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WO1994010269A1 - Nouveaux additifs anti-usure-antioxydant pour huiles lubrifiantes - Google Patents

Nouveaux additifs anti-usure-antioxydant pour huiles lubrifiantes Download PDF

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Publication number
WO1994010269A1
WO1994010269A1 PCT/EP1993/003042 EP9303042W WO9410269A1 WO 1994010269 A1 WO1994010269 A1 WO 1994010269A1 EP 9303042 W EP9303042 W EP 9303042W WO 9410269 A1 WO9410269 A1 WO 9410269A1
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Prior art keywords
oil
compound
composition
oils
antiwear
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PCT/EP1993/003042
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WO1994010269B1 (fr
Inventor
Jack Ryer
Abhimanyu Onkar Patil
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ExxonMobil Chemical Ltd
ExxonMobil Chemical Patents Inc
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Exxon Chemical Ltd
Exxon Chemical Patents Inc
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Priority to AU53391/94A priority Critical patent/AU5339194A/en
Publication of WO1994010269A1 publication Critical patent/WO1994010269A1/fr
Publication of WO1994010269B1 publication Critical patent/WO1994010269B1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
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    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/22—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
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    • C10L1/14—Organic compounds
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    • C10L1/2406—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides
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    • C10L1/2462—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
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    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2462—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds
    • C10L1/2475—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon to carbon bonds
    • C10L1/2481—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon to carbon bonds polysulfides (3 carbon to sulfur bonds)
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2462—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds
    • C10L1/2475—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon to carbon bonds
    • C10L1/2487—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon to carbon bonds polyoxyalkylene thioethers (O + S 3=)
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • C10M2223/047—Thioderivatives not containing metallic elements
    • C—CHEMISTRY; METALLURGY
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    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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    • C10N2040/25—Internal-combustion engines
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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    • C10N2040/251—Alcohol-fuelled engines
    • C—CHEMISTRY; METALLURGY
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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Definitions

  • the present invention relates to hydrocarbon soluble or dispersible adducts of benzoquinone and a thioalcohol or a phosphorodithioic acid, their method of preparation, and their utility as antiwear/antioxidant additives for oleaginous compositions such as fuel oils, lubricating oils, including power transmitting fluids and engine lubricating oils, and to the oleaginous compositions in which they are contained.
  • R and R' may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12 carbon atoms and including radicals such as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R and R' groups are alkyl groups of 2 to 8 carbon atoms.
  • the radicals may, for example, be ethyl, n-propyl, i-propyl, n-butyl, i- butyl, sec-butyl, a yl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl etc.
  • the total number of carbon atoms i.e.
  • R and R' in the above formula) in the dithiophosphoric acid will generally be about 5 or greater. While such zinc compounds afford excellent oxidation resistance and exhibit superior anti-wear properties, it has heretofore been believed that they significantly limit the ability to control the friction modification properties of the lubricant compositions in which they are contained.
  • Both anti-wear and friction modifying agents function by forming a coating on the surface of the moving metal parts.
  • the coating bonds are generally effected physically and/or chemically. Consequently, if the bonding between the anti-wear agent and the metal part is stronger than the bonding between the friction modifying agent and the metal part, the anti-wear agent will displace the friction modifying agent at the metal surface, i.e. at the metal/fluid lubrication boundary interface. This results in a loss in the ability of the friction modifying agent to exert its intended effect.
  • ZDDP is recognized as an industry wide standard for imparting anti-wear properties to lubricating compositions, it has been found that it also exhibits a greater affinity for the metal surface than available friction modifying agents.
  • U.S. patents 2,969,378 and 3,071,548 disclose dithiophosphate esters of stilbene quinone for such purposes. These materials are prepared by reacting stilbene quinone and a dialkyl dithiophosphoric acid. The alkyl groups may contain 3 to 20 carbon atoms and the addition of the thiophosphoric acid occurs at the stilbene double bond and not in the ring.
  • Reaction products of quinone and hydroquinone as well as ring substituted versions thereof, and thiophosphoric acid ester compounds having the structure (RO) 2 P(S)SH wherein R is C_, to C 4 alkyl are also known in the art, as disclosed in UK Patent Specification 952,294. These compounds preferably contain alkyl or halo substituent groups on the quinone ring.
  • the preferred method of synthesis employs a halogen substituted p-quinone as a starting material wherein ring halogens are displaced in forming the ester.
  • Monoalkylthiophosphonate esters of hydroquinone prepared by reacting the thioester with p- benzoquinone in alcoholic medium are also disclosed. The utility of such materials as pesticides or pharmaceutical intermediates is disclosed.
  • the present invention provides for an improved lubricating oil composition for automatic transmissions and internal combustion engines, as well as novel oil soluble or oil dispersible compounds which are useful as antiwear/antioxidant additives when incorporated in such oils.
  • the additives of this invention comprise substituted quinones which are the reaction product of a benzoquinone and a thio compound having the formula RSH or (R 1 -0) (R 2 -0) PSSH wherein R,R 1 and R 2 are hydrocarbyl radicals as defined below.
  • the substituted quinones useful as antiwear antioxidant additives may have the general formula 1:
  • R is a straight or branched chain organic radical containing from 5 to about 28 carbon atoms, inclusive of alkyl, alkenyl, alkoxy, aryloxy, oxygen or sulfur-containing heteroalkyl, cycloalkyl, aryl, alkaryl and aralkyl, as well as such radicals which contain substituent groups such as hydroxy, halogen or nitro, and n is 1 or 2.
  • R is an alkyl group and contains from about 5 to about 13 carbon atoms and n is 2.
  • the substituted quinones have the formula 2:
  • R 1 and R 2 are each independently selected from straight or branched chain alkyl, alkenyl, alkoxy, aryloxy, oxygen or nitrogen-containing heteroalkyl, cycloalkyl, aryl, alkaryl and aralkyl radicals containing from 5 to about 28 carbon atoms, as well as such radicals containing halogen, nitro or hydroxy substituent groups, and n is 1 or 2. Most preferably R 1 and R 2 contain from about 5 to about 13 carbon atoms, and n is 2.
  • oxygen or sulfur-containing heteroalkyl groups containing one or more recurring groups of the structure R—X-R 6 ) m wherein X is oxygen or sulfur, R is as defined above, R 6 is an alkylene group containing from 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and m is 1 to 5.
  • Adducts having the structure of formula 1 or 2 may be prepared by heating a mixture of the appropriate RSH thioalcohol compound or (R 1 -0) (R 2 -0) PSSH phosphorodithioic acid compound with benzoquinone in the presence of a suitable reaction solvent such as a lower alcohol (methanol or ethanol) , acetone, methyl ethyl ketone, benzene and the like.
  • a suitable reaction solvent such as a lower alcohol (methanol or ethanol) , acetone, methyl ethyl ketone, benzene and the like.
  • the reaction usually proceeds at room temperature up to about 50°C.
  • the reaction product may comprise a mixture of mono and di- substituted quinones (along with some unreacted quinone) , with the bulk of the reaction product being either the mono or disubstituted product as a function of the quantity of thioalcohol or thioacid used in the reaction.
  • the phosphorodithioic acids used to prepare compounds of formula 2 are prepared by the reaction of phosphorus pentasulfide with an alcohol or phenol or mixtures of alcohols, mixtures of phenols or mixtures of alcohols and phenols.
  • the reaction involves four moles of the alcohol or phenol per mole of phosphorus pentasulfide, and may be carried out within the temperature range from about 50°C to about 200°C, preferably from about 50°C to about 150°C.
  • the preparation of 0,0-di-n-hexyl phosphorodithioic acid involves the reaction of phosphorus pentasulfide with four moles of n-hexyl alcohol at about 100°C for about two hours. Hydrogen sulfide is liberated and the residue is the defined acid.
  • Suitable alcohols which may be reacted with phosphorous pentasulfide are R ⁇ H, R 2 OH or mixed R 1 OH/R 2 OH alcohols wherein the R 1 and R 2 groups are selected from phenyl and alkyl substituted phenyl, amyl, n-hexyl, methylisobutyl, carbinyl, heptyl, 2- ethylhexyl, diisobutyl, octyl, isooctyl, nonyl, behenyl, decyl, dodecyl, tridecyl, etc.
  • Illustrative lower alkylphenyl groups include xylyl, cresyl, butylphenyl, amylphenyl, heptyl- phenyl, etc. Cycloalkyl groups likewise are useful and these include chiefly cyclohexyl and the lower alkyl-cyclohexyl radicals. Many substituted hydrocarbon groups may also be used, e.g., chloropentyl, dichlorophenyl, and dichlorodecyl.
  • the R, R 1 and R 2 groups should be of sufficient chain length such that the quinone adduct is soluble or readily dispersible in the lubricating oil formulation into which it is incorporated.
  • the base lubricating oil into which the additive of this invention may be incorporated includes automotive crankcase and transmission oils of lubricating viscosity for both diesel and gasoline engines, including natural and synthetic lubricating oils and mixtures thereof, as well as gear oils and industrial oils.
  • Natural oils include animal oils and vegetable oils such as castor oil or lard oil, liquid petroleum oils and hydrorefined oils, 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.
  • Synthetic lubricating oils include hydrocarbon and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene- isobutylene copolymers, chlorinated polybutylenes, poly(l-hexenes) , poly(l-octenes) , poly(l-decenes) ; alkylbenezenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2- ethylhexyl) benzenes); and polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols) .
  • polymerized and interpolymerized olefins e.g., polybutylenes, polypropylenes, propylene- isobuty
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification or etherification constitute another class of known synthetic lubricating oils. These are exemplified by polyoxylalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and include the alkyl and aryl ethers of these polyoxyalkylene polymers such as methyl- polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of poly ⁇ ethylene glycol having a molecular weight of 500- 1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500, and ono-and polycarboxylic esters thereof such as acetic acid esters, mixed C ⁇ to C 6 fatty acid esters and the C 13 Oxo acid diester of tetraethylene glycol.
  • Another suitable class of synthetic lubricating oils comprises one or more esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fu aric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids and alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2- ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether and propylene glycol) .
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fu aric acid, adipic
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, dodecyl phthalate, dieicosyl sebacate, the 3-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebasic acid with two moles of tetraethylene glycol and two moles of 2- ethylhexanoic acid.
  • Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipenta- erythritol and tripentaerythritol.
  • Silicon-based oils such as the polyalkyl, polyaryl- polyalkoxy, or polyaryloxysiloxane oils and silicate oils comprise another useful class of synthetic lubricants. These include tetraethyl silicate, tetraisopropyl silicate, tetra-(2- ethylhexyl) silicate, tetra-4 (4-methyl-2- ethylhexyl) silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-pentoxy) disiloxane, poly(methyl)siloxanes and poly(methylphenyl) siloxanes.
  • Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
  • Unrefined, refined and rerefined oils can be used in the lubricants of the present invention.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • a shale oil obtained directly from retorting operations a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil.
  • 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. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art.
  • Rerefined oils are obtained by processes similar to those used to obtain refined oils, but applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
  • the quinone adduct of this invention is blended into the lube oil base stock in amounts which are effective to enhance the anti-wear and antioxidant properties of the oil.
  • effective amounts range from about 0.1 to about 2% by weight, more preferably from about 0.3 to 1.0% by weight, based on the weight of the oil.
  • the benefits of the additive of the present invention are particularly significant when employed in a lubricating oil adapted for use as an automatic transmission fluid.
  • Power transmitting fluids such as automatic transmission fluids, as well as lubricating oils in general, are typically compounded from a number of additives each useful for improving chemical and/or physical properties of the same.
  • the additives are usually sold as a concentrate package in which mineral oil or some other base oil is present.
  • the mineral lubricating oil in automatic transmission fluids typically is refined hydrocarbon oil or a mixture or refined hydrocarbon oils selected according to the viscosity requirements of the particular fluid, but typically would - have a viscosity range of 2.5-9, e.g. 3.5-9 cst. at 100°C.
  • Suitable base oils include a wide variety of light hydrocarbon mineral oils, such as naphthenic base oils, paraffin base oils, and mixtures thereof.
  • V.I. viscosity index
  • corrosion inhibitors corrosion inhibitors
  • oxidation inhibitors oxidation inhibitors
  • friction modifiers lube oil flow improvers
  • dispersants anti-foa ants
  • other supplemental anti-wear agents detergents
  • metal rust inhibitors seal swellants.
  • Suitable dispersants which may be employed are known in the art.
  • a preferred class of dispersant are the ashless dispersants which are normally nitrogen-containing, oil-soluble salts, amides, i ides or esters of mono or dicarboxylic acids.
  • a particularly preferred dispersant is the reaction product of a polyolefin-substituted succinic anhydride such as polyisobutenyl succinic anhydride and an alkylene polyamine, which can be further treated with a source of boron or copper.
  • a polyolefin-substituted succinic anhydride such as polyisobutenyl succinic anhydride and an alkylene polyamine, which can be further treated with a source of boron or copper.
  • Such a material is disclosed in U.S. Patent 4,938,880, the complete disclosure of which is incorporated herein by reference.
  • Such dispersants are generally added to the oil in amounts ranging from about 0.1 to about 10% by
  • Metal containing rust inhibitors and/or detergents are frequently used with ashless dispersants.
  • Such detergents and rust inhibitors include the metal salts of sulphonic acids, fatty acid esters such as glycerol mono and/or di stearate (which also function as friction modifiers) , alkyl phenols, sulfurized alkyl phenols, alkyl salicylates, naphthenates, and other oil soluble mono- and di ⁇ carboxylic acids.
  • Highly basic, that is overbased metal salts, which are frequently used as detergents include calcium or magnesium phenates, sulfurized phenates and/or sulfonates.
  • metal containing inhibitors and detergents are used in lubricating oil in amounts of about 0.01 to 10 wt.%, more preferably about 0.1 to 5 wt.%, based on the weight of the total lubricating composition.
  • Marine diesel lubricating oils typically employ such metal-containing rust inhibitors and detergents in amounts up to about 20 wt.%.
  • the oil may also contain one or more supplemental antioxidants and/or oxidation inhibitors.
  • Suitable antioxidants include phenols, hindered phenols, bis-phenols, sulfurized phenols, catechol, alkylated and sulfurized alkylated catechols, diphenylamine, alkylated diphenylamines and phenyl- 1-naphthylamines and alkyl and aryl borates, phosphites and phosphates.
  • antioxidants include oil soluble copper compounds.
  • the copper compound may be in the cuprous and cupric form.
  • the copper may be in the form of copper dihydrocarbyl thio- or dithio- phosphates.
  • the copper may be added as the copper salt of a synthetic or natural carboxylic acid. Examples include C 10 to c 18 fatty acids such as stearic or palmitic. Unsaturated acids such as oleic or branched carboxylic acids such as napththenic acids of molecular weight from 200 to 500 or synthetic carboxylic acids are preferred because of the improved handling and solubility properties of the resulting copper carboxylates. Also useful are oil soluble copper dithiocarbamates.
  • the copper antioxidant can comprise a copper salt of a hydrocarbyl substituted C to C 10 monounsaturated dicarboxylic acid producing reaction product, which reaction product is formed by reacting a polymer of a C 2 to C 10 monolefin having a number average molecular weight of 900 to 1400 (e.g., 700 to 1200) substituted with a C 4 to C 10 monounsaturated acid material.
  • Exemplary are copper salts of a hydrocarbyl substituted C 4 to C 10 monounsaturated dicarboxylic acid producing reaction product, which reaction product is formed by reacting a polymer of C 2 to C 10 monolefin having a number average molecular weight of from 900 to 1400 substituted with succinic moieties selected from the group consisting of acid, anhydride and ester groups, wherein there is an average of about 0.8 to 1.6 molar proportions of succinic moieties per molar proportion of the polymer.
  • the copper antioxidants will generally be added to the oil in an amount of from about 50-500 ppm by weight of the metal.
  • Corrosion inhibitors also known as anti-corrosive agents, reduce the degradation of the metallic parts contacted by the lubricating oil composition.
  • Illustrative of corrosion inhibitors are phosphosulfurized hydrocarbons and the products obtained by reaction of a phosphosulfurized hydrocarbon with an alkaline earth metal oxide or hydroxide, preferably in the presence of carbon dioxide.
  • Phosphosulfurized hydrocarbons are prepared by reacting a suitable hydrocarbon such as a terpene, a heavy petroleum fraction of a C 2 to C 6 olefin polymer such as polyisobutylene, with from 5 to 30 weight percent of a sulfide of phosphorus for 0.5 to 15 hours, at a temperature in the range of 150° to 600° C. Neutralization of the phosphosulfurized hydrocarbon may be effected in the manner taught in U.S. Patent 1,969,324.
  • Oxidation inhibitors reduce the tendency of mineral oils 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 viscosity growth.
  • oxidation inhibitors include alkaline earth metal salts of alkylphenolthioesters having preferably C 5 to C 12 alkyl side chains, calcium nonylphenol sulfide, barium t-octylphenyl sulfide, dioctylphenylamine, phenylalphanaphthylamine, phosphosulfurized or sulfurized hydrocarbons, etc.
  • Pour point depressants lower the temperature at which the oil will flow or can be poured. Such depressants are well known. Typical of those additives which usefully optimize the low temperature fluidity of the oil are 8 -C 18 dialkylfumarate/vinyl acetate copolymers, polymethacrylates, and wax naphthalene.
  • Foam control can be provided by an antifoa ant of the polysiloxane type, e.g. silicone oil and polydimethyl siloxane.
  • an antifoa ant of the polysiloxane type e.g. silicone oil and polydimethyl siloxane.
  • the oil of the present invention may also contain one or more alkoxylated amine friction modifier components as are known in the art.
  • Preferred additives have the general formula:
  • R 3 is a branched or straight chain hydrocarbyl or oxyhydrocarbyl group having from about 8 to about 30 carbon atoms
  • R 4 and R 5 are independently the same or different alkylene radicals containing from 2 to 4 carbon atoms and (a) and (b) are independently integers ranging from 1 to 4. Both (a) and (b) are preferably 1.
  • alkoxylated amines are those of the formula and wherein R 4 and R 5 each have 2 carbon atoms and include:
  • the hydroxyl amine compounds may be used as such. However they may also be used in the form of an adduct or reaction product with a boron compound, such as a boric oxide, a boron halide, a metaborate, boric acid, or a mono-, di-, or triorgano borate, such as a mono-, di-, and .-rialkyl borate.
  • a boron compound such as a boric oxide, a boron halide, a metaborate, boric acid, or a mono-, di-, or triorgano borate, such as a mono-, di-, and .-rialkyl borate.
  • a boronation agents include boric acid and boric acid esters, e.g., tributyl borate.
  • Anti-wear agents reduce wear of moving metallic parts.
  • Representative of conventional anti-wear agents which may be used to supplement the present thioquinone adducts are the zinc dialkyl-dithiophosphates and the zinc diaryldithiophosphates.
  • supplemental anti-wear agents do not have to be employed and, in fact, can be excluded from the compositions of this invention.
  • Viscosity modifiers impart high and low temperature operability to the lubricating oil and permit it to remain relatively viscous at elevated temperatures and also exhibit acceptable viscosity or fluidity at low temperatures. Viscosity modifiers are generally high molecular weight polymers, including polyesters, polyacrylates and polyolefins.
  • the viscosity modifiers may also be derivatized to include other properties or functions, such as the addition of dispersancy properties.
  • These oil soluble viscosity modifying polymers will generally have number average molecular weights of from 10 3 to 10 6 , preferably 10 4 to 10 6 , e.g., 20,000 to 250,000, as determined by gel permeation chromotography or osmometry.
  • suitable hydrocarbon polymers include homopolymers and copolymers of two or more C 2 to C ⁇ Q olefin monomers, e.g. C 2 to C 8 olefins, including both alpha olefins and internal olefins, which may be straight or branched, aliphatic, aromatic, alkyl-aromatic, cycloaliphatic, etc.
  • Particularly preferred polymers are polyisobutylenes, homopolymers and copolymers of C 2 and higher alpha olefins, atactic polypropylene, hydrogenated polymers and copolymers and terpolymers of styrene, e.g. with isoprene and/or butadiene and hydrogenated derivatives thereof.
  • the polymer may be degraded in molecular weight, for example by mastication, extrusion, oxidation or thermal degradation, and may contain oxygen.
  • These viscosity modifiers are normally added to the oil composition at a level within the range of from about 0.1 to about 10% by weight.
  • Seal swellants include mineral oils of the type that provoke swelling, including aliphatic alcohols of 8 to 13 carbon atoms such as tridecyl alcohol, with a preferred seal swellant being characterized as an oil-soluble, saturated, aliphatic or aromatic hydrocarbon ester of from 10 to 60 carbon atoms and 2 to 4 linkages, e.g. dihexylphthalate, as are described in U.S. Patent 3,974,081.
  • compositions when containing these additives, typically are blended into the base oil in amounts which are effective to provide their normal attendant function.
  • Effective amounts of such additives are illustrated as follows:
  • the additive of the present invention when employed in a lubricating oil composition, typically in a minor amount, is effective to impart enhanced anti-wear and friction stability properties thereto relative to the same composition in the absence of the present additive.
  • Additional conventional additives, particularly dispersants and friction modifiers, selected to meet the particular requirements of a selected type of lubricating oil composition also can be included as desired.
  • Example 1 was repeated except that 61.Og (.172mol) of the ester and 18.61g (.172mol) of benzoquinone were used in the reaction mixture.
  • the reaction product was primarily the 1:1 aduct having the structure:
  • This example shows the preparation of an adduct having the structure of formula 1 above wherein n is 1, substitution occurs at the 2 position on the quinone ring and R has 12 carbon atoms.
  • Control Test Base An ATF base fluid, designated hereinafter as the Control Test Base, was formulated with conventional amounts of a seal swell additive, an antioxidant and a viscosity index improver.
  • the composition of the Test Base is as follows:
  • Example 4 The Control Test Base of Example 4 was further formulated by thoroughly admixing it with 0.4% by weight of the anti-wear/antioxidant additive prepared in Example 1.
  • This test employs a gear box containing a wheel gear engaged with a pinion gear.
  • the pinion gear is connected by an axle to a motor.
  • the motor turns the pinion gear through the axle and the pinion gear serves to drive the wheel gear.
  • the wheel gear is connected to a different axle which extends out of the gear box.
  • a load is applied to the wheel gear during the test which creates resistance to the turning of the wheel gear by the pinion gear. This load is applied in several stages and increases in each stage. The load is expressed as torque (N.m) at the pinion gear.
  • test gear box Prior to the start of each run, the test gear box is carefully flushed twice with a suitable solvent (non-flammable) .
  • a suitable solvent non-flammable
  • the solvent is filled above the center of the shaft axles.
  • the machine is then turned one full rotation by hand to remove waste oil from the bearings assemblies.
  • the complete housing is then dried thoroughly.
  • test gears are likewise washed.
  • the tooth flanks are visually inspected from a fixed viewing distance of 25 cm. Existing irregularities are noted. Test wheels with any signs of rusting or corrosion are discarded.
  • the pinion and wheel gears are marked in such a way that when the test pieces are reassembled, the same teeth mesh as before.
  • the test gear box is filled with the oil formulation to be tested up to the center of the shafts.
  • a preliminary run is made at the first load stage while heating until the temperature has reached 90 + 3°C.
  • the motor and rig are turned off until the next load stage is run.
  • the pinion and wheel gears are disassembled at the end of each load stage, washed in solvent, allowed to cool to room temperature, washed again and this time dried with an air gun.
  • test gears are then separately examined at the fixed viewing distance for changes in appearance of the flanks.
  • smoothing of the grinding marks, scratches, scoring, seizure marks, discoloration of the tooth flanks, corrosion symptoms, deposits, the natural position, and extent of the change of the tooth flanks are all noted.
  • the inspected gears are then re-mounted on the shafts for the next load stage.
  • the same oil is used and the load stages are increased until a marked deviation (e.g. increase) in deterioration of the visible appearance of the gears is observed relative to the progressive deterioration observed in previous load stages.
  • a marked deviation e.g. increase
  • the oil fails that load stage and the test is completed.
  • the load stage at failure is reported as the FZG value.
  • the lubricant-multiple oxidation test is designed to measure the resistance to oxidation of lubricant materials. 50 grams of oil, 2.0 grams of iron filings and 0.5 gram of copper naphthenate are placed in a 100ml test tube. The tube with the contents is then placed in an aluminum heating block and heated to 150°C. Air is then continuously bubbled through the oil sample at a rate of about 25cc per minute while maintaining the temperature at 150°C. One drop of the oil sample is placed on a blotter strip every twenty four hours. When the oil spot becomes black, the test has failed. The number of days required to reach this point of failure is then recorded.
  • LMOT lubricant-multiple oxidation test
  • Example 5 The results for testing the Control formulation of Example 4 and the formulation of this invention (Example 5) were as follows:
  • Test results show that the oil formulation containing the additive of the present invention provides enhanced antiwear and antioxidant properties when compared with an identical formulation but without the additive.

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Abstract

Cette invention concerne une nouvelle composition d'huile lubrifiante destinée aux transmissions automatiques et aux moteurs à combustion interne, ainsi que de nouveaux composés qui se dispersent ou sont solubles dans l'huile, et sont d'utiles additifs anti-usure-antioxydant lorsqu'ils sont incorporés dans ces huiles. Les additifs de cette invention comprennent des quinones substituées qui sont le produit de réaction d'une benzoquinone et d'un composé thio de formule RSH ou (R?1-O) (R2¿-O) PSSH, dans laquelle R, R1 et R2 représentent des radicaux hydrocarbyle. On a découvert que ces additifs confèrent de bonnes propriétés anti-usure et antioxydante à ces huiles et à ces fluides, notamment lorsqu'on les associe à d'autres constituants d'additifs classiques pour l'huile.
PCT/EP1993/003042 1992-11-02 1993-10-30 Nouveaux additifs anti-usure-antioxydant pour huiles lubrifiantes Ceased WO1994010269A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU53391/94A AU5339194A (en) 1992-11-02 1993-10-30 Novel antiwear-antioxidant additives for lubricating oils

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US97101492A 1992-11-02 1992-11-02
US07/971,014 1992-11-02

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10955009B2 (en) 2018-04-03 2021-03-23 Borgwarner Inc. Clutch pack having different clutch plate materials

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB952294A (en) * 1961-06-30 1964-03-11 Bayer Ag Phosphorus-containing hydroquinone and quinone derivatives
US3143507A (en) * 1961-08-08 1964-08-04 Lubrizol Corp Reaction products of phosphorus thioic acids with quinoid compounds and lubricants containing same
US3328301A (en) * 1965-09-23 1967-06-27 Eastman Kodak Co Antioxidants for lubricating oils
FR2174021A1 (fr) * 1972-02-28 1973-10-12 Texaco Development Corp
GB1404567A (en) * 1972-05-25 1975-09-03 Texaco Developments Corp Lubricant composition containing tetra-t-dodecylmercapto- p-benzoquinone

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB952294A (en) * 1961-06-30 1964-03-11 Bayer Ag Phosphorus-containing hydroquinone and quinone derivatives
US3143507A (en) * 1961-08-08 1964-08-04 Lubrizol Corp Reaction products of phosphorus thioic acids with quinoid compounds and lubricants containing same
US3328301A (en) * 1965-09-23 1967-06-27 Eastman Kodak Co Antioxidants for lubricating oils
FR2174021A1 (fr) * 1972-02-28 1973-10-12 Texaco Development Corp
GB1404567A (en) * 1972-05-25 1975-09-03 Texaco Developments Corp Lubricant composition containing tetra-t-dodecylmercapto- p-benzoquinone

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10955009B2 (en) 2018-04-03 2021-03-23 Borgwarner Inc. Clutch pack having different clutch plate materials

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