Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/102—Aliphatic fractions
• • 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
  • C10M2207/26—Overbased carboxylic acid salts
  • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
• • 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
  • C10M2219/046—Overbasedsulfonic acid salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
  • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
  • C10M2219/066—Thiocarbamic type compounds
  • C10M2219/068—Thiocarbamate metal salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/045—Metal containing thio derivatives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
  • C10M2227/09—Complexes with metals
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/12—Groups 6 or 16
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/12—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
• • 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/72—Extended drain
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines

Definitions

• the present invention relates to lubricating oil compositions. More particularly, the present invention relates to lubricating oil compositions for use in engines comprising emission control systems.
• exhaust gas after-treatment devices may include exhaust gas recirculation arrangements and cooled exhaust gas recirculation arrangements, catalytic converters, which can contain one or more oxidation catalysts, NO x storage catalysts, and/or NH 3 reduction catalysts and/or a particulate trap. OEM's are also looking at using selective catalytic reduction (SCR) systems to further reduce NO x emissions.
• SCR selective catalytic reduction
• Oxidation catalysts can become poisoned and rendered less effective by exposure to certain elements/compounds present in engine exhaust gasses, particularly by exposure to phosphorus and phosphorus compounds introduced into the exhaust gas by the degradation of phosphorus-containing lubricating oil additives.
• Reduction catalysts are sensitive to sulfur and sulfur compounds in the engine exhaust gas introduced by the degradation of both the base oil used to blend the lubricant, and sulfur-containing lubricating oil additives.
• Particulate traps can become blocked by metallic ash, which is a product of degraded metal-containing lubricating oil additives.
• OEM's also require lubricating oil compositions to be formulated to reduce the presence of detrimental materials in the exhaust gas stream. At the same time, the selected lubricating oil composition must provide adequate lubricant performance, including adequate wear protection and detergency.
• European patent application 1 167 497 A2 discloses a lubricating oil composition having restricted sulfur, phosphorous and sulfated ash content comprising an ashless dispersant with a certain nitrogen content, a metal-containing detergent containing an organic acid metal salt selected from the group comprising an alkali or alkaline earth metal salt of an alkyl salicylic acid and an alkali or alkaline earth metal salt of an alkylphenol derivative having a Mannich base structure providing a certain sulphated ash content, a zinc dialkyldithiophosphate providing a specified phosphorus amount and an oxidation inhibitor.
• Lubricating oils formulated in accordance with this patent application are stated to exhibit good high temperature detergency despite the lower sulfur, phosphorus and sulphated ash levels of the compositions.
• a lubricating oil composition having a phosphorus content of up to 0.12 wt %, a sulfated ash content of up to 1.2 wt % comprising, (a) a major amount of an oil of lubricating viscosity; (b) an alkali metal or alkaline earth metal alkyl salicylate lubricating oil detergent providing from 7-15 mmol of salicylate soap per kilogram of lubricating oil composition; (c) one or more dispersants providing the lubricating oil composition with from at least 0.12 wt % to 0.20 wt % atomic nitrogen, based on the weight of the lubricating oil composition, and (d) a dispersant-viscosity modifier.
• a method of lubricating a vehicle engine comprising an exhaust gas recirculation (EGR) system comprising use in that engine of a lubricating oil composition according to the first aspect of the invention.
• EGR exhaust gas recirculation
• the engine further comprises a selective catalytic reduction (SCR) system.
• SCR selective catalytic reduction
• the oil of lubricating viscosity may be selected from Group I, II, III, IV or V base stocks, synthetic ester base stocks or mixtures thereof.
• the base stock groups are defined in the American Petroleum Institute (API) publication “Engine Oil Licensing and Certification System”, Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998.
• the base stock will have a viscosity preferably of 3-12, more preferably 4-10, most preferably 4.5-8 mm 2 /s (cSt.) at 100° C.
• Esters useful as synthetic base stock oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
• the oil of lubricating viscosity comprises less than 50 wt % of a Fischer-Tropsch base oil, suitably less than 30 wt %, preferably less than 10 wt % and most preferably substantially no Fischer-Tropsch base oil; wherein substantially no Fischer-Tropsch base oil means no more than an impurity amount.
• the present invention requires the presence of at least one alkali metal or alkaline earth lubricating oil salicylate detergent.
• the metal salicylate detergent may be C 8 -C 30 alkyl salicylates or mixtures thereof, with C 10 -C 20 alkyl salicylates being particularly preferred.
• the salicylate detergent will be a calcium and/or magnesium salicylate and will have a Total Base Number at 100% active mass (TBN) between 10 and 1000, more preferably between 20 and 850.
• TBN Total Base Number at 100% active mass
• the most preferred detergent for use in this invention is one or a mixture of overbased calcium alkyl salicylate detergents having a TBN between 300 and 600.
• the metal salicylate detergent comprises substantially no magnesium alkyl salicylate detergent.
• the amount of metal salicylate detergent used can vary broadly, but typically will be from about 0.1 to about 5 wt. %, preferably 0.5 to 1.5 wt. % based on the total weight of the composition, so as to provide from 7-15 mmoles of metal salicylate detergent per kilogram of the finished oil composition.
• the amount of metal salicylate detergent used in the present invention provides the composition with at least 8 mmol soap per kilogram of the finished oil composition.
• the amount of metal salicylate detergent used in the present invention provides the composition with no more than 11 mmol soap per kilogram of the finished oil composition.
• the metal salicylate detergent provides greater than 0.3 mass %, preferably at least 0.4 mass % metal as sulphated ash to the lubricating oil composition.
• the metal salicylate may be the sole metal lubricating oil detergent present in the lubricating oil compositions of the invention.
• other metal. containing detergents such as metal sulfonates or phenates, may be present in the lubricating composition.
• the lubricating oil composition comprises a mixture of detergent types
• the lubricating oil composition suitably comprises a mixture of metal salicylate and metal sulphonate detergents.
• the additional detergents may be either calcium or magnesium metal salts.
• the additional detergents are calcium metal salts and the lubricating oil composition comprises substantially no magnesium metal salts.
• the salicylate detergent provides the majority of the detergent additive in the lubricating oil composition.
• substantially no magnesium metal salt detergent and substantially no magnesium alkyl salicylate detergent it is meant no more than an impurity amount, such as an amount providing less than 50 ppm magnesium preferably less than 30 ppm magnesium and most preferably less than 10 ppm magnesium.
• Metal salts of organic acids typically used as lubricating oil detergents are present as stable colloidal dispersions of salt in oil.
• the components are generally made by neutralizing the organic acid with a strong metal base in the presence of process aids.
• the organic acid is neutralized with a strong metal base in the presence of an acidic gas (often carbon dioxide).
• an acidic gas often carbon dioxide
• the amounts of carbonate, sulfonate, and phenolic hydroxide present in a lubricant are inferred from the amounts present in the individual components that are blended to make the finished lubricant. And those amounts are in turn inferred from the charge ratios of raw materials used to make the detergents or by resort to analytical methods that can determine detectable moieties allowing inference of the remaining moieties.
• the moles of metal salt of an organic acid present can be determined directly in some cases and in others must be derived.
• the salt is a calcium sulfonate
• direct analysis is possible using the liquid chromatography method described in ASTM 3712.
• the moles of salt must be derived.
• titrimetry including two phase titrimetric methods, total acid number (TAN) as determined using ASTM D664, dialysis and other well known analytical techniques allow determination of the organic salt content.
• TAN total acid number
• phenates and carboxylates including salicylates
• the total amount of metal present is conveniently determined by inductively coupled plasma atomic emission spectrometry—ASTM D4951.
• Metal ratio is defined as the total amount of metal present divided by the amount of metal in excess of that required to neutralize any organic acid present, i.e., the amount of metal neutralizing inorganic acids. Metal ratios are quoted by manufacturers of commercial detergents and can be determined by a manufacturer having knowledge of the total amount of salts present and the average molecular weight of the organic acid.
• the amount of metal salt present in a detergent may be determined by dialyzing the detergent and quantifying the amount of the residue. If the average molecular weight of the organic salts is not known, the residue from the dialyzed detergent can be treated with strong acid to convert the salt to its acid form, analyzed by chromatographic methods, proton NMR, and mass spectroscopy and correlated to acids of known properties.
• the detergent is dialysed and then residue is treated with strong acid to convert any salts to their respective acid form.
• the hydroxide number of the mixture can then be measured by the method described in ASTM D1957. If the detergent contains non-phenolic hydroxyl groups on the phenolic compound (e.g., alcoholic derivatives of ethylene glycol used in manufacture of commercial phenates or carboxylic acid groups on salicylic acid), separate analyses must be conducted to quantify the amounts of those hydroxyl groups so that the hydroxide number determined by ASTM D1957 can be corrected. Suitable techniques to determine the quantity of non-phenolic hydroxyl groups include analyses by mass spectroscopy, liquid chromatography, and proton NMR and correlation to compounds having known properties.
• non-phenolic hydroxyl groups on the phenolic compound e.g., alcoholic derivatives of ethylene glycol used in manufacture of commercial phenates or carboxylic acid groups on salicylic acid
• a second method for deriving the number of moles of metal salt of an organic acid present assumes that all of the organic acid charged to make the component is in fact converted to the salt.
• the two methods can give slightly different results, but both are believed to be sufficiently precise to allow determination of the amount of salt present to the precision required to practice the present invention.
• the total amount of detergent present is limited by the maximum 1.2 wt % sulfated ash content of the finished oil composition.
• the total soap content of the lubricating oil is suitably no more than 1.5 wt %, preferably no more than 1.2 wt % and more preferably no more than 1.0 wt %.
• the total soap content of the lubricating oil composition is suitably at least 0.7 wt %, preferably at least 0.75 wt %.
• An ashless dispersant generally comprises an oil soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
• the dispersants comprise amine, alcohol, amide, or ester polar moieties attached to the polymer backbone often via a bridging group.
• the ashless dispersant of the present invention may be, for example, selected from oil soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of long chain hydrocarbons, long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine.
• the most common dispersant in use is the well known succinimide dispersant, which is a condensation product of hydrocarbyl-substituted succinic anhydride and a poly(alkyleneamine). Both mono-succinimide and bis-succinimide dispersants (and mixtures thereof) are well known.
• Preferred groups of dispersant include polyamine-derivatized poly ⁇ -olefin, dispersants, particularly ethylene/butene alpha-olefin and polyisobutylene-based dispersants.
• Particularly preferred are ashless dispersants derived from polyisobutylene substituted with succinic anhydride groups and reacted with polyethylene amines, e.g., polyethylene diamine, tetraethylene pentamine; or a polyoxyalkylene polyamine, e.g., polyoxypropylene diamine, trimethylolaminomethane; a hydroxy compound, e.g., pentaerythritol; and combinations thereof.
• One particularly preferred dispersant combination is a combination of (A) polyisobutylene substituted with succinic anhydride groups and reacted with (B) a hydroxy compound, e.g., pentaerythritol; (C) a polyoxyalkylene polyamine, e.g., polyoxypropylene diamine, or (D) a polyalkylene diamine, e.g., polyethylene diamine and tetraethylene pentamine using about 0.3 to about 2 moles of (B), (C) and/or (D) per mole of (A).
• Another preferred dispersant combination comprises a combination of (A) polyisobutenyl succinic anhydride with (B) a polyalkylene polyamine, e.g., tetraethylene pentamine, and (C) a polyhydric alcohol or polyhydroxy-substituted aliphatic primary amine, e.g., pentaerythritol or trismethylolaminomethane, as described in U.S. Pat. No. 3,632,511.
• Mannich base condensation products Another class of ashless dispersants comprises Mannich base condensation products. Generally, these products are prepared by condensing about one mole of an alkyl-substituted mono- or polyhydroxy benzene with about 1 to 2.5 moles of carbonyl compound(s) (e.g., formaldehyde and paraformaldehyde) and about 0.5 to 2 moles of polyalkylene polyamine, as disclosed, for example, in U.S. Pat. No. 3,442,808.
• carbonyl compound(s) e.g., formaldehyde and paraformaldehyde
• Such Mannich base condensation products may include a polymer product of a metallocene catalyzed polymerization as a substituent on the benzene group, or may be reacted with a compound containing such a polymer substituted on a succinic anhydride in a manner similar to that described in U.S. Pat. No. 3,442,808.
• Examples of functionalized and/or derivatized olefin polymers synthesized using metallocene catalyst systems are described in the publications identified supra.
• the dispersant can be further post treated by a variety of conventional post treatments such as boration, as generally taught in U.S. Pat. Nos. 3,087,936 and 3,254,025. Boration of the dispersant is readily accomplished by treating an acyl nitrogen-containing dispersant with a boron compound such as boron oxide, boron halide boron acids, and esters of boron acids, in an amount sufficient to provide from about 0.1 to about 20 atomic proportions of boron for each mole of acylated nitrogen composition.
• Useful dispersants contain from about 0.05 to about 2.0 mass %, e.g., from about 0.05 to about 0.7 mass % boron.
• the boron which appears in the product as dehydrated boric acid polymers (primarily (HBO 2 ) 3 ), is believed to attach to the dispersant imides and diimides as amine salts, e.g., the metaborate salt of the diimide.
• Boration can be carried out by adding from about 0.5 to 4 mass %, e.g., from about 1 to about 3 mass % (based on the mass of acyl nitrogen compound) of a boron compound, preferably boric acid, usually as a slurry, to the acyl nitrogen compound and heating with stirring at from about 135° C. to about 190° C., e.g., 140° C.
• the boron treatment can be conducted by adding boric acid to a hot reaction mixture of the dicarboxylic acid material and amine, while removing water.
• Other post reaction processes commonly known in the art can also be applied.
• the dispersant may also be further post treated by reaction with a so-called “capping agent”.
• a so-called “capping agent” nitrogen-containing dispersants have been “capped” to reduce the adverse effect such dispersants have on the fluoroelastomer engine seals.
• Numerous capping agents and methods are known. Of the known “capping agents”, those that convert basic dispersant amino groups to non-basic moieties (e.g., amido or imido groups) are most suitable.
• alkyl acetoacetate e.g., ethyl acetoacetate (EAA)
• EAA ethyl acetoacetate
• the dispersant is a thermally maleated dispersant fowled by reacting a polyalkenyl-substituted mono- or dicarboxylic acid, anhydride or ester; and a polyamine, having from greater than about 1.3 to less than about 1.7 mono- or di-carboxylic acid producing moieties per polyalkenyl moiety and wherein said polyalkenyl moiety has a molecular weight distribution (M w /M n ,) of from 1.5 to 2.0 and a number average molecular weight (M n ) of from about 1800 to about 3000.
• M w /M n molecular weight distribution
• M n number average molecular weight
• the ashless dispersant is suitably present in an amount of from 4 to 10 wt. %, preferably about 5 to 8 wt. % on a 100% active matter basis.
• the dispersant should provide the lubricating oil composition with at least 0.12 wt % of atomic nitrogen.
• the dispersant suitably provides the lubricating oil composition with no more than 0.2 wt % atomic nitrogen.
• the dispersant provides the lubricating oil composition with from 0.12 to 0.17 wt % atomic nitrogen.
• the nitrogen content provided to the lubricating oil composition by the dispersant can be determined in accordance with the procedures of ASTM D5762
• Preferred dispersants are borated or non-borated polyisobutenyl succinimide dispersants wherein the polyisobutenyl has a number average molecular weight (Mn) of about 400 to 3,000, preferably about 900 to 2,500.
• An embodiment of the present invention utilizes polyisobutenyl succinimide dispersants prepared using polyisobutylene prepared from a pure isobutylene stream or a Raffinate I stream to prepare reactive isobutylene polymers with terminal vinylidene olefins.
• these polymers referred to as highly reactive polyisobutylene (HR-PIB)
• HR-PIB highly reactive polyisobutylene
• HR-PIB highly reactive polyisobutylene
• HR-PIB highly reactive polyisobutylene
• the dispersant may comprise one dispersant or a combination of dispersants. If the dispersant comprises a combination of dispersants, the mixture suitable comprises a low molecular weight dispersant and a high molecular weight dispersant.
• a low molecular weight dispersant is a dispersant with a polymeric hydrocarbon backbone having a number average molecular weight (Mn) of about 500 to 1750.
• a high molecular weight dispersant is a dispersant with a polymeric hydrocarbon backbone having a number average molecular weight (Mn) of about 1800 to 3000.
• the total dispersant present in the lubricating oil composition comprises less than 40 mass %, less than 35 mass % or less than 30 mass % of low molecular weight dispersants.
• Polymer molecular weight can be determined by various known techniques.
• One convenient method is gel permeation chromatography (GPC), which additionally provides molecular weight distribution information (see W. W. Yau, J. J. Kirkland and D. D. Bly, “Modern Size Exclusion Liquid Chromatography”, John Wiley and Sons, New York, 1979).
• GPC gel permeation chromatography
• Another useful method for determining molecular weight, particularly for lower molecular weight polymers is vapor pressure osmometry (see, e.g., ASTM D3592).
• the viscosity index of the base stock is increased, or improved, by incorporating therein certain polymeric materials that function as viscosity modifiers (VM) or viscosity index improvers (VII).
• polymeric materials useful as viscosity modifiers are those having number average molecular weights (Mn) of from about 5,000 to about 250,000, preferably from about 15,000 to about 200,000, more preferably from about 20,000 to about 150,000.
• Suitable viscosity modifiers are polyisobutylene, olefin copolymers, such as copolymers of ethylene and propylene and higher alpha-olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, inter polymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene, and isoprene/butadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene and isoprene/divinylbenzene.
• Dispersant-viscosity modifiers are produced from grafting viscosity modifiers, such as those described above, with grafting materials such as, for example, maleic anhydride, and then reacting the grafted material with, for example, amines, amides, nitrogen-containing heterocyclic compounds or alcohol.
• grafting materials such as, for example, maleic anhydride
• dispersant-viscosity modifiers include amine, derivatized hydrocarbyl-substituted mono- or di-carboxylic acids in which the hydrocarbyl substituent comprises a chain of sufficient length to impart viscosity index improving properties to the compounds.
• the dispersant-viscosity modifier may be made from, for example, a polymer of a C 4 to C 24 unsaturated ester of vinyl alcohol or a C 3 to C 10 unsaturated mono-carboxylic acid or a C 4 to C 10 di-carboxylic acid derivatized with an unsaturated nitrogen-containing monomer having 4 to 20 carbon atoms; a polymer of a C 2 to C 20 olefin with an unsaturated C 3 to C 10 mono- or di-carboxylic acid derivatized with an amine, hydroxylamine or an alcohol; or a polymer of ethylene with a C 3 to C 20 olefin further reacted either by grafting a C 4 to C 20 unsaturated nitrogen-containing monomer thereon or by grafting an unsaturated acid onto the polymer backbone and then reacting carboxylic acid groups of the grafted acid with an amine, hydroxy amine or alcohol.
• Preferred dispersant-viscosity modifiers comprise an aromatic amine derivatized, maleic anhydride grafted polymer.
• a preferred aromatic amine is N-phenyl-1,4-phenylenediamine.
• the polymer is an ethylene-propylene copolymer.
• the polymer preferably has a number average molecular weight Mn of at least 5,000, preferably at least 8,000 and suitably at least 10,000.
• the polymer may have an Mn as high as 100,000, but is suitably no more than 60,000 and preferably around 40,000.
• Suitable commercially available dispersant-viscosity modifiers include, but are not limited to, HiTec 5777, available from Afton Chemicals, or multifunctional polymethacrylate viscosity modifiers such as the ViscoplexTM or AcryloidTM range of products available from Rohmax GmbH
• the present invention comprises a dispersant-viscosity modifier. It may be present in amounts of from 0.05 to 5 wt. %, preferably about 0.5 to 3 wt. % on an active matter basis.
• a lubricating oil composition according to the present invention may additionally comprise one or more standard crankcase lubricating oil additives; examples or which are discussed below.
• Antioxidants reduce the tendency of base stocks to deteriorate in service which deterioration can be evidenced by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces and by viscosity growth.
• they are suitably present in amount of from 0.1 to 5.0 wt.
• Suitable oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkylphenolthioesters having preferably C 5 to C 12 alkyl side chains, calcium nonylphenol sulfide, ashless oil soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons, alkyl substituted diphenylamine, alkyl substituted phenyl and napthylamines, phosphorous esters, metal thiocarbamates, ashless thiocarbamates and oil soluble copper compounds as described in U.S. Pat. No. 4,867,890.
• dialkyl substituted diphenylamines wherein the alkyl is C 4 -C 20 , such as dinonyl diphenylamine and the hindered phenols, such as isooctyl-3,5-di-tert-butyl-4-hydroxycinnamate and mixtures of same.
• Zinc dihydrocarbyl dithiophosphates are oil soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula:
• R and R′ may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals.
• Particularly preferred as R and R′ groups are alkyl groups of 2 to 8 carbon atoms.
• the radicals may, for example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.
• the total number of carbon atoms (i.e. R and R′) in the dithiophosphoric acid will generally be about 5 or greater.
• the zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
• ZDDP is the most commonly used antioxidant/antiwear agent in lubricating oil compositions for internal combustion engines, and in conventional passenger car diesel engines formulated to meet present European ACEA specifications.
• the lubricating oil compositions of the present invention suitably contain an amount of ZDDP (or other dihydrocarbyl dithiophosphate metal salt) that introduces about 0.02 to 0.12 wt. %, preferably 0.02 to 0.1 wt. %, more preferably 0.05 to 0.08 wt. % of phosphorus into the lubricating oil composition.
• the phosphorus content of the lubricating oil compositions is determined in accordance with the procedures of ASTM D5185.
• any suitable oil soluble organo-molybdenum compound may be employed.
• the molybdenum compound is thought to function both as an antiwear and antioxidant additive.
• dimeric and trimeric molybdenum compounds are used.
• oil soluble organo-molybdenum compounds are the dialkyldithiocarbamates, dialkyldithiophosphates, dialkyldithiophosphinates, xanthates, thioxanthates, carboxylates and the like, and mixtures thereof.
• Particularly preferred are molybdenum dialkylthiocarbamates.
• Suitable molybdenum dialkyldithiocarbamates include dimeric molybdenum dialkyldithiocarbamates such as those having the following formula:
• R 1 through R 4 independently denote a straight chain, branched chain or aromatic hydrocarbyl group; and X1 through X4 independently denote an oxygen atom or a sulfur atom.
• the four hydrocarbyl groups, R 1 through R 4 may be identical or different from one another.
• organo-molybdenum compounds useful in the lubricating compositions of this invention are trinuclear (trimeric) molybdenum compounds, especially those of the formula Mo 3 S k L n Q z and mixtures thereof wherein the L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble in the oil, n is from 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. At least 21 total carbon atoms should be present among all the ligands' organo groups, such as at least 25, at least 30, or at least 35 carbon atoms.
• the ligands are selected from the group consisting of
• organo groups are hydrocarbyl groups such as alkyl (e.g., in which the carbon atom attached to the remainder of the ligand is primary or secondary), aryl, substituted aryl and ether groups. More preferably, each ligand has the same hydrocarbyl group.
• hydrocarbyl denotes a substituent having carbon atoms directly attached to the remainder of the ligand and is predominantly hydrocarbyl in character within the context of this invention.
• substituents include the following:
• Hydrocarbon substituents that is, aliphatic (for example alkyl or alkenyl), alicyclic (for example cycloalkyl or cycloalkenyl) substituents, aromatic-, aliphatic- and alicyclic-substituted aromatic nuclei and the like, as well as cyclic substituents wherein the ring is completed through another portion of the ligand (that is, any two indicated substituents may together form an alicyclic group).
• aliphatic for example alkyl or alkenyl
• alicyclic for example cycloalkyl or cycloalkenyl
• Substituted hydrocarbon substituents that is, those containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbyl character of the substituent.
• suitable groups e.g., halo, especially chloro and fluoro, amino, alkoxyl, mercapto, alkylmercapto, nitro, nitroso, sulfoxy, etc.
• the organo groups of the ligands should have a sufficient number of carbon atoms to render the compound soluble in the oil.
• the number of carbon atoms in each group will generally range between about 1 to about 100, preferably from about 1 to about 30, and more preferably between about 4 to about 20.
• Preferred ligands include dialkyldithiophosphate, alkylxanthate, carboxylates, dialkyldithiocarbamate, and mixtures thereof. Most preferred are the dialkyldithiocarbamates. Those skilled in the art will realize that formation of the compounds requires selection of ligands having the appropriate charge to balance the core's charge (as discussed below).
• ligands which have net charges of +4. Consequently, in order to solubilize these cores the total charge among all the ligands must be ⁇ 4.
• monoanionic ligands are preferred. Without wishing to be bound by any theory, it is believed that two or more trinuclear cores may be bound or interconnected by means of one or more ligands and the ligands may be multidentate, i.e., having multiple connections to one or more cores. It is believed that oxygen and/or selenium may be substituted for sulfur in the core(s).
• Oil-soluble trinuclear molybdenum compounds are preferred and can be prepared by reacting in the appropriate liquid(s)/solvent(s) a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 .n(H 2 O), where n varies between 0 and 2 and includes non-stoichiometric values, with a suitable ligand source such as a tetralkylthiuram disulfide.
• a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 .n(H 2 O)
• oil-soluble trinuclear molybdenum compounds can be formed during a reaction in the appropriate solvent(s) of a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 .n(H 2 O), a ligand source such as tetralkylthiuram disulfide, dialkyldithiocarbamate, or dialkyldithiophosphate, and a sulfur abstracting agent such cyanide ions, sulfite ions, or substituted phosphines.
• a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 .n(H 2 O)
• a ligand source such as tetralkylthiuram disulfide, dialkyldithiocarbamate, or dialkyldithiophosphate
• a sulfur abstracting agent such cyanide ions, sulfite ions, or substituted phosphines.
• a trinuclear molybdenum-sulfur halide salt such [M′] 2 [Mo 3 S 7 A 6 ], where M′ is a counter ion, and A is a halogen such as Cl, Br, or I, may be reacted with a ligand source such as a dialkyldithiocarbamate or dialkyldithiophosphate in the appropriate liquid(s)/solvent(s) to form an oil-soluble trinuclear molybdenum compound.
• the appropriate liquid/solvent may be, for example, aqueous or organic.
• the ligand chosen must have a sufficient number of carbon atoms to render the compound soluble in the lubricating composition.
• oil-soluble does not necessarily indicate that the compounds or additives are soluble in the oil in all proportions. It does mean that they are soluble in use, transportation, and storage.
• a basic nitrogen compound selected from the group consisting of succinimide, a carboxylic acid amide, a hydrocarbyl monoamine, a phosphoramide, a thiophosphoramide, a Mannich base, a dispersant-viscosity index improver, or a mixture thereof.
• the sulfurized molybdenum containing compositions may be generally characterized as a molybdenum/sulfur complex of a basic nitrogen compound.
• the precise molecular formula of these molybdenum compositions is not known with certainty. However, they are believed to be compounds in which molybdenum, whose valences are satisfied with atoms of oxygen or sulfur, is either complexed by, or the salt of one or more nitrogen atoms of the basic nitrogen containing compound used in the preparation of these compositions.
• the lubricating compositions of the present invention may contain a minor amount of an oil soluble molybdenum compound. If present an amount of at least 10 ppm up to about 600 ppm of molybdenum from a molybdenum compound may be present in the lubricating oil composition. Preferably, about 10 ppm to 300 ppm of molybdenum from a molybdenum compound is used. More preferably, no more than 100 ppm of molybdenum from a molybdenum compound is used. These values are based upon the weight of the lubricating composition.
• the lubricating oil composition may contain an organic oil-soluble friction modifier.
• the friction modifier may make up about 0.02 to 2.0 wt. % of the lubricating oil composition.
• Friction modifiers include such compounds as aliphatic amines or ethoxylated aliphatic amines, aliphatic fatty acid amides, aliphatic carboxylic acids, aliphatic carboxylic esters of polyols such as glycerol esters of fatty acids as exemplified by glycerol oleate, which is preferred, aliphatic carboxylic ester-amides, aliphatic phosphonates, aliphatic thiophosphates, etc., wherein the aliphatic group usually contains above about eight carbon atoms so as to render the compound suitably oil soluble.
• aliphatic substituted succinimides formed by reacting one or more aliphatic succinic acids or anhydrides with ammonia.
• pour point depressants otherwise known as lube oil flow improvers, lower the minimum temperature at which the fluid will flow or can be poured.
• Such additives are well known. Typical of those additives which improve the low temperature fluidity of the fluid are C 8 to C 18 dialkyl fumarate/vinyl acetate copolymers, polyalkylmethacrylates and the like. These may be used in amounts of from 0.01 to 5.0 wt. %, preferably about 0.1 to 3.0 wt. %. They are preferably used when mineral oil base stocks are employed but are not generally required when the base stock is a PAO or synthetic ester,
• Foam control can be provided by many compounds including an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
• additives can provide a multiplicity of effects; thus for example, a single additive may act as a dispersant-oxidation inhibitor. This approach is well known and does not require further elaboration.
• each of the components can be added directly to the base stock or base oil blend by dispersing or dissolving it in the base stock or base oil blend at the desired level of concentration. Such blending may occur at ambient temperature or at an elevated temperature.
• the invention comprising the product results from the admixture of the additive components to form a lubricating oil composition.
• the additives are blended together to form a concentrate or additive package that is subsequently blended into base stock to make the finished lubricant.
• the concentrate or additive package may contain the viscosity modifier, or the viscosity modifier may be added separately from the concentrate or additive package to form the lubricating oil composition.
• the concentrate will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration in the final formulation when the concentrate is combined with a predetermined amount of a base lubricant.
• the final crankcase lubricating oil formulation may employ from 10 to 50 mass %, preferably 15 to 40 mass % of the concentrate or additive package, with the remainder being base stock.
• Lubricating oil composition Oil A was prepared by mixing an additive package comprising 4.8 mass % of a polyisobutenyl succinimide dispersant made from a polyisobutenyl with a number average molecular weight (Mn) of 2225, 1.08 mass % of polyisobutenyl succinimide dispersants made from a polyisobutenyl with a number average molecular weight (Mn) of 950, 0.74 mass % of a 321 TBN overbased calcium salicylate detergent and 0.34 mass % of a 565 TBN overbased calcium salicylate detergent, 0.43 mass % of 709 TBN overbased magnesium sulfonate detergent, 0.84 mass % of HiTec 5777 dispersant-viscosity modifier, and additional zinc dialkyl dithiophosphate, organic molybdenum dithiocarbamate and antioxidant into a base stock comprising a mixture of Group I and Group III base oils.
• Mn number average molecular weight
• Mn
• Oil A comprised 0.96 wt % sulphated ash, 0.08 wt % phosphorous, 0.21 wt % sulfur, 130 ppm of atomic boron, 50 ppm molybdenum, 0.153 mass % calcium and 0.069 mass % magnesium.
• the salicylate soap content of Oil A was 8.8 mmol and the total soap content of the Oil was 0.85 mass % soap.
• the calcium salicylate detergents provide the lubricating oil composition with 0.5 mass % calcium as sulphated ash.
• the dispersants provide the lubricating oil composition with 0.135 mass % nitrogen, with 0.096 mass % N being provided by the high molecular weigh dispersant and 0.039 mass % being provided by low molecular weight dispersant.
• Oil A was then run in the ASTM D7422 engine test, more commonly known as the Mack T-12.
• the Mack T-12 test is designed to evaluate the ability of an oil to minimize wear in an engine equipped with an EGR system.
• the Mack T-12 engine test is part of the API CJ-4 and ACEA E6 performance categories.
• the engine used is a modified Mack E7 E-Tech 460 rated at 460 bhp and 1,800 rpm, with EGR system.
• the test runs over 300 hours and at the end of the test piston ring wear, cylinder liner wear, lead bearing corrosion, oil consumption and oxidation are evaluated.
• Lubricating oil composition Oil B was prepared by mixing an additive package comprising 4.8 mass % of a polyisobutenyl succinimide dispersant made from a polyisobutenyl with a number average molecular weight (Mn) of 2225, 1.08 mass % of polyisobutenyl succinimide dispersants made from a polyisobutenyl with a number average molecular weight (Mn) of 950, 0.84 mass % of a 321 TBN overbased calcium salicylate detergent and 0.34 mass % of a 565 TBN overbased calcium salicylate detergent, 0.43 mass % a 709 TBN of overbased magnesium sulfonate detergent, 0.84 mass % of HiTec 5777 dispersant-viscosity modifier, and zinc dialkyl dithiophosphate, molybdenum dithiocarbamate and antioxidant, into a base stock comprising a mixture of Group I and Group III base oils.
• Mn number average molecular weight
• Oil B comprised 1.0 wt % sulphated ash, 0.08 wt % phosphorous, 0.21 wt % sulfur, 130 ppm of atomic boron 50 ppm molybdenum, 0.165 mass % calcium and 0.069 mass % magnesium.
• the salicylate soap content of Oil B was 9.8 mmol and the total soap content of the Oil was 0.92 mass % soap.
• the calcium salicylate detergents providing the lubricating oil composition with 0.54 mass % calcium as sulphated ash.
• the dispersants provide the lubricating oil composition with 0.135 mass % nitrogen, with 0.096 mass % nitrogen being provided by high molecular weight dispersant and 0.039 mass % being provided by low molecular weight dispersant.
• Oil B was then run in the Mercedes-Benz OM646 LA (CEC L-99-08) engine test, which is part of the ACEA and Daimler specifications .
• This 300-hour test uses the 2.2 L common rail diesel OM646 DE 22 LA engine to evaluate engine lubricant performance with respect to engine wear and overall cleanliness, as well as piston cleanliness and ring sticking.
• Oil B passes the OM646LA engine test at the required performance level for ACEA E6.
• the test also achieves all of the necessary parameters for the more stringent MB 228.51 specification level.

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