CA2659854A1 - A low phosphorus lubricating oil composition having lead corrosion control - Google Patents
A low phosphorus lubricating oil composition having lead corrosion control Download PDFInfo
- Publication number
- CA2659854A1 CA2659854A1 CA002659854A CA2659854A CA2659854A1 CA 2659854 A1 CA2659854 A1 CA 2659854A1 CA 002659854 A CA002659854 A CA 002659854A CA 2659854 A CA2659854 A CA 2659854A CA 2659854 A1 CA2659854 A1 CA 2659854A1
- Authority
- CA
- Canada
- Prior art keywords
- zinc
- lubricating oil
- oil composition
- dithiophosphate
- dialkyl dithiophosphate
- 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.)
- Granted
Links
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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
-
- 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
- C10M2215/28—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
-
- 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
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- 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
- C10N2030/40—Low content or no content compositions
- C10N2030/42—Phosphor free or low phosphor content compositions
-
- 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
- C10N2030/40—Low content or no content compositions
- C10N2030/43—Sulfur free or low sulfur content compositions
-
- 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
- C10N2030/40—Low content or no content compositions
- C10N2030/45—Ash-less or low ash content
-
- 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
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
The present invention provides a low phosphorus lubricating oil composition containing a mixture of zinc dithiophosphates in a certain ratio surprisingly yields improved lead corrosion. The synergistic combination of mixed zinc dithiophosphates containing a zinc primary dialkyl dithiophosphate, zinc secondary dialkyl dithiophosphate and zinc diaryl dithiophosphate in a respective ratio, based on the phosphorus content, of the zinc primary dialkyl dithiphosphate to zinc secondary dialkyl dithiophosphate from about 2:1 to about 1:2 and the ratio of the mixture of zinc primary dialkyl dithiophosphate and zinc secondary dialkyl dithiophosphate to zinc diaryl dithiophosphate from about 6:1 to about 1:1. When used in a lubricating oil composition having a total phosphorus content less than about 0.06 wt %, based on the total weight of the lubricating oil composition to lubricate internal combustion engines. The mixture of zinc dithiophosphates greatly reduces lead corrosion.
Description
A LOW PHOSPHORUS LUBRICATING OIL COMPOSITIION HAVING LEAD
:CORRO.SION CONTROL.
The;present-invention is 'related, in part,,to a lubricating oil cormposition.
More particularly, the present'invention relates,:to a Iow phosphorus'lubricating oil composition employing:,a rriixture of zinc dithiophosphates and wherein the lubricating oil eomposition has less than about 0:06 wt % total phosphorus content based on the total weight.of the lubricating oil composition. The low phosphorus lubricatin.g oiI compositionof,the present'.invention is effective in lead, corrosion control when used as a.lubricating`oil composition in internal combustion' en;gines.:
BACKGROUND OF THE INVENTION
Emissio.ns arising, from.autornotive.:exhaust has been a pr.oblem for several decades and approaches for addressing this problem have included the use of unleaded fuel (to deal, in.,part, with lead pollution arising from leaded fuels), oxygenated fuel (to reduce hyd(ocarbon..emissions),, the use of catalytic converters (al`so to reduce hydrocarbon emissions), etc.
`Catalytic converters are now universally employed iivith gasoline powered vehicles and the efficiency of these converters is directly related to the ability of the catalyst to effect.conversion of.unburnt orpartially burnt hydrocarbons generated during.cornbustion to carbon :dioxide:andwater. One: problem arising with the: use of.such converters is poisoning of the'catalyst:resulting in reduced catalyst efficiency. Since catalytic converters are intended for extended use, .catalyst poisoning.results'in higher levels of atmosp.heric'discharges of pollutants from internal combustion engines over prolonged periods of time.
.In order to minimize such poisoning, the industry has:set standards for both fuel and lubricant contents: For exarrmple; standards for fuels have included the use of unleaded gasoline: in.order to -avoid lead poisoning of the catalyst as well as lead .discharge into`the environment. See,`fot.example,. Buckley, III, "Long Chain Aliphatic 'Hydr.ocarhy,Arrmine: Additives Having an Oxyalkylene Hydroxy Connecting Group';. U.S.. Patent No. 4,97,5,096, issued December.4, 1990.
As to the lubricants; one additive: family currently being addressed by industry standards'isthe.phosphorus-containing additives such as zinc dithiophosphate wear inhibitors used :in.lubricant corrmpositions'employed to lubricate internal cornbustion engines.. Specificaliy, phosphorus-containing additives reach the catalytic:converter as a result of,.for example, exhaust gas recirculation and/or oil blow-by processes as well as other methods known in the art. See, for example;
Beck,.et al. "lrnpactaf:Oil-Derived .Catalyst.Poisons on FTP.Perfonnance of LEV
Catalyst` Systems"; SAE Technical.Paper :972842 (1997) andDarr et al. "Effects of Oil-Derived Contaminants on Emissions frorri TWC-Equipped Vehicles", SAE
2000-01-1:881 -(2000). In any event, the phosphorus is known to accumulate in the catalytic converter, at active metal sites; thus reducing catalyst efficiency and effectively ovet time, poisoning the catalyst. As aresult of the-.above, a new focus is to lower phosphorus in the lubricating oils. For example, the draft specifcations=.for lubricant.compositions have proposed significantly lower phosphorus contents than heretofore e"mployed..
A problem.arises when the level ofphosphorus is:, reduced in a lubricant comp.osition containing an oil-soluble, phosphor.us-containing, anti-wear compound::in that there is a significant`reduction in anti-wear performance arising from this d,imiriution in phosphorus.content. One well known class of antiwear additives-are metal;;alkylphosphates; especially zinc dialkyldithiophosphates, are .generally employed.'in lubricating oils at phosphor.ous levels above 0.1 weight percent when used for wear control. At lower levels, it is not:fo.und to be an effective.antiwear additive. For instanc'e, as exemplified' in U.S. Patent Nb.
6;696;393;. issued February,24;: 2004; lowering the level of phosphorus due to the presence of a metal dithiophosphate additive in alubricant composition by one-half from 0.095 weight percent,to 0.048 weight percent phosphorus results in .35 about a seven-fold. increase in'engine wear, Zinc dithiophosphates have eitherdialkyl ordiaryl groups. Zinc dialkyl dithiophosphates are further subdivided.into:primary..alkyl and secondary alkyl
:CORRO.SION CONTROL.
The;present-invention is 'related, in part,,to a lubricating oil cormposition.
More particularly, the present'invention relates,:to a Iow phosphorus'lubricating oil composition employing:,a rriixture of zinc dithiophosphates and wherein the lubricating oil eomposition has less than about 0:06 wt % total phosphorus content based on the total weight.of the lubricating oil composition. The low phosphorus lubricatin.g oiI compositionof,the present'.invention is effective in lead, corrosion control when used as a.lubricating`oil composition in internal combustion' en;gines.:
BACKGROUND OF THE INVENTION
Emissio.ns arising, from.autornotive.:exhaust has been a pr.oblem for several decades and approaches for addressing this problem have included the use of unleaded fuel (to deal, in.,part, with lead pollution arising from leaded fuels), oxygenated fuel (to reduce hyd(ocarbon..emissions),, the use of catalytic converters (al`so to reduce hydrocarbon emissions), etc.
`Catalytic converters are now universally employed iivith gasoline powered vehicles and the efficiency of these converters is directly related to the ability of the catalyst to effect.conversion of.unburnt orpartially burnt hydrocarbons generated during.cornbustion to carbon :dioxide:andwater. One: problem arising with the: use of.such converters is poisoning of the'catalyst:resulting in reduced catalyst efficiency. Since catalytic converters are intended for extended use, .catalyst poisoning.results'in higher levels of atmosp.heric'discharges of pollutants from internal combustion engines over prolonged periods of time.
.In order to minimize such poisoning, the industry has:set standards for both fuel and lubricant contents: For exarrmple; standards for fuels have included the use of unleaded gasoline: in.order to -avoid lead poisoning of the catalyst as well as lead .discharge into`the environment. See,`fot.example,. Buckley, III, "Long Chain Aliphatic 'Hydr.ocarhy,Arrmine: Additives Having an Oxyalkylene Hydroxy Connecting Group';. U.S.. Patent No. 4,97,5,096, issued December.4, 1990.
As to the lubricants; one additive: family currently being addressed by industry standards'isthe.phosphorus-containing additives such as zinc dithiophosphate wear inhibitors used :in.lubricant corrmpositions'employed to lubricate internal cornbustion engines.. Specificaliy, phosphorus-containing additives reach the catalytic:converter as a result of,.for example, exhaust gas recirculation and/or oil blow-by processes as well as other methods known in the art. See, for example;
Beck,.et al. "lrnpactaf:Oil-Derived .Catalyst.Poisons on FTP.Perfonnance of LEV
Catalyst` Systems"; SAE Technical.Paper :972842 (1997) andDarr et al. "Effects of Oil-Derived Contaminants on Emissions frorri TWC-Equipped Vehicles", SAE
2000-01-1:881 -(2000). In any event, the phosphorus is known to accumulate in the catalytic converter, at active metal sites; thus reducing catalyst efficiency and effectively ovet time, poisoning the catalyst. As aresult of the-.above, a new focus is to lower phosphorus in the lubricating oils. For example, the draft specifcations=.for lubricant.compositions have proposed significantly lower phosphorus contents than heretofore e"mployed..
A problem.arises when the level ofphosphorus is:, reduced in a lubricant comp.osition containing an oil-soluble, phosphor.us-containing, anti-wear compound::in that there is a significant`reduction in anti-wear performance arising from this d,imiriution in phosphorus.content. One well known class of antiwear additives-are metal;;alkylphosphates; especially zinc dialkyldithiophosphates, are .generally employed.'in lubricating oils at phosphor.ous levels above 0.1 weight percent when used for wear control. At lower levels, it is not:fo.und to be an effective.antiwear additive. For instanc'e, as exemplified' in U.S. Patent Nb.
6;696;393;. issued February,24;: 2004; lowering the level of phosphorus due to the presence of a metal dithiophosphate additive in alubricant composition by one-half from 0.095 weight percent,to 0.048 weight percent phosphorus results in .35 about a seven-fold. increase in'engine wear, Zinc dithiophosphates have eitherdialkyl ordiaryl groups. Zinc dialkyl dithiophosphates are further subdivided.into:primary..alkyl and secondary alkyl
2 zinc dithiophosphates. Pen:t.an=4-ol;and,3-methylbutan-2-o1 are illustrative of the primary and secondary:alcohols usedto prepare primary and seconda'ry, zinc dithiophosphafes. Different zinc dithiopho,sph'ate chemical types perform differently;(See belowj..
Perfo:rmance:Parameters of ZineDithiophosphate Types PrirriaryAlkyl Secondary Aikyl Aryl Thermai-Stability Mediurri Low High Antivuear Protection=
Mediurn High Low Hydrolytic Stability Mediurrt.: High Low Each type has irri,portant applications.:in modern additive packages. It is ther'efore .20 important to have the right rriix:of zinc dithiophosphates.in any;,given lubricating oil composition';ta provide adequateanti-wear=pertqrrnance' and'at the same time keeping the phosphorus levels, due to the presence ofa metal dithiophosphate.
additive, below 0 1`wt %~because phosphorus has a tendency to accumulate in the catalyticconverter thus reducingI catalyst efficiency, poisoning the catalyst:
S,UMMARY' OF THE:INVENTlON.
As previously: mentioned, the presentinvention is related, in part, to a lubricating oil,compositian: More particularly the present invention relates to a low phosphorus lubi'icating oil composition.employing a mixture of zinc, dithiophosphatesin a certain ratio arid wherein= the lubricating oil composition has less.than abo_ut 00.6 wt % total phosphorus content, based on:the total weight of the lubricating oil composition.. Theaõow phosphorus lubricating oil composition of the pTese=rit invention is effective. in lead >corr.osion control when used as a ,35; lubrica#ing oil composition,'in internal combustion engiries:
Accordingly, in its broadest aspect, the,presentinvention is related to a lubricating oil composition comprising a major amounf of base oil of lubricating
Perfo:rmance:Parameters of ZineDithiophosphate Types PrirriaryAlkyl Secondary Aikyl Aryl Thermai-Stability Mediurri Low High Antivuear Protection=
Mediurn High Low Hydrolytic Stability Mediurrt.: High Low Each type has irri,portant applications.:in modern additive packages. It is ther'efore .20 important to have the right rriix:of zinc dithiophosphates.in any;,given lubricating oil composition';ta provide adequateanti-wear=pertqrrnance' and'at the same time keeping the phosphorus levels, due to the presence ofa metal dithiophosphate.
additive, below 0 1`wt %~because phosphorus has a tendency to accumulate in the catalyticconverter thus reducingI catalyst efficiency, poisoning the catalyst:
S,UMMARY' OF THE:INVENTlON.
As previously: mentioned, the presentinvention is related, in part, to a lubricating oil,compositian: More particularly the present invention relates to a low phosphorus lubi'icating oil composition.employing a mixture of zinc, dithiophosphatesin a certain ratio arid wherein= the lubricating oil composition has less.than abo_ut 00.6 wt % total phosphorus content, based on:the total weight of the lubricating oil composition.. Theaõow phosphorus lubricating oil composition of the pTese=rit invention is effective. in lead >corr.osion control when used as a ,35; lubrica#ing oil composition,'in internal combustion engiries:
Accordingly, in its broadest aspect, the,presentinvention is related to a lubricating oil composition comprising a major amounf of base oil of lubricating
3 .5 viscasity and;a minor amount af a mixture ot' a zinc primary dialkyl dithiophosphate, a zinc-secondary dialkyl dithiophosphate and a zinc diaryl dithiopl1oSphate wherein'the. respective ratio, based on thephosphorus content, of the zinc primary dialkyl dithiophosphate.to zinc secondary di.alkyl dithiophosphate is from about 2;1 to abbut 1:2 and the ratio of the mixture of zinc primary dialkyl dithiophosphate and zinc secondary dialkyl dithiophospliate to zinc diaryl dithiophosphate is from'about 6:1 .to about 1:1 and wherein the total phosphorus content of the lubricating.oil composition is less than about 0.06 wt %, based on the;total weight of:the lubricating:oil composition.
The.rninor amount of:the mixture of a zinc primary dialkyl dithiophosphate, a zinc secondary;dialkyl dithiophosphate::and.a:zinc.diaryl dithiophosphate employed in.
the lubricating oil .composition of the present invention is from about 0.1 wt % to about 1.5 wt %, pr,eferably from about 0:3 wt % to about 1.2 wt %. and 'more preferably about 0:5 wt % to about 1.0 wt-%, based on the total weight of the lubricating oil.composition.
The lubricating oil.'.composition of the present invention will contain from about 0_05 wt % to.about 1:2 wt % ofa zinc primarydialkyl dithiophosphate,:from about 0.05 wt % to about,1.2 wt % of, a zinc secondary dialkyl dithiophosphate and from 25, 'about.Ø02 wt % to about 0.7 wt %=of a zinc diaryl dithiophosphate,based on the total weight of.the lubticating oil cornposition. Preferably, the lubricating oil -composition of:the present:invention~.will contain from about 0.1 Wt % to about 0.7 wt % of a zincprimary dialkyl;dithiophosphate, from about'0.1 wt !o to about 0.7 inct %-of a zi,nc'secondary dialkyl dithiophosphate and from about 0.05`wt %
to about 0.5 wt %:of a zinc.diaryl dithiophosphate, based on the total weight of the lubricating oil composition. More preferably, the lubricating oil composition of the present invention will contain from about 0:2wt % to about 0.5 wt % of a zinc prima,ry dialkyl dithiophosphate, from about 0:2 wt % to about 0.5 wt % of a zinc secondary dialkyl dithiophosphate and~from about,01.wt % to about 0.3 wt % of a zinc diaryl dthiophosphate, based.on the total. weight of the lubricating oil composition.
The.rninor amount of:the mixture of a zinc primary dialkyl dithiophosphate, a zinc secondary;dialkyl dithiophosphate::and.a:zinc.diaryl dithiophosphate employed in.
the lubricating oil .composition of the present invention is from about 0.1 wt % to about 1.5 wt %, pr,eferably from about 0:3 wt % to about 1.2 wt %. and 'more preferably about 0:5 wt % to about 1.0 wt-%, based on the total weight of the lubricating oil.composition.
The lubricating oil.'.composition of the present invention will contain from about 0_05 wt % to.about 1:2 wt % ofa zinc primarydialkyl dithiophosphate,:from about 0.05 wt % to about,1.2 wt % of, a zinc secondary dialkyl dithiophosphate and from 25, 'about.Ø02 wt % to about 0.7 wt %=of a zinc diaryl dithiophosphate,based on the total weight of.the lubticating oil cornposition. Preferably, the lubricating oil -composition of:the present:invention~.will contain from about 0.1 Wt % to about 0.7 wt % of a zincprimary dialkyl;dithiophosphate, from about'0.1 wt !o to about 0.7 inct %-of a zi,nc'secondary dialkyl dithiophosphate and from about 0.05`wt %
to about 0.5 wt %:of a zinc.diaryl dithiophosphate, based on the total weight of the lubricating oil composition. More preferably, the lubricating oil composition of the present invention will contain from about 0:2wt % to about 0.5 wt % of a zinc prima,ry dialkyl dithiophosphate, from about 0:2 wt % to about 0.5 wt % of a zinc secondary dialkyl dithiophosphate and~from about,01.wt % to about 0.3 wt % of a zinc diaryl dthiophosphate, based.on the total. weight of the lubricating oil composition.
4 The prima .ry'alkyl groupof the zinc primary:dialkyf dithiophosphate has from aboutCi to about C13:carbon -atorns,, preferably fro.rn about C3 to. about C,o carbon atoms and more preferably, from aboutC6 to about C8 carbon atoms.
The secondary alkyl.gr,oup,of the zincseconda .ry dialkyl di'thiophosphate has from about C3 to about~C.13 carbonatorns., pteferably from about C3 to about Ca carbon atoms: and::niore.preferably, from about C3 to about C6 carbon atoms.
The aryl group of the: zinc diaryl dithiophosphate has from about C6 to about carbon atoms, preferably from,about.Cs to about C24 carbon atoms and more preferably., from aboUt C6 to about CZa carbon atorns.
In a prefer%ed embodiment, the respective ratio,: based on the. phosphorus content, of zinc primary dialkyl dithiophosphate to zinc,secondary dialkyl dithiophosphate is from;about3:2 to about 2:3 More:pref.erably, the ratio is about 1:1.
In a preferred embodiment, the, respective ratio, based on the phosphorus content, of the mixture of zinc primary: dialkyl dithiophosphate and zinc secondary dialkyf dithiophosphate-to zincdia .ryl _dithiophosphate. is,from about 41 to about 1:1. Morepreferably,: the ratio is about 2:1.
In an especiatly preferred embodiment, the respective ratio,. based on the phosphorus content;, of the mixture of zinc primary dialk,yl dithiophosphate to zinc secondarydialkyl dithiophosp"hate to;zinadiaryl dithiophosphate is 1:1:1.
..30 In another embodiment, the total`p.hosphoru5:content.in the lubricating oil composition. of the present invention is preferably less than about 0.05 wt more preferably, based on.the total weight of the~lubricating oit composition.
In still another ernbodirnent, the sulfur cont,ent'in the lubricating oil ceimposition of the present invention is lessthan about 0..5 wt % and', preferably, less than about 0.2 ,wt %o, based on`the total weight:.of the lubricating oi9 composition and the total suffated ash co,ntent= in sthe lubricating oil :composition of'the present invention is
The secondary alkyl.gr,oup,of the zincseconda .ry dialkyl di'thiophosphate has from about C3 to about~C.13 carbonatorns., pteferably from about C3 to about Ca carbon atoms: and::niore.preferably, from about C3 to about C6 carbon atoms.
The aryl group of the: zinc diaryl dithiophosphate has from about C6 to about carbon atoms, preferably from,about.Cs to about C24 carbon atoms and more preferably., from aboUt C6 to about CZa carbon atorns.
In a prefer%ed embodiment, the respective ratio,: based on the. phosphorus content, of zinc primary dialkyl dithiophosphate to zinc,secondary dialkyl dithiophosphate is from;about3:2 to about 2:3 More:pref.erably, the ratio is about 1:1.
In a preferred embodiment, the, respective ratio, based on the phosphorus content, of the mixture of zinc primary: dialkyl dithiophosphate and zinc secondary dialkyf dithiophosphate-to zincdia .ryl _dithiophosphate. is,from about 41 to about 1:1. Morepreferably,: the ratio is about 2:1.
In an especiatly preferred embodiment, the respective ratio,. based on the phosphorus content;, of the mixture of zinc primary dialk,yl dithiophosphate to zinc secondarydialkyl dithiophosp"hate to;zinadiaryl dithiophosphate is 1:1:1.
..30 In another embodiment, the total`p.hosphoru5:content.in the lubricating oil composition. of the present invention is preferably less than about 0.05 wt more preferably, based on.the total weight of the~lubricating oit composition.
In still another ernbodirnent, the sulfur cont,ent'in the lubricating oil ceimposition of the present invention is lessthan about 0..5 wt % and', preferably, less than about 0.2 ,wt %o, based on`the total weight:.of the lubricating oi9 composition and the total suffated ash co,ntent= in sthe lubricating oil :composition of'the present invention is
5 less than about 1.2 wt %., preferably, less than about 1.0 wt %o, and more-preferably.less than about 0:8 wt %, based on the total weight of the lubricating oil comp:osition..
In one.of its rnethod,aspects, the present invention.further relates to a methodfor improving lead corrosion. The method involves operating an internal combustion engine with a:lubricating oilcornposition comprising a major, amount of base oil of lubricating viscosity and a minor amount of a mixture of a zinc primary dialkyl dithiophosphate a zinc secondary dialkyl dithiophosphate and a zinc dia:ryl dithiophosphate wherein the;respective ratio, b.ased on the phosphorus:content, of the zinc-primary dialkyl dithiophosphate to zinc-secondary. dialkyl dithiophosphate is-from::about:2,'1 to about 1:2 andthe ratio of the. mixture of, zinc primary dialkyl dithioph .osphate and zinc secondary dialkyl dithiophosphate to zinc diaryl.dithiophosphate is from about 6:1 to about 1:1 and wherein the total phosphorus content of the lubricating oil'composition is less,, than,about 0.06 wZ
%, based:on the total weight~of the lubricating=o'il cornposition:
Among:otherfactors; the present',invention provides a low phosphorus lubricating oil composition..containing a mixture of zinc dithiop:hosphates in a certain ratio surprisingly yields improved lead-corrosion_ The mixture'of zinc dithiophospates containsazinc primary dialkyl dithiophosphate, a zinc secondary dialkyl dithiophosphate and azinc diaryl dithiophosphate. The synergistic:combination of mixed zinc dithiophosphates whereinthe respective ratio, based on the phosphoruscontent, of the zinc;primary dialkyl dithiophosphate. to zinc-secondary dialkyl dithiophosphate is from about.2;1 to about 1:2 and the ratio of the mixture.
of zinc primary dialkyl dithiophosphate and zinc secondary':dialkyl dithiophosphateto zincdia.ryl dithiophosphate is from about 6:1 to about 1:1 when used;in a lubricating oil.composition having; a:total phosphorus content less than abouto.06 wt %oõ based on-the total weight of the:lubricating oil cornposition, greatiy reduces lead corrosion-when:used to (ubricate internal combustion 35. eng,ines:
In one.of its rnethod,aspects, the present invention.further relates to a methodfor improving lead corrosion. The method involves operating an internal combustion engine with a:lubricating oilcornposition comprising a major, amount of base oil of lubricating viscosity and a minor amount of a mixture of a zinc primary dialkyl dithiophosphate a zinc secondary dialkyl dithiophosphate and a zinc dia:ryl dithiophosphate wherein the;respective ratio, b.ased on the phosphorus:content, of the zinc-primary dialkyl dithiophosphate to zinc-secondary. dialkyl dithiophosphate is-from::about:2,'1 to about 1:2 andthe ratio of the. mixture of, zinc primary dialkyl dithioph .osphate and zinc secondary dialkyl dithiophosphate to zinc diaryl.dithiophosphate is from about 6:1 to about 1:1 and wherein the total phosphorus content of the lubricating oil'composition is less,, than,about 0.06 wZ
%, based:on the total weight~of the lubricating=o'il cornposition:
Among:otherfactors; the present',invention provides a low phosphorus lubricating oil composition..containing a mixture of zinc dithiop:hosphates in a certain ratio surprisingly yields improved lead-corrosion_ The mixture'of zinc dithiophospates containsazinc primary dialkyl dithiophosphate, a zinc secondary dialkyl dithiophosphate and azinc diaryl dithiophosphate. The synergistic:combination of mixed zinc dithiophosphates whereinthe respective ratio, based on the phosphoruscontent, of the zinc;primary dialkyl dithiophosphate. to zinc-secondary dialkyl dithiophosphate is from about.2;1 to about 1:2 and the ratio of the mixture.
of zinc primary dialkyl dithiophosphate and zinc secondary':dialkyl dithiophosphateto zincdia.ryl dithiophosphate is from about 6:1 to about 1:1 when used;in a lubricating oil.composition having; a:total phosphorus content less than abouto.06 wt %oõ based on-the total weight of the:lubricating oil cornposition, greatiy reduces lead corrosion-when:used to (ubricate internal combustion 35. eng,ines:
6 DETAILED DESCRIPTION OF THE INVEIdTION
The present i.nvention is related, in part, to a lubricating oil composition.
More particularly,: the present invention relates to a low phosphorus lubricating oil composition;eriiploying. a mixture of zinc dithiophosphates containing a zinc ;primarydialkyl dithiophosphate, a zinc'secondary dialkyl d,ithiophosphate and a zinc.diaryl dithiop.hosphatewherein the:respective=ratio, based on the phosphorus content; of the,zinc prirnary dialky,l dithiophosphate to zinc secondary dialkyl-dithiophosph'ate is from about2:1 to about;1:2:and the ratio of the-rnixture of. zinc primary dialkyl dithiophosphate;arid zinc secondarydialkyl "dithiophosphate to zinc diaryl dithiophosphate is from about 6:1 to about 1:1 and wherein the lubricating oil compositio.n has'less than about0.06 wt % total phosphorus content, based :on the total weight,of the lubricating oil composition.
The low phosphorus.lubricating oil composition:of the present invention is .effective in lead corrosion control when used'as-a lubricating .oil in internal combustion engines.
Each of these components in the claimed composition will be described in detail herein: However, prior to such a.description, the following terms will first be def'ined..
The terrri "alkyi" refers to bothstraight-.and'branched-chain alkyi groups.
The term "aryl" refe. rs to a substituted or unsubstituted.aromatic group, such as the phenyl, tolyl, xylyl, ethylphenyl.and cumen. yl groups:
The term "low phosphorus" refers to the phosphotus content of the lubricating oil cornpositionof the'present invention..The_phosphorus, content is in the range of about 0.005 weight:percent:to about,0.06 weightpercent based on the 'total weight of the.lubricating oil,composition:
The term "total'phosphorus" refers tothe totai amount of phosphorus in `the lubricant compositionregardtess: of whether such phosphorus,is present as part 'of anoil-soluble, phosphorus-.containing; anti-wear.compound or in the form ofa
The present i.nvention is related, in part, to a lubricating oil composition.
More particularly,: the present invention relates to a low phosphorus lubricating oil composition;eriiploying. a mixture of zinc dithiophosphates containing a zinc ;primarydialkyl dithiophosphate, a zinc'secondary dialkyl d,ithiophosphate and a zinc.diaryl dithiop.hosphatewherein the:respective=ratio, based on the phosphorus content; of the,zinc prirnary dialky,l dithiophosphate to zinc secondary dialkyl-dithiophosph'ate is from about2:1 to about;1:2:and the ratio of the-rnixture of. zinc primary dialkyl dithiophosphate;arid zinc secondarydialkyl "dithiophosphate to zinc diaryl dithiophosphate is from about 6:1 to about 1:1 and wherein the lubricating oil compositio.n has'less than about0.06 wt % total phosphorus content, based :on the total weight,of the lubricating oil composition.
The low phosphorus.lubricating oil composition:of the present invention is .effective in lead corrosion control when used'as-a lubricating .oil in internal combustion engines.
Each of these components in the claimed composition will be described in detail herein: However, prior to such a.description, the following terms will first be def'ined..
The terrri "alkyi" refers to bothstraight-.and'branched-chain alkyi groups.
The term "aryl" refe. rs to a substituted or unsubstituted.aromatic group, such as the phenyl, tolyl, xylyl, ethylphenyl.and cumen. yl groups:
The term "low phosphorus" refers to the phosphotus content of the lubricating oil cornpositionof the'present invention..The_phosphorus, content is in the range of about 0.005 weight:percent:to about,0.06 weightpercent based on the 'total weight of the.lubricating oil,composition:
The term "total'phosphorus" refers tothe totai amount of phosphorus in `the lubricant compositionregardtess: of whether such phosphorus,is present as part 'of anoil-soluble, phosphorus-.containing; anti-wear.compound or in the form ofa
7 contaminant in the lubricantcomposition such as residual phosphorus remaining due to.the presence:of P2S5 used to prepare metal dihydrocarbyl dithiophosphates: In :either event, theamount of phosphorus permitted in the lubricant cornposition is independent of.source. Preferably, however, the phbsphorus is part of. a lubricant additive:
Unless othenrvisespecified, all percentages arein weight percent.
The.Zinc Dithiophosphate Compound The lubricating oil composition of the present; invention will employ, in part; a mixture ofzinc.dithiophosphates. The zinc-dithiophosphates are independently characterized by-:formula I;
s RO ~ ---S. Zn RU ~
wherein each R is independently a gro.up containing from about 1 to about:30 carbon atoms.
The R-groups in the dithiophasphate can independently be about C, to:about:C,3 pr.imary alkyl, about C3 to<about Cy3.secondary alkylõand about C6,to about aryl group:. Preferably, the R groups inthe dithiophosphate can independently be about. C3 to about Cio prima ry alkyl, about C. to about C8 secondary alkyl, and about C6 to about C24 ary" I group: More preferably,;the R groups in the dithiophosphate can independently be about Cs to. about C8. primary alkyl, about C~ to about-Ce,secondary alkyl, and about C6 to about Caoaryl group. The R
groups rnay,be a substantially hydrocarbon group. By "substantially hydrocarbon"
is meant hydrocarbons'thafcontain:substituent:groups such as ether, ester, nitro, or halogen which do qot materially affect the hydrocarbon character of the,group.
Unless othenrvisespecified, all percentages arein weight percent.
The.Zinc Dithiophosphate Compound The lubricating oil composition of the present; invention will employ, in part; a mixture ofzinc.dithiophosphates. The zinc-dithiophosphates are independently characterized by-:formula I;
s RO ~ ---S. Zn RU ~
wherein each R is independently a gro.up containing from about 1 to about:30 carbon atoms.
The R-groups in the dithiophasphate can independently be about C, to:about:C,3 pr.imary alkyl, about C3 to<about Cy3.secondary alkylõand about C6,to about aryl group:. Preferably, the R groups inthe dithiophosphate can independently be about. C3 to about Cio prima ry alkyl, about C. to about C8 secondary alkyl, and about C6 to about C24 ary" I group: More preferably,;the R groups in the dithiophosphate can independently be about Cs to. about C8. primary alkyl, about C~ to about-Ce,secondary alkyl, and about C6 to about Caoaryl group. The R
groups rnay,be a substantially hydrocarbon group. By "substantially hydrocarbon"
is meant hydrocarbons'thafcontain:substituent:groups such as ether, ester, nitro, or halogen which do qot materially affect the hydrocarbon character of the,group.
8 The.R gr"oup of the.zinc,dithiophosphate may be derived, for example, from a primary alcohol such as methanol, ettianol, propanol,, butanol, pentanol, hexanol, heptanol, octanol, ~nonanol, decanol; dodecanol, octadecanol, propenol, butenol, 2=ethylhexanol; a secondary alcohol,such as isopropyl alcohol, secondary butyl alcohol, isobutanol,3-methylbutan-2-ol, 2-pentanol, 4-methyl-2-pentanol, 2-hexanol; 3.-hexanol; arimyl.al:cohof; an aryl alcahol such;as.phenol, substituted phenol (particularly atkylphenol such as butylphenol, octylphenol, ngnylphenol, dodecylphenoi); disubstituted. phenol, Preferably-the R group:will be independently a,primary alkyl, a secondary alkyl or 1.5: 7an aryl group.
Forthe;present: invention itis, contemplated that the mixture of a zinc,primary dialkyl dithiophosphate a zinc secondary diaakyl dithiophosphate and a zinc diaryl dithiophosphate will be in. a respective ratio,based on thephosphorus content, in ithe lubricatirig oil composition of the present invention. The, ratio of zinc. prirnary dialkyl dithiophosphate to zinc secondary dialkyl dithiophosphate will 'be from about:2:1.to ,about 1:2 and the ratio of the mixture .of zinc..prirrmary dialkyl dithiophosphate and zinc secondary dialkyl dithiophosphate.to zinc.diaryl dithiophosphate is from about 6:1 to ,about 1:1. Preferably, the respective ratio, based on the phosphorus content, of zinc primary dialkyl dithiophosphate.to zinc secondary ~dialkyl d,ithiophosphate is a range from about 3:2 to about 2:3;
more preferably about-1:1. Preferably;,the respective ratio, based on the phosphorus content, of the mixture of zinc primary dialkyl dithiophosphate and zinc secondary dialkyl dithiophosphate to zinc diaryl dith;iophosphate isa range from about 4:1 to about 1:.1, rriore preferably about 2:1. Most preferabfy,. the respective ratio, based on the phosphorus-co.ntent, of=the mizture of zinc primary dialkyl dithiophosphate to zinc secondary. dialkyl dithiophosphate to zinc diaryl dithiophosphate is 1:1:1.
Many :of the zinc.'dithiophosphates .useful in the presentinvehtion are available commercially: However, zinc dithiophosphatesare.widelyknown in the art and a' skilled; artisan can readily ~. synthesize such compounds for the purpose of the present:invention. Typically, zinc-dithiophosphates can be made by initial reaction of pliosphorous. pentasutfide and an alcohol or phenol or mixtures of alcohols
Forthe;present: invention itis, contemplated that the mixture of a zinc,primary dialkyl dithiophosphate a zinc secondary diaakyl dithiophosphate and a zinc diaryl dithiophosphate will be in. a respective ratio,based on thephosphorus content, in ithe lubricatirig oil composition of the present invention. The, ratio of zinc. prirnary dialkyl dithiophosphate to zinc secondary dialkyl dithiophosphate will 'be from about:2:1.to ,about 1:2 and the ratio of the mixture .of zinc..prirrmary dialkyl dithiophosphate and zinc secondary dialkyl dithiophosphate.to zinc.diaryl dithiophosphate is from about 6:1 to ,about 1:1. Preferably, the respective ratio, based on the phosphorus content, of zinc primary dialkyl dithiophosphate.to zinc secondary ~dialkyl d,ithiophosphate is a range from about 3:2 to about 2:3;
more preferably about-1:1. Preferably;,the respective ratio, based on the phosphorus content, of the mixture of zinc primary dialkyl dithiophosphate and zinc secondary dialkyl dithiophosphate to zinc diaryl dith;iophosphate isa range from about 4:1 to about 1:.1, rriore preferably about 2:1. Most preferabfy,. the respective ratio, based on the phosphorus-co.ntent, of=the mizture of zinc primary dialkyl dithiophosphate to zinc secondary. dialkyl dithiophosphate to zinc diaryl dithiophosphate is 1:1:1.
Many :of the zinc.'dithiophosphates .useful in the presentinvehtion are available commercially: However, zinc dithiophosphatesare.widelyknown in the art and a' skilled; artisan can readily ~. synthesize such compounds for the purpose of the present:invention. Typically, zinc-dithiophosphates can be made by initial reaction of pliosphorous. pentasutfide and an alcohol or phenol or mixtures of alcohols
9 and/or pheriols. such as those illustrated:above for the R,group. The reaction involves four moles of the alcohol or phenol:per mole of phosphorous pentasulfide, :and.may be carried out within the temperature range from about 50 C-to about 200 C. Thus; the preparation of O;O-di-n-hexyl phosphorodithioic acid, for example, involves the-reaction.of phosphorouspentasulfidewith four moles of n-hexyl alcohol atabout 100 Cfor abouttwo ho:urs. Hydrogen sulfide is liberated and; the residue is phosphorodithioic acid. The preparation of the metal salt of`this acid ~may be effected.by.reaction with either zinc oxide or zinc hydroxid;e.to yield the zrnc:dithiophosphate. Simply.mixing and heating thesetwo reactants:is. sufficient to;cause the reaction;to take:- place and the resulting product i`,s!sufficiently: pure for the purposes of the present inv.ention.
Paterlts describing the synthesis of such zinc dithiophosphates include U.S.
Patent Nos: 2,684,123;.31000,822; 3.,151,075; 3,385;791; 4,377,527; 4,495,075 and 4,778,906: Each of these patents 'is .incorporated herein by reference in their entirety.
The Lubricating Oil Composition Therniicture;of zinc.dithiaphosphates of the;present invention is typically added to a base.oil in sufficient amountsto provideaead corrosion control in. internal comb.ustion engines. Generally, the lubricafing oil composition of the present invention will contain a major amount ofbase oil of.lubricating viscosity and a minor arnount of the mixture of zinc dithiophosphates ofthe present invention.
Base;Oil of Lubricating Viscosity Base oil as used herein is defined as a base stock or blend of base stocks which is a lubricant componentthat is produced by each manufacturer to the same specifications.(independent of feed. source or manufacturer's location); that meets the same~manufacturer's specification; and:#hat: is identified by a unique formula, product.identificatiorr number,. or both. Base;stocks. may be manufactured using a variety of'different:proce.sses including but`not limitedto distillation, solvent refinin,g, hydrogen processing; oligornerization., esterification, and rerefining.
.Rerefined:stock shall be substaritially free from materials introduced through manufacturing,, contaminatron; or previous use. The base oil of this.invention may be any natural or:synthetic* Iubricating base.oil fraction particularly those having a kinematic viscosity at:100 Centigrade.( C).and about.4 centistokes. (cSt) to about 20 cSt: Hydrocarbon synthetic oils may include, for example, oils prepared from the polymerization of ethylene,, polyalphaolefin or PAO, or from hydrocarbon synthe,sis procedures using carbon monoxide,and hydrogen;gases such as in.a Fisher-Tropsch:process. A preferred base oil is one,that comprises little, if any, heavy, fraction, e:g.,: little, if any; lube oil`fraction.of viscosity about 20. cSt or higher=at about;100. C> :Oiis used.as the base oil will be'selected or;blended depending on the desired end use:an6the additives in the finished oil to give the desired grade of engine oil, .e:g. a lubrieating'oil composition having an SAE
Viscos,ity Grade of OW, OW-20, OW30, UW=40, QW-50, OW=60, 5W, 5W-20, 5W-30, 5W40, 5W-50, 5W-6.0, 10W, 1OW-20; 10W-30, 10W-40, 10W-50, 15W, 15W-20; 15W-30, or.1.5W-40.
The.base oil may'be derived frominatural I,ubricating bils, synthetic lubricating oils or mixtures thereof:_ Suitabl.e base oil. includes base,stocks obtained by isomerization of synthetic wax and slack :wax, as well as hydrocrackate base stocks produced by hydrocracking'(rather thansolvent.extracting) the arotnatic and polar components. of the.crude: Suitable:base oils include those, in all API
,categories I, 11, III;.IV'and V as defined in,API Publication 150,9, 14th Edition, Addendum I; December 1998. Saturates leveis and viscosity indices.for Group I, II and`Ill base-oils are:listed in Table'I. Group 1V'base oils are polyalphaolefins .(PAO). Group V baseoils inctude. all other base oils~not included in Group I, II, III, or IV. Group III base oils are preferred.
. 5 TABLE.I.
SATURATES, SULFUR:AND VISCOSITY INDEX OF GROUP I,.II, III, IV AND
V BASE STOCKS
Saturates (As determined by ASTM Viscosity lndex D2007) Group (As determinedb.y ASTM D4294, Sulfur (As determined by ASTM
D2270) ASTM .D4297 or ASTM D3120) Less than 90 %o saturates and/or Greater than or equal to 80and Greater than to 0.03 %o~sulfur less,than 120 Greater than or equai to 90 %
II saturates, and less than or equal to Greater than or equal to 80 and 0.03- u sulfur less .than 120 Greater than or equal to -90 %
Ill saturates and. less than or e.qual to Greater than or equal to 1,20 0:03 Io sulfur iV. AII Polyalphaolefins (PAOs) V All others not included in.Groups I, 11, III,,-or IV
Natural lubricatirig oils may incf.ude. animal oils, vegetable oils (e.g., rapeseed oils, castor oils~and lard oil), petroieum oils, mineral.oils, and oils derived from coal or shale.
Synthetic oils may include hydrocarbon .oils and halo-substituted hydrocarbon oils such as polyinetized and inter-polyrnerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl~sulfides, as well astheir derivatives, .anal:ogues and homologues thereof; and the like. Synthetic lubricating oils also include. alkylene oxide polymers, interpolym.ers, copolymers and derivatives thereof"wherein the terminal hydroxyl. groups have been modified by esterification, etherification, etc. Another suitable class of ~synthetic lubricating oils comprise"s the esters:of d'icarboxylic acids with a variety of alcohols.
Esters, useful as synthetic oils also include those made from about-C5 to about C12 monocarboxylic acids and polyols and polyol ethers: Td=alkyl phosphate ester oils such as those ezernplifed by: tri-n-butyfphosphate and tri=iso-butyl phosphate are also:suitable for use-as, base oils.
Silicon=.based oil& (such as the polyalkyl-,, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise:another useful class of synthetic lubricatirig oits. Othet'synthetic Iubricatirig oils include liquid, esters of phosphorus-containing acids, polymeric, tetrahydrofurans, polyalphaolefins, and the:like.
The base oil may be derived from unrefined, refined, rerefined oils; or mixtures thereof. Unrefined oils are obtained:directly from a natural sourceor synthetic ;source (e:g.,_ coal; shale, or tar sand bitumen); without further purif'ication or treatment: Examples of unrefined oils::include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directlyfro.m distillation, or an ester oil,obtained directly from an.:esterification process, each of-which may then be used without'further treatment. Refined oils:are-similar to the unrefined oils except:that refined oilshave been treated, in one or more purification steps to =improve. one or more properties. Suitable purification techniques include distillation, hydrocracking, hydrotreating, dewaxing,,solvent.extraction, acid or base extraction, f ltration, and percolation, all of which are known to those skilled.
in the art:: Rerefined oils are obtained b.y tr"eating used oils in processes similar to those used to obtain the refined oils. These rerefined oils.are also known as reclaimed or reproce"ssed oils and often are additionally processed by techniques for removal of spent additives and oil.breakdown products.
Base oil derived f'rom the hydroisomerization of wax.may also be used, either alone or in combination with the aforesaid natural.and/or synthetic base oil.
Such waxisomerate oil is produced by the hydroisomerization of natural or synthetic waxes ormixtures thereof:over-a hydroisomerization catalyst.
It is preferred'to use:a major amount::of base oil in tlie:lubricating oil composition of the p.resent invention. A major amount of base oil as defined herein comprises about 40 wt'% or more. Preferred amounts of base oil comprise about 40 wt %a:
to about:97 wt /a, preferably greater than about 50 wt %o to about.97 wt %,, more preferably about 60 wf %o to about 97 wt %. and most preferably about 80 wt %
to about 95 wt:Wof the:lubricating oil composition. (When weight percent is used herein, it is referring'to weig"ht percent of the,lubricating oil unless otherwise specified.) The amount of the:mixture of zinc dithiophosphates employed in the lubricating oil.compvsition of the present'invention will be in.a minor amount compared to the: base oil of. lubricatingviscosity: Generally, it will be in an amount from about 0.1 wt:% to:about 1'.5 wt%; preferably fromabout 0:3 wt % to about 1.2 wt %and more preferably frorn about 0.5 wt % to about 1.0 wt %, based on the total weight of the lubricating oil composition.
The lubricating oil composition: of the.present invention will contain from about 0.05 wt.% to about 1.2,wt preferabl,y.from about 0:1 wt'% to about 0.7 wt and more preferably from about 0:2 wt % to about 0:5 wt %.of a.zinc primary dia.lkyl dithiophosphate, based on the total weight of the-lubricating.oil composition.
The lubricating oil composition;of the ptes'entinvention will contain from about 0.05. wt %: to about.1.2 wt preferably from about 0.1 wt % to about 0.7 wt %, and more preferably,from about, 0.2 wt:% to abou. t 0:5 wt % of .a zinc.
secondary dialkyl dithiophosphate, based.on the`total weight::of the lubricating oil composition..
The lubricating oil composition of the p"resent invention will contain from about 0.02 wt;%o; to about:0.7 wt %,;preferably from about 0.05 wt % to. about 0.5 wt %, and.:more preferably from about.0:1 wt % to about 0.3 wt %o of a zinc primary diaryl dithioph'osphate,.based. on the total weight of the lubricating oil composition.
In a preferred ernbodiment, the lubricating oil composition of the present invention "will have a phosphorus content preferably less than about 0.05 wt based on the;aotaf weight of'ttie lubricating oil composition.
In another erimbodiment, the lubricating oil composition.of the present:
invention will further have a.-sulfur content less=than about 0:5 wt % and, preferably less Ahan.,about 0,2 wt %, based on thetotal weight of the lubricating oil composition and'the total. sulfated ash content in the. lubricating.oil composition of the present invention is less than about 1.2 wt %, preferabty; less than about 1.0 wt %, and more.preferably1ess than:about 0.8 wt %, based on the.total weight of the ,lubricating oil:cornposition.
Other Additive Components Ttie following additive compon.ents are examples,of components, that can.be favorably employed in combination with the lubricating additive. of the present invention. These examples of additives are; provided to illustrate the present invention, but they are nof intended to limit it, (A) Detergents are,additivesdesigned to'hold the acid-neutralizing..co.mpounds in solution in-theoil:.They are usually alkaline and, react with the strong acids (sulfuric=and:nitric) which for"rnduring the combustion:of the fuel and which would cause corr.osion:to the engine: parts if left unchecked. Examples are carboxylates, sulfurize.d or unsulfurized,:alkyl' or alkenyl phenates, alkyl or alkenyl:arortiatic sulfonates; sulfurized or unsulfurized metal salts of multi-hydroxy alkyl or=alkenyl :aromatic compounds;:alkyl oralkenyl hydroxy aromatic sulfonates, sulfurized or unsulfurized alkyl or alkenyl naphthenates, rnetal.-salts of: alkanoic,acids, nietal salts:of;an alkyl or alkenyl multiacids and cherriical and physical,mixtures thereof.
(B) Dispersants are additives. that keep soot and combustion products in suspension in.the. body of the oil and therefore prevent deposition as sludge or lacquer Typically; the ashless dispersant"s ate nitrogen=containing dispersantsformed by reacting alkenyl:.succinic.acid anhydride with an amine.
Examples are alkenyl succinirnides, alkenyl succinimides modified with other organic cornpounds, e.g:;; ethylene carbonating post-treatment and alkenyl succinimides-modified with.boric- acid', polys.uccinimides, alkenyl succinic ester.
(C) .Oxidation Inhibitors;
T) Phenoltype (phenolic) oxidation i'nhibitors: 4;4'-methylenebis (2;6-di-tert-butylphenol);4,4'-bis(2,6-di-tert-butylphenol), 4;4'-bis(2-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6=tert-butyl-phenol), 4,..4'=
butyldienebis(3-cnethyl-6-tert=butylphenol), 4,4'-isopiopylidenebis(2,6-di-tert-.butytpheno.I), 2,2'-methylenebis(4-methyl=6=nonylphenol), 2,2'-isobutyldiene-bis(4,6-d'imethylphenol), 2,2'-rrmethylenebis(4-methyl-6-cyclohexylphenol), 2,6-d;i-tert-butyt-4-methylphenol, 2;6-di=tert-butyl-4-ethylphenol, 2,4-dirnethyl-tert-butyt=phenol, :2,6-di-tert-a-dimethylamino-p-cresol, 2;6-di-tert-4(N,N' dimethylarninomethylphenol);4,4'-thiobis(2-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl=6-tert=butylphenol), bis(.3-methyl-4-hydroxy-5-tert-butyt0enzyl)-sulfide and bis (315-di=tert-butyf-4-hydroxybenzyl).
2) Diphertylamine type:oxidation inhibitor: alkylated diphenylamine, phenyl=a-haphthylarnine and alkylated a-naphthylamine..
3) Other types: metal dithiocarbarnate (e;g., zinc dithiocarbamate) and rnethylenebis(dibutyldithiocarbamate).
(D);Rust Inhibitors (Anti-rust'agents):
1) Nonionicpolyoxyethylene surface active agents: polyoxyethylene lauryl ether;
polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octyiphenyl ether; p.olyoxyethyle.ne octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene:sorbitol mono=oleate akid polyethylene glycol monooleate.
2) Other compounds: stearic acid:and:otherfatty acids, diearboxylic acids, metal soaps, fatty acid amine salts; metal salts of heavy;sulfonic acid; partial carboxylicacid ester of polyhydric alcohol and phosphoric ester.
(E) Demulsifiers: addition product of alkylphenol and-ethyleneoxide, polyoxyethylene alkyl ether and polyoxyethylene sorbitane ester.
(F) 'Extreme pressure agents (EP agents): sUlfurized oils, diphenyl sulfide, methyl trich(orbstearate, chlorinated naphthalene, benzyl iodide, fluoroalkylpolysiloxane and lead naphthenate..
(G) Fr'iction modifiers: ,fatty alcohol, fatty, acid, amine, borated ester and other esters.
-(H) Multifunctional additives:: sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum organo phosphorodithioate, oxymolybdenum monoglyceride, oxymolybdenum diethylate amide, amine-molybdenum complex compound and sulfur-containing molybdenum complex compound.
(I) Viscosity IndexJmprovers (VII): polymethac ,rylate type.polymers, ethylene-prop.yle.ne copolymers, :styrene-isoprene copolymers, hydrogenated styrene-20" isoprene copolymers, hydrogenated star.-branched polyisoprene, polyisobutylene, hydrogenated star=branched styrene-isoprene copolymer and dispersant;.type; viscosity index improvers.
(J) Pour point depressants: polyrriethyl methacrylates; alkyfinetha.crylates and, dialkyi fumarate-vinyl acetate copolymers.
(K) Foam Inhibitors; alkyl methacrylatepolymers and dimethyl silicone-polymers.
EXAMPLES
The,present invention will be further illustrated by,the following examples, Which set forth particularly advantageous method embodiments. While-the.Examples are;.provid.ed:to, illustrate thepresent inWention, they are notintended to limit it.
Example 1 The low phosphorus lubricating oil cornpositionof the present invention was prepared by blending a 0:78 wt % rnixture:of zirtc` bis(0,O'-di-(2-ethyl-l-hexyl) dithiophosphate (0.24 wt.%o, primary.), zinc bis(O,O'=di-(2-butyl/4-methyl-2-pentyl) dithiophosphate (0:,15 wt %, secondary).and,zinc:bis(O,O'-di-(dodecylphenyl) dithiophosphate (0.39 wt%; aryl),with a G>=oup II base oil of lubricating viscosity.
The. ratio ofzinc:bis(O,O'-di(2-ethyl-l-hexyl) dithiophosphate to zinc bis(O,O'-di-(2-butyl/4-methyl=2=pentyl) dithiophosphate was about 1:1, based on the phosphorus:coritent. The...ratio of'the mixture of zinc bis(O;O'=di(2=ethyl-1-hexyl) dithiophosphate ani,l,zinc bis(O,O'-di-(2-butyll4-methyl-2-pentyl) dithiophosphate to zinc bis(O;O'-di-(dodecylphenyl) dithiophosphate was about 2:1, based on the phosphorus content. The resulting ratio of the three-way mixture of zinc bis(O.;O'-.di(2-ethyl-1-hexyl),dithiophosphate to zinc bis(O,0'-di=(2=butyl/4-methyl-2-pentyl) dithiophosphate.to zinc bis(0,Q'=di-(dodecylphenyl),.dithiophosphate was 1:1:1, based on the. ,phosphorus content: The.'wt. % of phosphorus-in the prepared lubricating Oil composition was less than about:0.06 wt % based on the total weight of the Jubri,cating oil composition. Further, the sulfur content and sulfated -ash content~were 0.2 wt % and 0.8 wt.%o, respectively, based on the total weight of the lubricating,oil''composition..The wt % balance of'the lubricating oil composition containing a 1200molecular weight (MW) isobutyleoe bis-succinimide dispersant, a~ 2300.MW isobutylene bis-succinimide dispersant, a neutral sulfonate detergent; an overbased calcium. phenate, 'a molybdenum oxidation irihibitor, diphenylamine oxidation inhibitor, aphenolic oxidation inhibitor, anti=foam agent, pourpoinf depi=essant:and a viscosity index improver to complete the 100 Wt %lubricating oil composition:.
Comparative Example.A
Comparative Example.A was prepared according.to Example 1 except.only about 1.16"wt % aryl zinc bis(O;O'-di-(dodecylphenyl) dithiophosphate was added, instead of.the mixture of.zincbis(Q,0'-di=(2=ethyl-.1-hexyl) dithiophosphate, zinc bis(O,O"-di-(2-butyl/4-methyl-2=pentyl) dithiophosphate and zinc bis(O,0'-di-(dodecylphenyl) dithiophosphate_ Coiiiparative Example B
Comparative Exanlple B was prepared accordingto Example 1 except only about 0.46 wt % zinc bis(O,O'-di-(2-butyU4-me,thyl-2-pentyl) dithiophosphate was :added, instead of the mixture of zinc bis(O;O'-di-(2-ethyl-1-hexyl) dithiophosphate; zinc bis(O,O'-di-(2-butyl/4-methyl-2-pentyl) dithiophbsphate and zinc bis(O,O'-di-(dodecylp.hen,yl) dithiophosphate.
Comparative -:Exarnple C
1.5 Comparative Example C was.:prepared according to Example 1 except only about 0.71 wt % zinc.bis(O,O'-di-(2=ethyl-1-hexyl.) dithiophosphate was added, instead of the mixture of zinc-, bis(O,O'=di-(2-ethyl=1-hexyl) dithiophosphate, zinc bis(O,O'-di-(2-butyl/4=methyl-2-pentyl) dithi,op,hospha.te and zinc.bis(O,O'-di-(dodecylphenyl) dithiophosphate.
Comparative Example D.
Comparative:ExampleDvas prepared according'to Example 1$xcept about 0.81. wt %of a mixture. of zinc bis (O,0'-di-(2-butyl/4=methyl-2-pentyl) dithiophosphate and zinc:bis (O;O'~di-(dodecytphenyl)'dithiophosphate in about a 1:1 ratio were added, instead of,the mixture of zinc bis(O,0'-di=(2-ethy.l-1-hexyl) dithiophosphate,: zinc bis(.O,O'-di-(2-butyl/4-methyl-2-pentyl) dithiophosphate and zinc bis.(O,O'-di-(d"odecylphenyl) dithiophosphate.
Comparative Example E
C.omparative Example E was pre.par:ed according. to Example '1 exceptabout 0:94 wt % of a rnixture of zi.nc bis(Q,O'-di-(2-~ethyl-1-hexyij dithiophosphate and zinc bis(O,O'-di-(dodecylphenyl) dithiophosphate in about a* 1:1 ratio vi-ere added, .35 instead. of `the mixture of zinG bis(O,O'-di-(2-ethyl-l-hexyl) dithiophosphate, :zinc bis(Q,O'-di-(2-butyl/4.=methyl=2-pentyl) dithiophosphate.and zinc bis(Q,O'-di-~(dodecyiphenyl) dithiophosphate:
.,Comparative Example F
C:omparatiVe Exanlple F was prepared according to EXample 1 except about 0.59 wt~%o of..a-mixture ofzinc bis(0;0'-di-(2-ethyl=1-hexyl) dithiophosphate and zinc bis(O,O'-di:=(2-butyl/4-methyl-2-pentyl) dithiophosphate.in about a 1:1 ratio were added, instead of the mixture.of zinc bis(O,O'-di-(2-ethyl-1=hexyl) dithiophosphate, zinc bis(O,O'-di-(2-butyl/4-methyl-2-pentyl) dithiophosphate and zinc bis(O,0'-di=(dodecylphenyl) dithiophosphate.
Each.formulation according to Example:1 and Compatative Example A-F were tested for lead corrosion using the High Temperature Corrosion Bench Test (HTCBT)(ASTM 06594) which is an industry, standard bench testto measure corrosion.performance of a motor oil;,.Briefly, four metal specimens of copper, Iead,.tin, and. phosphor,bronze,are immersed in a measured amount -of engine oil.
The oil, at::an elevated tem.perature, is blown with, air for, a period of time. When the test is completed, the lead specirnen and the.stressed oil are examined to detect corrosion and corrosionr products, respectively. A reference oil is tested with:each group of test,s; to verify test acceptabil.ity.
The-test results are surr.iniarized in Tabie II.
Table1I. HTCBT Results Example Comparative Examples 1 A. B C D E F
Lead, 48:4. 113.4 93.4 305 64.6 87.3 99.4 PPm These results demonstrate that the low phosphorus lubricating oil composition of the present.invention (Example 1) containing a m.ixture'of,iincprimary dialkyl dithiophosptiate; zinc secondary dialkyl dithiophosphate and zinc diaryl dithiophosphate.>in a 1`.1:1 ratio, and whereinthe phosphorus content of the lubricating: oil composition: is.less than 0:06 wt%, provides excellent lead corrosion;performance when compared to the.comparative examples not having 'a.mixtur.e of all three dithiophosphates. The amount of lead corrosion is significantly redueed. by the lubricating oil composition'of the present invention.
Paterlts describing the synthesis of such zinc dithiophosphates include U.S.
Patent Nos: 2,684,123;.31000,822; 3.,151,075; 3,385;791; 4,377,527; 4,495,075 and 4,778,906: Each of these patents 'is .incorporated herein by reference in their entirety.
The Lubricating Oil Composition Therniicture;of zinc.dithiaphosphates of the;present invention is typically added to a base.oil in sufficient amountsto provideaead corrosion control in. internal comb.ustion engines. Generally, the lubricafing oil composition of the present invention will contain a major amount ofbase oil of.lubricating viscosity and a minor arnount of the mixture of zinc dithiophosphates ofthe present invention.
Base;Oil of Lubricating Viscosity Base oil as used herein is defined as a base stock or blend of base stocks which is a lubricant componentthat is produced by each manufacturer to the same specifications.(independent of feed. source or manufacturer's location); that meets the same~manufacturer's specification; and:#hat: is identified by a unique formula, product.identificatiorr number,. or both. Base;stocks. may be manufactured using a variety of'different:proce.sses including but`not limitedto distillation, solvent refinin,g, hydrogen processing; oligornerization., esterification, and rerefining.
.Rerefined:stock shall be substaritially free from materials introduced through manufacturing,, contaminatron; or previous use. The base oil of this.invention may be any natural or:synthetic* Iubricating base.oil fraction particularly those having a kinematic viscosity at:100 Centigrade.( C).and about.4 centistokes. (cSt) to about 20 cSt: Hydrocarbon synthetic oils may include, for example, oils prepared from the polymerization of ethylene,, polyalphaolefin or PAO, or from hydrocarbon synthe,sis procedures using carbon monoxide,and hydrogen;gases such as in.a Fisher-Tropsch:process. A preferred base oil is one,that comprises little, if any, heavy, fraction, e:g.,: little, if any; lube oil`fraction.of viscosity about 20. cSt or higher=at about;100. C> :Oiis used.as the base oil will be'selected or;blended depending on the desired end use:an6the additives in the finished oil to give the desired grade of engine oil, .e:g. a lubrieating'oil composition having an SAE
Viscos,ity Grade of OW, OW-20, OW30, UW=40, QW-50, OW=60, 5W, 5W-20, 5W-30, 5W40, 5W-50, 5W-6.0, 10W, 1OW-20; 10W-30, 10W-40, 10W-50, 15W, 15W-20; 15W-30, or.1.5W-40.
The.base oil may'be derived frominatural I,ubricating bils, synthetic lubricating oils or mixtures thereof:_ Suitabl.e base oil. includes base,stocks obtained by isomerization of synthetic wax and slack :wax, as well as hydrocrackate base stocks produced by hydrocracking'(rather thansolvent.extracting) the arotnatic and polar components. of the.crude: Suitable:base oils include those, in all API
,categories I, 11, III;.IV'and V as defined in,API Publication 150,9, 14th Edition, Addendum I; December 1998. Saturates leveis and viscosity indices.for Group I, II and`Ill base-oils are:listed in Table'I. Group 1V'base oils are polyalphaolefins .(PAO). Group V baseoils inctude. all other base oils~not included in Group I, II, III, or IV. Group III base oils are preferred.
. 5 TABLE.I.
SATURATES, SULFUR:AND VISCOSITY INDEX OF GROUP I,.II, III, IV AND
V BASE STOCKS
Saturates (As determined by ASTM Viscosity lndex D2007) Group (As determinedb.y ASTM D4294, Sulfur (As determined by ASTM
D2270) ASTM .D4297 or ASTM D3120) Less than 90 %o saturates and/or Greater than or equal to 80and Greater than to 0.03 %o~sulfur less,than 120 Greater than or equai to 90 %
II saturates, and less than or equal to Greater than or equal to 80 and 0.03- u sulfur less .than 120 Greater than or equal to -90 %
Ill saturates and. less than or e.qual to Greater than or equal to 1,20 0:03 Io sulfur iV. AII Polyalphaolefins (PAOs) V All others not included in.Groups I, 11, III,,-or IV
Natural lubricatirig oils may incf.ude. animal oils, vegetable oils (e.g., rapeseed oils, castor oils~and lard oil), petroieum oils, mineral.oils, and oils derived from coal or shale.
Synthetic oils may include hydrocarbon .oils and halo-substituted hydrocarbon oils such as polyinetized and inter-polyrnerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl~sulfides, as well astheir derivatives, .anal:ogues and homologues thereof; and the like. Synthetic lubricating oils also include. alkylene oxide polymers, interpolym.ers, copolymers and derivatives thereof"wherein the terminal hydroxyl. groups have been modified by esterification, etherification, etc. Another suitable class of ~synthetic lubricating oils comprise"s the esters:of d'icarboxylic acids with a variety of alcohols.
Esters, useful as synthetic oils also include those made from about-C5 to about C12 monocarboxylic acids and polyols and polyol ethers: Td=alkyl phosphate ester oils such as those ezernplifed by: tri-n-butyfphosphate and tri=iso-butyl phosphate are also:suitable for use-as, base oils.
Silicon=.based oil& (such as the polyalkyl-,, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise:another useful class of synthetic lubricatirig oits. Othet'synthetic Iubricatirig oils include liquid, esters of phosphorus-containing acids, polymeric, tetrahydrofurans, polyalphaolefins, and the:like.
The base oil may be derived from unrefined, refined, rerefined oils; or mixtures thereof. Unrefined oils are obtained:directly from a natural sourceor synthetic ;source (e:g.,_ coal; shale, or tar sand bitumen); without further purif'ication or treatment: Examples of unrefined oils::include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directlyfro.m distillation, or an ester oil,obtained directly from an.:esterification process, each of-which may then be used without'further treatment. Refined oils:are-similar to the unrefined oils except:that refined oilshave been treated, in one or more purification steps to =improve. one or more properties. Suitable purification techniques include distillation, hydrocracking, hydrotreating, dewaxing,,solvent.extraction, acid or base extraction, f ltration, and percolation, all of which are known to those skilled.
in the art:: Rerefined oils are obtained b.y tr"eating used oils in processes similar to those used to obtain the refined oils. These rerefined oils.are also known as reclaimed or reproce"ssed oils and often are additionally processed by techniques for removal of spent additives and oil.breakdown products.
Base oil derived f'rom the hydroisomerization of wax.may also be used, either alone or in combination with the aforesaid natural.and/or synthetic base oil.
Such waxisomerate oil is produced by the hydroisomerization of natural or synthetic waxes ormixtures thereof:over-a hydroisomerization catalyst.
It is preferred'to use:a major amount::of base oil in tlie:lubricating oil composition of the p.resent invention. A major amount of base oil as defined herein comprises about 40 wt'% or more. Preferred amounts of base oil comprise about 40 wt %a:
to about:97 wt /a, preferably greater than about 50 wt %o to about.97 wt %,, more preferably about 60 wf %o to about 97 wt %. and most preferably about 80 wt %
to about 95 wt:Wof the:lubricating oil composition. (When weight percent is used herein, it is referring'to weig"ht percent of the,lubricating oil unless otherwise specified.) The amount of the:mixture of zinc dithiophosphates employed in the lubricating oil.compvsition of the present'invention will be in.a minor amount compared to the: base oil of. lubricatingviscosity: Generally, it will be in an amount from about 0.1 wt:% to:about 1'.5 wt%; preferably fromabout 0:3 wt % to about 1.2 wt %and more preferably frorn about 0.5 wt % to about 1.0 wt %, based on the total weight of the lubricating oil composition.
The lubricating oil composition: of the.present invention will contain from about 0.05 wt.% to about 1.2,wt preferabl,y.from about 0:1 wt'% to about 0.7 wt and more preferably from about 0:2 wt % to about 0:5 wt %.of a.zinc primary dia.lkyl dithiophosphate, based on the total weight of the-lubricating.oil composition.
The lubricating oil composition;of the ptes'entinvention will contain from about 0.05. wt %: to about.1.2 wt preferably from about 0.1 wt % to about 0.7 wt %, and more preferably,from about, 0.2 wt:% to abou. t 0:5 wt % of .a zinc.
secondary dialkyl dithiophosphate, based.on the`total weight::of the lubricating oil composition..
The lubricating oil composition of the p"resent invention will contain from about 0.02 wt;%o; to about:0.7 wt %,;preferably from about 0.05 wt % to. about 0.5 wt %, and.:more preferably from about.0:1 wt % to about 0.3 wt %o of a zinc primary diaryl dithioph'osphate,.based. on the total weight of the lubricating oil composition.
In a preferred ernbodiment, the lubricating oil composition of the present invention "will have a phosphorus content preferably less than about 0.05 wt based on the;aotaf weight of'ttie lubricating oil composition.
In another erimbodiment, the lubricating oil composition.of the present:
invention will further have a.-sulfur content less=than about 0:5 wt % and, preferably less Ahan.,about 0,2 wt %, based on thetotal weight of the lubricating oil composition and'the total. sulfated ash content in the. lubricating.oil composition of the present invention is less than about 1.2 wt %, preferabty; less than about 1.0 wt %, and more.preferably1ess than:about 0.8 wt %, based on the.total weight of the ,lubricating oil:cornposition.
Other Additive Components Ttie following additive compon.ents are examples,of components, that can.be favorably employed in combination with the lubricating additive. of the present invention. These examples of additives are; provided to illustrate the present invention, but they are nof intended to limit it, (A) Detergents are,additivesdesigned to'hold the acid-neutralizing..co.mpounds in solution in-theoil:.They are usually alkaline and, react with the strong acids (sulfuric=and:nitric) which for"rnduring the combustion:of the fuel and which would cause corr.osion:to the engine: parts if left unchecked. Examples are carboxylates, sulfurize.d or unsulfurized,:alkyl' or alkenyl phenates, alkyl or alkenyl:arortiatic sulfonates; sulfurized or unsulfurized metal salts of multi-hydroxy alkyl or=alkenyl :aromatic compounds;:alkyl oralkenyl hydroxy aromatic sulfonates, sulfurized or unsulfurized alkyl or alkenyl naphthenates, rnetal.-salts of: alkanoic,acids, nietal salts:of;an alkyl or alkenyl multiacids and cherriical and physical,mixtures thereof.
(B) Dispersants are additives. that keep soot and combustion products in suspension in.the. body of the oil and therefore prevent deposition as sludge or lacquer Typically; the ashless dispersant"s ate nitrogen=containing dispersantsformed by reacting alkenyl:.succinic.acid anhydride with an amine.
Examples are alkenyl succinirnides, alkenyl succinimides modified with other organic cornpounds, e.g:;; ethylene carbonating post-treatment and alkenyl succinimides-modified with.boric- acid', polys.uccinimides, alkenyl succinic ester.
(C) .Oxidation Inhibitors;
T) Phenoltype (phenolic) oxidation i'nhibitors: 4;4'-methylenebis (2;6-di-tert-butylphenol);4,4'-bis(2,6-di-tert-butylphenol), 4;4'-bis(2-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6=tert-butyl-phenol), 4,..4'=
butyldienebis(3-cnethyl-6-tert=butylphenol), 4,4'-isopiopylidenebis(2,6-di-tert-.butytpheno.I), 2,2'-methylenebis(4-methyl=6=nonylphenol), 2,2'-isobutyldiene-bis(4,6-d'imethylphenol), 2,2'-rrmethylenebis(4-methyl-6-cyclohexylphenol), 2,6-d;i-tert-butyt-4-methylphenol, 2;6-di=tert-butyl-4-ethylphenol, 2,4-dirnethyl-tert-butyt=phenol, :2,6-di-tert-a-dimethylamino-p-cresol, 2;6-di-tert-4(N,N' dimethylarninomethylphenol);4,4'-thiobis(2-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl=6-tert=butylphenol), bis(.3-methyl-4-hydroxy-5-tert-butyt0enzyl)-sulfide and bis (315-di=tert-butyf-4-hydroxybenzyl).
2) Diphertylamine type:oxidation inhibitor: alkylated diphenylamine, phenyl=a-haphthylarnine and alkylated a-naphthylamine..
3) Other types: metal dithiocarbarnate (e;g., zinc dithiocarbamate) and rnethylenebis(dibutyldithiocarbamate).
(D);Rust Inhibitors (Anti-rust'agents):
1) Nonionicpolyoxyethylene surface active agents: polyoxyethylene lauryl ether;
polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octyiphenyl ether; p.olyoxyethyle.ne octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene:sorbitol mono=oleate akid polyethylene glycol monooleate.
2) Other compounds: stearic acid:and:otherfatty acids, diearboxylic acids, metal soaps, fatty acid amine salts; metal salts of heavy;sulfonic acid; partial carboxylicacid ester of polyhydric alcohol and phosphoric ester.
(E) Demulsifiers: addition product of alkylphenol and-ethyleneoxide, polyoxyethylene alkyl ether and polyoxyethylene sorbitane ester.
(F) 'Extreme pressure agents (EP agents): sUlfurized oils, diphenyl sulfide, methyl trich(orbstearate, chlorinated naphthalene, benzyl iodide, fluoroalkylpolysiloxane and lead naphthenate..
(G) Fr'iction modifiers: ,fatty alcohol, fatty, acid, amine, borated ester and other esters.
-(H) Multifunctional additives:: sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum organo phosphorodithioate, oxymolybdenum monoglyceride, oxymolybdenum diethylate amide, amine-molybdenum complex compound and sulfur-containing molybdenum complex compound.
(I) Viscosity IndexJmprovers (VII): polymethac ,rylate type.polymers, ethylene-prop.yle.ne copolymers, :styrene-isoprene copolymers, hydrogenated styrene-20" isoprene copolymers, hydrogenated star.-branched polyisoprene, polyisobutylene, hydrogenated star=branched styrene-isoprene copolymer and dispersant;.type; viscosity index improvers.
(J) Pour point depressants: polyrriethyl methacrylates; alkyfinetha.crylates and, dialkyi fumarate-vinyl acetate copolymers.
(K) Foam Inhibitors; alkyl methacrylatepolymers and dimethyl silicone-polymers.
EXAMPLES
The,present invention will be further illustrated by,the following examples, Which set forth particularly advantageous method embodiments. While-the.Examples are;.provid.ed:to, illustrate thepresent inWention, they are notintended to limit it.
Example 1 The low phosphorus lubricating oil cornpositionof the present invention was prepared by blending a 0:78 wt % rnixture:of zirtc` bis(0,O'-di-(2-ethyl-l-hexyl) dithiophosphate (0.24 wt.%o, primary.), zinc bis(O,O'=di-(2-butyl/4-methyl-2-pentyl) dithiophosphate (0:,15 wt %, secondary).and,zinc:bis(O,O'-di-(dodecylphenyl) dithiophosphate (0.39 wt%; aryl),with a G>=oup II base oil of lubricating viscosity.
The. ratio ofzinc:bis(O,O'-di(2-ethyl-l-hexyl) dithiophosphate to zinc bis(O,O'-di-(2-butyl/4-methyl=2=pentyl) dithiophosphate was about 1:1, based on the phosphorus:coritent. The...ratio of'the mixture of zinc bis(O;O'=di(2=ethyl-1-hexyl) dithiophosphate ani,l,zinc bis(O,O'-di-(2-butyll4-methyl-2-pentyl) dithiophosphate to zinc bis(O;O'-di-(dodecylphenyl) dithiophosphate was about 2:1, based on the phosphorus content. The resulting ratio of the three-way mixture of zinc bis(O.;O'-.di(2-ethyl-1-hexyl),dithiophosphate to zinc bis(O,0'-di=(2=butyl/4-methyl-2-pentyl) dithiophosphate.to zinc bis(0,Q'=di-(dodecylphenyl),.dithiophosphate was 1:1:1, based on the. ,phosphorus content: The.'wt. % of phosphorus-in the prepared lubricating Oil composition was less than about:0.06 wt % based on the total weight of the Jubri,cating oil composition. Further, the sulfur content and sulfated -ash content~were 0.2 wt % and 0.8 wt.%o, respectively, based on the total weight of the lubricating,oil''composition..The wt % balance of'the lubricating oil composition containing a 1200molecular weight (MW) isobutyleoe bis-succinimide dispersant, a~ 2300.MW isobutylene bis-succinimide dispersant, a neutral sulfonate detergent; an overbased calcium. phenate, 'a molybdenum oxidation irihibitor, diphenylamine oxidation inhibitor, aphenolic oxidation inhibitor, anti=foam agent, pourpoinf depi=essant:and a viscosity index improver to complete the 100 Wt %lubricating oil composition:.
Comparative Example.A
Comparative Example.A was prepared according.to Example 1 except.only about 1.16"wt % aryl zinc bis(O;O'-di-(dodecylphenyl) dithiophosphate was added, instead of.the mixture of.zincbis(Q,0'-di=(2=ethyl-.1-hexyl) dithiophosphate, zinc bis(O,O"-di-(2-butyl/4-methyl-2=pentyl) dithiophosphate and zinc bis(O,0'-di-(dodecylphenyl) dithiophosphate_ Coiiiparative Example B
Comparative Exanlple B was prepared accordingto Example 1 except only about 0.46 wt % zinc bis(O,O'-di-(2-butyU4-me,thyl-2-pentyl) dithiophosphate was :added, instead of the mixture of zinc bis(O;O'-di-(2-ethyl-1-hexyl) dithiophosphate; zinc bis(O,O'-di-(2-butyl/4-methyl-2-pentyl) dithiophbsphate and zinc bis(O,O'-di-(dodecylp.hen,yl) dithiophosphate.
Comparative -:Exarnple C
1.5 Comparative Example C was.:prepared according to Example 1 except only about 0.71 wt % zinc.bis(O,O'-di-(2=ethyl-1-hexyl.) dithiophosphate was added, instead of the mixture of zinc-, bis(O,O'=di-(2-ethyl=1-hexyl) dithiophosphate, zinc bis(O,O'-di-(2-butyl/4=methyl-2-pentyl) dithi,op,hospha.te and zinc.bis(O,O'-di-(dodecylphenyl) dithiophosphate.
Comparative Example D.
Comparative:ExampleDvas prepared according'to Example 1$xcept about 0.81. wt %of a mixture. of zinc bis (O,0'-di-(2-butyl/4=methyl-2-pentyl) dithiophosphate and zinc:bis (O;O'~di-(dodecytphenyl)'dithiophosphate in about a 1:1 ratio were added, instead of,the mixture of zinc bis(O,0'-di=(2-ethy.l-1-hexyl) dithiophosphate,: zinc bis(.O,O'-di-(2-butyl/4-methyl-2-pentyl) dithiophosphate and zinc bis.(O,O'-di-(d"odecylphenyl) dithiophosphate.
Comparative Example E
C.omparative Example E was pre.par:ed according. to Example '1 exceptabout 0:94 wt % of a rnixture of zi.nc bis(Q,O'-di-(2-~ethyl-1-hexyij dithiophosphate and zinc bis(O,O'-di-(dodecylphenyl) dithiophosphate in about a* 1:1 ratio vi-ere added, .35 instead. of `the mixture of zinG bis(O,O'-di-(2-ethyl-l-hexyl) dithiophosphate, :zinc bis(Q,O'-di-(2-butyl/4.=methyl=2-pentyl) dithiophosphate.and zinc bis(Q,O'-di-~(dodecyiphenyl) dithiophosphate:
.,Comparative Example F
C:omparatiVe Exanlple F was prepared according to EXample 1 except about 0.59 wt~%o of..a-mixture ofzinc bis(0;0'-di-(2-ethyl=1-hexyl) dithiophosphate and zinc bis(O,O'-di:=(2-butyl/4-methyl-2-pentyl) dithiophosphate.in about a 1:1 ratio were added, instead of the mixture.of zinc bis(O,O'-di-(2-ethyl-1=hexyl) dithiophosphate, zinc bis(O,O'-di-(2-butyl/4-methyl-2-pentyl) dithiophosphate and zinc bis(O,0'-di=(dodecylphenyl) dithiophosphate.
Each.formulation according to Example:1 and Compatative Example A-F were tested for lead corrosion using the High Temperature Corrosion Bench Test (HTCBT)(ASTM 06594) which is an industry, standard bench testto measure corrosion.performance of a motor oil;,.Briefly, four metal specimens of copper, Iead,.tin, and. phosphor,bronze,are immersed in a measured amount -of engine oil.
The oil, at::an elevated tem.perature, is blown with, air for, a period of time. When the test is completed, the lead specirnen and the.stressed oil are examined to detect corrosion and corrosionr products, respectively. A reference oil is tested with:each group of test,s; to verify test acceptabil.ity.
The-test results are surr.iniarized in Tabie II.
Table1I. HTCBT Results Example Comparative Examples 1 A. B C D E F
Lead, 48:4. 113.4 93.4 305 64.6 87.3 99.4 PPm These results demonstrate that the low phosphorus lubricating oil composition of the present.invention (Example 1) containing a m.ixture'of,iincprimary dialkyl dithiophosptiate; zinc secondary dialkyl dithiophosphate and zinc diaryl dithiophosphate.>in a 1`.1:1 ratio, and whereinthe phosphorus content of the lubricating: oil composition: is.less than 0:06 wt%, provides excellent lead corrosion;performance when compared to the.comparative examples not having 'a.mixtur.e of all three dithiophosphates. The amount of lead corrosion is significantly redueed. by the lubricating oil composition'of the present invention.
Claims (28)
1. A lubricating oil composition comprising a major amount of base oil of lubricating viscosity and a minor amount of a mixture of a zinc primary dialkyl dithiophosphate, a zinc secondary dialkyl dithiophosphate and a zinc diaryl dithiophosphate wherein the respective ratio, based on the phosphorus content, of the zinc primary dialkyl dithiophosphate to zinc secondary dialkyl dithiophosphate is from about 2:1 to about 1:2 and the ratio of the mixture of zinc primary dialkyl dithiophosphate and zinc secondary dialkyl dithiophosphate to zinc diaryl dithiophosphate is from about 6:1 to about 1:1 and wherein the lubricating oil composition has less than about 0.06 wt % total phosphorus content, based on the total weight of the lubricating oil composition.
2. The lubricating oil composition according to Claim 1, wherein the minor amount of the mixture of zinc primary dialkyl dithiophosphate, zinc secondary dialkyl dithiophosphate and zinc diaryl dithiophosphate is from about 0.1 wt % to about 1.5 wt %, based on the total weight of the lubricating oil composition.
3. The lubricating oil composition according to Claim 1, wherein the minor amount of the mixture of zinc primary dialkyl dithiophosphate, zinc secondary dialkyl dithiophosphate and zinc diaryl dithiophosphate is from about 0.3 wt % to about 1.2 wt %, based on the total weight of the lubricating oil composition.
4. The lubricating oil composition according to Claim 1, wherein the minor amount of the mixture of zinc primary dialkyl dithiophosphate, zinc secondary dialkyl dithiophosphate and zinc diaryl dithiophosphate is from about 0.5 wt % to about 1.0 wt %, based on the total weight of the lubricating oil composition.
5. The lubricating oil composition according to Claim 1, wherein the mixture contains from about 0.05 wt % to about 1.2 wt % zinc primary dialkyl dithiophosphate from about 0.05 wt % to about 1.2 wt % zinc secondary dialkyl dithiophosphate and from about 0.02 wt % to about 0.7 wt % zinc diaryl dithiophosphate, based on the total weight of the lubricating oil composition.
6. The lubricating oil composition according to Claim 5, wherein the mixture contains from about 0.1 wt % to about 0.7 wt % zinc primary dialkyl dithiophosphate, from about 0.1 wt % to about 0.7 wt % zinc secondary dialkyl dithiophosphate and from about 0.05 wt % to about 0.5 wt % zinc diaryl dithiophosphate, based on the total weight of the lubricating oil composition.
7. The lubricating oil composition according to Claim 6, wherein the mixture contains from about 0.2 wt % to about 0.5 wt % zinc primary dialkyl dithiophosphate, from about 0.2 wt % to about 0.5 wt % zinc secondary dialkyl dithiophosphate and from about 0.1 wt % to about 0.3 wt % zinc diaryl dithiophosphate, based on the total weight of the lubricating oil composition.
8. The lubricating oil composition according to Claim 1, wherein the primary alkyl group of the zinc primary dialkyl dithiophosphate has from about C1 to about C13 carbon atoms.
9. The lubricating oil composition according to Claim 8, wherein the primary alkyl group of the zinc primary dialkyl dithiophosphate has from about C3 to about C10 carbon atoms.
10. The lubricating oil composition according to Claim 9, wherein the primary alkyl group of the zinc primary dialkyl dithiophosphate has from about C6 to about C8 carbon atoms.
11. The lubricating oil composition according to Claim 1, wherein the secondary alkyl group of the zinc secondary dialkyl dithiophosphate has from about C3 to about C13 carbon atoms.
12. The lubricating oil composition according to Claim 11, wherein the secondary alkyl group of the zinc secondary dialkyl dithiophosphate has from about C3 to about C8 carbon atoms.
13. The lubricating oil composition according to Claim 12, wherein the secondary alkyl group of the zinc secondary dialkyl dithiophosphate has from about C3 to about C6 carbon atoms.
14. The lubricating oil composition according to Claim 1, wherein the aryl group of the zinc diaryl dithiophosphate has from about C6 to about C30 carbon atoms.
15. The lubricating oil composition according to Claim 14, wherein the aryl group of the zinc diaryl dithiophosphate has from about C6 to about C24 carbon atoms.
16. The lubricating oil composition according to Claim 15, wherein the aryl group of the zinc diaryl dithiophosphate has from about C6 to about C20 carbon atoms.
17. The lubricating oil composition according to Claim 1, wherein the respective ratio of zinc primary dialkyl dithiophosphate to zinc secondary dialkyl dithiophosphate is a range from about 3:2 to about 2:3, based on the phosphorus content.
18. The lubricating oil composition according to Claim 17, Wherein the respective ratio of zinc primary dialkyl dithiophosphate to zinc secondary dialkyl dithiophosphate is about 1:1, based on the phosphorus content.
19. The lubricating oil composition according to Claim 1, wherein the respective ratio of the mixture of zinc primary dialkyl dithiophosphate and zinc secondary dialkyl dithiophosphate to zinc diaryl dithiophosphate is a range from about 4:1 to about 1:1, based on the phosphorus content.
20. The lubricating oil composition according to Claim 19, wherein the respective ratio of the mixture of zinc primary dialkyl dithiophosphate and zinc secondary dialkyl dithiophosphate to zinc diaryl dithiophosphate is a about 2:1, based on the,phosphorus content.
21. The lubricating oil composition according to Claim 1, wherein the respective ratio of the mixture of zinc primary dialkyl dithiophosphate to zinc secondary dialkyl dithiophosphate to zinc diaryl dithiophosphate is 1:1:1, based on the phosphorus content.
22. The lubricating oil composition according to Claim 1, wherein the total phosphorus content of the lubricating oil composition in less than 0.05 wt %, based on the total weight of the lubricating oil composition.
23. The lubricating oil composition according to Claim 1, wherein the total sulfur content of the lubricating oil composition in less than 0.5 wt %, based on the total weight of the lubricating oil composition.
24. The lubricating oil composition according to Claim 23, wherein the total sulfur content of the lubricating oil composition in less than 0.2 wt %, based on the total weight of the lubricating oil composition.
25. The lubricating oil composition according to Claim 1, wherein the total sulfated ash content of the lubricating oil composition in less than 1.2 wt %, based on the total weight of the lubricating oil composition.
26. The lubricating oil composition according to Claim 25, wherein the total sulfated ash content of the lubricating oil composition in less than 1.0 wt %, based on the total weight of the lubricating oil composition.
27. The lubricating oil composition according to Claim 26, wherein the total sulfated ash content of the lubricating oil composition in less than 0.8 wt %, based on the total weight of the lubricating oil composition.
28. A method for improving lead corrosion, said method comprising operating an internal combustion engine with a lubricating oil composition comprising a major amount of base oil of lubricating viscosity and a minor amount of a mixture of zinc primary dialkyl dithiophosphate, zinc secondary dialkyl dithiophosphate and zinc diaryl dithiophosphate wherein the respective ratio, based on the phosphorus content, of the zinc primary dialkyl dithiophosphate to zinc secondary dialkyl dithiophosphate is from about 2:1 to about 1:2 and the ratio of the mixture of zinc primary dialkyl dithiophosphate and zinc secondary dialkyl dithiophosphate to zinc diaryl dithiophosphate is from about 6:1 to about 1:1 and wherein the lubricating oil composition has less than about 0.06 wt % total phosphorus content, based on the total weight of the lubricating oil composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/463,532 US20080039348A1 (en) | 2006-08-09 | 2006-08-09 | Low phosphorus lubricating oil composition having lead corrosion control |
| US11/463,532 | 2006-08-09 | ||
| PCT/US2007/075507 WO2008021901A2 (en) | 2006-08-09 | 2007-08-08 | A low phosphorus lubricating oil composition having lead corrosion control |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2659854A1 true CA2659854A1 (en) | 2008-02-21 |
| CA2659854C CA2659854C (en) | 2016-05-10 |
Family
ID=39051541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2659854A Expired - Fee Related CA2659854C (en) | 2006-08-09 | 2007-08-08 | A low phosphorus lubricating oil composition having lead corrosion control |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US20080039348A1 (en) |
| EP (1) | EP2049631B1 (en) |
| JP (1) | JP5345935B2 (en) |
| CA (1) | CA2659854C (en) |
| WO (1) | WO2008021901A2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110237474A1 (en) * | 2010-03-25 | 2011-09-29 | R.T. Vanderbilt Company, Inc. | Ultra Low Phosphorus Lubricant Compositions |
| JP5756353B2 (en) * | 2011-06-21 | 2015-07-29 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition |
| JP5771103B2 (en) * | 2011-09-16 | 2015-08-26 | 昭和シェル石油株式会社 | Lubricating oil composition |
| US20150299598A1 (en) * | 2014-04-18 | 2015-10-22 | Exxonmobil Research And Engineering Company | Method for improving antiwear performance and demulsibility performance |
| WO2019106817A1 (en) * | 2017-11-30 | 2019-06-06 | コスモ石油ルブリカンツ株式会社 | Lubricating oil composition |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3923669A (en) * | 1974-10-31 | 1975-12-02 | Sun Oil Co Pennsylvania | Antiwear hydraulic oil |
| US4116871A (en) * | 1977-06-29 | 1978-09-26 | Chevron Research Company | Preparation of phosphorus-containing acids and salts |
| US4975096A (en) * | 1988-09-09 | 1990-12-04 | Chevron Research Company | Long chain aliphatic hydrocarbyl amine additives having an oxyalkylene hydroxy connecting group |
| DE69004550T2 (en) * | 1989-12-27 | 1994-05-11 | Nissan Motor | Grease for homokinetic coupling. |
| ES2169785T3 (en) * | 1995-02-01 | 2002-07-16 | Lubrizol Corp | LUBRICANT COMPOSITION WITH LOW CONTENT IN ASHES. |
| US5972853A (en) * | 1997-11-12 | 1999-10-26 | Exxon Chemical Patents Inc. | Wear control with dispersants employing poly alpha-olefin polymers |
| DE69936203T2 (en) * | 1998-06-30 | 2008-01-31 | Chevron Phillips Chemical Co. Lp, Houston | POLYALPHAOLEFINS WITH IMPROVED OXIDATION STABILITY AND METHOD FOR THE PRODUCTION THEREOF |
| US6730638B2 (en) * | 2002-01-31 | 2004-05-04 | Exxonmobil Research And Engineering Company | Low ash, low phosphorus and low sulfur engine oils for internal combustion engines |
| US6696393B1 (en) * | 2002-08-01 | 2004-02-24 | Chevron Oronite Company Llc | Methods and compositions for reducing wear in internal combustion engines lubricated with a low phosphorus content lubricating oil |
| EP1403359A1 (en) * | 2002-09-13 | 2004-03-31 | Infineum International Limited | Combination of a low ash lubricating oil composition and low sulfur fuel |
| US20040087451A1 (en) * | 2002-10-31 | 2004-05-06 | Roby Stephen H. | Low-phosphorus lubricating oil composition for extended drain intervals |
| US7056871B2 (en) * | 2003-04-25 | 2006-06-06 | Chevron Oronite Company Llc | Lubricating oil composition which decreases copper corrosion and method of making same |
| US20040220059A1 (en) * | 2003-05-01 | 2004-11-04 | Esche Carl K. | Low sulfur, low ash, low and phosphorus lubricant additive package using overbased calcium oleate |
| JP2005306913A (en) * | 2004-04-16 | 2005-11-04 | Chevron Texaco Japan Ltd | Engine lubricating oil composition |
| JP4612393B2 (en) * | 2004-10-29 | 2011-01-12 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition suitable for lead-containing metal materials |
-
2006
- 2006-08-09 US US11/463,532 patent/US20080039348A1/en not_active Abandoned
-
2007
- 2007-08-08 WO PCT/US2007/075507 patent/WO2008021901A2/en active Application Filing
- 2007-08-08 CA CA2659854A patent/CA2659854C/en not_active Expired - Fee Related
- 2007-08-08 JP JP2009523982A patent/JP5345935B2/en not_active Expired - Fee Related
- 2007-08-08 EP EP07840789A patent/EP2049631B1/en not_active Expired - Fee Related
-
2013
- 2013-01-22 US US13/746,724 patent/US20130137616A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| CA2659854C (en) | 2016-05-10 |
| WO2008021901A3 (en) | 2008-04-17 |
| US20130137616A1 (en) | 2013-05-30 |
| JP2010500457A (en) | 2010-01-07 |
| EP2049631A4 (en) | 2011-09-14 |
| EP2049631B1 (en) | 2013-03-13 |
| JP5345935B2 (en) | 2013-11-20 |
| US20080039348A1 (en) | 2008-02-14 |
| WO2008021901A2 (en) | 2008-02-21 |
| EP2049631A2 (en) | 2009-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2802284C (en) | Uses and compositions | |
| EP2633009B1 (en) | Non-aqueous lubricant and fuel compositions comprising fatty acid esters of hydroxy- carboxylic acids, and uses thereof | |
| US6642191B2 (en) | Lubricating oil additive system particularly useful for natural gas fueled engines | |
| EP3303528B1 (en) | Borated polyol ester of hindered phenol antioxidant/friction modifier with enhanced performance | |
| CN104919027B (en) | Alkaline ashless additive | |
| EP3253853B1 (en) | Use of a boron-containing additive as an inhibitor of lead corrosion | |
| EP1364955B1 (en) | Phosphorothionates | |
| CN103502403A (en) | Molybdenum dialkyldithiocarbamate compositions and lubricating compositions containing the same | |
| CA2772646A1 (en) | Natural gas engine lubricating oil compositions | |
| GB2103651A (en) | Reduction of fuel consumption of internal combustion engines and composition therefor | |
| EP3310885B1 (en) | Multifunctional molybdenum containing compounds, method of making and using, and lubricating oil compositions containing same | |
| CA2659854A1 (en) | A low phosphorus lubricating oil composition having lead corrosion control | |
| EP2825621B1 (en) | Friction modifier composition for lubricants | |
| US20060276351A1 (en) | Molybdenum-containing lubricant for improved power or fuel economy | |
| US20040142827A1 (en) | Sulfur containing lubricating oil additive system particularly useful for natural gas fueled engines | |
| EP1730107B1 (en) | Dithiocarbamate derivatives useful as lubricant and fuel additives | |
| CN105296062A (en) | Preparation method of anti-oxidative natural gas engine lubricating oil | |
| AU2003293266B2 (en) | Molybdenum-containing lubricant for improved power or fuel economy | |
| JP2006524263A5 (en) | ||
| WO2023148697A1 (en) | Lubricating engine oil for hybrid or plug-in hybrid electric vehicles | |
| EP2816098A1 (en) | Use of a sulfur compound for improving the oxidation stability of a lubricating oil composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20220301 |
|
| MKLA | Lapsed |
Effective date: 20200831 |