Classifications

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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
  • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
  • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
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  • 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
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  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
  • C10M2207/042—Epoxides
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  • 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
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/24—Epoxidised acids; Ester derivatives thereof
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  • 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
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  • 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
  • C10M2207/28—Esters
  • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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  • 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
  • C10M2207/28—Esters
  • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
• • 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
  • C10M2207/28—Esters
  • C10M2207/287—Partial esters
  • C10M2207/288—Partial esters containing free carboxyl groups
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  • 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
  • C10M2207/28—Esters
  • C10M2207/287—Partial esters
  • C10M2207/289—Partial esters containing free hydroxy groups
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  • 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
  • C10M2215/08—Amides
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C10M2215/08—Amides
  • C10M2215/082—Amides containing hydroxyl groups; Alkoxylated 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/086—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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/12—Partial amides of polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/22—Heterocyclic nitrogen compounds
  • C10M2215/223—Five-membered rings containing nitrogen and carbon only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/22—Heterocyclic nitrogen compounds
  • C10M2215/223—Five-membered rings containing nitrogen and carbon only
  • C10M2215/224—Imidazoles
• • C—CHEMISTRY; METALLURGY
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  • 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
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  • 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
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
  • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
  • C10M2219/089—Overbased 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
  • C10M2223/043—Ammonium or amine 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
  • 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
  • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
  • C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
• • 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
  • C10N2030/40—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

Definitions

• the invention provides a method of lubricating an internal combustion engine comprising an aluminium composite surface by supplying to the surface a lubricating composition comprising an oil of lubricating viscosity and an ashless antiwear agent.
• lubricating oils It is well known for lubricating oils to contain a number of additives used to protect the mechanical devices such as internal combustion engines from wear, soot deposits and acidity build up.
• a common antiwear additive for engine lubricating oils is zinc dialkyldithiophosphate (ZDDP). It is believed that ZDDP antiwear additives protect the engine by forming a protective film on metal surfaces.
• non-ferric engines or components thereof are based on aluminium-alloy, silicates, oxides, or other ceramic materials.
• antiwear agents ZDDP are believed to result in poorer engine wear performance in aluminium-alloy based engine compared with ferric based engines.
• WO 2004/106711 and US 5 624 890 disclose internal combustion engines with aluminium composite engines and lubricating oil compositions for these engines.
• US Patent Application 2006/0025315 discloses a method of lubricating an aluminium alloy surface with a lubricating composition containing an effective friction reducing amount of an oil soluble tri-nuclear organo-molybdenum compound.
• Canadian Patent CA 1 183 125 discloses lubricants for gasoline engines containing alkyl-ester tartrates, where the sum of carbon atoms on the alkyl groups is at least 8.
• WO 2006/044411 discloses lubricating oil compositions comprising tartaric acid ester or imides as ashless antiwear agents.
• an alternative antiwear agent capable of at least one of (i) reducing or preventing phosphorus emissions, (ii) reducing or preventing sulphur emissions, and (iii) wholly or partially replacing ZDDP in lubricating oils.
• the present invention provides an antiwear agent capable of achieving at least one of (i), (ii) or (iii).
• the antiwear agent may also be desirable for the antiwear agent to not have a detrimental affect on other components of a mechanical device e.g., a seal or to provide lead and/or copper corrosion inhibition.
• the invention provides a method of lubricating an internal combustion engine comprising an aluminium composite surface, the method comprising supplying to the surface a lubricating composition comprising an oil of lubricating viscosity and an ashless, phosphorus-free, sulphur-free antiwear agent as defined in the appended claims.
• the aluminium composite surface is an aluminium-silicate surface.
• the invention provides for the use of a lubricating composition comprising an ashless antiwear agent as defined in the claims to lubricate an internal combustion engine comprising an aluminium composite surface.
• the lubricating composition comprises an ashless, phosphorus-free, sulphur-free antiwear agent, and the lubricating composition is characterised as having at least one of (i) a sulphur content of 0.8 wt % or less, (ii) a phosphorus content of 0.2 wt % or less, or (iii) a sulphated ash content of 2 wt % or less.
• the lubricating composition comprises an ashless, phosphorus-free, sulphur-free antiwear agent, and the lubricating composition is characterised as having (i) a sulphur content of 0.5 wt % or less, (ii) a phosphorus content of 0.1 wt % or less, and (iii) a sulphated ash content of 1.5 wt % or less.
• the lubricating compositions disclosed herein further comprise a molybdenum compound.
• a molybdenum compound include molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine salts of molybdenum compounds, or mixtures thereof.
• the lubricating compositions disclosed herein contain 0 ppm to 500 ppm, or 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum.
• a molybdenum compound is present in an amount to provide 0.5 ppm to 2000 ppm, 1 ppm to 700 ppm, or 20 ppm to 250 ppm molybdenum.
• the present invention provides a method for lubricating an engine as disclosed above.
• the ashless, phosphorus-free, sulphur-free antiwear agent includes imides, di-esters, di-amides, di-imides, ester-amides, ester-imides as defined in the appended claims.
• the antiwear agent includes imides, di-esters, di-amides, or ester-amides.
• the ashless antiwear agent is derived from at least one of a hydroxy-carboxylic acid di-ester, a hydroxy-carboxylic acid di-amide, a hydroxy-carboxylic acid di-imide, a hydroxy-carboxylic acid ester-amide, a hydroxy-carboxylic acid ester-imide, and a hydroxy-carboxylic acid imide-amide.
• the ashless antiwear agent is derived from at least one of the group consisting of a hydroxy-carboxylic acid di-ester, a hydroxy-carboxylic acid di-amide, and a hydroxy-carboxylic acid ester-amide.
• a suitable a hydroxycarboxylic acid examples include citric acid, tartaric acid, malic acid (or hydroxy-succinic acid), lactic acid, oxalic acid, glycolic acid, hydroxy-propionic acid, hydroxyglutaric acid, or mixtures thereof.
• ashless antiwear agent is derived from tartaric acid, citric acid, hydroxy-succinic acid, dihydroxy mono-acids, mono-hydroxy diacids, or mixtures thereof.
• the ashless antiwear agent includes a compound derived from tartaric acid. In another embodiment it is derived from citric acid.
• di-esters, di-amides, di-imides, ester-amide, ester-imide, imide-amide compounds are derived from a compound of Formula (1a) and/or (1b). In one embodiment the di-esters, di-amides, ester-amide, compounds are derived from a compound of Formula (1a) and/or (1b).
• the ashless antiwear agent includes imide, di-esters, di-amides, ester-amide derivatives of tartaric acid.
• the ashless antiwear agent of the invention may also function as rust and corrosion inhibitors, friction modifiers, antiwear agents and demulsifiers.
• R 1 and R 2 are independently hydrocarbyl groups, typically containing 1 to 150, 4 to 30, or 6 to 20, or 10 to 20, or 11 to 18 carbon atoms;
• R 3 is a hydrocarbyl group;
• R 4 and R 5 are independently keto-containing groups (such as acyl groups), ester groups or hydrocarbyl groups; and
• R 6 is hydrogen.
• the compound of Formula (1b) contains an imide group.
• the compound of Formula (1a) and/or (1b) has n, X, and R', R 2 and R 6 defined as follows: n is 1 to 2, X is >CHOR 6 ; and R 1 , R 2 and R 6 are independently hydrocarbyl groups containing 4 to 30 carbon atoms.
• Y and Y' are both -O-.
• the compound of Formula (1a) and/or (1b) has n, X, Y, Y' and R 1 , R 2 and R 6 defined as follows: n is 1 to 2, X is >CHOR 6 ; Y and Y' are both -O-, and R 1 , R 2 and R 6 are independently hydrocarbyl groups containing 4 to 30 carbon atoms.
• the di-esters, di-amides, di-imides, ester-amide, ester-imide, imide-amide compounds of Formula (1a) and/or (1b) may be prepared by reacting a dicarboxylic acid (such as tartaric acid), with an amine or alcohol, optionally in the presence of a known esterification catalyst.
• a dicarboxylic acid such as tartaric acid
• the amine or alcohol typically has sufficient carbon atoms to fulfill the requirements of R 1 and/or R 2 as defined in Formula (1a) and/or (1b).
• Derivatives of the hydroxycarboxylic acid include imides, di-esters, di-amides, di-imides (applicable for tetra-acids and higher), ester-amides, ester-imides (applicable for tri-acids and higher, such as citric acid), imide-amides (applicable for tri-acids and higher, such as citric acid).
• the antiwear agent includes imides, di-esters, di-amides, or ester-amides.
• R 1 and R 2 are independently linear or branch hydrocarbyl groups. In one embodiment the hydrocarbyl groups are branched. In one embodiment the hydrocarbyl groups are linear.
• the R 1 and R 2 may be incorporated into Formula (1a) and/or (1b) by either an amine or an alcohol.
• the alcohol includes both monohydric alcohol and polyhydric alcohol.
• the ashless antiwear agent is derived from a compound of Formula (1b).
• branched alcohol examples include 2-ethylhexanol, isotridecanol, Guerbet alcohols, or mixtures thereof.
• Examples of a monohydric alcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, or mixtures thereof.
• the monohydric alcohol contains 5 to 20 carbon atoms.
• the alcohol includes either a monohydric alcohol or a polyhydric alcohol.
• suitable polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,5-pentane diol, 1,6-hexane diol, glycerol, sorbitol, pentaerythritol, trimethylolpropane, starch, glucose, sucrose, methylglucoside, or mixtures thereof.
• the polyhydric alcohol is used in a mixture along with a monohydric alcohol. Typically, in such a combination the monohydric alcohol constitutes at least 60 mole percent, or at least 90 mole percent of the mixture.
• ashless antiwear agent is derived from tartaric acid.
• the tartaric acid used for preparing the tartrates of the invention can be commercially available (for instance obtained from Sargent Welch), and it is likely to exist in one or more isomeric forms such as d -tartaric acid, l -tartaric acid or mesotartaric acid, often depending on the source (natural) or method of synthesis (e.g. from maleic acid).
• These derivatives can also be prepared from functional equivalents to the diacid readily apparent to those skilled in the art, such as esters, acid chlorides, or anhydrides.
• resultant tartrates may be solid, semi-solid, or oil depending on the particular alcohol used in preparing the tartrate.
• tartrates are advantageously soluble and/or stably dispersible in such oleaginous compositions.
• compositions intended for use in oils are typically oil-soluble and/or stably dispersible in an oil in which they are to be used.
• oil-soluble as used in this specification and appended claims does not necessarily mean that all the compositions in question are miscible or soluble in all proportions in all oils.
• composition is soluble in an oil (mineral, synthetic, etc.) in which it is intended to function to an extent which permits the solution to exhibit one or more of the desired properties.
• oil mineral, synthetic, etc.
• solutions it is not necessary that such "solutions" be true solutions in the strict physical or chemical sense. They may instead be micro-emulsions or colloidal dispersions which, for the purpose of this invention, exhibit properties sufficiently close to those of true solutions to be, for practical purposes, interchangeable with them within the context of this invention.
• the ashless antiwear agent is present at 0.1 to 5 wt % of the lubricating composition.
• the lubricating composition comprises an oil of lubricating viscosity.
• oils include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined and re-refined oils and mixtures thereof.
• Unrefined oils are those obtained directly from a natural or synthetic source generally without (or with little) further purification treatment.
• Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
• Purification techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation and the like.
• Re-refined oils are also known as reclaimed or reprocessed oils, and are obtained by processes similar to those used to obtain refined oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
• Natural oils useful in making the inventive lubricants include animal oils, vegetable oils (e.g., castor oil), mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
• animal oils e.g., castor oil
• mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
• Synthetic lubricating oils are useful and include hydrocarbon oils such as polymerised and interpolymerised olefins (e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers); poly(1-hexenes), poly(1-octenes), poly(1-decenes), and mixtures thereof; alkyl-benzenes (e.g.
• dodecylbenzenes tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes
• polyphenyls e.g., biphenyls, terphenyls, alkylated polyphenyls
• oils include polyol esters (such as Prolube®3970), diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans.
• Synthetic oils may be produced by Fischer-Tropsch reactions and typically may be hydroisomerised Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
• Oils of lubricating viscosity may also be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines.
• the five base oil groups are as follows: Group I (sulphur content >0.03 wt %, and/or ⁇ 90 wt % saturates, viscosity index 80-120); Group II (sulphur content ⁇ 0.03 wt %, and ⁇ 90 wt % saturates, viscosity index 80-120); Group III (sulphur content ⁇ 0.03 wt %, and ⁇ 90 wt % saturates, viscosity index ⁇ 120); Group IV (all polyalphaolefins (PAOs)); and Group V (all others not included in Groups I, II, III, or IV).
• PAOs polyalphaolefins
• the oil of lubricating viscosity comprises an API Group I, Group II, Group III, Group IV, Group V oil or mixtures thereof. Often the oil of lubricating viscosity is an API Group I, Group II, Group III, Group IV oil or mixtures thereof. Alternatively the oil of lubricating viscosity is often an API Group II, Group III or Group IV oil or mixtures thereof.
• the amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 wt % the sum of the amount of the ashless antiwear agent and the other performance additives.
• the lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the ashless antiwear agent is in the form of a concentrate (which may be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of the of components of the invention to the oil of lubricating viscosity and/or to diluent oil include the ranges of 1:99 to 99:1 by weight, or 80:20 to 10:90 by weight.
• the composition optionally comprises other performance additives.
• the other performance additives comprise at least one of metal deactivators, viscosity modifiers, detergents, friction modifiers, antiwear agents (other than the ashless antiwear agent of the invention), corrosion inhibitors, dispersants, dispersant viscosity modifiers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, pour point depressants, seal swelling agents and mixtures thereof.
• fully-formulated lubricating oil will contain one or more of these performance additives.
• the lubricating composition comprises the ashless antiwear agent and further comprises at least one of a viscosity modifier, an antioxidant, an overbased detergent, a succinimide dispersant, or mixtures thereof.
• the lubricating composition comprising the ashless antiwear agent further comprises a phosphorus-containing antiwear agent.
• the lubricating composition comprising the ashless antiwear agent further comprises a molybdenum compound.
• the lubricant composition optionally further comprises other known neutral or overbased detergents.
• Suitable detergent substrates include phenates, sulphur containing phenates, sulphonates, salixarates, salicylates, carboxylic acid, phosphorus acid, mono- and/or di- thiophosphoric acid, alkyl phenol, sulphur coupled alkyl phenol compounds, or saligenins.
• the detergent substrate is typically salted with a metal such as calcium, magnesium, potassium, sodium, or mixtures thereof.
• the lubricating composition further includes an overbased detergent.
• the overbased detergent includes phenates, sulphur containing phenates, sulphonates, salixarates, salicylates, or mixtures thereof.
• the detergent may be present at 0 wt % to 10 wt %, or 0.1 wt % to 8 wt %, or 1 wt % to 4 wt %, or greater than 4 to 8 wt %.
• Dispersants are often known as ashless-type dispersants because, prior to mixing in a lubricating oil composition, they do not contain ash-forming metals and they do not normally contribute any ash forming metals when added to a lubricant and polymeric dispersants.
• Ashless type dispersants are characterised by a polar group attached to a relatively high molecular weight hydrocarbon chain.
• Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimide with number average molecular weight of the polyisobutylene substituent in the range 350 to 5000, or 500 to 3000.
• Succinimide dispersants and their preparation are disclosed, for instance in US Patent 3,172,892 or US Patent 4,234,435 . Succinimide dispersants are typically the imide formed from a polyamine, typically a poly(ethyleneamine).
• the invention further comprises at least one polyisobutylene succinimide dispersant derived from polyisobutylene with number average molecular weight in the range 350 to 5000, or 500 to 3000.
• the polyisobutylene succinimide may be used alone or in combination with other dispersants.
• the invention further comprises at least one dispersant derived from polyisobutylene succinic anhydride, an amine and zinc oxide to form a polyisobutylene succinimide complex with zinc.
• the polyisobutylene succinimide complex with zinc may be used alone or in combination.
• Mannich bases Another class of ashless dispersant is Mannich bases.
• Mannich dispersants are the reaction products of alkyl phenols with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines).
• the alkyl group typically contains at least 30 carbon atoms.
• the dispersants may also be post-treated by conventional methods by a reaction with any of a variety of agents. Among these are boron, urea, thiourea, dimercaptothiadiazoles, carbon disulphide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitrites, epoxides, and phosphorus compounds.
• the dispersant may be present at 0 wt % to 20 wt %, or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 6 wt %, or 7 wt % to 12 wt % of the lubricating composition.
• Antioxidant compounds include for example, sulphurised olefins, alkylated diphenylamines (typically di-nonyl diphenylamine, octyl diphenylamine, di-octyl diphenylamine), hindered phenols, molybdenum compounds (such as molybdenum dithiocarbamates), or mixtures thereof. Antioxidant compounds may be used alone or in combination. The antioxidant may be present in ranges 0 wt % to 20 wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 5 wt %, of the lubricating composition.
• the hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
• the phenol group is often further substituted with a hydrocarbyl group and/or a bridging group linking to a second aromatic group.
• hindered phenol antioxidants examples include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol.
• the hindered phenol antioxidant is an ester and may include, e.g., IrganoxTM L-135 from Ciba. A more detailed description of suitable ester-containing hindered phenol antioxidant chemistry is found in US Patent 6,559,105 .
• molybdenum dithiocarbamates which may be used as an antioxidant include commercial materials sold under the trade names such as Molyvan 822TM and MolyvanTM A from R. T. Vanderbilt Co., Ltd., and Adeka Sakura-LubeTM S-100, S-165 and S-600 from Asahi Denka Kogyo K. K and mixtures thereof.
• Viscosity modifiers include hydrogenated copolymers of styrenebutadiene, ethylene-propylene copolymers, polyisobutenes, hydrogenated styrene-isoprene polymers, hydrogenated isoprene polymers, polymethacrylates, polyacrylates, polyalkyl styrenes, hydrogenated alkenyl aryl conjugated diene copolymers, polyolefins, esters of maleic anhydride-styrene copolymers.
• Dispersant viscosity modifiers include functionalised polyolefins, for example, ethylene-propylene copolymers that have been functionalized with the reaction product of maleic anhydride and an amine; polymethacrylates functionalised with an amine, or esterified maleic anhydride-styrene copolymers reacted with an amine.
• the total amount of viscosity modifier and/or dispersant viscosity modifier may be 0 wt % to 20 wt %, or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, of the lubricating composition
• the lubricant composition optionally further comprises at least one other antiwear agent other than the ashless antiwear agent of the invention.
• suitable antiwear agents include phosphate esters, sulphurised olefins, sulphur-containing anti-wear additives including metal dihydrocarbyldithiophosphates (such as zinc dialkyldithiophosphates or molybdenum dialkyldithiophosphates), thiocarbamate-containing compounds including, thiocarbamate esters, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulphides.
• the dithiocarbamate-containing compounds may be prepared by reacting a dithiocarbamate acid or salt with an unsaturated compound.
• the dithiocarbamate containing compounds may also be prepared by simultaneously reacting an amine, carbon disulphide and an unsaturated compound. Generally, the reaction occurs at a temperature of 25 °C to 125 °C.
• US Patents 4,758,362 and 4,997,969 describe dithiocarbamate compounds and methods of making them.
• Suitable olefins that may be sulphurised to form the sulphurised olefin include propylene, butylene, isobutylene, pentene, hexane, heptene, octane, nonene, decene, undecene, dodecene, undecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene or mixtures thereof.
• hexadecene, heptadecene, octadecene, nonadecene, eicosene or mixtures thereof and their dimers, trimers and tetramers are especially useful olefins.
• the olefin may be a Diels-Alder adduct of a diene such as 1,3-butadiene and an unsaturated ester, such as butylacrylate.
• sulphurised olefin includes fatty acids and their esters.
• the fatty acids are often obtained from vegetable oil or animal oil and typically contain 4 to 22 carbon atoms.
• suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid or mixtures thereof.
• the fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures thereof.
• fatty acids and/or ester are mixed with olefins such as ⁇ -olefins.
• the ashless antiwear agent (which may also be described as a friction modifier) may be a monoester of a polyol and an aliphatic carboxylic acid, often an acid containing 12 to 24 carbon atoms.
• the monoester of a polyol and an aliphatic carboxylic acid is in the form of a mixture with a sunflower oil or the like, which may be present in the ashless antiwear agent mixture include 5 to 95, or in other embodiments 10 to 90, or 20 to 85, or 20 to 80 weight percent of said mixture.
• the aliphatic carboxylic acids (especially a monocarboxylic acid) which form the esters are those acids typically containing 12 to 24 or 14 to 20 carbon atoms. Examples of carboxylic acids include dodecanoic acid, stearic acid, lauric acid, behenic acid, and oleic acid.
• Polyols include diols, triols, and alcohols with higher numbers of alcoholic OH groups.
• Polyhydric alcohols include ethylene glycols, including di-, tri- and tetraethylene glycols; propylene glycols, including di-, tri- and tetrapropylene glycols; glycerol; butane diol; hexane diol; sorbitol; arabitol; mannitol; sucrose; fructose; glucose; cyclohexane diol; erythritol; and pentaerythritols, including di- and tripentaerythritol.
• the polyol is diethylene glycol, triethylene glycol, glycerol, sorbitol, pentaerythritol or dipentaerythritol.
• the commercial material known as glycerol monoleate is believed to include about 60 ⁇ 5 percent by weight of the chemical species "glycerol monooleate,” along with 35 ⁇ 5 percent glycerol dioleate, and less than about 5 percent trioleate and oleic acid.
• the amounts of the monoesters, described below, are the amounts of the commercial grade material.
• the antiwear agent may be present in ranges including 0 wt % to 15 wt %, or 0 wt % to 10 wt %, or 0.05 wt % to 5 wt %, or 0.1 wt % to 3 wt % of the lubricating composition.
• the lubricating composition is free of zinc dihydrocarbyl dithiophosphate. In one embodiment the lubricating composition further includes zinc dihydrocarbyl dithiophosphate.
• EP agents include chlorinated wax; organic sulphides and polysulphides such as dibenzyldisulphide, bis-(chlorobenzyl) disulphide, dibutyl tetrasulphide, sulphurised methyl ester of oleic acid, sulphurised alkylphenol, sulphurised dipentene, sulphurised terpene, and sulphurised Diels-Alder adducts; phosphosulphurised hydrocarbons such as the reaction product of phosphorus sulphide with turpentine or methyl oleate; phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphites, e.g., dibutyl phosphite, diheptyl phosphite,
• the friction modifier may be present in ranges including 0 wt % to 10 wt %, or 0.05 wt % to 8 wt %, or 0.1 wt % to 4 wt %.
• Suitable friction modifiers include long chain fatty acid derivatives of long chain fatty acid derivatives of amines, esters, or epoxides; fatty imidazolines (that is to say, long chain fatty amides, long chain fatty esters, long chain fatty epoxide derivatives, long chain fatty imidazolines); and amine salts of alkylphosphoric acids.
• Friction modifiers may also encompass materials such as sulphurised fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamatcs, sunflower oil or monoester of a polyol and an aliphatic carboxylic acid (all these friction modifiers have been described as antioxidants or antiwear agents).
• the friction modifier friction modifier is selected from the group consisting of long chain fatty amides, long chain fatty esters, long chain fatty epoxide derivatives, long chain fatty imidazolines, and amine salts of alkylphosphoric acids; fatty alkyl tartrates such as C12-14 tartrates; fatty alkyl tartrimides (such as tridecyl tartrimide, oleyl tartrimide, or 2-ethylhexyl tartrimide); and fatty alkyl tartramides
• the friction modifier is a long chain fatty acid ester (previously described above as an ashless antiwear agent).
• the long chain fatty acid ester is a mono-ester and in another embodiment the long chain fatty acid ester is a (tri)glyceride.
• corrosion inhibitors include those described in paragraphs 5 to 8 of US Application US05/038319 (filed on October 25, 2004 McAtee and Boyer as named inventors), octylamine octanoate, condensation products of dodecenyl succinic acid or anhydride and a fatty acid such as oleic acid with a polyamine.
• the corrosion inhibitors include the Synalox® corrosion inhibitor.
• the Synalox® corrosion inhibitor is typically a homopolymer or copolymer of propylene oxide.
• the Synalox® corrosion inhibitor is described in more detail in a product brochure with Form No. 118-01453-0702 AMS, published by The Dow Chemical Company.
• the product brochure is entitled "SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications.”
• Metal deactivators including derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides.
• benzotriazoles typically tolyltriazole
• dimercaptothiadiazole derivatives 1,2,4-triazoles
• benzimidazoles 2-alkyldithiobenzimidazoles
• the lubricating composition may be utilised in a range aluminium-alloy or aluminium composite surfaces typically found in mechanical devices.
• the mechanical devices include an internal combustion engine, a gearbox, an automatic transmission, a hydraulic device or a turbine.
• the lubricating composition may be an engine oil, a gear oil, an automatic transmission oil, a hydraulic fluid, a turbine oil, a metal working fluid or a circulating oil.
• the mechanical device is an internal combustion engine.
• aluminium-alloy and “aluminium composite” are used interchangeably to describe a surface comprising aluminium and another component intermixed or reacted on a microscopic or nearly microscopic level, regardless of the detailed structure thereof. This would include any conventional alloys with metals other than aluminium as well as composite or alloy-like structures with non-metallic elements or compounds such as with ceramic-like materials.
• the aluminium-alloy or aluminium composite thus includes aluminium silicates, aluminium oxides, or other ceramic materials. In one embodiment the aluminium-alloy is an aluminium-silicate surface.
• the internal combustion engine may be a diesel fuelled engine, a gasoline fuelled engine, a natural gas fuelled engine or a mixed gasoline/alcohol fuelled engine. In one embodiment the internal combustion engine may be a diesel fuelled engine and in another embodiment a gasoline fuelled engine.
• the internal combustion engine may be a 2-stroke or 4-stroke engine.
• Suitable internal combustion engines include marine diesel engines, aviation piston engines, low-load diesel engines, and automobile and truck engines.
• the lubricant composition for an internal combustion engine may be suitable for any engine lubricant irrespective of the sulphur, phosphorus or sulphated ash (ASTM D-874) content.
• the sulphur content of the engine oil lubricant may be 1 wt % or less, or 0.8 wt % or less, or 0.5 wt % or less, or 0.3 wt % or less. In one embodiment the sulphur content may be in the range of 0.001 wt % to 0.5 wt %, or 0.01 wt % to 0.3 wt %.
• the phosphorus content may be 0.2 wt % or less, or 0.1 wt % or less, or 0.085 wt % or less, or even 0.06 wt % or less, 0.055 wt % or less, or 0.05 wt % or less. In one embodiment the phosphorus content may be 100 ppm to 1000 ppm, or 325 ppm to 700 ppm.
• the total sulphated ash content may be 2 wt % or less, or 1.5 wt % or less, or 1.1 wt % or less, or 1 wt % or less, or 0.8 wt % or less, or 0.5 wt % or less. In one embodiment the sulphated ash content may be 0.05 wt % to 0.9 wt %, or 0.1 wt % or 0.2 wt % to 0.45 wt %.
• the lubricating composition is an engine oil, wherein the lubricating composition is characterised as having (i) a sulphur content of 0.5 wt % or less, (ii) a phosphorus content of 0.1 wt % or less, and (iii) a sulphated ash content of 1.5 wt % or less.
• the sulphur content is 0.4 wt % or less, the phosphorus content is 0.08 wt % or less, and the sulphated ash is 1 wt % or less.
• the sulphur content is 0.3 wt% or less, the phosphorus content is 0.05 wt % or less, and the sulphated ash is 0.8 wt % or less.
• the lubricating composition is suitable for a 2-strokc or a 4-stroke marine diesel internal combustion engine.
• the marine diesel combustion engine is a 2-stroke engine.
• the ashless antiwear agent of the invention may be added to a marine diesel lubricating composition at 0.01 to 20 wt %, or 0.05 to 10 wt %, or 0.1 to 5 wt %.
• Example 1 A lubricating composition is prepared containing 1 wt % of di-2-ethylhexyl tartrate, 0.6 wt % of other antiwear agents, 7.9 wt % of dispersants. 1.5 wt % of detergents, 3.6 wt % of antioxidants, 6.1 wt % of viscosity modifier, 0.1 wt % of corrosion inhibitor, and 0.1 wt % of friction modifier.
• the lubricating composition has a sulphated ash content of 0.6 wt %, a phosphorus content of about 570 ppm, and a sulphur content of 0.17 wt %.
• Comparative Example 1 is similar to Example 1 except the composition does not contain the di-2-ethylhexyl tartrate.
• Example 1 and Comparative Example 1 are evaluated by employing the lubricating compositions in an internal combustion engine fitted with an aluminium silicate liner and a steel top ring. The engine is then run under varying loads and speeds and wear analysis is conducted when the engine is running at 5000 rpm. Data obtained from the wear analysis (wear rate of nanometers per hour) of the aluminium silicate liner is as follows: Example Wear Rate (nm/h) Example 1 0.5 Comparative Example 1 2.1
• lubricating an aluminium-alloy surface with a lubricating composition as disclosed herein is capable of at least one of (i) reducing or preventing phosphorus emissions, (ii) reducing or preventing sulphur emissions, and (iii) wholly or partially replacing ZDDP in lubricating oils, and (iv) having no detrimental affect on other components of the internal combustion engine.
• each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.
• the amount of each chemical component is presented inclusive of any solvent or diluent oil, which may be customarily present in the commercial material, unless otherwise indicated. It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention may be used together with ranges or amounts for any of the other elements.
• hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
• hydrocarbyl groups include:
• Heteroatoms include sulphur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
• substituents as pyridyl, furyl, thienyl and imidazolyl.
• no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group.

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• 2008
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