EP2598489B1 - Utilisation de bis-phosphates de diphényle pour améliorer la résistance contre la formation de dépôts d'huiles de turbine contenant des antioxydants aminés - Google Patents

Utilisation de bis-phosphates de diphényle pour améliorer la résistance contre la formation de dépôts d'huiles de turbine contenant des antioxydants aminés Download PDF

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EP2598489B1
EP2598489B1 EP11813081.4A EP11813081A EP2598489B1 EP 2598489 B1 EP2598489 B1 EP 2598489B1 EP 11813081 A EP11813081 A EP 11813081A EP 2598489 B1 EP2598489 B1 EP 2598489B1
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alkyl
turbine
group
range
hydrogen
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EP2598489A4 (fr
EP2598489A1 (fr
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Michael R. Douglass
Douglas Eugene Johnson
Susan C. Ardito
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/2805—Esters used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/041—Triaryl phosphates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/12—Gas-turbines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/12—Gas-turbines
    • C10N2040/13—Aircraft turbines

Definitions

  • the present disclosure relates to turbine oils containing antiwear additives and antioxidants and to the improvement of the resistance to deposit formation of such turbine oils.
  • Turbine oils especially aviation jet engine oils, are complex liquid lubricants designed to function under extreme conditions of temperature, pressure and load. At such conditions the turbine oil experiences volatilization of vital components as well as a loss of the ability to control or inhibit wear of critical engine parts.
  • liquid lubricant typically employs additives specifically designed as antiwear additives.
  • Typical turbine antiwear additives are addressed and described in the prior art.
  • EP 0,521,628 is directed to a combination of aryl phosphates useful as antiwear additives in fuels, lubricants and functional fluids which are subjected to high temperatures under actual service conditions.
  • the combination of aryl phosphates is comprised of: (1) at least one oil-soluble aryl phosphate of the formula: (RO) 3 PO wherein each R is, independently, phenyl or an alkyl-substituted phenyl group; and (2) at least one oil-soluble aryl phosphate of the formula: wherein each R is, independently, phenyl or an alkyl-substituted phenyl group, Ar is m-phenylene or an alkyl-substituted m-phenylene group, and n is a number from 1 to 4, said combination containing from 2 to 30% by weight of component (1).
  • n is a whole or fractional number from 1 to 4, because n in that case represents
  • lubricant compositions which can be benefitted by the use of the composition combination are lubricating oils of lubricating viscosity, including oils composed by volume of at least 50% up to and including 100% of one or more mineral oils or one or more synthetic ester oils.
  • aryl phosphates use can be made of phenol and/or one or more alkyl phenols containing from 1 to 5 alkyl groups on the ring.
  • Each alkyl group can contain up to about 18 carbon atoms provided the alkyl substituents do not sterically hinder the hydroxyl group to such an extent that the substituted phenol cannot undergo reaction to form the desired aryl phosphate.
  • TOP tri-n-octyl phosphate
  • TCP tricresyl phosphate
  • TEP tri- n -butoxy-ethyl phosphate
  • CDP cresyl diphenyl phosphate
  • the combination When used as lubricating oil antiwear additive, the combination is employed in the range 0.005 to 20 wt% based on the total weight of the finished lubricant.
  • the finished lubricant can contain additional additives, including ashless dispersants, zinc hydrocarbyl dithiophosphates, one or more oil-soluble sulfur-containing antiwear and/or extreme pressure agents.
  • U.S. Patent 5,560,849 is directed to improving the antiwear properties of synthetic ester lubricants intended for use at high temperatures (150 to 350°C) by adding to the lubricant a hydrocarbon-insoluble, synthetic ester-soluble, aryl diphosphate ester composition containing a major amount of an aryl diphosphate ester of the formula: wherein Ar is an unsubstituted or alkyl (C 1 to C 12 )-substituted arylene and R is unsubstituted or alkyl (C 1 to C 12 )-substituted aryl.
  • the alkyl diphosphate ester exhibits high thermal stability, making it suitable for use as an antiwear additive in lubricants used at high temperature as a replacement for a tri-aryl phosphate ester (e.g., TCP).
  • TCP tri-aryl phosphate ester
  • the aryl diphosphate ester is employed in synthetic ester base stocks including polyol esters, diesters and phosphate esters in amounts in the range 0.1 to 10%, preferably 0.5 to 5%, based on the weight of the synthetic ester.
  • Other additives may also be present in the synthetic ester lubricant and include lubricating agents, other antiwear additives, antioxidants, metal passivators, rust and/or corrosion inhibitors, viscosity index (VI) improvers, detergents/dispersants, defoamers/antifoamants, emulsion modifiers, seal swell agents, tackifiers, stabilizers, dyes and odor-masking agents.
  • Antioxidants include hindered phenols, aromatic amines and zinc dialkyl/diaryl phosphate (ZDDP).
  • EP 0,612,837 is directed to a polyphenylene ether lubricant containing hydrocarbyl bis(dihydrocarbyl phosphate) compounds of the formula: wherein R is either unsubstituted or substituted hydrocarbyl alkyl or aryl group, A is a bridging group alkylene, haloalkylene, arylene, two arylene groups joined by a bridging group (e.g., -C(CH 3 ), -SO 2 or -CO) or a bridging group containing biarylene, the di-phosphate compound being used as an antiwear additive in an amount in the range of about 0.1 to 10% by weight of the lubricating composition.
  • R is either unsubstituted or substituted hydrocarbyl alkyl or aryl group
  • A is a bridging group alkylene, haloalkylene, arylene, two arylene groups joined by a bridging group (e.g., -C(CH
  • U.S. Published Application 2007/0179069 is directed to high temperature, stable lubricant compositions comprising at least one polyol polyester derived from the reaction product of a neopentyl polyol with 5,7,7-trimethyl-2-(1,3,3-trimethylbutyl)-octanoic acid.
  • This polyolester can be used in combination with other conventional polyolesters as well as in combination with other additives, including metal protecting additives such as t-butyl phenyl phosphate, mono-hexyl and di-hexyl phosphates, isopropylphenyl phosphates, tri-cresyl phosphates, tri-xylyl phosphates, di(n-octyl) phosphate, alkylated tri-phenyl phosphorothionate, tri-phenyl thiophosphate, benzotriazole, tolyltriazole and mixtures, derivatives and combinations thereof in amounts in the range of about 0.1 to 10%, preferably up to about 5%, by weight of the total composition.
  • metal protecting additives such as t-butyl phenyl phosphate, mono-hexyl and di-hexyl phosphates, isopropylphenyl phosphates, tri-cresyl phosphates,
  • lubricant additives include alkylated di-phenyl amines, nonylated di-phenylamine, styrenated di-phenyl amine and hindered alkyl phenols.
  • U.S. Patent 5,206,404 is directed to a composition of alkylated phenyl phosphate esters comprising 1 to 20 wt% tri-alkyl phenyl phosphate, 10 to 50 wt% di-alkyl phenyl mono-phenyl phosphate, 15 to 60 wt% mono-alkyl phenyl di-phenyl phosphate and less than 2 wt% tri-phenyl phosphate exhibiting a combination of excellent thermal, oxidative and hydrolytic stability.
  • Unexpectedly superior thermal and hydrolytic stability properties are obtained when the alkyl moiety is a tertiary alkyl, preferably a t-butyl moiety.
  • the phosphate esters are an ashless antiwear base stock of reduced volatility and find further use as a lubricant additive.
  • TBPP tert-butyl phenyl phosphate
  • Vapor-Phase Lubrication Reaction of Phosphate Ester Vapors with Iron and Steel
  • Johnson D. W. et al., Chem Mater, 2002, 14, 3767-3775 .
  • tri-alkyl phenyl phosphates are useful as antiwear additives in polyester base turbine oil formulations containing monomeric amine antioxidants, their performance has been found to be no more beneficial than tri-cresyl phosphate when employed in turbine oil formulation containing polymeric amine antioxidants. In fact, their performance as antiwear additives is negatively impacted when employed in high performance turbine oil formulations containing polymeric amine antioxidants.
  • an IDP antiwear additive of the formula: wherein R 5 is a C 1 to C 5 alkyl group and m is an integer ranging from zero to 4, n is an integer ranging from 1 to 7, R 6 is hydrogen or a C 1 to C 5 alkyl group, R 7 is hydrogen or a C 1 to C 5 alkyl group, each Ar is independently a phenyl or naphthyl group, R A , R B , R C and R D are the same or different selected from the group consisting of hydrogen, C 1 to C 18 alkyl groups, and when any of R A to R D are other than hydrogen the corresponding Z A , Z B , Z C and Z D are the same or different and range from 1 to up to the available valence of each Ar group, the IDP being present in an amount in the range of 0.
  • SPC Standard Performance Category
  • turbine oils comprising a synthetic ester base oil and one or more monomeric aminic antioxidants
  • the present disclosure is directed to a use for improving the deposit formation resistance performance of turbine oils containing aminic antioxidant, especially High Performance Category (HPC) turbine oils, especially gas turbine oils, particularly aviation turbine oils or jet engine oils containing polymerized amine antioxidants.
  • HPC High Performance Category
  • Turbine oils in general are made up of a number of components which include the base oil, which is one or a mixture of synthetic esters such as polyol esters and diesters, antioxidants, antiwear agents, friction reducers, corrosion inhibitors, metal passivators and dispersants.
  • the base oil which is one or a mixture of synthetic esters such as polyol esters and diesters, antioxidants, antiwear agents, friction reducers, corrosion inhibitors, metal passivators and dispersants.
  • HPC turbine oils are being formulated containing polymeric amine antioxidants to enhance oxidation stability.
  • Most Standard Performance Category (SPC) oils contain monomeric amine antioxidants and most HPC oils contain polymeric amine antioxidants.
  • the present disclosure is a method for improving the deposit resistance performance of turbine oils containing aminic antioxidant additives, especially HPC turbine oil containing polymeric amine antioxidants, and phosphate-type antiwear agents by using as the antiwear agent an additive amount of a polyphosphate ester antiwear agent consisting of 4,4'-(isopropylidenediphenyl) bis(diphenyl phosphate) of the formula: wherein R 5 is a C 1 to C 5 alkyl group and m is an integer ranging from zero to 4, preferably zero to 2, more preferably zero, n is an integer ranging from 1 to 7, R 6 is hydrogen or a C 1 to C 5 alkyl group, preferably hydrogen or a C 1 to C 2 alkyl group, more preferably hydrogen or a C 1 alkyl group, R 7 is hydrogen or a C 1 to C 5 alkyl group, preferably hydrogen or a C 1 to C 2 alkyl group, more preferably hydrogen or a C 1 alkyl group, each Ar is independently a pheny
  • the IDP is used in an amount in the range 0.01 to 10 wt% (active ingredient), preferably 0.1 to 5 wt% (active ingredient), more preferably 1 to 4 wt% (active ingredient), contributing from 500 to 6000 ppm phosphorus, preferably 1000 to 4000 ppm phosphorus, to the formulation.
  • Turbine oils e.g. gas turbine oils, aviation turbine oils and jet engine turbine oils, employ synthetic esters and especially polyol esters as base oils.
  • the synthetic ester which can be used as the base oil is formed by the esterification of an aliphatic monohydric or polyhydric alcohol with linear or branched carboxylic acids.
  • the synthetic esters employed as base oils for the turbine oil have kinematic viscosities at 100°C in the range of 2 to 12 mm 2 /s, preferably 3 to 8 mm 2 /s, more preferably 4 to 6 mm 2 /s.
  • Monohydric alcohols suitable for making ester base stocks include methyl, butyl, isooctyl, didecyl and octadecyl alcohols.
  • "Oxo" alcohols prepared by the reaction of olefins with carbon monoxide and hydrogen are suitable.
  • Neo-alcohols i.e., alcohols having no hydrogens on the beta carbon atom, are preferred. Examples of such alcohols are 2,2,4-trimethyl-pentanol and 2,2-dimethyl propanol.
  • the polyhydric alcohols which can be reacted with the linear acid are, by way of example, polyols represented by the general formula: R(OH) n wherein R is any aliphatic or cyclo-aliphatic hydrocarbyl group (preferably an alkyl) and n is at least 2.
  • R is any aliphatic or cyclo-aliphatic hydrocarbyl group (preferably an alkyl) and n is at least 2.
  • the hydrocarbyl group may contain from about 2 to about 20 or more carbon atoms, and the hydrocarbyl group may also contain substituents such as chlorine, nitrogen and/or oxygen atoms.
  • the polyhydroxyl compounds generally may contain one or more oxyalkylene groups and, thus, the polyhydroxyl compounds include compounds such as polyetherpolyols.
  • the number of carbon atoms (i.e., carbon number, wherein the term "carbon number” as used throughout this application refers to the total number of carbon atoms in either the acid or alcohol as the case may be) and number of hydroxyl groups contained in the polyhydroxyl compound used to form the carboxylic esters may vary over a wide range.
  • the following alcohols are particularly useful as polyols: 2-ethyl-1,3-hexanediol, 2-propyl-3,3-heptanediol, 2-butyl-1,3-butanediol, 2,4-dimethyl-1,3-butanediol, neopentyl glycol, 2,2-dimethylol butane, trimethylol ethane, trimethylol propane, trimethylol butane, mono-pentaerythritol, technical grade pentaerythritol, di-pentaerythritol, tri-pentaerythritol, ethylene glycol, propylene glycol and polyalkylene glycols (e.g., polyethylene glycols, polypropylene glycols, polybutylene glycols, etc., and blends thereof such as polymerized mixture of ethylene glycol and propylene glycol). Mixtures of such alcohols may also be
  • the carboxylic acid reactant used to produce the synthetic polyol ester base oil is selected from aliphatic monocarboxylic acids or a mixture of aliphatic monocarboxylic acids and aliphatic dicarboxylic acids.
  • the carboxylic acids contain from 4 to 20 carbon atoms and includes the straight and branched chain aliphatic acids.
  • the aliphatic chain may include aryl substituents. Mixtures of acids may be used.
  • the carboxylic acid used is a branched or linear C 4 to C 20 carboxylic acid.
  • the branched acid is preferably a mono-carboxylic acid which has a carbon number in the range between about C 4 to C 20 , more preferably about C 5 to C 10 wherein methyl or ethyl branches are preferred.
  • the mono-carboxylic acid is preferably at least one acid selected from the group consisting of: 2,2-dimethylpropionic acid (neopentanoic acid), neoheptanoic acid, neooctanoic acid, neononanoic acid, isohexanoic acid, neodecanoic acid, 2-ethylhexanoic acid (2EH), 3,5,5-trimethylhexanoic acid (TMH), isoheptanoic acid, isooctanoic acid, isononanoic acid and isodecanoic acid.
  • 2,2-dimethylpropionic acid neopentanoic acid
  • neoheptanoic acid neoo
  • branched acid is 3,5,5-trimethylhexanoic acid.
  • the term "neo" as used herein refers to a trialkyl acetic acid, i.e. an acid which is triply substituted at the alpha carbon with alkyl groups. These alkyl groups are equal to or greater than CH 3 , as shown in the general structure set forth herebelow: wherein R 1 , R 2 and R 3 are greater than or equal to CH 3 and not equal to hydrogen.
  • the mono-carboxylic linear acids are any linear saturated alkyl carboxylic acid having a carbon number in the range between about C 4 to C 20 , preferably C 5 to C 10 .
  • linear acids include butyric, valeric, sebacic, azelaic, suberic, succinic, adipic, oxalic, malonic, glutaric, pentadecanedicarboxylic, diglycolic, thidiglycolic, acetic, propionic, lauric, palmitic, pimilic, n-hexanoic, n-heptanoic, n-octanoic, n-nonanoic, and n-decanoic acids and mixtures thereof.
  • ester base oils are ethyl palmitate, ethyl laurate, butyl stearate, di-(2-ethylhexyl) sebacate, di(2-ethylhexyl) azealate, ethyl glycol dilaurate, di-(2-ethylhexyl) phthalate, di-(1,3-methylbutyl) adipate, di-(1-ethylpropyl) azelate, diisopropyloxylate, dicyclohexyl sebacate, glycerol tri-n-heptoate, di(undecyl) azelate, and tetraethylene glycol di-(2-ethyl caproate), and mixtures thereof.
  • the synthetic ester can also include a polybasic acid selected from the group consisting of: any C 2 to C 12 polybasic acids, e.g. adipic, azelaic, sebacic and dodecanedioic acids.
  • polyol ester base oils are those ones prepared from technical pentaerythritol and a mixture of linear and branched C 4 to C 20 carboxylic acids.
  • Technical pentaerythritol is a mixture which includes about 85 to 92% monopentaerythritol and 8 to 15% dipentaerythritol.
  • a typical commercial technical pentaerythritol contains about 88% monopentaerythritol having the formula: and about 12% of dipentaerythritol having the formula:
  • the technical pentaerythritol may also contain some tri- and tetrapentaerythritol that is normally formed as by-products during the manufacture of technical pentaerythritol.
  • esters from alcohols and carboxylic acids can be accomplished using conventional methods and techniques known and familiar to those skilled in the art.
  • the monohydric alcohol or polyhydric alcohol e.g. technical pentaerythritol
  • the desired carboxylic acid or mixture of acids either neat or in the presence of a solvent such as an aromatic hydrocarbon and optionally in the presence of catalyst such as, e.g. titanium, zirconium and tin catalysts such as titanium, zirconium or tin alcohalates, carboxylates and chelates, HCl, HF, HBr, H 2 SO 4 , BF 3 , etc.
  • catalyst such as, e.g. titanium, zirconium and tin catalysts such as titanium, zirconium or tin alcohalates, carboxylates and chelates, HCl, HF, HBr, H 2 SO 4 , BF 3 , etc.
  • esters of technical pentaerythritol may be used without further purification or may be further purified using conventional techniques such as distillation or other methods known to those of skill in the art.
  • polyol esters useful as turbine oil base oils are those made by synthesizing the polyol esters from a polyol and a branched or linear carboxylic acid in such a way that it has a substantial amount of unreacted hydroxyl groups, that is the product is not fully esterified. The presence of the unreacted hydroxyl group in the ester is believed to allow this "high" hydroxyl ester to exhibit increased thermal/oxidation stability, as measured by high pressure differential scanning calorimetry (HPDSC).
  • HPDSC high pressure differential scanning calorimetry
  • the high hydroxyl polyester is the reaction product of a linear or branched alcohol and at least one branched and/or linear carboxylic acid, the resulting synthetic ester having a hydroxyl number between 5 to 180 depending on the acid and polyol used (e.g. 1 to 25% unconverted hydroxyl groups, based on the total amount of hydroxyl groups in the branched or linear alcohol), preferably between about 5 to 100 (e.g. 1 to 15% unconverted hydroxyl groups), more preferably between 10 to 80 (e.g. 2 to 10% unconverted hydroxyl groups).
  • a hydroxyl number between 5 to 180 depending on the acid and polyol used (e.g. 1 to 25% unconverted hydroxyl groups, based on the total amount of hydroxyl groups in the branched or linear alcohol), preferably between about 5 to 100 (e.g. 1 to 15% unconverted hydroxyl groups), more preferably between 10 to 80 (e.g. 2 to 10% unconverted hydroxyl groups).
  • Hydroxyl number measures the free hydroxyl groups by determining the amount of acetic anhydride that the sample will react with under certain conditions. Anhydride is introduced in excess with the sample. Once the reaction is complete, the remaining anhydride is determined by titration with a base solution. The hydroxyl number is reported as milligrams of KOH/gram of sample. A standard method for measuring hydroxyl number is detailed by the American Oil Chemist's Society as A.O.C.S. Cd. 13-60. For highly converted esters, e.g. 99% or more conversion to ester (almost no unreacted hydroxyl groups), the hydroxyl number is generally less than or equal to 5.
  • the alcohols and acids employed can be the same, the only difference in the products being, as previously indicated, that in one instance the product is fully esterified and in the other the product has free hydroxyl groups.
  • Esters suitable for use as base stocks for turbine oils are esters of monocarboxylic acids having three to twelve carbons and polyalcohols such as pentaerythritol, dipentaerythritol and trimethylolpropane.
  • esters are pentaerythrityl tetrabutyrate, pentaerythrityl tetravalerate, pentaerythrityl tetracaproate, pentaerythrityl dibutyratedicaproate, pentaerythrityl butyratecaproate divalerate, pentaerythrityl butyrate trivalerate, pentaerythrityl butyrate tricaproate, pentaerythrityl tributyratecaproate, mixed C 4 - to C 10 -saturated fatty acid esters of pentaerythritol, dipentaerythrityl hexavalerate, dipentaerythrityl
  • the synthetic esters e.g. fully esterified and/or esters containing free hydroxyl groups
  • can be further used with other base stocks such as mineral oil, highly refined mineral oil, polyalpha olefins, polyalkylene glycols, phosphate esters, silicone oils, other polyol esters, as well as hydrocarbon oils made by hydrodewaxing/hydroisomerizing waxy feeds such as hydrodewaxed/hydroisomerized slack wax or Fischer-Tropsch synthesis waxes.
  • the synthetic ester be it a fully esterified material or an ester containing free hydroxyl groups either be used individually or only in the mixture of two or more esters.
  • Aromatic amine antioxidants are well known and are one or more hydrocarbyl-substituted or unsubstituted diphenyl amines, one or more hydrocarbyl-substituted or unsubstituted phenyl naphthyl amines, one or more hydrocarbyl-substituted or unsubstituted phenothiazines and mixtures thereof wherein the hydrocarbyl-substituent is styrene or C 1 to C 30 alkyl, preferably C 1 to C 30 alkyl, more preferably C 4 to C 10 alkyl.
  • Other monomeric aryl amines have been described in the patent literature.
  • Polymeric amine antioxidants are the polymerization reaction products of one or more unsubstituted or hydrocarbyl-substituted diphenyl amines, one or more unsubstituted or hydrocarbyl-substituted phenyl naphthyl amines or both one or more of unsubstituted or hydrocarbyl-substituted diphenylamine with one or more unsubstituted or hydrocarbyl-substituted phenyl naphthylamine.
  • the polymeric amine antioxidant may contain nonpolymerized aryl amine antioxidant starting materials as a result of the preparation procedure.
  • additional monomeric amine antioxidants may be added to the lubricant to impart desired properties.
  • monomeric amine antioxidants include but are not limited to diphenyl amine, alkylated diphenyl amines, styrenated diphenyl amines, phenyl-N-naphthyl amine, alkylated phenyl-N-naphthyl amines, styrenated phenyl-N-naphthyl amines, phenothiazine, alkylated phenothiazine and styrenated phenothiazine.
  • Other antioxidants such as hindered phenols and zinc dithiophosphates can also be added to the lubricant in addition to the polymerized amine antioxidant.
  • the aromatic amine, preferably polymeric amine, antioxidant is present in an amount in the range 0.5 to 10 wt% (active ingredient), preferably 2 to 5 wt% (active ingredient) of aminic antioxidant.
  • active ingredient preferably 2 to 5 wt% (active ingredient) of aminic antioxidant.
  • polymeric aminic antioxidant is employed, the amounts recited above are exclusive of any unpolymerized aryl amine which may be present or of any added antioxidants.
  • IDP antiwear additive of the formula: wherein R 5 is a C 1 to C 5 alkyl group and m is an integer ranging from zero to 4, preferably zero to 2, more preferably zero, n is an integer ranging from 1 to 7, R 6 is hydrogen or a C 1 to C 5 alkyl group, preferably hydrogen or a C 1 to C 2 alkyl group, more preferably hydrogen or a C 1 alkyl group, R 7 is hydrogen or a C 1 to C 5 alkyl group, preferably hydrogen or a C 1 to C 2 alkyl group, more preferably hydrogen or a C 1 alkyl group, each Ar is independently a phenyl or naphthyl group, R A , R B , R C and R D are the same or different selected from the group consisting of hydrogen, C 1 to C 18 alkyl groups, preferably hydrogen and C 1 to C 5 al
  • the IDP antiwear additive is used in an amount in the range 0.01 to 10 wt% (active ingredient), preferably 0.1 to 5 wt% (active ingredient), more preferably 1 to 4 wt% (active ingredient), contributing from 500 to 6000 ppm phosphorus, preferably 1000 to 4000 ppm phosphorus to the formulation.
  • the turbine oils benefitted by the present method include turbine oils further containing additive amounts of any of the additives common to turbine oil formulations including by way of example and not limitation corrosion inhibitors such as combinations of one or more dicarboxylic acids and a linear or branched alkyl or alkenyl succinic acid/anhydride ester or hemiester or hydroxylated derivative of such esters or hemiesters or linear or branched alkyl or alkenyl-substituted succinimides or amino-substituted succinimides, as well as additional other antioxidants including phenolic and monomeric aminic antioxidants, extreme pressure additives, antifoamants, detergents, hydrolytic stabilizers, metal deactivators, rust inhibitors, colorants, odorants, deodorants, viscosity modifiers, viscosity index improvers, etc. as desired by the practitioner.
  • corrosion inhibitors such as combinations of one or more dicarboxylic acids and a linear or branched alkyl or alken
  • the deposit formation resistance performance of HPC turbine oils containing IDP may be 30 mg lower, or 40 mg lower, or 50 mg lower, or 60 mg lower, or 70 mg lower, that is better, than the performance of turbine oils containing the same ester base stock and polymeric aminic antioxidant but containing tricresyl phosphate in place of the IDP.
  • the deposit formation resistance performance of turbine oils containing monomeric aminic antioxidants can also be improved by employing IDP, the deposit formation resistance performance being improved compared to the deposit formation performance exhibited by turbine oils containing the same base stock and monomeric aminic antioxidants but containing tricresyl phosphate in place of the IDP.
  • the improvement may be seen as a reduction in the deposits formed by at least 40 mg, or at least 60 mg, or at least 80 mg, or at least 100 mg, or at least 130 mg, compared to turbine oils containing the same ester base stock and monomeric aminic antioxidants, but tricresyl phosphate in place of the IDP.
  • the two polymeric amine antioxidants were prepared according to the teachings of U.S. 3,573,206 .
  • Polymeric Antioxidant 1 and polymeric Antioxidant 2 were prepared by combining C 8 -alkylated phenyl- ⁇ -aphthylamine and dioctyldiphenyl amine in a 3-to-2 ratio oligomerized to different degrees through the use of various amounts of alkyl peroxide.
  • the treat rates of the antioxidants were adjusted based on the variations in percent active ingredient of the antioxidants to achieve an active ingredient treat level in each formulation of 2.8 wt% (active ingredient).
  • compositional profiles of the turbine (jet) engine oils are provided in Table 3, Table 4 and Table 5: Table 3 Standard Performance Category (SPC) Turbine (Jet) Oils Component, wt% Blend 1 Blend 2 Blend 3 Blend 4 Blend 5 Blend 6 Blend 7 Jet Ester 1 95.515 95.225 94.675 94.585 94.865 95.015 94.845 Monomeric Amine Antioxidants 2 2 2 2 2 2 2 2 2 Metal passivators 0.145 0.145 0.145 0.145 0.145 0.145 Defoamant 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 A: RDP 2.33 -- -- -- -- -- -- B. IDP -- 2.62 -- -- -- -- C. Butylated triphenyl phosphate of which 11.8% is TPP -- -- 3.17 -- -- -- -- D.
  • SPC Standard Performance Category
  • Turbine (Jet) Oils Component wt% Blend 1 Blend 2 Blend 3 Blend 4 Blend 5 Blend 6 Blend 7 Jet Ester 1 95.515 95.225 94.675 94.585 94.865 95.015
  • Blends 2 vary from blend to blend.
  • the amount of IDP added to Blend 2 was an amount sufficient to provide an amount of phosphorus equal to 100% of the amount of phosphorus contributed to Blend 7 by the Durad 125 (TCP).
  • Blend 8A contains sufficient IDP to equal 75% of the amount of phosphorus contained in Ref. 8 contributed by the Durad 125 (TCP) while Blend 8B contains sufficient IDP to equal 125% of the amount of phosphorus contained in Ref. 8.
  • Blends 9A, 9B and 9C contain amounts of IDP sufficient to equal 75%, 100% and 125%, respectively, of the amount of phosphorus contained in Ref. 9 contributed by the Durad 120XC (TCP/TXP).
  • Blends 10A and 10B contain amounts of IDP sufficient to equal 75% and 125%, respectively, of the amount of phosphorus contained in Ref. 10 contributed by Durad 120XC (TCP/TXP).
  • VPC test results were obtained using the Vapor Phase Coker (VPC) test at 700°F (371°C).
  • VPC Test is described in Aerospace Recommended Practice (ARP) 5921 Vapor Phase Coking. This ARP, still in draft form, is available from Mr. James McDonnell, Fuel & Lubricants Division, Naval Air Systems Command, 22229 Elmer Road, Patuxent River, MD 20670, U.S.A .
  • Table 3 shows that formulations containing the IDP exhibited superior deposit formation resistance performance compared to any of the other formulations containing any of the other phosphate-type antiwear additives when employed in combination with monomeric aminic antioxidants.
  • Table 4 shows that the formulations containing the IDP exhibited superior deposit formation resistance performance compared to those formulations containing RDP, tricresyl phosphate and butylated triphenyl phosphate (of which a small portion is unsubstituted triphenyl phosphate) when employed in combination with polymeric aminic antioxidant to produce a HPC turbine oil.
  • Blends 8A and 8B in Table 5 compare the resistance to deposit formation of a HPC turbine oil containing a mixture of pentaerythritol/dipentaerythritol esters of n-C 5 , n-C 7 , C 8 and C 10 acids (Jet Ester 3), a polymeric aminic antioxidant and IDP against a turbine oil containing the same ester base stock and antioxidant but tricresyl phosphate in place of the IDP (Blend 8).
  • Blends 9A, 9B, and 9C in Table 5 compare the resistance to deposit formation of a HPC turbine oil containing pentaerythritol/dipentaerythritol esters of i-C 5 , n-C 5 , C 7 and C 9 acids (Jet Ester 2), a polymeric aminic antioxidant and IDP against a turbine oil containing the same ester base stock and antioxidant but tricresyl phosphate in place of the IDP (Blend 9)
  • Blends 10A and 10 B in Table 5 compare the resistance to deposit formation of an SPC turbine oil containing pentaerythritol/dipentaerythritol esters of i-C 5 , n-C 5 , C 7 , C 8 and C 10 acids (Jet Ester 1), a mixture of monomeric aminic antioxidants, and IDP against a turbine oil containing the same ester base stock and antioxidant but tricresyl phosphate in place of the IDP (Blend 10)
  • All formulation groups containing the IDP exhibited deposit formation resistance performance superior to that of the formulations containing tricresyl phosphate.
  • Those formulations (Blends 8 and 9) using either Jet Ester 2 or Jet Ester 3 exhibited deposit formation performance at least 35 mg lower, preferably about 45 mg lower, more preferably about 60 mg lower, still more preferably about 90 mg lower than the deposit formation performance exhibited by the reference oils employing tricresyl phosphate and containing the polymeric aminic antioxidants.
  • Formulations 10A and 10B using Jet Ester 1 and a monomeric aminic antioxidant exhibited deposit formation performance of about 115 mg to about 120 mg lower than the deposit formation performance exhibited by Ref. 10 containing the same ester base stock and monomeric amine antioxidant but tricresyl phosphate in place of the IDP.

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Claims (7)

  1. Utilisation d'un additif antiusure de la formule :
    Figure imgb0024
     dans laquelle R5 est un groupe alkyle en C1 à C5 et m est un entier allant de zéro à 4, n est un entier allant de 1 à 7, R6 est hydrogène ou un groupe alkyle en C1 à C5, R7 est hydrogène ou un groupe alkyle en C1 à C5, chaque Ar est indépendamment un groupe phényle ou naphtyle, RA, RB, RC et RD sont identiques ou différents choisis dans le groupe constitué par hydrogène, des groupes alkyle en C1 à C18, et, lorsque de quelconques radicaux parmi RA à RD ne sont pas des hydrogènes, les ZA, ZB, ZC et ZD correspondants sont identiques ou différents et vont de 1 à la valence disponible de chaque groupe Ar, l'additif antiusure étant présent dans une quantité dans la gamme de 0,01 à 10 % en poids, rapporté à l'ingrédient actif, et contribuant pour 500 à 6000 ppm de phosphore,
    pour l'amélioration de la résistance à la formation de dépôts d'huile pour turbine de catégorie haute performance (HPC) comprenant une huile de base à base d'ester synthétique et un ou plusieurs antioxydants aminiques polymères, ou des huiles pour turbine de catégorie de performance standard (SPC) comprenant une huile de base à base d'ester synthétique et un ou plusieurs antioxydants aminiques monomères, dans lequel la résistance à la formation de dépôts telle que mesurée par l'essai de cokéfaction en phase vapeur à 700 °F (371 °C) de l'huile pour turbine étant au moins 30 mg inférieure à la formation de dépôts d'huiles pour turbine HPC contenant la même huile de base à base d'ester et le même antioxydant aminique polymère, mais contenant du phosphate de tricrésyle à la place de l'additif antiusure ou au moins 40 mg inférieure à la formation de dépôts d'huiles pour turbine SPC contenant la même huile de base à base d'ester et le même antioxydant aminique monomère, mais contenant du phosphate de tricrésyle à la place de l'additif antiusure, les définitions des huiles pour turbine de catégorie haute performance (HPC) et des huiles pour turbine de catégorie de performance standard (SPC) étant données dans la spécification SAE AS5780, et l'essai de cokéfaction en phase vapeur étant décrit dans l'Aerospace Recommended Practice (ARP) 5921, Vapor Phase Coking.
  2. Utilisation de la revendication 1 dans laquelle le ou les antioxydants aminiques polymères sont les produits de réaction polymérisé d'une ou plusieurs diphénylamines, une ou plusieurs phénylnaphtylamines ou à la fois une ou plusieurs diphénylamines avec une ou plusieurs phénylnaphtylamines.
  3. Utilisation de la revendication 1 dans laquelle l'un ou plusieurs antioxydants aminiques polymères est le produit de réaction de :
    Figure imgb0025
     dans lesquels (a) et (b) vont chacun de zéro à 10 à condition que (a)+(b) vaille au moins 2, R2 est un styrène ou un alkyle en C1 à C30, R3 est un styrène ou un alkyle en C1 à C30, R4 est un styrène ou un alkyle en C1 à C10, p, q et y vont individuellement de zéro à la valence du groupe aryle auquel les groupes R respectifs sont attachés.
  4. Utilisation de la revendication 1 dans laquelle, dans l'additif antiusure, n va de zéro à 2, RA, RB, RC et RD sont identiques ou différents et sont choisis parmi l'hydrogène et les groupes alkyle en C1 à C5, et ZA, ZB, ZC et ZD sont identiques ou différents et vont de 1 à 2.
  5. Utilisation de la revendication 1 dans laquelle l'additif antiusure est utilisé dans une quantité dans la gamme de 0,1 à 5 % en poids, rapporté à l'ingrédient actif, contribuant pour 1000 à 4000 ppm de phosphore.
  6. Utilisation de l'une quelconque des revendications 1 à 5 dans laquelle l'antioxydant aminique polymère est employé dans une quantité dans la gamme de 0,5 à 10 % en poids, rapporté à l'ingrédient actif.
  7. Utilisation de l'une quelconque des revendications 1 à 5 dans laquelle l'ester synthétique est constitué par des esters de monopentaérythritol / dipentaérythritol et d'acides en i-C5, n-C5, C7 et C9, un mélange d'esters de monopentaérythritol / dipentaérythritol et d'acide en n-C5, C8 et C10.
EP11813081.4A 2010-07-27 2011-07-27 Utilisation de bis-phosphates de diphényle pour améliorer la résistance contre la formation de dépôts d'huiles de turbine contenant des antioxydants aminés Not-in-force EP2598489B1 (fr)

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US36813610P 2010-07-27 2010-07-27
US13/190,865 US20130025887A1 (en) 2011-07-26 2011-07-26 Degradable layer for temporarily protecting a seal
PCT/US2011/045467 WO2012015873A1 (fr) 2010-07-27 2011-07-27 Procédé pour améliorer les performances de résistance à la formation de dépôt d'huiles de turbine contenant des antioxydants aminés

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US20190093040A1 (en) * 2017-09-22 2019-03-28 Exxonmobil Research And Engineering Company Lubricating oil compositions with viscosity and deposit control
FR3110593B1 (fr) 2020-05-20 2022-12-16 Nyco Utilisation d’huiles comprenant des additifs anti-usure non neurotoxiques
US11230683B2 (en) 2020-05-20 2022-01-25 Nyco Use of oils comprising non-neurotoxic anti-wear additives
US20230242830A1 (en) 2020-05-20 2023-08-03 Nyco Use of oils comprising non-neurotoxic anti-wear additives

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US3573206A (en) * 1966-03-28 1971-03-30 Mobil Oil Corp Lubricant compositions
US4157971A (en) * 1977-12-27 1979-06-12 Texaco Inc. Synthetic aircraft turbine oil
EP0612837A1 (fr) * 1993-01-06 1994-08-31 Akzo Nobel N.V. Lubrifiant, polyphénylène éther, contenant un composé bis(dihydrocarbylphosphate) hydrocarbyl
JP3964471B2 (ja) * 1995-06-16 2007-08-22 東燃ゼネラル石油株式会社 耐熱性潤滑油組成物
DE19681044B4 (de) * 1995-10-23 2008-08-28 Nsk Ltd. Schmiermittel-Zusammensetzung und deren Verwendung
WO2004018594A1 (fr) * 2002-08-21 2004-03-04 Citizen Watch Co., Ltd. Composition graisseuse pour equipement de precision et appareil horaire la contenant
US20080058235A1 (en) * 2004-03-25 2008-03-06 Katsuya Takigawa Lubricative Composition for Industrial Machinery and Equipment
US20090247436A1 (en) * 2008-03-31 2009-10-01 Exxonmobil Research And Engineering Company Lubricant composition with improved varnish deposit resistance

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