EP0376997A1 - Composition fluide synthetique stable a la chaleur et a l'oxydation. - Google Patents

Composition fluide synthetique stable a la chaleur et a l'oxydation.

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Publication number
EP0376997A1
EP0376997A1 EP89904950A EP89904950A EP0376997A1 EP 0376997 A1 EP0376997 A1 EP 0376997A1 EP 89904950 A EP89904950 A EP 89904950A EP 89904950 A EP89904950 A EP 89904950A EP 0376997 A1 EP0376997 A1 EP 0376997A1
Authority
EP
European Patent Office
Prior art keywords
composition according
hydrocarbyl group
carbon atoms
carboxylic acid
acid ester
Prior art date
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Granted
Application number
EP89904950A
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German (de)
English (en)
Other versions
EP0376997B2 (fr
EP0376997B1 (fr
Inventor
Richard M Lange
Mary F Salomon
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Lubrizol Corp
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Lubrizol Corp
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Classifications

    • 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 the preparation of 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 base stock is composed of a blend of (1) a pentaerythritol ester product consisting essentially of pentaerythritol material completely esterified by straight chain C.-C, Q alkanoic acid material, and (2) trimellitate ester product consisting essentially of trimellitic acid completely esterified by C.-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.
  • U.S. Patent 4,157,990 (Linder et al, June 12, 1979) refers to the development of lubricant and detackifying compositions with a content of
  • R is a neo hydrocarbyl group containing from about 5 to about 18 carbon atoms, with the proviso that R is not a cycloalkyl substituted neo hydrocarbyl group, R, is a mono, di, tri or tetra functional hydrocarbyl group containing from 1 to about 18 carbon atoms, n is an integer from about 2 to about 4 and represents the total number of carboxylic acid ester groups on the aromatic moiety, a is an integer from 1 to about 4, when a is 1 R. is mon valent, when a is 2 R. is divalent, when a is 3 R.
  • a primary object of this invention is to provide a novel thermally and oxidatively stable synthetic fluid composition of an aromatic carboxylic acid ester.
  • a feature of the invention is that the aromatic carboxylic acid esters which function as 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 ester compositions provide lubricating properties which are desirable for synthetic fluid compositions.
  • thermal stability of a chemical compound is its resistance to change brought about solely by thermal energy.
  • 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:
  • R is a neo hydrocarbyl group containing from about 5 to about 18 carbon atoms, with the proviso that R is not a cycloalkyl substituted neo hydrocarbyl group, R, is a mono, di, tri or tetra functional hydrocarbyl group containing from 1 to about 18 carbon atoms, n is an integer from about 2 to about 4 and represents the total number of carboxylic acid ester groups on the aromatic moiety, a is an integer from 1 to about 4, when a is 1 R- is monovalent, when a is 2 R is divalent, when a is 3 R.. is trivalent and when a is 4 R is tetravalent, R_ is a hydrocarbyl group derived from a diol containing from about 2 to about 18 carbon atoms and x is an integer from 0 to about 4.
  • the aromatic carboxylic acid ester is prepared by reacting an alcohol with an aromatic acid or anhydride, or their esters (as in transesterification) .
  • an excess of the alcohol is employed.
  • the alcohol is present in a 100% excess on an equivalent basis.
  • 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-toluene- sulfonic 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:
  • Hydrocarbon groups that is, aliphatic (e.g., alkyl, aromatic, aliphatic- substituted aromatic, aromatic-substituted aliphatic and alicyclic groups, and the like.
  • Typical hydrocarbon groups are known to those skilled in the art. These hydrocarbon groups may be monovalent, as well as di-, tri- or tetravalent. That is, there may be one or more points of attachment of the hydrocarbon groups to carboxy groups within the same complex ester molecule.
  • Examples include octyl, decyl, octadecyl, propylene, butylene, butanetriyl, pentanetriyl, the tetra valent moiety derived from pentaerythritol, etc.
  • Hetero groups that is, groups which, while predominantly hydrocarbon in character within the context of this invention, contain atoms other than carbon in a chain or ring otherwise composed of carbon atoms. Suitable heteroatoms will be apparent to those skilled in the art and include, for example, nitrogen, oxygen and sulfur.
  • 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 the group consisting of 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 the group consisting of. aromatic carboxylic acids, aromatic anhydrides and aromatic esters.
  • aromatic carboxylic acids aromatic carboxylic acids
  • aromatic anhydrides aromatic esters
  • single ring Ar moieties are the following wherein R, and a are as defined in the Summary of the Invention:
  • fused ring aromatic moieties Ar are:
  • Z is selected from the group consisting of
  • Aromatic carboxylic acids are represented by the formula Ar-(-COOH)n where Ar is an aromatic moiety and n is an integer between 2 and 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 are also within the scope of the present invention.
  • Anhydrides are represented by the formula
  • 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
  • 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: ?2
  • R_, R, and R. 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, and R. 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-l-heptanol, 2,2-di-methyl- 1-octanol, 2-methyl-2-ethyl-l-pentanol, 2-methyl-2-ethyl- 1-hexanol, 2-methyl-2-ethyl-l-heptanol, 2-methyl-2-ethyl- 1-octanol, 2,2-diethyl-l-butanol, 2,2-diethyl-l-pentanol, 2,2-diethyl-l-hexanol, 2,2-diethyl-l-heptanol, 2,2-di- ethyl-1-oct
  • the hydrocarbyl group R. is a mono, di, tri or tetra functional hydrocarbyl group containing from 1 to about 18 carbon atoms, preferably from about 5 to about 16 carbon atoms and most preferably from about 5 to about 12 carbon atoms.
  • the hydrocarbyl group R_. is derived from an alcohol containing from 1 to 4 hydroxyl groups and may be represented as R_.-(-OH) wherein a is from 1 to 4.
  • R. is derived from a mono alcohol.
  • the mono alcohols may be the neo alcohols as described and also non neo alcohols.
  • 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.
  • CO-1214 is a fatty alcohol mixture containing 0.5 percent of C 1Q alcohol, 66.0 percent of C.par alcohol, 26.0 percent of C.. alcohol and
  • Neodol 23 is a mixture of C, 2 and C. _ alcohols; and Neodol 45 is a mixture of C.. and C- j ,_ 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
  • R. is derived from a diol.
  • Suitable examples of R--(-0H) 2 are 2,2-dimethyl-l,3-propanediol;
  • R.. is derived from a triol.
  • the triol is derived from a triol.
  • R.,-(-OH) 3 is represented by the formula
  • R fi is a hydrocarbyl group containing from 1 to about 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.. is derived from a tetraol represented by the structure:
  • R R .b,, , R.e and Rd may ⁇ * be the same or different and are hydrocarbyl groups containing from zero up to about 3 carbon atoms.
  • R j contain no carbon atoms, R.. is derived from d i pentaerythritol.
  • R is a neo hydrocarbyl group containing from about 5 to about 10 carbon atoms, R, is a di, tri or tetra functional hydrocarbyl group containing from about 5 to about 16 carbon atoms, n is an integer from about 2 to about 4 and represents the total number of carboxylic acid ester groups on the aromatic moeity; a is an integer from about 2 to about 4 with the proviso that when a is 2 R 1 is divalent, when a is 3 R_. is trivalent and when a is 4 R.. is tetravalent, R réelle is a hydrocarbyl group from a diol containing from about 2 to about 12 carbon atoms and x is an integer from 0 to about 4.
  • R 5 is a hydrocarbyl group containing from about 2 to about 18 carbon atoms, preferably from about 5 to about 18, and most preferably from about 5 to about 16, with the proviso that R 5 is a primary hydrocarbyl group other than a neo hydrocarbyl group and n is an integer from 1 to about 4 with the proviso that there can be no more than four -(-C00R 5 ) groups total in the ester.
  • Another embodiment of this invention comprises an aromatic carboxylic acid ester of the general formula R — -OOC — r — COO — R 2 - - ⁇ 00C — r — COO— ⁇ R, (VI) fC ° OR 5 ) n-2 X ( c/ ° OR 5 ) n-2 wherein Ar is an aromatic moiety, R g is a linear hydrocarbyl group containing from about 2 to about 18 carbon atoms, R, is a di, tri or tetra functional hydrocarbyl group containing from 1 to about 18 carbon atoms, n is an integer from about 2 to about 4 and represents the total number of carboxylic acid ester groups on the aromatic moiety, a is an integer from about 2 to about 4, when a is 2 R.
  • a further embodiment of this invention comprises an aromatic carboxylic acid ester of the general formula
  • R dilemma comprises a mixture of R and R_ wherein R is a neo hydrocarbyl group containing from about 5 to about 18 carbon atoms, with the proviso that R is not a cycloalkyl substituted neo hydrocarbyl group, R is a linear primary hydrocarbyl group containing from about 2 to about 18 carbon atoms, R.
  • a still further embodiment of this invention comprises an aromatic carboxylic acid ester of the general formula
  • R is a mono functional primary hydrocarbyl group containing from 1 to about 18 carbon atoms
  • R 2 is a hydrocarbyl group derived from a diol containing from about 2 to about 18 carbon atoms
  • x is an integer from 1 to about 4.
  • the hydrocarbyl group R_ is derived from a di-hydric alcohol containing between 2 and 18 carbon atoms.
  • R caution contains between 2 and 12 carbon atoms, and most preferably between 2 and 8 carbon atoms.
  • Suitable di-hydric 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.
  • Example 1 A one-liter flask, equipped with a Dean-Stark trap, condenser, thermowell, stirrer and nitrogen inlet tube, is charged with 166 parts (1 mole) of terephthalic acid, 144 parts of Alfol 8-10 alcohol (1 mole) , 144 parts of 2,2,4-trimethyl-l-pentanol (1.1 mole), 10 parts of p-toluenesulfonic acid monohydrate and 200 parts xylene. The contents are heated to reflux under a slow nitrogen purge, and water is removed by azeotropic distillation over an 8-hour period.
  • 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) 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.
  • Example 3 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-l-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.
  • Example 4 To a flask fitted per Example 1 is added 498 parts (3 moles) of isophthalic acid and 700 parts xylene. The solution is heated to 65°C under a slow nitrogen purge, and 384 parts (3 moles) of 2-methyl-2-ethyl-l-pentanol are added. At 70°C, 120 parts (1 mole) of tri ethylolethane and 10 parts of p-toluenesulfonic acid monohydrate are added, and the temperature is increased to reflux. Water is removed by azeotropic distillation over a 12-hour period, and the reaction mixture is then stripped at 140°C/10 Torr to remove volatiles. The reaction mixture is cooled to 90°C, treated with 15 parts of calcium hydroxide for 30 minutes with rapid stirring, then filtered slowly through a thin pad of diatomaceous earth in a Buchner funnel to give the ester product.
  • a one-liter flask equipped as in Example 1 is charged with 200 parts (1 mole) tridecyl alcohol and 122 parts (0.5 moles) dimethyl-2, 6-naphthalene dicarboxylate.
  • trimellitic anhydride (2 moles) of trimellitic anhydride and 500 parts of xylene.
  • the mixture is heated to 60°C, and 68 parts (0.5 mole) of pentaerythritol and 286 parts (2.2 moles) of
  • 2,2,4-trimethylpentanol are added.
  • the reaction mixture is further heated to 85°C with good stirring, and 15 grams of p-toluenesulfonic acid monohydrate are added.
  • the reaction mixture is taken to reflux and water is removed by azeotropic distillation over a 2-hour period.
  • An additional 260 parts (2 moles) of 2,2,4-trimethylpentanol are added, and the mixture dehydrated at reflux over a 12-hour period.
  • 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, 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.
  • a one-liter flask equipped as in Example 1 is charged with 122 parts (0.5 moles) dimethyl-2,6-naphthalene dicarboxylate, 216 parts (1.5 moles) Alfol 8-10 alcohol and 4 parts tetraisopropyl titanate.
  • the contents are heated to 150°C and held for 3 hours, the temperature is increased to 165°C for 2 hours, and finally 185°C for 4 hours.
  • the contents are stripped at 180°C and 10 mm mercury and filtered to give a product that at 100°C is solid.
  • a one-liter flask is charged with 99 parts (0.5 moles) 1,8-naphthalene anhydride, 172 parts (1.2 moles) Alfol 8-10 alcohol and 100 parts xylene.
  • the flask is fitted with a thermowell, stirrer and Dean-Stark trap. Stirring is begun and 4 parts para-toluene sulfonic acid are added. Water is removed by azeotropic distillation until 9 parts water are obtained. At 90°C, 4 parts calcium hydroxide are added to neutralize the para-toluene sulfonic acid catalyst. Volatiles are removed by vacuum distillation at 220°C and 2 mm mercury. The contents are filtered at room temperature to give a product having a neutralization number to phenolphthalein of 1.0.
  • compositions 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
  • polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene poly ⁇ mers (e.g., methyl-polyisopropylene 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 3 -C 8 fatty acid esters and C 13 Oxo acid diester of tetraethylene glycol.
  • 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 onoether, 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
  • 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 ⁇ to C, 2 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 lubri- eating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate. diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
  • liquid esters of phosphorus-containing acids e.g., tricresyl phosphate, trioctyl phosphate. diethyl ester of decylphosphonic acid
  • polymeric tetrahydrofurans e.g., tricresyl phosphate, trioctyl phosphate. diethyl ester of decylphosphonic acid
  • 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 distil ⁇ lation 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. Normally the amount employed of the thermally oxidatively stable lubricants of the present invention will be about 10% to about 100%, preferably about 20% to about 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.
  • compositions of this invention contain a "major amount” of a specific material that amount is more than 50 percent by v/eight of the composition.
  • 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 common ⁇ ly 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 temper- ature 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 there ⁇ fore 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:
  • Interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecu ⁇ lar 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.
  • polymeric dispersants examples thereof are disclosed in the following U.S. patents: 3 , 329 , 658 ; 3 , 366 , 730 ; 3 , 449 , 250 ; 3 , 687 , 849 ; 3 , 519 , 565 and 3 , 702 , 300 .
  • Extreme pressure agents and corrosion- and oxidation- inhibiting agents which may be included in this invention are exemplified by 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
  • Zinc dialkylphosphorodithioates are a well known example.
  • Pour point depressants are a particularly useful type of additive often included in the lubricating oils de ⁇ scribed herein. The use of such pour point depressants in oil-based compositions to improve low temperature proper- ties 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; conden ⁇ sation products of haloparaffin waxes and aromatic com ⁇ pounds; 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 prepara ⁇ tion 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 which are hereby incorporated by reference for their relevant disclosures.
  • 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 the compositions 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.
  • Emery 3004 (baseline) 238
  • Emery 2982 (baseline) 250
  • PDSC pressure differential scanning calorimetry
  • DSC Differential Scanning Calorimeter
  • Emery 3004 (baseline)
  • 198 Emery 2982 (baseline) 211

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Abstract

On a mis au point une composition fluide stable à la chaleur et à l'oxydation. Ladite composition se compose essentiellement d'un ester d'acide carboxylique aromatique de la formule générale (I) dans laquelle Ar représente une fraction aromatique, R représente un groupe néo hydrocarbyle contenant environ 5 à 18 atomes de carbone, à condition que R ne soit pas un groupe néo hydrocarbyle à substitution de cycloalkyle. R1 représente un groupe hydrocarbyle mono, di, tri ou tétra fonctionnel contenant 1 à environ 18 atomes de carbone, n est un nombre entier compris entre environ 2 et 4 et représente le nombre total de groupes d'esters d'acide carboxylique dans la fraction aromatique, a est un nombre entier compris entre environ 1 et 4, lorsque a représente 1 R1 est monovalent, lorsque a représente 2 R1 est divalent, lorsque a représente 3 R1 est trivalent et lorsque a représent 4 R1 est tétravalent. R2 représente un groupe hydrocarbyle dérivé d'un diol contenant environ 2 à 18 atomes de carbone et x représente un nombre entier compris entre 0 et environ 4.
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)

Application Number Priority Date Filing Date Title
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

Publications (3)

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

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EP89904950A Expired - Lifetime EP0376997B2 (fr) 1988-04-18 1989-04-07 Composition fluide synthetique stable a la chaleur et a l'oxydation

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EP (1) EP0376997B2 (fr)
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)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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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

Non-Patent Citations (1)

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See references of WO8910345A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
WO1989010345A1 (fr) 1989-11-02
EP0376997B2 (fr) 1999-03-31
ATE117288T1 (de) 1995-02-15
DE68920723D1 (en) 1995-03-02
AU616010B2 (en) 1991-10-17
EP0376997B1 (fr) 1995-01-18
CA1339451C (fr) 1997-09-09
DE68920723T2 (de) 1995-05-18
MX173426B (es) 1994-03-03
JP2991732B2 (ja) 1999-12-20
AU3445389A (en) 1989-11-24
IL89909A0 (en) 1989-12-15
JPH03502588A (ja) 1991-06-13
DE68920723T3 (de) 1999-07-22
ZA892794B (en) 1989-12-27
IL89909A (en) 1993-02-21

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