EP2614131B1 - Dérivés d'hydroxychromane comme antioxydants - Google Patents

Dérivés d'hydroxychromane comme antioxydants Download PDF

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Publication number
EP2614131B1
EP2614131B1 EP11755481.6A EP11755481A EP2614131B1 EP 2614131 B1 EP2614131 B1 EP 2614131B1 EP 11755481 A EP11755481 A EP 11755481A EP 2614131 B1 EP2614131 B1 EP 2614131B1
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Prior art keywords
lubricant composition
composition
antioxidant
oil
groups
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EP11755481.6A
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German (de)
English (en)
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EP2614131A1 (fr
Inventor
Seth L. Crawley
Virginia A. Carrick
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Lubrizol Corp
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Lubrizol Corp
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Priority to EP16164519.7A priority Critical patent/EP3070153B1/fr
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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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/16—Ethers
    • C10M129/20—Cyclic ethers having 4 or more ring atoms, e.g. furans, dioxolanes
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
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    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
    • C10L1/2235—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom hydroxy containing
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    • C10L1/2406—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides
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    • 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
    • C10M141/06—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 nitrogen-containing compound
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    • 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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    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
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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
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    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
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    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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    • 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
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

Definitions

  • compositions suitable for use as lubricants and lubricant additive compositions which contain a hydroxychroman derived antioxidant, where said antioxidants themselves may also be described hydroxychroman compounds, and further optionally containing other additives suitable for lubricants such as a detergent or a dispersant.
  • the present invention provides an economical antioxidant which has good performance properties when used in lubricant formulations especially for heavy duty diesel engines and passenger car crankcase engines.
  • Antioxidants are an important class of additives since they are used to provide and/or improve the anti-oxidation performance of organic compositions, including lubricant compositions that contain organic components, by preventing or retarding oxidative and thermal decomposition. Antioxidants in some applications can result in an increase in volatility which can be undesirable due to required environmental regulations and/or performance standards.
  • U.S. Patent 3,285,855, Dexter et al., November 15, 1966 discloses stabilization of organic material with esters containing an alkylhydroxyphenyl group.
  • the ester can have the structure in which x has a value of from 0 to 6, inclusively, and y has a value of from 6 to 30, inclusively.
  • the "lower alkyl” groups can be t-butyl.
  • Organic materials which can be stabilized include, among many others, lubricating oil of the aliphatic ester type, and mineral oil.
  • U.S. Patent 5,206,414, Evans et al., April 27, 1993 discloses a process for the preparation of compounds of the general formula wherein R1 and R2 are identical or different and are hydrogen, C1-C18 alkyl, phenyl, C1-C4 alkyl-substituted phenyl, C7-C9 phenylalkyl, C5-C12 cycloalkyl or C1-C4 alkyl-substituted C5-C12 cycloallcyl, R3 is hydrogen or methyl, m is 0,1,2, or 3 and n is a number from 1 to 4 or 6, and A can be -OR4 where R4 can be C2-C45 alkyl.
  • U.S. Patent No. 6,559,105 of Abraham et al. involves lubricant compositions containing ester-substituted hindered phenol antioxidants. wherein R3 is an alkyl group containing 2 to 6 carbon atoms, and a dispersant or a detergent, is a useful additive package for lubricant compositions.
  • U.S Patent 6,787,663, Adams et al., September 7, 2004 discloses a process for the preparation of a hindered ester-substituted phenol and its use in a lubricant composition of the general formula wherein R3 is an alkyl group containing 2 to 6 carbon atoms.
  • current engine technology is leading to increasing operating temperatures for engines and the lubricating oils on which they rely.
  • modern EGR, turbochargers, and the increased usage of smaller, more powerful and fuel efficient engines are leading to an increase in average engine operating temperatures. Therefore, there is a need for new antioxidant technology that provides at least as good performance as known antioxidant technology while also providing improved thermal stability and/or performance at elevated temperatures.
  • the present invention provides for a lubricating composition containing an oil of lubricating viscosity and an antioxidant having the formula:
  • the invention further provides for lubricant compositions as described above where the composition contains no more than 1200 ppm phosphorus, has a sulfur content of no more than 0.4 percent by weight, has a sulfated ash content of no more than 1.0 percent by weight, has a zinc dialkyldithiophosphate at a level of no less than 300 ppm, or any combinations thereof.
  • the composition may have a phosphorus level of at least 300 ppm.
  • the invention further provides for methods of lubricating an internal combustion engine. Such methods include the step of supplying to the engine any of the lubricant compositions described herein.
  • the invention further provides a lubricant composition suitable for lubricating an internal combustion engine, comprising: (A) a major amount of an oil of lubricating viscosity; (B) a minor amount of at least one hydroxychroman antioxidant, as described herein; and (C) a minor amount of at least one other additive selected from the group consisting of viscosity modifiers, pour point depressants, dispersants, detergents, antiwear agents, antioxidants are different from component (B), friction modifiers, corrosion inhibitors, seal swell agents, metal deactivators, foam inhibitors, and mixtures thereof.
  • the invention further provides for a lubricant concentrate suitable for use in preparing a lubricating composition suitable for lubricating an internal combustion engine, comprising: (A) a concentrate-forming amount of an oil of lubricating viscosity; (B) a minor amount of at least one hydroxychroman antioxidant, as described herein; and (C) at least one other additive selected from the group consisting of viscosity modifiers, pour point depressants, dispersants, detergents, antiwear agents, antioxidants that are different from component (B), friction modifiers, corrosion inhibitors, seal swell agents, metal deactivators, foam inhibitors, and mixtures thereof.
  • a lubricant concentrate suitable for use in preparing a lubricating composition suitable for lubricating an internal combustion engine, comprising: (A) a concentrate-forming amount of an oil of lubricating viscosity; (B) a minor amount of at least one hydroxychroman antioxidant, as described herein; and (C) at least one other additive selected from the group
  • the present invention further provides a method for lubricating an internal combustion engine, comprising: (A) supplying to said engine a lubricant comprising: (i) an oil of lubricating viscosity; (ii) a minor amount of at least one hydroxychroman antioxidant, as described herein; and (iii) a minor amount of at least one other additive selected from the group consisting of viscosity modifiers, pour point depressants, dispersants, detergents, antiwear agents, antioxidants that are different from component (ii), friction modifiers, corrosion inhibitors, seal swell agents, metal deactivators, foam inhibitors, and mixtures thereof.
  • a lubricant comprising: (i) an oil of lubricating viscosity; (ii) a minor amount of at least one hydroxychroman antioxidant, as described herein; and (iii) a minor amount of at least one other additive selected from the group consisting of viscosity modifiers, pour point depressants, dispersants, detergents,
  • the present invention provides various compositions that comprise one or more hydroxychroman derived antioxidants, wherein said antioxidants may themselves also be described as hydroxychroman compounds, and methods of lubricating internal combustion engines utilizing such antioxidants.
  • Such antioxidants have been discovered to provide superior performance in the harsher operating conditions becoming more and more common in modem engine technology.
  • the drive to design smaller and more powerful engines along with the drive to increase fuel economy and reduce emissions, has led to higher demands on lubricants and lubricant additive technology.
  • the antioxidants of the present invention have been found to provide superior performance compared to conventional antioxidants.
  • compositions of the present invention comprise an oil of lubricant viscosity, one or more hydroxychroman derived antioxidants, and optionally one or more additional performance additives.
  • the lubricant composition of this invention can find use in various applications to include as a lubricant composition for an internal combustion engine to include a gasoline or spark-ignited engine such as a passenger car engine, a diesel or compression-ignited engine such as a heavy duty diesel truck engine, a natural gas fueled engine such as a stationary power engine, a two-cycle engine, aviation piston and turbine engines, marine and railroad diesel engines; for power transmissions such as an automatic or transaxle or farm tractor transmission; for gears such as industrial or automotive gears; for metalworking; for hydraulic systems; for special applications such as bearings which can require that the lubricant composition be a grease.
  • a gasoline or spark-ignited engine such as a passenger car engine
  • a diesel or compression-ignited engine such as a heavy duty diesel truck engine
  • a natural gas fueled engine such as a stationary power engine, a two-cycle engine, aviation piston and turbine engines, marine and railroad diesel engines
  • for power transmissions such as an automatic or transaxle or
  • the lubricant composition of the present invention can comprise (A) a major amount of an oil of lubricating viscosity.
  • the oil of lubricating viscosity can function by providing lubrication and by serving as a medium to dissolve or disperse the other components or additives of the lubricant composition.
  • the oil of lubricating viscosity can be a single oil or a mixture of two or more oils.
  • the lubricating oil composition comprises of one or more base oils which are generally present in a major amount (i.e. an amount greater than 50 percent by weight). Generally, the base oil is present in an amount greater than 60 percent, or greater than 70 percent, or greater than 80 percent by weight of the lubricating oil composition.
  • the base oil sulfur content can be 0.001 to 0.2 percent by weight, in another embodiment 0.0001 to 0.1 or 0.05 percent by weight.
  • the lubricating oil composition may have a kinematic viscosity as measured in ASTM D445, of up to about 16.3 mm 2 /s at 100°C, and in one embodiment 5 to 16.3 mm 2 /s (cSt) at 100°C, and in one embodiment 6 to 13 mm 2 /s (cSt) at 100°C.
  • the lubricating oil composition has an SAE Viscosity Grade of 0W 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40 or 10W-50.
  • the lubricating oil composition may have a high-temperature/high-shear viscosity at 150°C as measured by the procedure in ASTM D4683 of up to 4 mm 2 /s (cSt), and in one embodiment up to 3.7 mm 2 /s (cSt), and in one embodiment 2 to 4 mm 2 /s (cSt), and in one embodiment 2.2 to 3.7 mm 2 /s (cSt), and in one embodiment 2.7 to 3.5 mm 2 /s (cSt).
  • cSt high-temperature/high-shear viscosity at 150°C as measured by the procedure in ASTM D4683 of up to 4 mm 2 /s (cSt), and in one embodiment up to 3.7 mm 2 /s (cSt), and in one embodiment 2 to 4 mm 2 /s (cSt), and in one embodiment 2.2 to 3.7 mm 2 /s (cSt), and in one embodiment 2.7 to 3.5 mm 2 /s
  • the base oil used in the lubricant composition may be a natural oil, synthetic oil or mixture thereof, provided the sulfur content of such oil does not exceed the above-indicated sulfur concentration limit required for the inventive low-sulfur, low-phosphorus, low-ash lubricating oil composition.
  • the natural oils that are useful include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as 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. Oils derived from coal or shale are also useful.
  • Synthetic lubricating oils include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, and propylene isobutylene copolymers); poly(1-hexenes), poly-(1-octenes), poly(1-decenes), etc.
  • hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, and propylene isobutylene copolymers); poly(1-hexenes), poly-(1-octenes), poly(1-decenes), etc.
  • alkylbenzenes e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, and di-(2-ethylhexyl)benzenes
  • polyphenyls e.g., biphenyls, terphenyls, alkylated polyphenyls
  • alkylated diphenyl ethers and the derivatives, analogs and homologs thereof.
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by e.g., esterification, etherification constitute another class of known synthetic lubricating oils that can be used. These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polypropylene glycol ether having an average molecular weight of about 1000, diphenyl ether of polyethylene glycol having a molecular weight of about 500-1000, diethyl ether of polypropylene glycol having a molecular weight of about 1000-1500, etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3 -C 8 fatty acid esters, or the carboxylic acid diester of tetraethylene glycol.
  • the oils prepared through polymerization of ethylene oxide or propylene oxide
  • esters of dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, dodecanedioic acid
  • alcohols e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether and propylene glycol
  • these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctylic acids
  • Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol and tripentaerythritol.
  • the oil can be a poly-alpha-olefin (PAO).
  • PAOs are derived from monomers having from 4 to 30, or from 4 to 20, or from 6 to 16 carbon atoms.
  • useful PAOs include those derived from octene, decene and mixtures thereof. These PAOs may have a viscosity from 2 to 15, or from 3 to 12, or from 4 to 8 mm 2 /s (cSt), at 100°C.
  • Examples of useful PAOs include 4 mm 2 /s (cSt) at 100°C poly-alpha-olefins, 6 mm 2 /s (cSt) at 100°C poly-alpha-olefins, and mixtures thereof. Mixtures of mineral oil with one or more of the foregoing PAOs may be used.
  • Unrefined, refined and rerefined oils either natural or synthetic (as well as mixtures of two or more of any of these) of the type disclosed hereinabove 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 primary 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.
  • Rerefined oils are obtained by processes similar to those used to obtain refined oils 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 directed to removal of spent additives and oil breakdown products.
  • synthetic oils may be produced by Fischer-Tropsch gas to liquid synthetic procedure as well as other gas-to-liquid oils.
  • the polymer composition of the present invention is useful when employed in a gas-to-liquid oil. Often Fischer-Tropsch hydrocarbons or waxes may be hydroisomerised.
  • antioxidant additives of the present invention are derived from hydroxychroman.
  • suitable antioxidants can be represented by the formula: wherein R 3 is a methyl group, both R 2 groups are methyl groups, all R 1 groups are hydrogen and R 4 is a branched alkyl group containing from 1 to 10 carbon atoms.
  • R 4 is a branched alkyl group containing from 3 to 10 or 8 carbon atoms. In some embodiments R 4 is a tert-butyl group.
  • the antioxidant (B) can be present on a weight basis in the lubricant composition of this invention at 0.3 to 8%, or 0.6 to 6%.
  • the lubricant composition of the invention can optionally comprise (C) a minor amount of at least one other additive.
  • the other additive (C) can comprise a member selected from the group consisting of a viscosity modifier, a pour point depressant, a dispersant, a detergent, an antiwear agent, an antioxidant that is different from component (B), a friction modifier, a corrosion inhibitor, a seal swell agent, a metal deactivator, a foam inhibitor, and a mixture thereof.
  • the mixture of other additives can be 2 or more additives of the same type such as for example a sulfonate and phenate detergent, 2 or more additives of different types such as for example a detergent and dispersant and antiwear agent, or 2 or more additives of the same type as well as 2 or more additives of different types such as for example a sulfonate and phenate detergent and a dispersant and an antiwear agent.
  • the lubricant composition of the present invention may contain one or more dispersants.
  • Carboxylic dispersants are reaction products of carboxylic acylating agents (acids, anhydrides, esters, etc.) containing at least 34 and preferably at least 54 carbon atoms which are reacted with nitrogen containing compounds (such as amines), organic hydroxy compounds (such as aliphatic compounds including monohydric and polyhydric alcohols, or aromatic compounds including phenols and naphthols), and/or basic inorganic materials.
  • nitrogen containing compounds such as amines
  • organic hydroxy compounds such as aliphatic compounds including monohydric and polyhydric alcohols, or aromatic compounds including phenols and naphthols
  • reaction products include imide, amide, and ester reaction products of carboxylic ester dispersants.
  • Succinimide dispersants are a species of carboxylic dispersants. They are the reaction product of a hydrocarbyl substituted succinic acylating agent with an organic hydroxy compound or, an amine containing at least one hydrogen attached to a nitrogen atom, or a mixture of said hydroxy compound and amine.
  • succinic acylating agent refers to a hydrocarbon-substituted succinic acid or succinic acid-producing compound (which term also encompasses the acid itself).
  • Such materials typically include hydrocarbyl-substituted succinic acids, anhydrides, esters (including half esters) and halides.
  • Succinic based dispersants have a wide variety of chemical structures including typically structures such as
  • each R 1 is independently a hydrocarbyl group, such as a polyolefin-derived group having an M n of 500 or 700 to 10,000.
  • the hydrocarbon based group is an alkyl group, frequently a polyisobutylene group derived from polyisobutylene having a molecular weight of 500 or 700 to 5000, or alternatively 1500 or 2000 to 5000.
  • the R 1 groups can contain 40 to 500 carbon atoms, for instance at least 50, e.g., 50 to 300 carbon atoms, such as aliphatic carbon atoms.
  • the R 2 are alkylene groups, commonly ethylene (C 2 H 4 ) groups. X is an integer and is not overly limited.
  • X has the value within the range of zero, 1 or even 2 up to 10, or 6 or 4.
  • Such molecules are commonly derived from reaction of an alkenyl acylating agent with a polyamine, and a wide variety of linkages between the two moieties is possible beside the simple imide structure shown above, including a variety of amides and quaternary ammonium salts.
  • Succinimide dispersants are more fully described in U.S. Patents 4,234,435 , 3,172,892 and 6,165,235 .
  • Ammonium dispersants are reaction products of relatively high molecular weight aliphatic halides and amines, preferably polyalkylene polyamines. Examples thereof are described, for example, in the following U.S. Patents: 3,275,554 , 3,438,757 , 3,454,555 , and 3,565,804 .
  • Mannich dispersants are the reaction products of alkyl phenols in which the alkyl group contains at least 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines).
  • aldehydes especially formaldehyde
  • amines especially polyalkylene polyamines.
  • the materials described in the following U.S. Patents are illustrative: 3,036,003 , 3,236,770 , 3,414,347 , 3,448,047 , 3,461,172 , 3,539,633 , 3,586,629 , 3,591,598 , 3,634,515 , 3,725,480 , 3,726,882 , and 3,980,569 .
  • Post-treated dispersants are obtained by reacting carboxylic, amine or Mannich dispersants with reagents such as dimercaptothiadiazoles, urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles epoxides, boron compounds, phosphorus compounds or the like. Exemplary materials of this kind are described in the following U.S.
  • Patents 3,200,107 , 3,282,955 , 3,367,943 , 3,513,093 , 3,639,242 , 3,649,659 , 3,442,808 , 3,455,832 , 3,579,450 , 3,600,372 , 3,702,757 , and 3,708,422 .
  • Polymeric dispersants are interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, e.g., aminoalkyl acrylates or acrylamides and poly-(oxyethylene)-substituted acrylates.
  • polar substituents e.g., aminoalkyl acrylates or acrylamides and poly-(oxyethylene)-substituted acrylates.
  • Examples of polymer dispersants thereof are disclosed in the following U.S. Patents: 3,329,658 , 3449,250 , 3,519,656 , 3,666,730 , 3,687,849 , and 3,702,300 .
  • the composition can also contain one or more detergents, which are normally salts, and specifically overbased salts.
  • detergents which are normally salts, and specifically overbased salts.
  • overbased materials are well known to those skilled in the art.
  • Patents describing techniques for making basic salts of sulfonic acids, carboxylic acids, (hydrocarbyl-substituted) phenols, phosphonic acids, and mixtures of any two or more of these include U.S. Patents 2,501,731 ; 2,616,905 ; 2,616,911 ; 2,616,925 ; 2,777,874 ; 3,256,186 ; 3,384,585 ; 3,365,396 ; 3,320,162 ; 3,318,809 ; 3,488,284 ; and 3,629,109 .
  • Overbased materials otherwise referred to as overbased or superbased salts, are generally single phase, homogeneous Newtonian systems characterized by an amount of excess metal that which would be necessary for neutralization according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal.
  • the amount of excess metal is commonly expressed in terms of substrate to metal ratio.
  • substrate to metal ratio is the ratio of the total equivalents of the metal to the equivalents of the substrate. A more detailed description of the term metal ratio is provided in " Chemistry and Technology of Lubricants", Second Edition, Edited by R. M. Mortier and S. T. Orszulik, pages 85 and 86, 1997 .
  • the overbased alkali or alkaline earth metal detergents suitable for use in the present invention may have a metal ratio of 0.8 to 10 or 3 to 9, or 4 to 8, or 5 to 7.
  • the detergents may be overbased with calcium hydroxide.
  • the alkali or alkaline earth metal detergents may have a total base number (TBN) of 30 or 50 to 400; or 200 to 350; or 220 to 300, and in another embodiment 255.
  • the detergent has a TBN in the range of 30, 40 or 50 to 220, 205, or 190, and in another embodiment 150.
  • the detergent has a TBN of 300 or more, 350 or more, or 400 or more, or from 300 or 350 to 400, and in another embodiment 395.
  • the lubricant of the present invention can contain an overbased sulfonate detergent.
  • Suitable sulfonic acids include sulfonic and thio-sulfonic acids.
  • Sulfonic acids include the mono- or polynuclear aromatic or cycloaliphatic compounds.
  • Oil-soluble sulfonates can be represented for the most part by one of the following formulas: R 2 -T-(SO 3 - ) a and R 3 -(SO 3 - ) b , where T is a cyclic nucleus such as typically benzene; R 2 is an aliphatic group such as alkyl, alkenyl, alkoxy, or alkoxyalkyl; (R 2 )+T typically contains a total of at least about 15 carbon atoms; and R 3 is an aliphatic hydrocarbon based group typically containing at least 15 carbon atoms. Examples of R 3 are alkyl, alkenyl, alkoxyalkyl, and carboalkoxyalkyl groups.
  • the groups T, R 2 , and R 3 in the above formulas can also contain other inorganic or organic substituents in addition to those enumerated above such as, for example, hydroxy, mercapto, halogen, nitro, amino, nitroso, sulfide, or disulfide.
  • a and b are at least 1.
  • the phenols useful in making phenate detergents can be represented by the formula (R 1 ) a -Ar-(OH) b , wherein R 1 is defined above; Ar is an aromatic group (which can be a benzene group or another aromatic group such as naphthalene); a and b are independently numbers of at least one, the sum of a and b being in the range of two up to the number of displaceable hydrogens on the aromatic nucleus or nuclei of Ar. In one embodiment, a and b are independently numbers in the range of 1 to 4, or 1 to 2. R 1 and a are typically such that there is an average of at least 8 aliphatic carbon atoms provided by the R 1 groups for each phenol compound. Phenate detergents are also sometimes provided as sulfur-bridged species.
  • the overbased material is an overbased detergent selected from the group consisting of overbased salixarate detergents, overbased saligenin detergents, overbased salicylate detergents, and overbased glyoxylate detergents, and mixtures thereof.
  • Overbased saligenin detergents are commonly overbased magnesium salts which are based on saligenin derivatives.
  • a general example of such a saligenin derivative can be represented by the formula wherein X comprises -CHO or -CH 2 OH, Y comprises -CH 2 - or -CH 2 OCH 2 -, and wherein such -CHO groups typically comprise at least 10 mole percent of the X and Y groups; M is hydrogen, ammonium, or a valence of a metal ion, R 1 is a hydrocarbon based group containing 1 to 60 carbon atoms, m is 0 to typically 10, and each p is independently 0, 1, 2, or 3, provided that at least one aromatic ring contains an R 1 substituent and that the total number of carbon atoms in all R 1 groups is at least 7. When m is 1 or greater, one of the X groups can be hydrogen.
  • M is an equivalent of a Mg ion or a mixture of Mg and hydrogen (and so in some embodiments can be less than a full Mg ion and/or include a partial Mg ion).
  • Other metals include alkali metals such as lithium, sodium, or potassium; alkaline earth metals such as calcium or barium; and other metals such as copper, zinc, and tin.
  • the expression "represented by the formula” indicates that the formula presented is generally representative of the structure of the chemical in question. However, it is well known that minor variations can occur, including in particular positional isomerization, that is, location of the X, Y, and R groups at different position on the aromatic ring from those shown in the structure. The expression “represented by the formula” is expressly intended to encompass such variations.
  • Saligenin detergents are disclosed in greater detail in U.S. Patent 6,310,009 , with special reference to their methods of synthesis (Column 8 and Example 1) and preferred amounts of the various species of X and Y (Column 6).
  • Salixarate detergents are overbased materials that can be represented by a substantially linear compound comprising at least one unit of formula (A) or formula (B): and wherein each end of the compound has a terminal group of formula (C) or formula (D): such groups being linked by divalent bridging groups A, which may be the same or different for each linkage; wherein in formulas (A)-(D) R 3 is hydrogen or a hydrocarbyl group; R 2 is hydroxyl or a hydrocarbon based group and j is 0, 1, or 2; R 6 is hydrogen, a hydrocarbyl group, or a hetero-substituted hydrocarbyl group; either R 4 is hydroxyl and R 5 and R 7 are independently either hydrogen, a hydrocarbyl group, or hetero-substituted hydrocarbyl group, or else R 5 and R 7 are both hydroxyl and R 4 is hydrogen, a hydrocarbyl group, or a hetero-substituted hydrocarbyl group; provided that at least one of R 4
  • the divalent bridging group "A,” which may be the same or different in each occurrence, includes -CH 2 -(methylene bridge) and -CH 2 OCH 2 - (ether bridge), either of which may be derived from formaldehyde or a formaldehyde equivalent (e.g., paraform, formalin).
  • Salixarate derivatives and methods of their preparation are described in greater detail in U.S. patent number 6,200,936 and PCT Publication WO 01/56968 . It is believed that the salixarate derivatives have a predominantly linear, rather than macrocyclic, structure, although both structures are intended to be encompassed by the term "salixarate.”
  • Glyoxylate detergents are similar overbased materials which are based on an anionic group which, in one embodiment, may have the structure and more specifically, wherein each R is independently an alkyl group containing at least 4, and preferably at least 8 carbon atoms, provided that the total number of carbon atoms in all such R groups is at least 12, preferably at least 16 or 24. Alternatively, each R can be an olefin polymer substituent.
  • the acidic material upon from which the overbased glyoxylate detergent is prepared is the condensation product of a hydroxyaromatic material such as a hydrocarbyl-substituted phenol with a carboxylic reactant such as glyoxylic acid and other omega-oxoalkanoic acids. Overbased glyoxylic detergents and their methods of preparation are disclosed in greater detail in U.S. Patent 6,310,011 and references cited therein.
  • the alkylsalicylate can be an alkali metal salt or an alkaline earth metal salt of an alkylsalicylic acid which can in turn be prepared from an alkylphenol by Kolbe-Schmitt reaction.
  • the alkylphenol can be prepared by a reaction of ⁇ -olefin having 8 to 30 carbon atoms (mean number) with phenol.
  • calcium salicylate can be produced by direct neutralization of alkylphenol and subsequent carbonation.
  • the lubricant composition comprises an antioxidant comprising an aminic antioxidant that is different from component (B).
  • this additional antioxidant comprises one or more of the antioxidants described above.
  • the additional antioxidant is a hindered phenol that is different from component (B), a diarylamine, a sulfurized olefinic compound, a molybdenum containing antioxidant, and a mixture thereof.
  • the antioxidant can comprise an alkyl 3-(3,5-di-t-alkyl-4-hydroxyphenyl)propionate, such as an alkyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate where the alkyl group of the ester moiety has 1 or more carbon atoms, 2 or more carbon atoms, 2 to 30 carbon atoms, 2 to 20 carbon atoms, or 2 to 10 carbon atoms. In some embodiments this combination of antioxidants leads to additional improvements in the performance of the composition.
  • Component (C) can comprise an antiwear agent.
  • the antiwear agent can comprise a zinc dialkyldithiophosphate.
  • the compositions of the present invention contain a zinc dialkyldithiophosphate, and in some of these embodiments, the zinc dialkyldithiophosphate is present at a level of no less than 300 ppm (or in other embodiments the zinc dialkyldithiophosphate is present at a level such that the amount of phosphorus delivered to the composition from the additive is no less than 300 ppm), such that, in combination with some of the limits below, essentially all of the phosphorus present in the composition is delivered by the zinc dialkyldithiophosphate.
  • compositions of the present invention further comprises a friction modifier, such as a hydroxy acid derived friction modifier, for example oleyl tartrimide, or amide-based friction modifier such as oleyl amide.
  • a friction modifier such as a hydroxy acid derived friction modifier, for example oleyl tartrimide, or amide-based friction modifier such as oleyl amide.
  • the other additive or additives of component (C) can each be present in the lubricant composition on a weight basis at 0.001 to 14%, 0.001 to 11%, or 0.001 to 8%.
  • the present invention provides a composition as described above.
  • the composition has total sulfur content of no more than 0.4 percent weight and in other embodiments of no more than 0.3, 0.2, or even 0.1 percent by weight.
  • the sulfur content of the compositions described herein is at least 0.01 or even 0.05 percent by weight.
  • the major source of sulfur in the composition of the invention is derived from conventional diluent oil.
  • compositions described herein have a total phosphorus content of no more than 1200 ppm, and in other embodiments no more than 1000, 800, 500, 300, 200 or even 100 ppm. In some embodiments the compositions described herein have a phosphorus content within a range that includes a minimum value of 100 ppm.
  • the composition has a total sulfated ash content as determined by ASTM D-874 of no more than 1.0 percent by weight, and in other embodiments of no more than 0.7, 0.4, 0.3, 0.05 percent by weight.
  • the sulfur content of the compositions described herein is at least 0.01 or even 0.05 percent by weight.
  • the lubricant composition can be a lubricant composition for an application comprising those listed above.
  • the lubricant composition can be a lubricant composition for an internal combustion engine.
  • the internal combustion engine can comprise a spark-ignited engine or a compression-ignited engine.
  • Components (B) and (C) of the invention can be combined in a concentrated form as a concentrate composition for convenient and efficient handling and shipping prior to being diluted in a base stock or oil of lubricating viscosity for use in a lubricant composition for an application.
  • a concentrate composition of the present invention can comprise a concentrate-forming amount of an oil of lubricating viscosity, at least one hindered-phenol-containing diester antioxidant as described above, and at least one other additive as described above.
  • Each of the antioxidant and other additive or additives can be present in the concentrate composition on a weight basis at 1 to 99%, 5 to 85%, or 10 to 75%.
  • the oil of lubricating viscosity can be present in the concentrate composition on a weight basis at 99 to 1%, 95 to 15%, or at 90 to 25%.
  • the lubricant and concentrate compositions of the invention can be prepared by admixing or mixing, usually with a mixing device, the components in any suitable order from ambient to an elevated temperature of 60°C, 80°C, or 100°C until the composition is homogeneous or the components are dispersed.
  • a method of the present invention for improving the performance of a lubricant composition comprises incorporating into the lubricant composition a performance-improving amount of a hydroxychroman derived antioxidant as described above where the lubricant composition comprises an oil of lubricating viscosity and at least one other additive as described above.
  • the improvement in performance can comprise a decrease in volatility, an increase in oxidation inhibition, a reduction in deposits, or a combination thereof.
  • the lubricant composition can be a lubricant composition for an internal combustion engine.
  • the internal combustion engine can comprise a spark-ignited engine or a compression-ignited engine.
  • the spark-ignited or compression-ignited engine can have an exhaust gas recirculation system.
  • the spark-ignited or compression-ignited engine can have at least one exhaust treatment device comprising a catalytic converter, a catalyzed diesel particulate trap, a noncatalyzed diesel particulate trap, a diesel oxidation catalyst, a selective catalytic reduction catalyst, a lean NO x catalyst, or a combination thereof.
  • the lubricant composition can have normal or reduced levels of sulfated ash, phosphorus and sulfur as described above.
  • a hydroxychroman derivative is prepared by adding to a 1-liter round bottom flask, equipped with a mechanical stirrer, thermowell, nitrogen inlet, Dean-Stark/Fredrich's condenser, 116.5 grams of 2-tert-butylbenzene-1,4-diol, 124.2 grams of 2-methylpentane-2,4-diol, 150 grams of heptane and 23.3 grams of Amberlyst 15.
  • the reaction mixture is heated to reflux temperature to azeotrope water for a total of about 14 hours.
  • the resulting material is then filtered using a frit funnel in order to remove the catalyst and the solvent is removed via vacuum stripping.
  • the final material is a tan solid.
  • a hydroxychroman derivative is prepared by adding to a 1-liter round bottom flask, equipped with a mechanical stirrer, thermowell, nitrogen inlet, Dean-Stark/Fredrich's condenser, 102.0 grams of 2-tert-butylbenzene-1,4-diol, 107.7 grams of 2,5-dimethyl-2,5-hexanediol, 150 grams of heptane and 22.0 grams of Amberlyst 15. The reaction mixture is heated to reflux temperature to azeotrope water for a total of about 14 hours. The resulting material is then filtered using a frit funnel in order to remove the catalyst and the solvent is removed via vacuum stripping. The final material is a tan solid.
  • Each sample is prepared by blending the antioxidant additive being evaluated, if any, at the specified level, into a fully formulated engine oil composition. Each composition was blended into the same base oil, a mix of commercially available 100N and 160N mineral oils. Also included in each sample is an additive package. The additive package contains a combination of various lubricant additives including dispersants, detergents, antifoams, corrosion inhibitors, etc. The exact same additive package is present at the exact same treat level in each sample unless otherwise noted. The table below summarizes the samples prepared for the testing.
  • Examples A, B and C compare the additives of the present invention against a conventional hindered phenol antioxidant on an equal treat rate basis, with treat rate measured by percent by weight.
  • Example D when compared to Example B, and Examples E and F, compare the additives of the present invention against a conventional hindered phenol antioxidant on an equal actives basis.
  • Examples E and F were prepared using an additive package identical to that used in each of the other examples except that an alkaryl amine additive present in the full additive package, which is believed to possibly contribute to lubricant antioxidancy, was removed. Thus these examples ensure any improvement in antioxidancy performance is the result of the inventive additive.
  • the tests used to evaluate the samples are commonly used in the lubricant industry to evaluate the performance of antioxidant additives.
  • the testing completed includes: (i) ASTM D7097, a bench-scale passenger car motor oil qualification test for GF-4 and GF-5. The test measures the amount of deposit generated on a steel rod heated at 285C. A lower result indicates a lower amount of deposit generation and so better performance.
  • ASTM D6335 a bench-scale passenger car motor oil qualification test for GF-2. The test measures the amount of deposit generated on a steel rod when cycling the rod temperature from 200C to 480C. A lower result indicates a lower amount of deposit generation and so better performance.
  • An in-house PDSC test was also used. This test uses a calorimetry method to determine the onset of oxidation activity in an oil sample and is used to rank the relative oxidative stabilities of a set of samples. Higher onset times indicate greater oxidative stability and so better performance.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Combustion & Propulsion (AREA)
  • Lubricants (AREA)

Claims (5)

  1. Composition de lubrifiant comprenant une huile de viscosité lubrifiante et un antioxydant ayant la formule :
    Figure imgb0018
     dans laquelle R3 est un groupe méthyle, les deux groupes R2 sont des groupes méthyle, tous les groupes R1 sont des hydrogènes et R4 est un groupe alkyle ramifié contenant de 1 à 10 atomes de carbone ;
    l'antioxydant étant présent dans la composition de lubrifiant à 0,1 à 10 pour cent en poids ;
    la composition de lubrifiant comprenant en outre un antioxydant aminique;
    la composition de lubrifiant étant une composition de lubrifiant pour moteurs à combustion interne, une composition de lubrifiant pour transmissions de puissance, une composition de lubrifiant pour engrenages, une composition de lubrifiant pour le travail des métaux, une composition de lubrifiant pour circuits hydrauliques, une composition de lubrifiant pour roulements où la composition de lubrifiant est une graisse.
  2. Composition de lubrifiant de la revendication 1, la composition ne contenant pas plus de 1200 ppm de phosphore.
  3. Composition de lubrifiant de la revendication 2, la composition ayant une teneur en soufre de pas plus de 0,4 pour cent en poids et une teneur en cendres sulfatées de pas plus de 1,0 pour cent en poids.
  4. Composition de lubrifiant de la revendication 2 comprenant en outre un dialkyldithiophosphate de zinc présent à un niveau tel que la quantité de phosphore délivrée à la composition n'est pas inférieure à 300 ppm.
  5. Procédé de lubrification d'un moteur à combustion interne comprenant les étapes consistant à : (I) fournir audit moteur une composition de lubrifiant comprenant une huile de viscosité lubrifiante et un antioxydant ayant la formule :
    Figure imgb0019
     dans laquelle R3 est un groupe méthyle, les deux groupes R2 sont des groupes méthyle, tous les groupes R1 sont des hydrogènes et R4 est un groupe alkyle ramifié contenant de 1 à 10 atomes de carbone ;
    l'antioxydant étant présent dans la composition de lubrifiant à 0,1 à 10 pour cent en poids ;
    la composition de lubrifiant comprenant en outre un antioxydant aminique.
EP11755481.6A 2010-09-07 2011-08-30 Dérivés d'hydroxychromane comme antioxydants Active EP2614131B1 (fr)

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BR112013005296A2 (pt) 2016-08-16
ES2586242T3 (es) 2016-10-13
CN103201361A (zh) 2013-07-10
WO2012033668A1 (fr) 2012-03-15
EP3070153B1 (fr) 2018-12-05
EP2614131A1 (fr) 2013-07-17
CA2809975A1 (fr) 2012-03-15
CA2809975C (fr) 2018-09-18
US20130165355A1 (en) 2013-06-27
EP3070153A1 (fr) 2016-09-21

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