Classifications

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  • 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
  • C10M141/10—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 phosphorus-containing compound
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  • 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
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  • 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
  • C10M141/12—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 compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
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  • 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
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  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
  • C10M2207/044—Cyclic ethers having four or more ring atoms, e.g. furans, dioxolanes
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  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
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  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/284—Esters of aromatic monocarboxylic acids
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  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/287—Partial esters
  • C10M2207/289—Partial esters containing free hydroxy groups
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  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
  • C10M2215/064—Di- and triaryl amines
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  • 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
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  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
  • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
  • C10M2219/066—Thiocarbamic type compounds
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  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
  • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
  • C10M2219/066—Thiocarbamic type compounds
  • C10M2219/068—Thiocarbamate metal salts
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  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/045—Metal containing thio derivatives
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  • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
  • C10M2227/09—Complexes with metals
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C10N2010/12—Groups 6 or 16
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • 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
  • C10N2030/08—Resistance to extreme temperature
• • C—CHEMISTRY; METALLURGY
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  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/38—Catalyst protection, e.g. in exhaust gas converters
• • C—CHEMISTRY; METALLURGY
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  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/42—Phosphor free or low phosphor content compositions
• • C—CHEMISTRY; METALLURGY
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  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/54—Fuel economy
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  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines

Definitions

• the invention concerns additive compositions and lubricating compositions for use in a low phosphorus environment, which provide improved resistance to lead and copper corrosion.
• OEMs Original Equipment Manufacturers
• lubricant companies expect government to mandate even stricter fuel economy and emission requirements in the future.
• Many, if not all, of the vehicles now on the road contain pollution control devices to reduce pollution.
• Engine oils are formulated with antioxidants, friction modifiers, dispersants and antiwear additives to improve vehicle fuel economy, cleanliness and wear. Unfortunately, many of these additives contribute to the fouling of the pollution control devices. When this occurs, vehicles emit high levels of pollution because of the failing performance of the pollution control devices.
• U.S. Pat. No. 6,806,241 which is incorporated herein by reference, teaches a three-component antioxidant additive comprising: (1) an organomolybdenum compound, (2) an alklyated diphenylamine and (3) a sulfur compound being a thiadiazole and/or dithiocarbamate.
• U.S. Pat. No. 7,879,777 teaches a lubricating oil composition comprising a major portion of a lubricating base oil and an antioxidant additive at about 0.1-1.5 mass percent, the additive comprising (a) a secondary diarylamine at about 0.5 mass percent; (b) (i) a molybdenum dialkyldithiocarbamate or molybdate ester in an amount which provides about 50 to about 200 ppm molybdenum, or (ii) an ammonium molybdate in an amount which provides about 50 ppm molybdenum; and (c) di-(C 11-14 -branched and linear alkyl) amine tungstate or mono-succinimide tungstate in an amount which provides about 100 to 500 ppm tungsten.
• Molybdenum additives are well known to those skilled in the art of oil formulation to act as friction modifiers to reduce engine friction and thereby improve vehicle fuel economy. However, it is also well known that high levels of molybdenum in engine oil can cause engine corrosion and wear. When this occurs, engine life expectancy is greatly reduced.
• a novel lubricant composition has been discovered that contains friction modifiers, antiwear additives, antioxidants and corrosion inhibitors with a tungsten source and low phosphorus content that offers excellent fuel economy while maintaining good corrosion and wear protection.
• a particular embodiment is substantially free of molybdenum.
• the novel lubricant composition contains 600 ppm or less of phosphorus and 800 ppm or less of tungsten. It can be used as a top treat to existing fully formulated gasoline or diesel engine oils or combined with one or more dispersants, detergents, VI improvers, base oils and any other additive(s) needed to make fully formulated engine oil.
• An embodiment which achieves the desired result is a lubricating composition comprising at least 85 weight percent of a base blend blend, and the following additive, based on weight percent of the total lubricating composition:
• an tungstate salt preferably an amine tungstate, at an amount to provide 0.1 to 1400 ppm W, preferably 200 to 1200 ppm W.
• an alkylated diphenylamine at about 0.1-2.0%, preferably 0.5-1.5%; and (3) a dithiocarbamate, at about 0.1-2.0%, preferably 0.50-1.5%.
• the lubricating composition is substantially free of molybdenum.
• Amine tungstates are known to those skilled in the art.
• U.S. Pat. No. 7,335,625 and U.S. Pat. No. 7,879,777, incorporated herein by reference teach the reaction product of a metal acid hydrate of formula MO 4 H 2 .H 2 O with at least one alkyl amine, having the formula:
• R 1 and R 2 may be identical or different, and are selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated C 2 -C 40 alkyl, C 3 -C 40 cycloalkyl, C 6 -C 40 aryl, C 7 -C 40 alkaryl and aralkyl.
• the products are a di-(C 11-14 -branched and linear alkyl) amine tungstate or a mono-succinimide tungstate.
• a preferred amine tungstate is dialkylammonium tungstate, as exemplified in Table 1, available as Vanlube® W 324 from R.T. Vanderbilt Company, Inc.
• tungsten dithiocarbamates examples include a soluble tungstate salt prepared, most commonly through the incorporation of alkylammonium cations; ammonium 4-t-butyl catechol vanadate and tungstate salts; tungsten carboxylates; diarene tungsten tricarbonyl, arene tungsten, or a dichlorotetranaphthyloxy tungsten; trinuclear thiotungstate; tungsten dialkyldithiophosphate; tungsten dithiocarbamates.
• an organic tungsten complex may be prepared by reacting a tungsten salt and a fatty acid derivative, wherein the tungsten salt is the reaction product of an acidic tungsten and a nitrogenous base.
• These compositions contain an organic tungsten complex defined as either the reaction product of a mono- or diglyceride and a tungsten source, or as the reaction product of a secondary amine, a fatty acid derivative, and a tungsten source.
• ADPA Alkylated Diphenyl Amines
• Alkylated diphenyl amines are widely available antioxidants for lubricants.
• One possible embodiment of an alkylated diphenyl amine for the invention are secondary alkylated diphenylamines such as those described in U.S. Pat. No. 5,840,672, which is hereby incorporated by reference.
• X and Y each independently represent a substituted or unsubstituted phenyl group having wherein the substituents for the phenyl group include alkyl groups having 1 to 20 carbon atoms, preferably 4-12 carbon atoms, alkylaryl groups, hydroxyl, carboxy and nitro groups and wherein at least one of the phenyl groups is substituted with an alkyl group of 1 to 20 carbon atoms, preferably 4-12 carbon atoms.
• ADPAs including VANLUBE®SL (mixed alklyated diphenylamines), DND, NA (mixed alklyated diphenylamines), 81 (p,p′-dioctyldiphenylamine) and 961 (mixed oxylated and butylated diphenylamines) manufactured by R.T. Vanderbilt Company, Inc., Naugalube® 640, 680 and 438L manufactured by Chemtura Corporation and Irganox®L-57 and L-67 manufactured by Ciba Specialty Chemicals Corporation and Lubrizol 5150A & C manufactured by Lubrizol.
• Another possible ADPA for use in the invention is a reaction product of N-phenyl-benzenamine and 2,4,4-trimethylpentene.
• Alkylated diphenylamines also known as diarylamine antioxidants, include, but are not limited to diarylamines having the formula:
• R′ and R′′ each independently represents a substituted or unsubstituted aryl group having from 6 to 30 carbon atoms.
• substituents for the aryl group include aliphatic hydrocarbon groups such as alkyl having from 1 to 30 carbon atoms, hydroxy groups, halogen radicals, carboxylic acid or ester groups, or nitro groups.
• the aryl group is preferably substituted or unsubstituted phenyl or naphthyl, particularly wherein one or both of the aryl groups are substituted with at least one alkyl having from 4 to 30 carbon atoms, preferably from 4 to 18 carbon atoms, most preferably from 4 to 9 carbon atoms. It is preferred that one or both aryl groups be substituted, e.g. mono-alkylated diphenylamine, di-alkylated diphenylamine, or mixtures of mono- and di-alkylated diphenylamines.
• the diarylamines may be of a structure containing more than one nitrogen atom in the molecule.
• the diarylamine may contain at least two nitrogen atoms wherein at least one nitrogen atom has two 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 nitrogen atoms.
• diarylamines examples include, but are not limited to: diphenylamine; various alkylated diphenylamines; 3-hydroxydiphenylamine; N-phenyl-1,2-phenylenediamine; N-phenyl-1,4-phenylenediamine; monobutyldiphenylamine; dibutyldiphenylamine; monooctyldiphenylamine; dioctyldiphenylamine; monononyldiphenylamine; dinonyldiphenylamine; monotetradecyldiphenylamine; ditetradecyldiphenylamine, phenyl-alpha-naphthylamine; monooctyl phenyl-alpha-naphthylamine; phenyl-beta-naphthylamine; monoheptyldiphenylamine; diheptyldiphenylamine; p-oriented styrenated
• diarylamines examples include, for example, diarylamines available under the trade name IRGANOX® from Ciba Specialty Chemicals; NAUGALUBE® from Crompton Corporation; GOODRITE® from BF Goodrich Specialty Chemicals; VANLUBE® from R. T. Vanderbilt Company Inc.
• Another class of aminic antioxidants includes phenothiazine or alkylated phenothiazine having the chemical formula:
• R 1 is a linear or branched C 1 to C 2-4 alkyl, aryl, heteroalkyl or alkylaryl group and R 2 is hydrogen or a linear or branched C 1 to C 2-4 alkyl, heteroalkyl, or alkylaryl group.
• Alkylated phenothiazine may be selected from the group consisting of monotetradecylphenothiazine, ditetradecylphenothiazine, monodecylphenothiazine, didecylphenothiazine, monononylphenothiazine, dinonylphenothiazine, monoctylphenothiazine, dioctylphenothiazine, monobutylphenothiazine, dibutylphenothiazine, monostyrylphenothiazine, distyrylphenothiazine, butyloctylphenothiazine, and styryloctylphenothiazine.
• the compounds are characterized by R 4 , R 5 , R 6 and R 7 which are the same or different and are hydrocarbyl groups having 1 to 13 carbon atoms.
• Embodiments for the present invention include bisdithiocarbamates wherein R 4 , R 5 , R 6 and R 7 are the same or different and are branched or straight chain alkyl groups having 1 to 8 carbon atoms.
• R 8 is an aliphatic group such as straight and branched alkylene groups containing 1 to 8 carbons.
• a preferred ashless dithiocarbamate is methylene-bis-dialkyldithiocarbamate, where alkyl groups contain 3-16 carbon atoms, and is available commercially under the tradename VANLUBE® 7723 from R.T. Vanderbilt Company, Inc.
• the ashless dialkyldithiocarbamates include compounds that are soluble or dispersable in the additive package. It is also preferred that the ashless dialkyldithiocarbamate be of low volatility, preferably having a molecular weight greater than 250 daltons, most preferably having a molecular weight greater than 400 daltons.
• ashless dithiocarbamates examples include, but are not limited to, methylenebis(dialkyldithiocarbamate), ethylenebis(dialkyldithiocarbamate), isobutyl disulfide-2,2′-bis(dialkyldithiocarbamate), hydroxyalkyl substituted dialkyldithiocarbamates, dithiocarbamates prepared from unsaturated compounds, dithiocarbamates prepared from norbornylene, and dithiocarbamates prepared from epoxides, where the alkyl groups of the dialkyldithiocarbamate can preferably have from 1 to 16 carbons.
• dialkyldithiocarbamates that may be used are disclosed in the following patents: U.S. Pat. Nos. 5,693,598; 4,876,375; 4,927,552; 4,957,643; 4,885,365; 5,789,357; 5,686,397; 5,902,776; 2,786,866; 2,710,872; 2,384,577; 2,897,152; 3,407,222; 3,867,359; and 4,758,362.
• the most preferred ashless dithiocarbamate is methylenebis(dibutyldithiocarbamate).
• the compounds of formula III are characterized by groups R 9 , R 10 , R 11 and R 12 which are the same or different and are hydrocarbyl groups having 1 to 13 carbon atoms.
• VANLUBE® 732 (dithiocarbamate derivative) and VANLUBE® 981 (dithiocarbamate derivative) are commercially available from R.T. Vanderbilt Company, Inc.
• a preferred metal dithiocarbamate is zinc diamyldithiocarbamate, available as Vanlube® AZ, but may also be zinc dibutyldithiocarbamate or piperidinium pentamethylene dithiocarbamate
• the components of the additive compositions of the invention can either be added individually to a base blend to form the lubricating composition of the invention or they can be premixed to form an additive composition which can then be added to the base blend.
• the resulting lubricating composition should comprise a major amount (i.e. at least 85% by weight) of base blend and a minor amount (i.e. less than 10% by weight, preferably about 2-5%) of the additive composition.
• the phosphorus level should be less than 600 ppm, preferably less than 300 ppm.
• the phosphorus may be provided in the form of zinc dialklydithiophosphate (ZDDP), in either conventional or fluorinated form (F-ZDDP), or as any ashless phosphorus source. It is also noted that while the inventive additive composition works to surprisingly reduce corrosion in ultra-low phosphorus oils, use of the additive composition is contemplated for base oils regardless of the phosphorus level.
• ZDDPs Zinc dialkyl dithiophosphates
• lubricating oils Zinc dialkyl dithiophosphates
• ZDDPs have good antiwear and antioxidant properties and have been used to pass cam wear tests, such as the Seq. IVA and TU3 Wear Test.
• Many patents address the manufacture and use of ZDDPs including U.S. Pat. Nos. 4,904,401; 4,957,649; and 6,114,288.
• Non-limiting general ZDDP types are primary, secondary and mixtures of primary and secondary ZDDPs. mixtures of primary and secondary ZDDPs and low volatility phosphorous compounds described in, and function the same as the antiwear additives described in, the non-limiting patent applications US 2010/0062956 and US 2010/0056407.
• low volatility phosphorus containing antiwear additive it is not necessary for the low volatility phosphorus containing antiwear additive to contain zinc. Nitrogen containing compounds can also be used in place of zinc.
• the terms low volatility is defined by the GF-5 specification.
• the GF-5 specification is the next passenger car motor oil specification which limits phosphorous volatility. Modification to this term in subsequent gasoline and diesel engine oil specifications are also included for reference. In general, any low volatile, phosphorus containing antiwear additive is suitable for use with this invention.
• a suitable base blend is any fully formulated engine oil for any gasoline, diesel, natural gas, bio-fuel powered vehicle that is top treated with the inventive composition.
• a base blend can also be any partially formulated engine oil consisting of one or more base oils, dispersants, detergents, VI improvers and any other additives such that when combined with the inventive composition constitutes a fully formulated motor oil.
• Base oils suitable for use in formulating the compositions, additives and concentrates described herein may be selected from any of the synthetic or natural oils or mixtures thereof.
• the synthetic base oils include alkyl esters of dicarboxylic acids, polyglycols and alcohols, poly-alpha-olefins, including polybutenes, alkyl benzenes, organic esters of phosphoric acids, polysilicone oils, and alkylene oxide polymers, interpolymers, copolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, and the like.
• Natural base oils include animal oils and vegetable oils (e.g., castor oil, lard oil), liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
• the base oil typically has a viscosity of about 2.5 to about 15 cSt and preferably about 2.5 to about 11 cSt at 100° C.
• Table 1 demonstrate the superior Cu/Pb corrosion protection offered by the inventive additive composition, where numbers indicate weight percent as part of the entire lubricant composition. Corrosion resistance is measured according to HTCBT, High Temperature Corrosion Bench Test (ASTM D 6594), wherein lower number indicates less corrosion.
• the comparative prior art compounds C1, C2 and C3 are prepared according to U.S. Pat. No. 6,806,241. The molybdenum ester/amide can be found commercially as Molyvan® 855, manufactured by R.T. Vanderbilt Company.

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