US20080139430A1 - Additives and lubricant formulations for improved antiwear properties - Google Patents

Additives and lubricant formulations for improved antiwear properties Download PDF

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Publication number
US20080139430A1
US20080139430A1 US11/608,269 US60826906A US2008139430A1 US 20080139430 A1 US20080139430 A1 US 20080139430A1 US 60826906 A US60826906 A US 60826906A US 2008139430 A1 US2008139430 A1 US 2008139430A1
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Prior art keywords
lubricant composition
magnesium compound
amount
magnesium
lubricant
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William Y. Lam
Mark T. Devlin
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Afton Chemical Corp
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Afton Chemical Corp
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Assigned to SUNTRUST BANK reassignment SUNTRUST BANK SECURITY AGREEMENT Assignors: AFTON CHEMICAL CORPORATION
Assigned to AFTON CHEMICAL CORPORATION reassignment AFTON CHEMICAL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DEVLIN, MARK T., LAM, WILLIAM Y.
Priority to JP2007284824A priority patent/JP2008144142A/ja
Priority to DE102007056248A priority patent/DE102007056248A1/de
Priority to GB0723037A priority patent/GB2444608A/en
Priority to FR0759574A priority patent/FR2909684A1/fr
Priority to RU2007145492/04A priority patent/RU2007145492A/ru
Priority to CN2007103035784A priority patent/CN101245278B/zh
Publication of US20080139430A1 publication Critical patent/US20080139430A1/en
Assigned to AFTON CHEMICAL CORPORATION reassignment AFTON CHEMICAL CORPORATION RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: SUNTRUST BANK
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    • 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
    • C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • 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
    • C10M2207/283—Esters of polyhydroxy compounds
    • 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
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • 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
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • 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 embodiments described herein relate to particular oil soluble magnesium additives and use of such magnesium additives in lubricating oil formulations to improve antiwear properties of the formulations.
  • Zn DDPs Zinc dialkyl dithiophosphates
  • STYLE Zinc dialkyl dithiophosphates
  • Many patents address the manufacture and use of Zn DDPs including U.S. Pat. Nos. 4,904,401; 4,957,649; 6,114,288, all of which are incorporated herein by reference in their entirety.
  • Sulfur-containing antiwear are also well known and include dihydrocarbyl polysulfides; sulfurized olefins; sulfurized fatty acid esters of both natural and synthetic origins; trithiones; sulfurized thienyl derivatives; sulfurized terpenes; sulfurized polyenes; sulfurized Diels-Alder adducts, etc.
  • sulfurized isobutylene sulfurized diisobutylene, sulfurized triisobutylene, dicyclohexyl polysulfide, diphenyl polysulfide, dibenzyl polysulfide, dinonyl polysulfide, and mixtures of di-tert-butyl polysulfides such as mixtures of di-tert-butyl trisulfide, di-tert-butyl tetrasulfide and di-tert-butyl pentasulfide, among others.
  • sulfurized olefins are used in many applications. Methods of preparing sulfurized olefins are described in U.S. Pat. Nos.
  • exemplary embodiments disclosed herein provide a lubricated surface, a method for reducing wear between moving parts, and lubricants, and lubricant additive concentrates containing a wear reducing agent.
  • the lubricated surface contains a base oil of lubricating viscosity and an amount of at least one hydrocarbon soluble magnesium compound effective to provide a reduction in surface wear greater than a reduction surface wear for a lubricant composition devoid of the magnesium compound.
  • the lubricant composition contains no more than about 0.05 wt. % phosphorus and is substantially devoid of calcium detergents.
  • a vehicle having moving parts wherein the vehicle contains a lubricant for lubricating the moving parts.
  • the lubricant is an oil of lubricating viscosity having therein an amount of antiwear agent providing an amount of at least one hydrocarbon soluble magnesium compound effective to provide a reduction in surface wear of the moving parts greater than a reduction surface wear of the moving parts for a lubricant composition devoid of the magnesium compound.
  • the lubricant composition contains no more than about 0.05 wt. % phosphorus and is substantially devoid of calcium detergents.
  • a fully formulated lubricant composition include a base oil component of lubricating viscosity and an amount of antiwear agent providing an amount of at least one hydrocarbon soluble magnesium compound effective to provide wear reduction greater than an amount of wear reduction for a lubricant composition devoid of the magnesium compound.
  • the lubricant composition contains no more than about 500 ppm phosphorus and is substantially devoid of calcium detergents.
  • a further embodiment of the disclosure provides a lubricant additive concentrate for providing improved antiwear properties to a lubricant composition.
  • the concentrate is substantially devoid of calcium compounds and has a hydrocarbyl carrier fluid and an amount of at least one hydrocarbon soluble magnesium compound sufficient to provide from about 120 to about 2000 ppm magnesium to a lubricant composition containing the concentrate.
  • an antiwear additive including a hydrocarbon soluble magnesium compound that may significantly improve the antiwear performance of a lubricant composition thereby enabling a decrease in the amount of phosphorus and sulfur antiwear additives required for equivalent antiwear performance.
  • the additive may be mixed with an oleaginous fluid that is applied to a surface to reduce surface wear.
  • the additive may be provided in a fully formulated lubricant composition.
  • the additive is particularly directed to meeting the currently proposed GF-4 standards for passenger car motor oils and PC-10 standards for heavy duty diesel engine oil.
  • compositions and methods described herein are particularly suitable for reducing contamination of pollution control devices on motor vehicles or, in the alternative, the compositions are suitable for improving the performance of antiwear agents in lubricant formulations.
  • Other features and advantages of the compositions and methods described herein may be evident by reference to the following detailed description which is intended to exemplify aspects of the disclosed embodiments without intending to limit the embodiments described herein.
  • a magnesium compound that is useful as a component in lubricating oil compositions.
  • the magnesium compound comprises a hydrocarbon soluble magnesium compound selected from the group consisting of magnesium sulfonates, magnesium phenates, magnesium salicylates, and mixture thereof.
  • hydrocarbon soluble means that the compound is substantially suspended or dissolved in a hydrocarbon material, as by reaction or complexation of a magnesium compound with a hydrocarbon material.
  • hydrocarbon means any of a vast number of compounds containing carbon, hydrogen, and/or oxygen in various combinations.
  • hydrocarbyl refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include:
  • the magnesium compound is desirably a basic or overbased magnesium salt that contains an excess of the magnesium cation.
  • the basic or overbased salts will have metal ratios of up to about 40 and more particularly will have a metal ratio of about 2 to about 30 or 40.
  • a commonly employed method for preparing the basic (or overbased) magnesium salts comprises heating a mineral oil solution of an acid with a stoichiometric excess of a metal neutralizing agent, e.g., a metal oxide, hydroxide, carbonate, bicarbonate, sulfide, etc., at temperatures above about 50° C.
  • a metal neutralizing agent e.g., a metal oxide, hydroxide, carbonate, bicarbonate, sulfide, etc.
  • various promoters may be used in the overbasing process to aid in the incorporation of the large excess of metal.
  • These promoters include such compounds as the phenolic substances, e.g., phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol and the various condensation products of formaldehyde with a phenolic substance; alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve carbitol, ethylene, glycol, stearyl alcohol, and cyclohexyl alcohol; amines such as aniline, phenylenediamine, phenothiazine, phenyl-beta-naphthylamine, and dodecyl amine, etc.
  • phenolic substances e.g., phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol and the various condensation products of formaldehyde with a phenolic substance
  • alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve carbito
  • the acidic organic compound from which the magnesium salt is derived may be at least one sulfur acid, carboxylic acid, phosphorus acid, or phenol or mixtures thereof.
  • the sulfur acids may be sulfonic acids, thiosulfonic, sulfinic, sulfenic, partial ester sulfuric, sulfurous and thiosulfuric acids. Sulfonic acids are particularly desirable for use in making the hydrocarbon soluble magnesium compounds.
  • component (B) The sulfonic acids which are useful in preparing component (B) include those represented by the formulae
  • R 1 is an aliphatic or aliphatic-substituted cycloaliphatic hydrocarbon or essentially hydrocarbon group free from acetylenic unsaturation and containing up to about 60 carbon atoms.
  • R 1 is aliphatic, it usually contains at least about 15 carbon atoms; when it is an aliphatic-substituted cycloaliphatic group, the aliphatic substituents usually contain a total of at least about 12 carbon atoms.
  • R 1 examples are alkyl, alkenyl and alkoxyalkyl radicals, and aliphatic-substituted cycloaliphatic groups wherein the aliphatic substituents are alkyl, alkenyl, alkoxy, alkoxyalkyl, carboxyalkyl and the like.
  • the cycloaliphatic nucleus is derived from a cycloalkane or a cycloalkene such as cyclopentane, cyclohexane, cyclohexene or cyclopentene.
  • R 1 are cetylcyclohexyl, laurylcyclohexyl, cetyloxyethyl, octadecenyl, and groups derived from petroleum, saturated and unsaturated paraffin wax, and olefin polymers including polymerized monoolefins and diolefins containing about 2-8 carbon atoms per olefinic monomer unit.
  • R 1 may also contain other substituents such as phenyl, cycloalkyl, hydroxy, mercapto, halo, nitro, amino, nitroso, lower alkoxy, lower alkylmercapto, carboxy, carbalkoxy, oxo or thio, or interrupting groups such as —NH—, —O— or —S—, as long as the essentially hydrocarbon character thereof is not destroyed.
  • substituents such as phenyl, cycloalkyl, hydroxy, mercapto, halo, nitro, amino, nitroso, lower alkoxy, lower alkylmercapto, carboxy, carbalkoxy, oxo or thio, or interrupting groups such as —NH—, —O— or —S—, as long as the essentially hydrocarbon character thereof is not destroyed.
  • R in Formula I is generally a hydrocarbon or essentially hydrocarbon group free from acetylenic unsaturation and containing from about 4 to about 60 aliphatic carbon atoms, for example, an aliphatic hydrocarbon group such as alkyl or alkenyl.
  • the compound may also, however, contain substituents or interrupting groups such as those enumerated above provided the essentially hydrocarbon character thereof is retained. In general, any non-carbon atoms present in R 1 or R do not account for more than 10% of the total weight thereof.
  • T is a cyclic nucleus which may be derived from an aromatic hydrocarbon such as benzene, naphthalene, anthracene or biphenyl, or from a heterocyclic compound such as pyridine, indole or isoindole.
  • T is an aromatic hydrocarbon nucleus, especially a benzene or naphthalene nucleus.
  • the subscript x in the above formulas is at least 1 and is generally 1-3.
  • the subscripts r and y have an average value of about 1-2 per molecule and are generally 1.
  • the sulfonic acids are generally petroleum sulfonic acids or synthetically prepared alkaryl sulfonic acids.
  • the most useful products are those prepared by the sulfonation of suitable petroleum fractions with a subsequent removal of acid sludge, and purification.
  • Synthetic alkaryl sulfonic acids are prepared usually from alkylated benzenes such as the Friedel-Crafts reaction products of benzene and polymers such as tetrapropylene. The following are specific examples of sulfonic acids useful in preparing hydrocarbon soluble magnesium compounds described herein.
  • Such sulfonic acids include, but are not limited to, mahogany sulfonic acids, bright stock sulfonic acids, petrolatum sulfonic acids, mono- and polywax-substituted naphthalene sulfonic acids, cetylchlorobenzene sulfonic acids, cetylphenol sulfonic acids, cetylphenol disulfide sulfonic acids, cetoxycapryl benzene sulfonic acids, dicetyl thianthrene sulfonic acids, dilauryl beta-naphthol sulfonic acids, dicapryl nitronaphthalene sulfonic acids, saturated paraffin wax sulfonic acids, unsaturated paraffin wax sulfonic acids, hydroxy-substituted paraffin wax sulfonic acids, tetra-isobutylene sulfonic acids, tetra-amylene sulfonic acids,
  • Alkyl-substituted benzene sulfonic acids wherein the alkyl group contains at least 8 carbon atoms including dodecyl benzene “bottoms” sulfonic acids are particularly useful.
  • the latter are acids derived from benzene which has been alkylated with propylene tetramers or isobutene trimers to introduce 1, 2, 3, or more branched-chain C 12 substituents on the benzene ring.
  • Dodecyl benzene bottoms principally mixtures of mono- and di-dodecyl benzenes, are available as by-products from the manufacture of household detergents. Similar products obtained from alkylation bottoms formed during manufacture of linear alkyl sulfonates (LAS) are also useful in making the sulfonates described herein.
  • LAS linear alkyl sulfonates
  • Suitable carboxylic acids from which the hydrocarbon soluble magnesium compounds may be prepared include aliphatic, cycloaliphatic and aromatic mono- and polybasic carboxylic acids free from acetylenic unsaturation, including naphthenic acids, alkyl- or alkenyl-substituted cyclopentanoic acids, alkyl- or alkenyl-substituted cyclohexanoic acids, and alkyl- or alkenyl-substituted aromatic carboxylic acids.
  • the aliphatic acids generally contain from about 8 to about 50, and desirably from about 12 to about 25 carbon atoms.
  • the cycloaliphatic and aliphatic carboxylic acids are particularly suitable, and they may be saturated or unsaturated. Specific examples include 2-ethylhexanoic acid, linolenic acid, propylene tetramer-substituted maleic acid, behenic acid, isostearic acid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid, lauric acid, oleic acid, ricinoleic acid, undecyclic acid, dioctylcyclopentanecarboxylic acid, myristic acid, dilauryldecahydronaphthalene-carboxylic acid, stearyl-octahydroindenecarboxylic acid, palmitic acid, alkyl- and alkenylsuccinic acids, acids formed by oxidation of petrolatum or of hydrocarbon waxes, and commercially available mixtures of two or more carboxylic acids such as tall oil acids, ros
  • the hydrocarbon soluble magnesium compound may also be prepared from phenols; that is, compounds containing a hydroxy group bound directly to an aromatic ring.
  • phenol as used herein includes compounds having more than one hydroxy group bound to an aromatic ring, such as catechol, resorcinol and hydroquinone. It also includes alkylphenols such as the cresols and ethylphenols, and alkenylphenols.
  • Phenols containing at least one alkyl substituent containing about 3-100 and especially about 6-50 carbon atoms such as heptylphenol, octylphenol, dodecylphenol, tetrapropene-alkylated phenol, octadecylphenol and polybutenylphenols are particularly suitable. Phenols containing more than one alkyl substituent may also be used, but the monoalkylphenols are more suitable because of their availability and ease of production.
  • condensation products of the above-described phenols with at least one lower aldehyde or ketone are also useful, the term “lower” denoting aldehydes and ketones containing not more than 7 carbon atoms.
  • Suitable aldehydes include formaldehyde, acetaldehyde, propionaldehyde, the butyraldehydes, the valeraldehydes and benzaldehyde.
  • aldehyde-yielding reagents such as paraformaldehyde, trioxane, methylol, methyl formcel, and paraldehyde.
  • the amount of hydrocarbon soluble magnesium compound included in the lubricants of the exemplary embodiments also may be varied, and useful amounts in any particular lubricating oil composition may be readily determined by one skilled in the art.
  • the amount of the magnesium compound contained in a lubricant described herein may vary from about 0.15% to about 2.0% or more by weight.
  • the amount of magnesium compound included in the oil composition is an amount which is sufficient to provide the desired wear inhibiting properties.
  • the additives in the form of 1 to 99 wt. % active ingredient concentrates in hydrocarbon oil, e.g. mineral lubricating oil, or other suitable solvent. Usually these concentrates may be added with 0.05 to 10 parts by weight of lubricating oil per part by weight of the additive package in forming finished lubricants, e.g. crankcase motor oils.
  • the purpose of concentrates is to make the handling of the various materials less difficult and awkward as well as to facilitate solution or dispersion in the final blend.
  • Lubricant compositions made with the hydrocarbon soluble magnesium compound described above are used in a wide variety of applications.
  • Lubricant compositions according to the foregoing GF-4 or API-CI-4 standards include a base oil and an oil additive package to provide a fully formulated lubricant.
  • the base oil for lubricants according to the disclosure is an oil of lubricating viscosity selected from natural lubricating oils, synthetic lubricating oils and mixtures thereof.
  • Such base oils include those conventionally employed as crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, such as automobile and truck engines, marine and railroad diesel engines, and the like.
  • Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil), liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
  • the synthetic lubricating oils used in the exemplary embodiments of the disclosure include one of any number of commonly used synthetic hydrocarbon oils, which include, but are not limited to, poly-alpha-olefins, alkylated aromatics, alkylene oxide polymers, interpolymers, copolymers and derivatives thereof here the terminal hydroxyl groups have been modified by esterification, etherification etc, esters of dicarboxylic acids and silicon-based oils.
  • Fully formulated lubricants conventionally contain an additive package, referred to herein as a dispersant/inhibitor package or DI package, that will supply the characteristics that are required in the formulations.
  • DI package a dispersant/inhibitor package
  • Suitable DI packages are described for example in U.S. Pat. Nos. 5,204,012 and 6,034,040 for example.
  • additives included in the additive package may be dispersants, friction modifiers, seal swell agents, antioxidants, foam inhibitors, lubricity agents, rust inhibitors, corrosion inhibitors, demulsifiers, viscosity index improvers, and the like.
  • these components are well known to those skilled in the art and are generally used in conventional amounts with the additives and compositions described herein.
  • Another component of lubricant compositions is at least one dispersant derived from a polyalkylene compound.
  • the polyalkylene compound may have a number average molecular weight ranging from about 400 to about 5000 or more.
  • Dispersants which may be used include, but are not limited to, amine, alcohol, amide, or ester polar moieties attached to the polymer backbone often via a bridging group. Dispersants may be selected from Mannich dispersants as described, for example, in U.S. Pat. Nos. 3,697,574 and 3,736,357; ashless succinimide dispersants as described in U.S. Pat. Nos. 4,234,435 and 4,636,322; amine dispersants as described in U.S. Pat.
  • a particularly suitable dispersant is a polyalkylene succinimide dispersant derived from a polyisobutene (PIB) compound.
  • the dispersant may be a mixture of dispersants having number average molecular weights ranging from about 800 to about 3000 and reactive PIB contents of from about 50 to about 60%.
  • the total amount of dispersant in the lubricant composition may range from about 1 to about 10 percent by weight of the total weight of the lubricant composition.
  • An oil soluble friction modifier may be incorporated in the lubricating oil compositions described herein.
  • the friction modifier may be selected from nitrogen-containing, nitrogen-free and/or amine free friction modifiers.
  • the friction modifier may be used in an amount ranging from about 0.02 to 2.0 wt. % of the lubricating oil composition. Desirably, from 0.05 to 1.0, more desirably from 0.1 to 0.5, wt. % of the friction modifier is used.
  • nitrogen containing friction modifiers examples include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, amino guanadine, alkanolamides, and the like.
  • Such friction modifiers may contain hydrocarbyl groups that may be selected from straight chain branched chain or aromatic hydrocarbyl groups or admixtures thereof, and may be saturated or unsaturated. Hydrocarbyl groups are predominantly composed of carbon and hydrogen but may contain one or more hetero atoms such as sulfur or oxygen. Suitable hydrocarbyl groups range from 12 to 25 carbon atoms and may be saturated or unsaturated. More desirable are those with linear hydrocarbyl groups.
  • Exemplary friction modifiers include amides of polyamines. Such compounds may have hydrocarbyl groups that are linear, either saturated or unsaturated or a mixture thereof and contain no more than about 12 to about 25 carbon atoms.
  • exemplary friction modifiers include alkoxylated amines and alkoxylated ether amines, with alkoxylated amines containing about two moles of alkylene oxide per mole of nitrogen being the most desirable.
  • alkoxylated amines containing about two moles of alkylene oxide per mole of nitrogen being the most desirable.
  • Such compounds can have hydrocarbyl groups that are linear, either saturated, unsaturated or a mixture thereof. They contain no more than about 12 to about 25 carbon atoms and may contain one or more hetero atoms in the hydrocarbyl chain.
  • Ethoxylated amines and ethoxylated ether amines are particularly suitable nitrogen-containing friction modifiers.
  • the amines and amides may be used as such or in the form of an adduct or reaction product with a boron compound such as a boric oxide, boron halide, metaborate, boric acid or a mono-, di- or tri-alkyl borate.
  • a boron compound such as a boric oxide, boron halide, metaborate, boric acid or a mono-, di- or tri-alkyl borate.
  • the ashless organic polysulfide compounds that may be used as friction modifiers include organic compounds expressed by the following formulae, such as sulfides of oils or fats or polyolefins, in which a sulfur atom group having two or more sulfur atoms adjoining and bonded together is present in a molecular structure.
  • R 2 and R 3 independently denote a straight-chain, branched-chain, alicyclic or aromatic hydrocarbon group in which a straight chain, a branched chain, an alicyclic unit and an aromatic unit may be selectively contained in any combined manner.
  • An unsaturated bond may be contained, but a saturated hydrocarbon group is desirable.
  • alkyl group, aryl group, alkylaryl group, benzyl group, and alkylbenzyl group are particularly desired.
  • R 3 and R 4 independently denote a straight-chain, branched-chain alicyclic or aromatic hydrocarbon group which has two bonding sites and in which a straight chain, a branched chain, an alicyclic unit and an aromatic unit may be selectively contained in any combined manner.
  • An unsaturated bond may be contained, but a saturated hydrocarbon group is desirable.
  • an alkylene group is particularly desirable.
  • R 6 and R 7 independently denote a straight-chain or branched-chain hydrocarbon group.
  • the subscripts “x” and “y” denote independently an integer of two or more.
  • sulfurized sperm oil sulfurized pinene oil, sulfurized soybean oil, sulfurized polyolefin, dialkyl disulfide, dialkyl polysulfide, dibenzyl disulfide, di-tertiary butyl disulfide, polyolefin polysulfide, thiadiazole type compound such as bis-alkyl polysulfanyl thiadiazole, and sulfurized phenol.
  • dialkyl polysulfide, dibenzyl disulfide, and thiadiazole type compound are desirable. Particularly desirable is bis-alkyl polysulfanyl thiadiazole.
  • a metal-containing compound such as Ca phenate having a polysulfide bond may be used.
  • this compound has a large coefficient of friction, use of such compound may not always be suitable.
  • the above organic polysulfide compound may be an ashless compound containing no metal, and exhibits excellent performance in maintaining a low coefficient of friction for a long time when used in combination other friction modifiers.
  • polysulfide compound The above ashless organic polysulfide compound (hereinafter referred to briefly as “polysulfide compound”) is added in an amount of 0.01 to 0.4 wt %, typically 0.1-0.3 wt %, and desirably 0.2-0.3 wt %, when calculated as sulfur (S), relative to the total amount of the lubricant composition. If the addition amount is less than 0.01 wt %, it is difficult to attain the intended effect, whereas if it is more than 0.4 wt %, there is a danger that corrosive wear increase.
  • Organic, ashless (metal-free), nitrogen-free friction modifiers which may be used in the lubricating oil compositions disclosed herein are known generally and include esters formed by reacting carboxylic acids and anhydrides with alkanols or glycols, with fatty acids being particularly suitable carboxylic acids.
  • Other useful friction modifiers generally include a polar terminal group (e.g. carboxyl or hydroxyl) covalently bonded to an oleophilic hydrocarbon chain.
  • Esters of carboxylic acids and anhydrides with alkanols are described in U.S. Pat. No. 4,702,850.
  • a particularly desirable friction modifier to use in combination with the magnesium compound is an ester such as glycerol monooleate (GMO).
  • GMO glycerol monooleate
  • the friction modifier described above is included in the lubricating oil compositions disclosed herein an amount effective to allow the composition to reliably pass a high frequency reciprocating rig wear test (HFRR) in combination with the magnesium compound.
  • HFRR high frequency reciprocating rig wear test
  • the friction modifier may be added to the magnesium-containing lubricating oil composition in an amount sufficient to obtain a average HFRR wear scar of less than about 100 square microns.
  • the friction modifier may be added in an amount of from about 0.25 wt. % to about 2.0 wt. % (AI), based on the total weight of the lubricating oil composition.
  • Metal dihydrocarbyl dithiophosphate antiwear agents may be added to the lubricating oil composition according to the exemplary embodiments in combination with the magnesium compound.
  • Such antiwear agents comprise dihydrocarbyl dithiophosphate metal salts wherein the metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium, or zinc.
  • the zinc salts are most commonly used in lubricating oils.
  • Dihydrocarbyl dithiophosphate metal salts may be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohol or a phenol with P 2 S 5 and then neutralizing the formed DDPA with a metal compound.
  • DDPA dihydrocarbyl dithiophosphoric acid
  • a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols.
  • multiple dithiophosphoric acids may be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character.
  • any basic or neutral metal compound may be used but the oxides, hydroxides and carbonates are most generally used. Commercial additives frequently contain an excess of metal due to the use of an excess of the basic metal compound in the neutralization reaction.
  • ZDDP zinc dihydrocarbyl dithiophosphates
  • R 8 and R 9 may be the same or different hydrocarbyl radicals containing from 1 to 18, typically 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals. Particularly desired as R 8 and R 9 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 8 and R 9 ) in the dithiophosphoric acid will generally be about 5 or greater.
  • the zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
  • the ZDDP should desirably be added to the lubricating oil compositions in amounts no greater than from about 1.0 wt. %, based upon the total weight of the lubricating oil composition.
  • the magnesium-containing detergent and the amount of phosphorus from ZDDP in the lubricating oil is desirably no more than about 500 ppm and more desirable from about 250 to about 500 ppm phosphorus to provide the best wear scar results.
  • additives such as the following, may also be present in lubricating oil compositions disclosed herein.
  • Viscosity modifiers function to impart high and low temperature operability to a lubricating oil.
  • the VM used may have that sole function, or may be multifunctional.
  • Multifunctional viscosity modifiers that also function as dispersants are also known.
  • Suitable viscosity modifiers are polyisobutylene, 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.
  • Oxidation inhibitors or 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.
  • oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkylphenolthioesters having C 5 to C 12 alkyl side chains, calcium nonylphenol sulfide, ashless oil soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons, phosphorus esters, metal thiocarbamates and oil soluble copper compounds as described in U.S. Pat. No. 4,867,890.
  • Rust inhibitors selected from the group consisting of nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, and anionic alkyl sulfonic acids may be used.
  • Copper and lead bearing corrosion inhibitors may be used, but are typically not required with the formulations of the disclosed embodiments.
  • such compounds are the thiadiazole polysulfides containing from 5 to 50 carbon atoms, their derivatives and polymers thereof.
  • Derivatives of 1,3,4 thiadiazoles such as those described in U.S. Pat. Nos. 2,719,125; 2,719,126; and 3,087,932; are typical.
  • Other similar materials are described in U.S. Pat. Nos. 3,821,236; 3,904,537; 4,097,387; 4,107,059; 4,136,043; 4,188,299; and 4,193,882.
  • additives are the thio and polythio sulfenamides of thiadiazoles such as those described in UK Patent Specification No. 1,560,830. Benzotriazoles derivatives also fall within this class of additives. When these compounds are included in the lubricating composition, they are typically present in an amount not exceeding 0.2 wt. % active ingredient.
  • a small amount of a demulsifying component may be used.
  • a suitable demulsifying component is described in EP 330,522.
  • the demulsifying component may be made by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide with a polyhydric alcohol.
  • the demulsifying component may be used at a level not exceeding 0.1 mass % active ingredient.
  • a treat rate of 0.001 to 0.05 mass % active ingredient is convenient.
  • 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.
  • Foam control can be provided by many compounds including an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
  • additives may 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 magnesium compound additives may be added directly to the lubricating oil composition. In one embodiment, however, they are diluted with a substantially inert, normally liquid organic diluent such as mineral oil, synthetic oil, naphtha, alkylated (e.g. C 10 -C 13 alkyl) benzene, toluene or xylene to form an additive concentrate. These concentrates usually contain from about 1% to about 100% by weight and in one embodiment about 10% to about 90% by weight of the magnesium compound.
  • a substantially inert, normally liquid organic diluent such as mineral oil, synthetic oil, naphtha, alkylated (e.g. C 10 -C 13 alkyl) benzene, toluene or xylene.
  • These concentrates usually contain from about 1% to about 100% by weight and in one embodiment about 10% to about 90% by weight of the magnesium compound.
  • Base oils suitable for use in formulating the compositions, additives and concentrates described herein may be selected from any of the synthetic or natural oils or mixtures thereof.
  • the synthetic base oils include alkyl esters of dicarboxylic acids, polyglycols and alcohols, poly-alpha-olefins, including polybutenes, alkyl benzenes, organic esters of phosphoric acids, and polysilicone oils.
  • Natural base oils include mineral lubrication oils which may vary widely as to their crude source, e.g., as to whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic.
  • the base oil typically has a viscosity of about 2.5 to about 15 cSt and desrirably about 2.5 to about 11 cSt at 100° C.
  • the base oil used which may be used may be selected from any of the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines.
  • Such base oil groups are as follows:
  • Group 1 Saturates Viscosity Base Oil Group 1 Sulfur (wt. %) (wt. %) Index Group I >0.03 and/or ⁇ 90 80 to 120 Group II ⁇ 0.03 And >90 80 to 120 Group III ⁇ 0.03 And >90 >120 Group IV all polyalphaolefins (PAOs) Group V all others not included in Groups I–IV 1 Groups I–III are mineral oil base stocks.
  • PEOs polyalphaolefins
  • the additives used in formulating the compositions described herein may be blended into the base oil individually or in various sub-combinations. However, it is desirable to blend all of the components concurrently using an additive concentrate (i.e., additives plus a diluent, such as a hydrocarbon solvent).
  • an additive concentrate i.e., additives plus a diluent, such as a hydrocarbon solvent.
  • the use of an additive concentrate takes advantage of the mutual compatibility afforded by the combination of ingredients when in the form of an additive concentrate. Also, the use of a concentrate reduces blending time and lessens the possibility of blending errors.
  • the embodiments provide a lubricating oil for internal combustion engines in which the concentration of the added hydrocarbon soluble magnesium compound is relatively low, providing from about 120 to about 2000 parts per million (ppm) magnesium in terms of elemental magnesium in the oil.
  • the magnesium compound is present in the lubricating oil compositions in an amount sufficient to provide from about 250 to about 1500 ppm magnesium, and in a further embodiment from about 450 to about 1000 ppm magnesium metal.
  • HFRR high frequency reciprocating test rig
  • Each of the lubricant compositions contained a conventional DI package providing about 9 percent by weight of the lubricant composition.
  • the DI package contained conventional amounts of detergents, dispersants, antiwear additives, friction modifiers, antifoam agents, and antioxidants.
  • the formulations also contained small amounts or no ZDDP and 0.35 or no glycerol monooleate friction modifier.
  • Samples 1-4 contained no ZDDP and contained either calcium or magnesium detergents.
  • Samples 5-8 contained 0.05 weight percent ZDDP and either calcium or magnesium detergents.
  • Samples 9-12 contained 0.025 weight percent ZDDP and either calcium or magnesium detergents. The formulations and results are given in the following table.
  • Samples 6, 8, 10, and 12 formulated with a magnesium-containing detergent and ZDDP produced lower wear scars compared to Samples 5, 7, 9, and 11 formulated with calcium-containing detergents and ZDDP.
  • the lowest wear scars were produced by lubricants containing 0.025 wt. % ZDDP (Samples 9-12) as compared to lubricants containing 0.05 wt. % ZDDP (Samples 5-8).
  • Samples 1 and 3 produced lower wear scars than Samples 2 and 4 which indicated that calcium-containing detergents prevent wear better than magnesium-containing detergents in the absence of ZDDP. Comparing the wear results for Samples 3 and 4 to the results for Samples 1 and 2 showed that the addition of a surface active friction modifier interfered with the antiwear properties of both calcium and magnesium detergents. However, friction modifiers are necessary to improve the fuel efficiency properties of oils and would typically be included in fully formulated oils.
  • Samples 6 and 8 produced lower wear scars than Samples 5 and 7, respectively, even though the magnesium-containing detergent was present in Samples 6 and 8.
  • Samples 9 to 12 containing less ZDDP produced even lower wear scars.
  • the presence of glycerol monooleate friction modifier in Sample 12 along with the magnesium-containing detergent prevented wear better than Sample 11 formulated with a calcium-containing detergent.
  • formulations containing from about 120 to about 2000 ppm magnesium compound in the form of a hydrocarbon soluble magnesium compound will enable a reduction in conventional phosphorus and sulfur antiwear agents thereby improving the performance of pollution control equipment on vehicles while achieving a similar or improved antiwear performance or benefit.

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JP2007284824A JP2008144142A (ja) 2006-12-08 2007-11-01 耐摩耗性を改善する添加剤および潤滑剤組成物
DE102007056248A DE102007056248A1 (de) 2006-12-08 2007-11-22 Additive und Schmiermittel-Formulierungen für verbesserte Antiverschleißeigenschaften
GB0723037A GB2444608A (en) 2006-12-08 2007-11-23 Lubricant formulations with improved antiwear properties
FR0759574A FR2909684A1 (fr) 2006-12-08 2007-12-05 Additifs et formulations de lubrifiants utilises pour obtenir des proprietes antiusure ameliorees
RU2007145492/04A RU2007145492A (ru) 2006-12-08 2007-12-07 Присадки и составы смазочных материалов для улучшенный противоизносных свойств
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US20120247412A1 (en) * 2011-03-31 2012-10-04 Chevron Oronite Company Llc Method for improving fuel economy of a heavy duty diesel engine
US20170022441A1 (en) * 2014-01-31 2017-01-26 Exxonmobil Research And Engineering Company Lubricating oil composition
US10947475B2 (en) * 2014-01-31 2021-03-16 Exxonmobil Research And Engineering Company Lubricating oil composition

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JP2008144142A (ja) 2008-06-26
RU2007145492A (ru) 2009-06-20
DE102007056248A1 (de) 2008-07-10
FR2909684A1 (fr) 2008-06-13
CN101245278A (zh) 2008-08-20
GB0723037D0 (en) 2008-01-02
GB2444608A (en) 2008-06-11

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