacceptable viscosity increases and/or deposit formation.
• antiwear agents form a thin film on metal surfaces which prevents metal to metal contact, resulting in a decrease in the amount of wear.
• a well-known and commonly used antiwear agent is zinc dialkyldithiophosphate (ZDDP).
• a lubricating oil composition to comprise reduced phosphorus containing compound concentrations while also containing improved additives mat reduce the oxidative degradation of lubricating oils.
• an additive composition comprising (i) a triazole compound substituted with an aryl moiety; (ii) at least one nitrogen containing compound chosen from an alkylated phenothiazine and a compound represented by the formula (I):
• R 0 , R 1 and R 2 are each independently selected from the group consisting of an aryl moiety comprising from about 6 about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amido, phosphoro, and sulfono, with the proviso that at least one of R 0 , R 1 and R 2 are chosen to be an aryl moiety comprising from about 6 to about 30 carbon atoms; and (iii) a metal detergent with a soap/TBN ratio ranging from about 0.05 to about 1.5.
• a lubricant composition comprising a a major amount of a base oil; and a minor amount of an additive composition comprising (i) a triazole compound substituted with an aryl moiety; (ii) at least one nitrogen containing compound chosen from an alkylated phenothiazine and a compound represented by the formula (I).
• R 0 , R 1 and R 2 are each independently selected from the group consisting of an aryl moiety comprising from about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amido, phosphoro, and sulfono, with the proviso that at least one of R 0 , R 1 and R 2 are chosen to be an aryl moiety comprising from about 6 to about 30 carbon atoms; and (iii) a metal detergent with a soap/TBN ratio ranging from about 0.05 to about 1.5.
• a method of delaying the onset of viscosity increase in a lubricant composition comprising providing to a machine a lubricant composition comprising a major amount of a base oil; and a minor amount of an additive comprising (i) a triazole compound substituted with an aryl moiety; (ii) at least one nitrogen containing compound chosen from an alkylated phenothiazine and a compound represented by the formula (I):
• R 0 , R 1 and R 2 are each independently selected from the group consisting of an aryl moiety comprising from about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amido, phosphoro, and sulfono, with the proviso that at least one of R 0 , R 1 and R 2 are chosen to be an aryl moiety comprising from about 6 to about 30 carbon atoms; and (iii) a metal detergent with a soap/TBN ratio ranging from about 0.05 to about 1.5.
• Another aspect of the present disclosure is directed to a method of lubricating at least one moving part of a machine.
• the method comprises contacting the at least one moving pad with a lubricant composition comprising a major amount of a base oil and a minor amount of an additive composition.
• the additive composition comprises a triazole compound substituted with an aryl moiety; at least one nitrogen containing compound chosen from an alkylated phenothiazine and a compound represented by the formula (I):
• R 0 , R 1 and R 2 are each independently selected from the group consisting of an aryl moiety comprising from about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amido, phosphoro, and sulfono, with the proviso that at least one of R 0 , R 1 and R 2 are chosen to be an aryl moiety comprising from about 6 to about 30 carbon atoms; and a metal detergent with a soap/TBN ratio ranging from about 0.05 to about 1.5.
• a method for operating a machine comprising adding to the machine a lubricant composition comprising a major amount of a base oil; and a minor amount of an additive composition comprising (i) a triazole compound substituted with an aryl moiety; (ii) at least one nitrogen containing compound chosen from an alkylated phenothiazine and a compound represented by the formula (I):
• R 0 , R 1 and R 2 are each independently selected from the group consisting of an aryl moiety comprising from about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amido, phosphoro, and sulfono, with the proviso that at least one of R 0 , R 1 and R 2 are chosen to be an aryl moiety comprising from about 6 to about 30 carbon atoms; and (iii) a metal detergent with a soap/TBN ratio ranging from about 0.05 to about 1.5.
• the present disclosure generally relates to an additive composition
• an additive composition comprising (i) a triazole compound substituted with an aryl moiety; (ii) at least one nitrogen containing compound chosen from an alkylated phenothiazine and a compound represented by the formula (I):
• R 0 , R 1 and R 2 are each independently selected from the group consisting of an aryl moiety comprising from about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amido, phosphors, and sulfono, with the proviso that at least one of R 0 , R 1 and R 2 are chosen to be an aryl moiety comprising from about 6 to about 30 carbon atoms; and a metal detergent with a soap/TBN ratio ranging from about 0.05 to about 1.5.
• the present application is also directed to a lubricant composition comprising a major amount of a base oil and a minor amount of the above described additive composition.
• the term “major amount” is understood to mean an amount greater than or equal to 50 wt. % for example from about 80 to about 98 wt. % relative to the total weight of the composition.
• the term “minor amount” is understood to mean en amount less than 50 wt. % relative to the total weight of the composition.
• aromatic refers to substituted or unsubstituted non-aliphatic hydrocarbyl or heterocyclic moieties of this class, e.g., a polyunsaturated, typically aromatic, cyclical hydrocarbyl, or heterocyclic substituent, which can have a single ring or multiple rings (up to three rings) that are fused together or linked covalently.
• hydrocarbyl aromatic moieties include phenyl, naphthyl, biphenylenyl, phenanthrenyl, phenalenyl, and the like. Such moieties are optionally substituted with one or more hydrocarbyl substituents.
• heterocyclic aryl or aromatic moieties refers to unsaturated cyclical moieties containing carbon atoms in the ring and additionally one or more hetero atoms, such as oxygen, nitrogen, sulfur and/or phosphorus.
• suitable heterocyclic aryl or aromatic moieties include pyridyl, thienyl, furyl, thiazolyl, pyranyl, pyrrolyl, pyrazolyl, imidazolyl, pyrazinyl, thiazolyl, etc.
• Such moieties are optionally substituted with one or more substituents such as hydroxy, optionally substituted lower alkyl, optionally substituted lower alkoxy, amino, amide, ester moieties and carbonyl moieties (e.g., aldehyde or ketonic moieties).
• substituents such as hydroxy, optionally substituted lower alkyl, optionally substituted lower alkoxy, amino, amide, ester moieties and carbonyl moieties (e.g., aldehyde or ketonic moieties).
• alkaryl refers to an alkyl group substituted by any of the substituted or unsubstituted non-aliphatic hydrocarbyl or heterocyclic moieties described above, such as phenyl, naphthyl, benzyl, and the like. Such moieties are optionally substituted with one or more substituents, such as hydroxy, alkyl, alkoxy amino, amide, eater and carbonyl moieties (e.g., aldehyde or ketonic moieties).
• a triazole compound suitable for use in the compositions of the present disclosure can be any triazole, including a substituted or unsubstituted triazole compound.
• the triazole compound is a 1,2,3-triazole compound.
• the triazole compound is a 1,2,4-triazole compound.
• the triazole compound is not an alkyl bis-3-amino-1,2,4-triazole.
• the triazole compound can be substituted with a substituted or unsubstituted aryl moiety comprising a single ring or multiple rings, for example covalently linked rings.
• substituted aromatic moieties comprising covalently linked rings include biphenyl, 1,1′-binaphthyl, p,p′-bitolyl, biphenylenyl, and the like.
• the aryl moiety can comprise multiple fused rings.
• Non-limiting examples of aryl moieties comprising multiple fused rings include naphthyl, anthryl, pyrenyl, phenanthrenyl, phenalenyl, and the like.
• the aryl moiety can compose a single ring covalently linked to the triazole.
• aryl moieties comprising a single ring covalently linked to the triazole include phenyl and the like.
• the aryl moiety can comprise a single ring fused to the triazole.
• aryl moieties comprising a single ring fused to the triazole include benzotriazole and tolyltriazole.
• a commercially available triazole compound suitable for use herein is a tolyltriazole, which is a light brown powder having a melting point ranging from 80-83° C., a flashpoint of 182° C.; and a boiling point of 160° C.
• the triazole compound can ba present in the disclosed lubricant and additive compositions in any effective amount, which can be readily determined by one of ordinary skill in the art.
• the lubricating composition of the present disclosure can comprise from about 0.05 wt. % to about 0.5 wt. %, and for example from about 0.1 wt. % to about 0.3 wt. % of the triazole compound, relative to the total weight of the composition.
• the additive composition of the present disclosure can comprise from about 0.48 wt. % to about 5 wt. % of the triazole compound, relative to the total weight of the additive composition.
• compositions cars also comprise at least one nitrogen containing compound.
• the nitrogen containing compound can be chosen from compounds represented by the formula (I), as described below, and alkylated phenothiazine compounds.
• the nitrogen-containing compound is chosen to be a compound of formula (I):
• R 0 , R 1 and R 2 are each independently selected from the group consisting of an aryl moiety comprising from about 6 to about 30 carbon atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amido, phosphoro, and sulfono, with the proviso that at least one of R 0 , R 1 and R 2 are chosen to be an aryl moiety comprising from about 6 to about 30 carbon atoms.
• R 0 , R 1 and R 2 can each independently be chosen from a substituted or unsubstituted aryl group comprising from about 6 to about 30 carbon atoms.
• Non-limiting examples of nitrogen-containing compounds of Formula (I) that are suitable include: phenylamine; diphenylamine; triphenylamine; various alkylated phenylamines, diphenylamines and triphenylamines; N,N′-bis(4-aminophenyl)-alkylamine; 3-hydroxydiphenylamine; N-phenyl-1,2-phenylenediamine; N-phenyl-1,4-phenylenediamine; dibutyldiphenylamine; dioctyldiphenylamine; diheptyldiphenylamine; phenyl-alpha-naphthylamine; phenyl-beta-naphthylamine; diheptyldiphenylamine; and p-oriented styrenated diphenylamine.
• the nitrogen-containing compound can compose multiple nitrogen groups, provided that at least one nitrogen has at least one aryl group attached thereto, e.g., as in the case of various diamines having a secondary nitrogen atom as wall as an aryl attached to one of the nitrogens.
• diamines include N-Phenyl Phenylene Diamine adducts.
• the nitrogen containing compound is chosen to he an alkylated phenothiazine.
• suitable alkylated phenothiazines can include monotetradecylphenothiazine, ditetradecylphenothiazine, monodecylphenothiazine, didecylphenothiazine, monostyrylphenothiazine, dinonylphenothiazine, monoctylphenothiazine, dioctylphenothiazine, monobutylphenothiazine, dibutylphenothiazine, monostyrylphenothiazine, distyrylphenothizine, butyloctylphenothiazine, styryloctylphenothiazine.
• the nitrogen-containing compounds used herein can have antioxidant properties in the disclosed compositions when used alone or in combination as described herein.
• the nitrogen-containing compounds used herein should be soluble in a final lubricant composition.
• the amount of the nitrogen-containing compound in the additive and lubricant compositions can vary depending upon specific requirements and applications, in an embodiment, the lubricating composition of the present disclosure can comprise from about 0.2 wt. % to about 1.2 wt. %, and for example from about 0.4 wt. % to about 1.0 wt. %, of the nitrogen-containing compound, relative to the total weight of the lubricating composition. In another embodiment, the additive compositions of the present disclosure can comprise from about 2 wt. % to about 12 wt. % of the nitrogen-containing compound, relative to the total weight of the additive composition.
• the additive and lubricant compositions of the present application can comprise a metal containing detergent, referred to herein as “metal detergent,” with a soap/TBN ratio ranging from about 0.05 to about 1.5, such as from about 0.1 to about 1.4, or from about 0.15 to about 1.
• the metal detergent can include one or more compounds chosen from sulfonates, sulfurized phenates and salicylates.
• the metal detergent can be a neutral “soap” compound, such as a neutral sulfonate, neutral sulfurized phenate or neutral salicylate; or the detergent can be overdosed sulfonate, overbased sulfurized phenate or overbased salicylate; or a combination of both neutral and overbased compounds, such as one or more neutral sulfonates, neutral sulfurized phenates or neutral salicylates in combination with one or more overbased sulfonates, overbased sulfurized phenates or overbased salicylates.
• a neutral “soap” compound such as a neutral sulfonate, neutral sulfurized phenate or neutral salicylate
• the detergent can be overdosed sulfonate, overbased sulfurized phenate or overbased salicylate
• a combination of both neutral and overbased compounds such as one or more neutral sulfonates, neutral sulfurized phenates or neutral salicylates in combination with one or more overbased sulfonates, overbased
• Suitable neutral and overbased sulfonates, sulfurized phenates and salicylates are well known in the art, and any suitable sulfonates, sulfurized phenates arid salicylates can be employed in the compositions of the present disclosure.
• soap for purposes of tins disclosure means a neutral detergent compound that contains approximately the stoichiometric amount of metal to achieve the neutralization of the acidic group or groups present in the acid used to make the detergent.
• neutral sulfonates means metal salts of sulfonic acids, which salts contain approximately the stoichiometric amount of metal to achieve the neutralization of the acidic group or groups present in the acid.
• TBN is the amount of potassium hydroxide, in milligrams, that is equivalent to the unneutralized base found in the overbased detergent per gram of metal detergent.
• overbased detergent is a salt that contains significantly more than the stoichiometric amount of metal that would result in neutralization of the acid.
• Overbased detergents are well known in the art and any suitable overbased detergents can be employed.
• suitable overbased detergents include overbased sulfonates, such the calcium carbonate overbased calcium polyisobutenyl sulfonates and magnesium carbonate overbased magnesium polyisobutenyl sulfonates, such overbased sulfonates are disclosed, for example, in U.S. Pat. No. 4,137,184, issued to N. Bakker on Jan. 30, 1979, the disclosure of which is hereby incorporated by reference in its entirety.
• Overbased salicylates and sulfurized phenates are also well known in the art. Examples of well known overbased salicylates and sulfurized phenates are described in U.S. Pat. No. 5,919,276, issued to Gareth Charles Jeffrey on Jul. 6, 1999, the disclosure of which is herein incorporated by reference in its entirety.
• Detergents can be overbased to various TBN levels.
• the soap/TBN ratio can vary based upon the degree of overbasing.
• lubricant compositions that have soap/TBN ratios within relatively low ranges can be useful in the compositions of the present application.
• metal detergents that include higher amounts of soap, such as neutral sulfonate, in addition to the small amount of soap that may already be included in overbased detergents, are believed to provide additional benefits over the overbased detergents alone.
• compositions of the present application employing detergents having soap/TBN ratios of 0.1 or greater, such as 0.15 or greater, may provide improved antioxidant effects, reduction in viscosity increase over time of the lubricants during use, or may allow for loss antioxidant compounds, such as the nitrogen containing compounds described above, to be used in the additive and lubricant compositions.
• the metal detergent comprises at least one neutral sulfonate.
• the neutral sulfonates suitable for use in compositions of the present disclosure can be any neutral sulfonate compound provided that it is soluble in a lubricant composition.
• the neutral sulfonates can have the general formula (III),
• R 5 is a hydrocarbyl group and M is any of the Group I or Group II metals or lead which forms a salt with the sulfonic acid moiety.
• the hydrocarbyl group can be any hydrocarbyl that will render the sulfonate compound soluble in a lubricant.
• Suitable hydrocarbyl groups can be, for example, substantially saturated, aliphatic hydrocarbyl compounds containing from about 20 to 300 carbon atoms, such as from 50 to about 250.
• substantially saturated as used heresy means that at least about 95% of the carbon-to-carbon covalent linkages are saturated.
• suitable R 5 groups include polymers derived from olefins, such as polyisobutylene.
• Group I metals for the metal component M can include lithium, sodium and potassium; and the Group II metals can include magnesium, calcium, strontium, barium and zinc. In some aspects of the invention, M is chosen from calcium and magnesium.
• neutral sulfonate compounds include, Calcium polyisobutyenyl sulfonate, magnesium polyisobutenyl sulfonate, and sodium polyisobutyenl sulfonate.
• sulfonate compounds include HiTEC H614 and HiTEC 615, both available from Afton Chemical Corporation.
• the neutral sulfonate, neutral sulfurized phenate and neutral salicylate compounds can be present in the disclosed lubricant and additive compositions in any effective amount, which can be readily determined by one of ordinary skill in the art.
• the lubricating composition of the present disclosure can comprise from about 0.5 wt. % to about 2 wt. %, such as from about 0.8 wt. % to about 1.8 wt. % of the neutral sulfonate, neutral sulfurized phenate and/or neutral salicylate compounds, relative to the total weight of the composition.
• the additive composition of the present disclosure can comprise from about 5 wt. % to about 20 wt. % of the neutral sulfonate, neutral sulfurized phenate and/or neutral salicylate compounds, relative to the total weight of the additive composition.
• metal detergents including both neutral and overbased metal detergents
• suitable ranges for metal detergents in a lubricant composition can range from about 0.1 to about 15 wt. % based on the total weight of the composition, such as, for example, about 0.2 to about 8 wt. %.
• the anti-wear agents can be oil soluble phosphorus-containing compounds, such as, for example zinc dialkyldithiophosphate salts (ZDDP), which may be present in the additive and lubricant composition in an amount sufficient to provide from about 100 to about 1000 parts per million by weight of total phosphorus in a lubricant composition.
• ZDDP zinc dialkyldithiophosphate salts
• the phosphorus-containing compounds may be present in an amount sufficient to provide from about 600 to about 800 parts per million by weight of total phosphorus in a lubricant composition.
• the compositions can comprise various levels of at least one titanium-containing compound depending on the needs and requirements of the application.
• Base oils suitable for use in formulating the disclosed compositions can be selected from any of the synthetic or mineral oils or mixtures thereof.
• Mineral oils include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as other mineral lubricating oils such as liquid petroleum oils and solvent treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils derived from coal or shale are also suitable. Further, oils derived from a gas-to-liquid process are also suitable.
• the base oil can be present in a major amount, wherein “major amount” is understood to mean greater than or equal to 50%, for example from about 80 to about 98 percent by weight of the lubricant composition.
• the base oil typically has a viscosity of, for example, from about 2 to about 150 cSt and, as a further example, from about 5 to about 15 cSt at 100° C.
• the base oils can normally have a viscosity in the range of about SAE 15 to about SAE 250, and more usually can range from about SAE 20W to about SAE 50.
• Suitable automotive oils also include cross-grades such as 15W-40, 20W-50, 75W-140, 80W-90, 85W-140, 85W-90 and the like.
• Non-limiting, examples of synthetic oils include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes propylene isobutylene copolymers, etc.); polyalphaolefins such as poly(1-hexenes), poly-(1-octenes), poly(1-decenes), etc.
• hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes propylene isobutylene copolymers, etc.); polyalphaolefins such as poly(1-hexenes), poly-(1-octenes), poly(1-decenes), etc.
• alkylbenxenes e.g., dodecylbenzenes, tetradecylbenzenes, di-nonylbenzenes, di-(2-ethylhexyl)benzenes, etc.
• polyphenyls e.g., biphenyls, terphenyl, alkylated polyphenyls, etc.
• Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic oils that can be used.
• Such oils are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of about 1000, diphenyl ether of polyethylene glycol having a molecular weight of about 500-1000, diethyl ether of polypropylene glycol having a molecular weight of about 1000-1500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3-8 fatty acid esters, or the C 13 Oxo acid diester of tetraethylene glycol.
• esters of dicarboxylic acids e.g., phthalic acid, succinic acid, alky; succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.
• alcohols e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.
• these esters include dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecy
• Esters useful as synthetic oils also include those made from C 5-12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
• the base oil which can be used to make the compositions as described herein can be selected from any of the base oils in Groups I-V as specified in the American Petroleum institute (API) Base Oil Interchangeably Guidelines.
• API American Petroleum institute
• Group I contain less than 90% saturates and/or greater than 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120;
• Group II contain greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120;
• Group III contain greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and have a viscosity Index greater than or equal to 120;
• Group IV are polyalphaolefins (PAO); and Group V Include all other base oils not included in Group I, II, III or IV.
• PAO polyalphaolefins
• test methods used in defining the above groups are ASTM D2007 for saturates; ASTM D2270 for viscosity index; and one of ASTM D2622, 4294, 4927 and 3120 for sulfur.
• Group IV base oils i.e. polyalphaofefins (PAO) include hydrogenated oligomers of an alpha-olefin, the most important methods of oligomerisation being free radical processes, Ziegler catalysis, and canonic. Friedel-Crafts catalysis.
• PAO polyalphaofefins
• the polyalphaolefins typically have viscosities in the range of 2 to 100 cSt at 100° C., for example 4 to 8 cSt at 100° C. They can, for example, be oligomers of branched or straight chain alpha-olefins having from about 2 to about 30 carbon atoms, non-limiting examples include polypropenes, polyisobutenes, poly-1-butenes, poly-1-hexenes, poly-1-octanes and poly-1-decene. Included are homopolymers, interpolymers and mixtures.
• a “Group I base oil” also includes a Group I base oil with which base oil(s) from one or more other groups can be admixed, provided that the resulting admixture has characteristics falling within those specified above for Group I base oils.
• Exemplary base oils include Group I base oils and mixtures of Group II base oils with Group I bright stock.
• Base oils suitable for use herein can be made using a variety of different processes including but not limited to distillation, solvent refining, hydrogen processing, oligomerisation, esterification, and re-refining.
• the base oil can be an oil derived from Fischer-Tropsch synthesized hydrocarbons.
• Fischer-Tropsch synthesized hydrocarbons can be made from synthesis gas containing H 2 and CO using a Fischer-Tropsch catalyst.
• Such hydrocarbons typically require further processing in order to be useful as the base oil.
• the hydrocarbons can be hydroisomerized using processes disclosed in U.S. Pat. No. 6,103,099 or 6,180,575; hydrocracked and hydroisomerized using processes disclosed in U.S. Pat. No. 4,943,672 or 6,096,940; dewaxed using processes disclosed in U.S. Pat. No. 5,882,505; or hydroisomerized and dewaxed using processes disclosed in U.S. Pat. No. 6,013,171; 6,080,301; or 6,165,949.
• Unrefined, refined and rerefined oils either mineral or synthetic (as well as mixtures of two or more of any of these) of the type disclosed hereinabove can be used in the base oils.
• Unrefined oils are those obtained directly from a mineral or synthetic source without further purification treatment.
• a shale oil obtained directly from retorting operations a petroleum oil obtained directly from primary distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil.
• Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
• Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and open are additionally processed by techniques directed to removal of spent additives, contaminants, and oil breakdown products.
• compositions of the present application can contain concentrations of the various ingredients, including the optional additives and base oils disclosed above, that are effective for providing a desired result.
• concentrations of ingredients that can be employed in exemplary lubricant compositions of the present application are shown in range 1 and range 2 of Table 1, below:
• the term “delaying the onset of viscosity increase” is understood to mean delaying the start of an increase in the viscosity of a lubricant composition over a period of time due to the oxidation process, as compared to a composition that is devoid of the antioxidant compositions of the present application, including a triazole compound substituted with an aryl moiety, a nitrogen-containing compound, and a metal detergent compound, as disclosed herein.
• the method of delaying the onset of viscosity increase in a lubricant composition can comprise providing to a machine a lubricant composition composing a major amount of a base oil; and a minor amount of an additive comprising (i) a triazole compound substituted with an aryl moiety; (ii) at least one nitrogen-containing compound chosen from an alkylated phenothiazine and a compound represented by the formula (I):
• R 0 , R 1 and R 2 are each independently selected from the group consisting of at least one aryl moiety comprising from about 6 to about 30 atoms, hydrogen, halogen, hydroxy, hydrocarbyl, substituted hydrocarbyl, amino, amido, phosphoro, and sulfono, with the proviso that at least one of R 0 , R 1 and R 2 are chosen to be an aryl moiety comprising from about 6 to about 30 carbon atoms; and (iii) a metal detergent with a soap/TBN ratio ranging from about 0.05 to about 1.5.
• a method of lubricating at least one moving pad of a machine comprises contacting the at least one moving part with a lubricant composition comprising a major amount of a base oil; and a minor amount of the disclosed additive composition.
• a method for operating a machine comprising adding a lubricant composition comprising a major amount of a base oil and a minor amount of the disclosed additive composition.
• the machine in the disclosed methods can be selected from the group consisting of spark ignition and compression-ignition internal combustion engines.
• the at least one moving part can comprise a gear, piston, bearing, rod, spring, camshaft, crankshaft, and the like.
• the lubricant composition can be any composition that would be effective in lubricating a machine.
• the composition is selected from the group consisting of passenger car motor oils, medium speed diesel engine oils, and heavy duty diesel engine oils that comprise the additive compositions of the present disclosure.
• a lubricant composition according to the present application was formulated composing an antioxidant system, including a triazole compound substituted with an aryl moiety, an aryl amine compound, and a metal detergent compound, in a base composition, as shown in Table 2.
• the triazole compound employed in Example Composition 1 was a commercially available tolyltriazole (Cobratec TT-100, PMC Specialties Group, Cincinnati, Ohio).
• the aryl amine compound was an alkylated diphenylamine (Hi-TEC® 7190, Afton Chemical Corporation, Richmond, Va.), and the metal detergent compound included a commercially available sulfonate (HiTEC® H614, Alton Chemical Corporation, Richmond, Va.).
• Comparative examples 2 to 4 were formulated without a triazole compound, as shown in Tables 3 to 5, using the same aryl amine and base composition as in Example 1.
• the amount of neutral sulfonate shown in Tables 2 to 5 is the amount added to the composition, excluding any neutral sulfonate that may have been included in the overbased metal detergents.
• the base compositions for Example Compositions 1, 2, 3 and 4 included typical lubricant additives, ouch as a dispersed system, corrosion inhibitor, metal dihydroarbyl dithiophosphate, antifoaming agent, friction modifier, supplemental antiwear agents, pour point depressant, viscosity modifier and base oil.
• the base composition was formulated with a base oil meeting the GF-4 standards set forth by the International Lubricants Standardization and Approval Committee (ILSAC), which in the instant example, was a SAE Grade 5W-30 type motor oil.
• IMSAC International Lubricants Standardization and Approval Committee
• compositions were also evaluated to determine increases in viscosity at 40° C. by well known methods in the art for measuring kinematic viscosity.
• the composition was sampled and analyzed every 20 hours. The greater the increase in viscosity, the less stable a particular lubricant composition is to oxidation. A lubricant composition that demonstrates a viscosity increase greater than 150% fails this criterion.
• Example Composition 1 comprising the disclosed antioxidant system demonstrated a WPD rating of 5.29 and a Viscosity increase of 111.2%.
• Example Composition 2 which was devoid of the disclosed composition demonstrated a WPD rating of 3.88 and a Viscosity increase of 232.3%.
• Example Composition 3 which was devoid of the disclosed composition, but included an increased amount of the aryl amine antioxidant as compared to the Example Composition 1, demonstrated a WPD rating of 3.98 and a viscosity increase of 129%.
• Example Composition 4 which was also devoid of the disclosed composition, demonstrated a WPD rating of 2.97 and a viscosity increase of 148.5%.
• the disclosed composition surprisingly and significantly reduces piston deposits with reduced increase in kinematic viscosity for lubricant compositions, while allowing lower amounts of the aryl amine antioxidant nitrogen containing compounds to be employed.
• the reduction in aryl amine antioxidant compounds can be seen as an improvement, as these compounds are expensive and increase the cost of the additive and lubricant compositions.

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