EP0376997B1 - Composition fluide synthetique stable a la chaleur et a l'oxydation - Google Patents

Composition fluide synthetique stable a la chaleur et a l'oxydation Download PDF

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Publication number
EP0376997B1
EP0376997B1 EP89904950A EP89904950A EP0376997B1 EP 0376997 B1 EP0376997 B1 EP 0376997B1 EP 89904950 A EP89904950 A EP 89904950A EP 89904950 A EP89904950 A EP 89904950A EP 0376997 B1 EP0376997 B1 EP 0376997B1
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Prior art keywords
hydrocarbyl group
carbon atoms
carboxylic acid
acid ester
neo
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EP0376997B2 (fr
EP0376997A1 (fr
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Richard M. Lange
Mary F. Salomon
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Lubrizol Corp
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Lubrizol Corp
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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
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/36—Esters of polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/38—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
    • 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
    • C10M129/68—Esters
    • C10M129/72—Esters of polycarboxylic acids

Definitions

  • This invention relates to aromatic carboxylic acid esters and to the use of such esters as novel thermally and oxidatively stable synthetic fluids. More particularly, the invention relates to their use in the field of thermal oxidatively stable synthetic fluid lubrication.
  • U.S. Patent 3,947,369 (Liebfried, March 30, 1976) discloses a synthetic oil useful as a base stock for jet engine lubricating oils.
  • the patent describes a lubricating oil base stock, which meets both the 210 ° (99 °C) initial viscosity requirement, and the 72 hour no-freeze requirement.
  • the base stock is composed of a blend of (1) a pentaerythritol ester product consisting essentially of pentaerythritol material completely esterified by straight chain C 4 -C 10 alkanoic acid material, and (2) trimellitate ester product consisting essentially of trimellitic acid completely esterified by C4-C, 3 alkanol material.
  • the weight ratio of trimellitate ester product to the pentaerythritol ester product in the blend is generally in the range from about 1:10 to about 1:1.
  • U.S. Patent 3,974,081 (Rutkowski et al, August 10, 1976) relates to an improved lubricating fluid and particularly concerns an additive for such a fluid that will improve its seal swelling properties without at the same time imparting any detrimental effects thereto.
  • the invention is also directed to additive concentrate packages that are intended for formulation into mineral oil base stocks to provide transmission fluids of improved seal swelling characteristics thereby enhancing fluid retention. These transmission fluids have utility as a lubricant for rotary engines.
  • the additive is an oil soluble, saturated, aliphatic or aromatic hydrocarbon ester having from 10 to 60 carbon atoms and from 2 to 4 ester linkages.
  • an aliphatic alcohol having from 8 to 13 carbon atoms be present in up to equal amount with said ester as a co-swellant.
  • Preferred among the above class of esters is dihexyl phthalate and among the above class of alcohols is tridecyl alcohol.
  • G.B. Patent 851,205 relates to alcohol esters of aromatic tetracarboxylic acids suitable for use as lubricating oils.
  • EP-A3-0 157 583 also relates to oil-based lubricant compositions comprising esters of aromatic polycarboxylic acids.
  • the present invention provides an aromatic carboxylic acid ester of the general formula wherein Ar is an aromatic moiety, R is a neo hydrocarbyl group containing from 5 to 18 carbon atoms, with the proviso that R is not a cycloalkyl substituted neo hydrocarbyl group, R 1 is a mono, di, tri or tetravalent hydrocarbyl group, which is a neo hydrocarbyl group or another primary hydrocarbyl group, containing from 1 to 18 carbon atoms, n is an integer from 2 to 4 and represents the total number of carboxylic acid ester groups on the aromatic moiety, R 2 is a hydrocarbyl group derived from a diol containing from 2 to 18 carbon atoms; x is an integer from 0 to 4, and a is an integer from 1 to 4, and when a is 1, R 1 is is monovalent; when a is 2, R 1 is divalent; when a is 3, R 1 is trivalent and derived from a triol of formula
  • a primary aim of this invention is to provide a novel thermally and oxidatively stable synthetic fluid composition comprising an aromatic carboxylic acid ester.
  • a feature of the invention is that the aromatic carboxylic acid esters which function in the novel thermally and oxidatively stable synthetic fluid composition can be easily and economically manufactured.
  • An advantage of the present composition is that the aromatic carboxylic acid esters provide lubricating properties which are desirable for synthetic fluid compositions.
  • the thermal stability of a chemical compound is its resistance to change brought about solely by thermal energy.
  • the rate of thermal decomposition as a function of temperature precisely defines this property.
  • thermal stability In this jet and space age more and more emphasis is on thermal stability. Higher operating temperatures, for increased engine efficiency, require more thermally stable lubricants. For lubricants and hydraulic fluids it is apparent that other properties such as viscosity, pour point, oxidative stability and vapor pressure are quite important, but such properties are more amenable to improvement by additives and minor structural modifications than is thermal stability.
  • aromatic carboxylic acid esters possess a high degree of thermal and oxidative stability.
  • the aromatic carboxylic acid esters which are used in the composition in accordance with the present invention are compounds characterized by the structural formula: wherein R, R i , R 2 , Ar, n, x and a are as defined previously for formula (I).
  • the aromatic carboxylic acid ester is prepared by reacting an alcohol with an aromatic acid or anhydride, or their esters (as in transesterification). However, in order to force the esterification reaction to completion, an excess of the alcohol is employed. Normally, the total amount of alcohol is present in a 100% excess on an equivalent basis. Preferably, the alcohol is present in a 50% excess.
  • the unreacted alcohol may be removed by distillation after the esterification reaction is complete and reused in future esterification reactions.
  • the alcohol and aromatic acid or anhydride are added to a reaction vessel at room temperature. Stirring is begun and an acid catalyst is added to promote the reaction.
  • Catalysts that can be used in the practice of this invention are methanesulfonic acid, para-toluenesulfonic acid and tetraalkyl titanates.
  • the catalyst of choice is para-toluene sulfonic acid.
  • the catalyst is neutralized with an appropriate base, such as aqueous sodium hydroxide or calcium hydroxide.
  • hydrocarbyl denotes a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character within the context of this invention.
  • groups include the following:
  • no more than about three substituents or heteroatoms, and preferably no more than one, will be present for every 10 carbon atoms in the hydrocarbyl group.
  • the aromatic moiety, Ar can be a single aromatic nucleus such as a benzene nucleus or a polynuclear aromatic moiety.
  • Such polynuclear moieties can be of the fused type; that is, wherein at least two aromatic nuclei are fused at two points to another nucleus such as found in naphthalene, anthracene, etc.
  • Such aromatic moieties also can be of the linked type wherein at least two nuclei are linked through bridging linkages to each other.
  • Such bridging linkages can be chosen from carbon-to-carbon single bonds, ether linkages, keto linkages, alkylene linkages, and mixtures of such divalent bridging linkages.
  • aromatic moiety Ar in all cases is derived from aromatic carboxylic acids, aromatic anhydrides and aromatic esters.
  • Specific examples of compounds of formula (I) containing single ring Ar moieties are the following wherein R 1 and a are as previously defined:
  • Aromatic carboxylic acids which may be used to prepare the products of this invention are represented by the formula Ar-(-COOH) n where Ar is an aromatic moiety and n is an integer from 2 to 4.
  • Aromatic carboxylic acids falling within the parameters of the above structure include phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, pyromellitic acid, trimesic acid, naphthalene 1,8-dicarboxylic acid, naphthalene 2,3-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene 2,6-dicarboxylic acid and naphthalene 2,3,6-tricarboxylic acid.
  • Anhydrides corresponding to any of the above aromatic carboxylic acids may also be used to prepare the products of the present invention.
  • Anhydrides are represented by the formula wherein Ar is as defined above and z is an integer from 1 to 3, preferably 1 to 2.
  • Suitable anhydrides are phthalic anhydride, 1,8-naphthalic anhydride, 2,3-naphthalic anhydride, 2,3,7,8-naphthalic dianhydride, trimellitic anhydride, pyromellitic anhydride, mellitic anhydride and benzophenonetetracarboxylic acid dianhydride.
  • Aromatic carboxylic acid esters which may be used to prepare the products of this invention by transesterification are represented by the formula wherein Ar and n are defined above and R 7 is a hydrocarbyl group containing from 1 to 6 carbon atoms.
  • Aromatic esters that can be employed in this invention are dimethyl phthalate, trimethyl trimellitate, diethyl phthalate and dimethyl naphthalene-2,6-dicarboxylate.
  • the Ar moiety is normally a benzene nucleus, keto-bridged benzene nuclei or a naphthalene nucleus.
  • the neo hydrocarbyl group R is an aliphatic group.
  • the neo hydrocarbyl group R contains from 5 to 18 carbon atoms with the proviso that R is a neo hydrocarbyl group other than a cycloalkyl substituted neo hydrocarbyl group.
  • the neo hydrocarbyl group R has the structure: wherein R 2 , R 3 and R 4 are independently straight chain hydrocarbyl groups, branched chain hydrocarbyl groups or mixtures thereof.
  • the neo hydrocarbyl group contains from 8 to 16 carbon atoms, and most preferably the neo hydrocarbyl group is a neo octyl group. In all cases, the hydrocarbyl group is usually derived from an alcohol.
  • hydrocarbyl groups of R 2 , R 3 and R 4 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-betyl and t-butyl.
  • neo alcohols that may be employed in the practice of this invention are: 2,2-dimethyl-1-heptanol, 2,2-di-methyl-1-octanol, 2-methyl-2-ethyl-1-pentanol, 2-methyl-2-ethyl-1-hexanol, 2-methyl-2-ethyl-1-heptanol, 2-methyl-2-ethyl-1-octanol, 2,2-diethyl-1-butanol, 2,2-diethyl-1-pentanol, 2,2-diethyl-1-hexanol, 2,2-diethyl-1-heptanol, 2,2-diethyl-1-octanol, 2,2,3-trimethyl-1
  • the hydrocarbyl group R 1 is a mono, di, tri or tetra valent hydrocarbyl group containing from 1 to 18 carbon atoms, preferably from 5 to 16 carbon atoms and most preferably from 5 to 12 carbon atoms.
  • the hydrocarbyl group R 1 is derived from an alcohol containing from 1 to 4 hydroxyl groups and may be represented as R 1 -(-OH) a wherein a is from 1 to 4.
  • R 1 is derived from a mono alcohol.
  • the mono alcohols may be the neo alcohols as described and also non neo alcohols.
  • the non-neo alcohols which can be utilized to form the desired product of this invention are well-known alcohols. These alcohols are primary alcohols.
  • Suitable alcohols include, for example, 2-ethyl-hexanol, n-octanol, isooctanol, 2,2-dimethyloctanol, nonanol, n-decanol, isodecanol, dodecanol, tridecyl alcohol, tetradecanol, hexadecanol, octadecanol, etc.
  • Alfol 810 is a mixture containing alcohols consisting essentially of straight chain, primary alcohols having from 8 to 10 carbon atoms.
  • a variety of mixtures of monohydric fatty alcohols derived from naturally occurring triglycerides and ranging in chain length from C 8 to C 18 are available from Procter & Gamble Company. These mixtures contain various amounts of fatty alcohols containing mainly 12, 14, 16 or 18 carbon atoms.
  • CO-1214 is a fatty alcohol mixture containing 0.5 percent of C 10 alcohol, 66.0 percent of C 12 alcohol, 26.0 percent of C 14 alcohol and 6.5 percent of C 16 alcohol.
  • Neodol 23 is a mixture of C12 and C 13 alcohols
  • Neodol 45 is a mixture of C 14 and C 15 alcohols.
  • An example of a preferred branched chain monohydric alcohol suitable for use in the present invention is commercial tridecyl alcohol, a mixture of isomers in the C 13 range prepared by the Oxo process and which is available from Exxon Corporation.
  • R 1 is derived from a diol.
  • Suitable examples of R 1 -(-OH) 2 are 2,2-dimethyl-1,3-propanediol; 2,2,4,4-tetramethyl-1,5-pentanediol; 2,2,5,5-tetramethyl-1,6-hexanediol; 2,2,6,6-tetramethyl-1,7-heptanediol; 2,2,7,7-tetramethyl-1,8-octanediol.
  • R 1 is derived from a triol.
  • the triol R 1 -(-OH) 3 is represented by the formula wherein R 6 is a hydrocarbyl group containing from 1 to 14 carbon atoms, preferably 1 to 10 carbon atoms, and most preferably 1 to 6 carbon atoms. Suitable examples of this structure are trimethylolethane, trimethylolpropane, trimethylolbutane, trimethylolpentane, etc.
  • R 1 is derived from a tetraol represented by the structure: wherein R a , R b , R c and R d may be the same or different and are hydrocarbyl groups containing from zero up to 3 carbon atoms. When the hydrocarbyl groups R a , R b , R c and R d contain no carbon atoms, R 1 is derived from pentaerythritol.
  • a preferred embodiment of this invention comprises an aromatic carboxylic acid ester of the general formula wherein n, R 2 and x are as defined above in formula (I), R is a neo hydrocarbyl group containing from 5 to 10 carbon atoms, R 1 is a di, tri or tetravalent hydrocarbyl group as defined in formula (I) containing from 5 to 16 carbon atoms, and a is an integer from 2 to 4.
  • An alternative embodiment of this invention comprises an aromatic carboxylic acid ester of the formula wherein R 5 is a hydrocarbyl group containing from 2 to 18 carbon atoms, preferably from 5 to 18, and most preferably from 5 to 16, with the proviso that R 5 is a primary hydrocarbyl group other than a neo hydrocarbyl group and n is 2.
  • Another embodiment of this invention comprises an aromatic carboxylic acid ester of the general formula wherein Ar, n, R 2 and x are as defined in formula (I), R 5 is a linear hydrocarbyl group containing from 2 to 18 carbon atoms, R 1 is a di, tri or tetravalent hydrocarbyl group as defined in formula (I) and a is an integer from 2 to 4.
  • a further embodiment of this invention comprises an aromatic carboxylic acid ester of the general formula wherein Ar, n, R 1 , a and x are as defined in formula (I), and R 8 is independently R or R s , and at least one R and at least one R 5 group are present in the ester, wherein R is a neo hydrocarbyl group containing from 5 to 18 carbon atoms, with the proviso that R is not a cycloalkyl substituted neo hydrocarbyl group, and R 5 is a linear primary hydrocarbyl group containing from 2 to 18 carbon atoms, with the proviso that n is not 2, and with the further proviso that when Ar is a single ring, a is 1 and x is 0, n is an integer other than 4.
  • a still further embodiment of this invention comprises an aromatic carboxylic acid ester of the general formula wherein R 1 is a monovalent primary hydrocarbyl group containing from 1 to 18 carbon atoms, R 2 is a hydrocarbyl group derived from a diol containing from 2 to 18 carbon atoms and x is an integer from 1 to 4.
  • the hydrocarbyl group R 2 is derived from a dihydric alcohol containing between 2 and 18 carbon atoms.
  • R 2 contains between 2 and 12 carbon atoms, and most preferably between 2 and 8 carbon atoms.
  • Suitable dihydric alcohols include ethylene glycol; 1,3-propylene glycol; 1,4-butane diol; neopentyl glycol; 1,5-pentane diol; 1,6-hexane diol and mixtures thereof.
  • the temperature is gradually increased to 175°C over two hours by slow removal of toluene and azeotrope, and held at that temperature for two hours while additional volatiles are removed.
  • the reaction mixture is cooled to 150 ° C, and a vacuum (10 Torr)(1.3kPa) is applied to remove volatiles at that temperature.
  • the stripped mixture is then cooled to 90 °C, stirred for 30 minutes with 15 parts of calcium hydroxide to neutralize the acid catalyst, then filtered through a thin pad of diatomaceous earth to give the ester product.
  • reaction mixture was stripped at 120 ° C/15 Torr (1.9kPa), then treated with 7 parts of calcium hydroxide for 30 minutes. Filtration through a thin pad of diatomaceous earth in a Buchner funnel gave 834 parts of a light yellow, viscous ester product.
  • Example 2 To a flask fitted per Example 1 are added 47.1 parts (0.146 moles) benzophenone tetracarboxylic acid anhydride, 95 parts (0.73 moles) 2,2,4-trimethyl-1-pentanol, 100 parts xylene and 2 parts (0.01 moles) para-toluene sulfonic acid. The contents are heated to reflux and maintained for 11 hours. At 80 °C, 1.5 parts (0.02 moles) calcium hydroxide are added to neutralize the catalyst. The contents are stripped to 180 ° C and 10 mm mercury to obtain a product with a phenolphthalein neutralization number of 0.7.
  • the temperature is gradually raised to 175 ° C and held there for 3 hours, while volatiles are removed using a slow nitrogen purge.
  • the mixture is stripped at 150 ° C/10 Torr (1.3kPa), cooled to 85 ° C, stirred with 15 parts of calcium hydroxide for one hour, then filtered slowly through a pad of diatomaceous earth to give the ester product.
  • the compounds of this invention are useful as thermally and oxidatively stable synthetic fluids. They can be employed alone or in a variety of lubricants based on diverse oils of lubricating viscosity, including natural and synthetic lubricating and grease oils and mixtures thereof.
  • Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins [e.g., hydrogenated polybutylenes, hydrogenated polypropylenes, hydrogenated propylene-isobutylene copolymers, chlorinated hydrogenated polybutylenes, hydrogenated poly(1-hexenes), hydrogenated poly(1-octenes), hydrogenated poly(1-decenes)]; alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl) benzenes]; polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); and alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methylpolyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C a -C a fatty acid esters and C13 Oxo acid diester of tetraethylene glycol.
  • polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and hydrogenated alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and hydrogenated alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic 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, dipentaerythritol and tripentaerythritol.
  • Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils and silicate oils comprise another useful class of synthetic lubricants; they include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) 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 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 amount employed of the thermally oxidatively stable lubricants of the present invention will be 10% to 100%, preferably 20% to 90% of the total weight of the lubricating composition.
  • minor amount as used in the specification and appended claims is intended to mean that when a composition contains a “minor amount” of a specific material that amount is less than 50 percent by weight of the composition.
  • major amount as used in the specification and appended claims is intended to mean that when a composition contains a “major amount” of a specific material that amount is more than 50 percent by weight of the composition.
  • the invention also contemplates the use of additives in combination with the compositions of this invention sufficient to inhibit oxidation, corrosion, rust and improve extreme pressure antiwear properties.
  • additives include, for example, detergents and dispersants of the ash-producing or ashless type, corrosion- and oxidation-inhibiting agents, pour point depressing agents, extreme pressure agents, antiwear agents, color stabilizers and anti-foam agents.
  • the ash-producing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, or organic phosphorus acids characterized by at least one direct carbon-to-phosphorus linkage such as those prepared by the treatment of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride.
  • olefin polymer e.g., polyisobutene having a molecular weight of 1000
  • a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide,
  • basic salt is used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical.
  • the commonly employed methods for preparing the basic salts involve heating a mineral oil solution of an acid with an excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature about 50 ° C.
  • a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide
  • compound useful as the promoter examples include phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and 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; and amines such as aniline, phenylenediamine, phenothiazine, phenyl- naphthylamine, and dodecylamine.
  • a particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol promoter, and carbonating the mixture at an elevated temperature such as 60-200 ° C.
  • Ashless detergents and dispersants are so called despite the fact that, depending on its constitution, the dispersant may upon combustion yield a non-volatile material such as boric oxide or phosphorus pentoxide; however, it does not ordinarily contain metal and therefore does not yield a metal-containing ash on combustion.
  • a non-volatile material such as boric oxide or phosphorus pentoxide
  • Many types are known in the art, and any of them are suitable for use in the lubricant compositions of this invention. The following are illustrative:
  • chlorinated aliphatic hydrocarbons such as chlorinated wax
  • aromatic amines such as dioctyl diphenylamine, hindered phenols such as methylenebis-2,6-t-butyl phenol, organic sulfides and polysulfides such as benzyl disulfide, bis(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized terpene; phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate, phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phos
  • Zinc dialkylphosphorodithioates are a well known example.
  • pour point depressants are a particularly useful type of additive often included in the lubricating oils described herein.
  • the use of such pour point depressants in oil-based compositions to improve low temperature properties is well known in the art. See, for example, page 8 of "Lubricant Additives" by C.V. Smalheer and R. Kennedy Smith (Lezius-Hiles Co. publishers, Cleveland, Ohio, 1967).
  • pour point depressants examples include polymethacrylates, polyacrylates; polyacrylamides; condensation products of haloparaffin waxes and aromatic compounds; vinyl carboxylate polymers; and terpolymers of dialkylfumarates, vinylesters of fatty acids and alkylvinylethers.
  • Pour point depressants useful for the purposes of this invention techniques for their preparation and their uses are described in U.S. Patents 2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498; 2,666,746; 2,721,877; 2,721,878; and 3,250,715.
  • Anti-foam agents are used to reduce or prevent the formation of stable foam.
  • Typical anti-foam agents include silicones or organic polymers. Additional anti-foam compositions are described in "Foam Control Agents", by Henry T. Kerner (Noyes Data Corporation, 1976), pages 125-162.
  • thermal stability of a composition of this invention is shown in the following Table I.
  • Commercially available synthetic fluids that have utility as thermally stable fluids include Emery 3004, a poly alpha-olefin available from Emery Industries, Inc. and Emery 2982, a polyol neo ester available from Emery Industries, Inc. These commercially available fluids are shown as baselines in Table I.

Claims (17)

1. Un ester d'acide aromatique carboxylique de la formule générale
Figure imgb0052
dans laquelle Ar est une partie aromatique, R est un groupe néo-hydrocarbyle renfermant de 5 à 18 atomes de carbone, sous la condition que R n'est pas un groupe néo-hydrocarbyle à substitution cycloalkyle, R1 est un groupe hydrocarbyle mon-, di-, tri- ou tétravalent qui est un groupe néo-hydrocarbyle ou un autre groupe hydrocarbyle primaire, renfermant de 1 à 18 atomes de carbone, n est un nombre entier de 2 à 4 et représente le nombre total de groupes acide carboxylique estérifiés sur la partie aromatique, R2 est un groupe hydrocarbyle dérivé d'un diol renfermant de 2 à 18 atomes de carbone, x est un noire entier de 0 à 4, et a est un nombre entier de 1 à 4, et lorsque a est 1, R1 est monovalent; lorsque a est 2, R1 est divalent; lorsque a est 3, R1 est trivalant et dérivé d'un triol de formule
Figure imgb0053
dans laquelle R6 est un groupe hydrocarbyle renfermant de 1 à 14 atomes de carbone; et lorsque a est 4, R1 est tétravalent et dérivé d'un tétraol de la formule
Figure imgb0054
dans laquelle Ra, Rb, Re et Rd peuvent être identiques ou différents et sont des groupes hydrocarbyles renfermant de 0 jusqu'à 3 atomes de carbone, et lorsque les groupes hydrocarbyle Ra, Rb, Rc et Rd ne renferment pas d'atomes de carbone, R1 est dérivé du pentaérythritol, sous la condition que, lorsque Ar est un cycle unique, a est 1 et x est 0, n est un nombre entier différent de 4.
2. Un composé selon la revendication 1, dans lequel la partie aromatique est une partie benzénique ou naphtalénique.
3. Un composé selon l'une quelconque des revendications 1 et 2, dans lequel n est 2 ou 3.
4. Un composé selon l'une quelconque des revendications précédentes, dans lequel x est 0.
5. Un composé selon l'une quelconque des revendications précédentes, dans lequel a est 2, 3 ou 4.
6. Un ester d'acide aromatique carboxylique selon la revendication 1, ayant la formule
Figure imgb0055
dans laquelle R est un groupe néo-hydrocarbyle contenant de 5 à 18 atomes de carbone et Z est choisi parmi
Figure imgb0056
et -0-.
7. Un ester d'acide carboxylique aromatique selon la revendication 1, ayant la formule
Figure imgb0057
dans laquelle R est un groupe néo-hydrocarbyle renfermant de 5 à 18 atomes de carbone et Z est choisi parmi
Figure imgb0058
et -0-.
8. Un ester d'acide aromatique carboxylique selon la revendication 1, de la formule générale
Figure imgb0059
dans laquelle n, R2 et x sont tels que définis dans la revendication 1, R est un groupe néo-hydrocarbyle renfermant de 5 à 10 atomes de carbone, R1 est un groupe hydrocarbyle di-, tri- ou tétravalent, renfermant de 5 à 16 atomes de carbone, et a est un nombre entier de 2 à 4.
9. Un composé selon la revendication 8, dans lequel a est 2, 3 ou 4 et R1 est respectivement, un groupe hydrocarbyle di-, tri- ou tétravalent, renfermant de 5 à 12 atomes de carbone.
10. Un ester d'acide aromatique carboxylique de la formule
Figure imgb0060
dans laquelle R5 est un groupe hydrocarbyle renfermant de 2 à 18 atomes de carbone, sous la condition que R5 est un groupe hydrocarbyle primaire différent d'un groupe néo-hydrocarbyle, et n est 2.
11. Un composé selon la revendication 10, dans lequel R5 est un groupe hydrocarbyle renfermant de 5 à 18 atomes de carbone.
12. Un ester d'acide aromatique carboxylique de la formule générale
Figure imgb0061
dans laquelle Ar, n, R2 et x sont tels que définis dans la revendication 1, R5 est un groupe hydrocarbyle linéaire renfermant de 2 à 18 atomes de carbone, R1 est un groupe hydrocarbyle di-, tri-, ou tétravalent tel que défini dans la revendication 1.
13. Un ester d'acide aromatique carboxylique de la formule générale
Figure imgb0062
dans laquelle Ar, n, R1 , a et x sont tels que définis dans la revendication 1, et R8 représente indépendamment R ou Rs, et au moins un groupe R ainsi qu'au moins un groupe R5 sont présents dans l'ester, dans lequel R est un groupe néo-hydrocarbyle renfermant de 5 à 18 atomes de carbone, sous la condition que R n'est pas un groupe néo-hydrocarbyle à substitution cycloalkyle, R5 est un groupe hydrocarbyle linéaire primaire, renfermant de 2 à 18 atomes de carbone, sous la condition que n n'est pas 2, et en outre sous la condition que, lorsque Ar est un cycle unique, a est 1 et x est 0, n est un nombre entier différent de 4.
14. Un ester d'acide aromatique carboxylique de la formule générale
Figure imgb0063
dans laquelle R1 est un groupe hydrocarbyle monovalent primaire, renfermant de 1 à 18 atomes de carbone, R2 est un groupe hydrocarbyle dérivé d'un diol renfermant de 2 à 18 atomes de carbone et x est un nombre entier de 1 à 4.
15. Un concentré qui comprend une proportion mineure d'une huile lubrifiante et une proportion prépondérante d'un ester d'acide aromatique carboxylique selon l'une quelconque des revendications précédentes.
16. Une composition lubrifiante qui comporte une proportion prépondérante d'une huile lubrifiante et une proportion mineure d'un ester d'acide aromatique carboxylique selon l'une quelconque des revendications 1 à 14.
17. Une composition fluide synthétique stable à la chaleur et à l'oxydation, comportant un ester d'acide aromatique carboxylique selon l'une quelconque des revendications 1 à 14.
EP89904950A 1988-04-18 1989-04-07 Composition fluide synthetique stable a la chaleur et a l'oxydation Expired - Lifetime EP0376997B2 (fr)

Applications Claiming Priority (3)

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US18254488A 1988-04-18 1988-04-18
US182544 1988-04-18
PCT/US1989/001454 WO1989010345A1 (fr) 1988-04-18 1989-04-07 Composition fluide synthetique stable a la chaleur et a l'oxydation

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EP0376997A1 EP0376997A1 (fr) 1990-07-11
EP0376997B1 true EP0376997B1 (fr) 1995-01-18
EP0376997B2 EP0376997B2 (fr) 1999-03-31

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JP (1) JP2991732B2 (fr)
AT (1) ATE117288T1 (fr)
AU (1) AU616010B2 (fr)
CA (1) CA1339451C (fr)
DE (1) DE68920723T3 (fr)
IL (1) IL89909A (fr)
MX (1) MX173426B (fr)
WO (1) WO1989010345A1 (fr)
ZA (1) ZA892794B (fr)

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US5798319A (en) * 1996-01-16 1998-08-25 Exxon Chemical Patents Inc. High stability and low metals esters based on 3,5,5-trimethyl-1-hexanol

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1200141A (fr) * 1957-01-08 1959-12-18 American Cyanamid Co Nouveaux plastifiants pour résines vinyliques constitués par des esters dialiphatiques d'un acide dicarboxylique, et compositions de résines contenant ces plastifiants
NL230545A (fr) * 1957-08-21
NL234783A (fr) * 1958-01-02
US3329643A (en) 1965-11-15 1967-07-04 Eastman Kodak Co Polymeric compositions plasticized with 2, 2-dimethylalkyl esters of dibasic acids
US3624133A (en) * 1966-04-22 1971-11-30 Robert H Reitsema Liquid esters of naphthalene dicarboxylic acids
US3637501A (en) * 1968-11-05 1972-01-25 Ethyl Corp Complex esters
US3740625A (en) 1971-11-04 1973-06-19 Sprague Electric Co Electrical capacitors with ester impregnants
JPS5224626B2 (fr) * 1973-03-14 1977-07-02
JPS5230274B2 (fr) * 1973-12-19 1977-08-06
JPS5940489B2 (ja) * 1977-08-19 1984-10-01 東レ株式会社 ガス遠心分離機
GB8408017D0 (en) * 1984-03-28 1984-05-10 Bp Chem Int Ltd Oil-based lubricant compositions

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CA1339451C (fr) 1997-09-09
IL89909A (en) 1993-02-21
DE68920723D1 (en) 1995-03-02
DE68920723T2 (de) 1995-05-18
AU616010B2 (en) 1991-10-17
JP2991732B2 (ja) 1999-12-20
JPH03502588A (ja) 1991-06-13
DE68920723T3 (de) 1999-07-22
MX173426B (es) 1994-03-03
ATE117288T1 (de) 1995-02-15
IL89909A0 (en) 1989-12-15
WO1989010345A1 (fr) 1989-11-02
EP0376997B2 (fr) 1999-03-31
EP0376997A1 (fr) 1990-07-11
ZA892794B (en) 1989-12-27
AU3445389A (en) 1989-11-24

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