EP2274408B1 - Composition de lubrifiant à base de polyalkylène glycol pour des éoliennes - Google Patents

Composition de lubrifiant à base de polyalkylène glycol pour des éoliennes Download PDF

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Publication number
EP2274408B1
EP2274408B1 EP09739458A EP09739458A EP2274408B1 EP 2274408 B1 EP2274408 B1 EP 2274408B1 EP 09739458 A EP09739458 A EP 09739458A EP 09739458 A EP09739458 A EP 09739458A EP 2274408 B1 EP2274408 B1 EP 2274408B1
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percent
acid
ester
weight percent
weight
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German (de)
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EP2274408A1 (fr
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Martin Greaves
Michelle Valenzuela
Daniel Zweifel
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/106—Naphthenic fractions
    • C10M2203/1065—Naphthenic fractions 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/141—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings monocarboxylic
    • C—CHEMISTRY; METALLURGY
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    • 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
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M2207/32—Esters of carbonic acid
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C10M2209/1045—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only used as base material
    • C—CHEMISTRY; METALLURGY
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
    • C10M2209/1075—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • 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
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/043—Ammonium or amine salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/047—Thioderivatives not containing metallic elements
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
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    • 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
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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    • 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
    • C10N2030/14—Metal deactivation
    • C—CHEMISTRY; METALLURGY
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives

Definitions

  • This invention relates to lubricant compositions. More particularly, the invention relates to a polyalkylene glycol (PAG)-based lubricant composition that may be useful under extreme environmental and mechanical conditions, such as those experienced in wind turbine gearboxes.
  • PAG polyalkylene glycol
  • a typical wind turbine includes, among other parts, a gearbox that houses gears connecting a low-speed shaft to a high-speed shaft. These shafts enable rotational speeds to vary from 40 rotations per minute (rpm) - 60 rpm to 1,500 rpm - 1,800 rpm, the latter range representing a rotational speed required by most generators to produce electricity.
  • rpm rotations per minute
  • wind turbines have an impressive record of reliability, when failures occur, they are often traced to gearbox bearing failure.
  • the bearings must undertake extremely high loads, with constantly changing performance requirements. For example, under some operating conditions the bearings need to carry medium-sized loads at low speeds, while elsewhere the bearings need to carry much lower loads but at far higher speeds. Furthermore, light winds require bearings to carry high loads at low speeds.
  • lubricant formulations for wind turbine gear boxes generally now include synthetic, rather than natural oils, Synthetic oils generally use esters, polyalphaolefins (PAOs), combinations of PAOs and esters, and polyalkylene glycols.
  • PAOs often provide a high viscosity index (VI) and low pour point, which supports wide ranges of operating temperatures.
  • PAGs offer improved resistance to micropitting, but may in some cases be incompatible with coatings and/or seal materials, Recent approaches to the challenge may include the following.
  • USPAP United States Patent Application Publication 2005/009409 to Devlin et al.
  • a lubricant composition comprising a sulfur-containing compound, a phosphorous-containing compound, an alkylene amine friction modifying compound, a dispersant compound containing basic nitrogen, and a diluent or base oil.
  • a lubricant composition comprising at least ( ⁇ ) two base stocks, preferably synthetic base stocks, one with a kinematic viscosity at 100 degrees Centigrade (oC) (Kv100°C) of more than (>) 100 centistokes (cSt) and a second with a Kv100°C of less than ( ⁇ ) 10 cSt.
  • the compositions may include a variety of additives such as those available in various commercial gear oil packages.
  • compositions described as suitable for use in wind turbine gearboxes comprise a sulfur-containing compound, a hydrocarbylamine, compound, an alkylphosphorothioate compound, a friction modifier compound, and a diluent or base oil.
  • this invention is a lubricant composition comprising an effective amount of
  • this invention is a lubricant composition
  • a lubricant composition comprising
  • the lubricant composition appears to have utility in both land- and sea-based uses, and in a variety of extreme environmental and mechanical conditions. Such applications include, for example, wind turbine gearboxes, subsea hydraulics, compressors, and other uses where stable viscosity, corrosion inhibition, wear reduction, and long life are particularly necessary.
  • the lubricant composition preferably passes SKF-Emcor Test Method DIN 51802: 1990 (ISO 11 007) with distilled water and with salt water (0.5 weight percent sodium chloride, based upon total weight of the salt water) with a rating of zero. In order to pass such testing, a composition must have a rating of no more than one.
  • the lubricant also preferably passes ASTM D665B for at least 168 hours after initiation.
  • PAGs suitable for use in the above lubricant compositions are, in some non-limiting embodiments, selected from random and block copolymer glycols based on a mixed EO and PO feed. Because of their pour points, random copolymer glycols may be particularly useful herein.
  • One or more PAGs may be used, but the overall EO unit content preferably ranges from 30 wt percent to 95 wt percent, based on the total PAG weight, the remainder being PO units.
  • the EO unit content more preferably ranges from 50 wt percent to 85 wt percent, and still more preferably from 60 wt percent to 70 wt percent, based on the total PAG weight, the remainder being PO units.
  • the PAGs may be monols, diols, triols, tetrols, higher polyfunctional alcohols, or combinations thereof. In some non-limiting embodiments diols may be selected.
  • preparation of a suitable PAG may be by any means or method known to those skilled in the art.
  • ethene and propene may be oxidized to EO and PO, respectively, using, for instance, dilute acidic potassium permanganate or osmium tetroxide.
  • Hydrogen peroxide may alternatively be used, in a reaction transforming the alkene to the alkoxide.
  • EO and PO may then be polymerized to form random PAG co-polymers by simultaneous addition of the oxides to an initiator such as ethylene glycol or propylene glycol and using, for example, a base catalyst, such as potassium hydroxide, to facilitate the polymerization.
  • a PAG copolymer base fluid For example, SYNALOX TM and UCON TM lubricant fluids are available from The Dow Chemical Company.
  • those having a viscosity in the ISO viscosity range of 22 to 1000 that is, a KV of from 22 cSt (2.2 x 10 -5 m 2 /s) to 1,000 cSt (1 x 10 -3 m 2 /s) at 40°C
  • a viscosity ranging from 220 cSt (2.2 x 10 -4 m 2 /s) to 680 cSt (6.8 x 10 -4 m 2 /s) at 40°C may be selected for some applications.
  • an ISO viscosity grade of 320 may be selected. It may also be desirable to select a copolymer base fluid that is water soluble, rather than water insoluble, as a water soluble base fluid may provide improved friction control in certain applications.
  • Polyol esters may be formed by the reaction of polyols (for example, neopentyl glycol; pentaerythritol, trimethylol propane) with acids.
  • acids include mono-acids having from 5 carbon atoms (C 5 ) to 18 carbon atoms (C 18 ), such as C 5 (valeric acid), C 10 (decanoic acid) and C 18 (oleic acid), and di- and tri-acids.
  • Synthetic Lubricants & Functional Fluids ed. by Ronald Shubk in provides teachings about manufacturing synthetic esters, including polyol esters.
  • the polyol ester is preferably a pentaerythritol ester of an alkanoic acid.
  • Alkylene oxide polymers and interpolymers and derivatives thereof with terminal hydroxyl groups modified by esterification may be employed in place of some or all of the above polyol esters.
  • These may be exemplified by mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3 -C 8 fatty acid esters, esters formed from reaction with anhydrides, for example, maleic anhydride and succinic anhydride, and combinations thereof.
  • esters of dicarboxylic acids for example, phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, alkenyl malonic acids, etc.
  • alcohols for example, butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol diethylene glycol monoether, propylene glycol, etc.
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azealate, dioctyl phthalate, dodecyl phthalate, dicicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the like.
  • Additional useful esters include those made from C 5 to C 12 monocarboxylic acids, polyols and polyol ethers, such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol, polymeric tetrahydrofurans, combinations thereof, and the like.
  • polyol esters and diesters such as di-aliphatic diesters of alkyl carboxylic acids such as di-2-ethylhexylazelate, diisodecyladipate, and di-tridecyladipate, commercially available under the brand name EMERYTM 2960 by Emery Chemicals, described in U.S. Pat. No. 4,859,352 .
  • Other suitable polyol esters are manufactured by Exxon-Mobil Chemicals. Exxon-Mobil Chemical's polyol ester P-43, NP343 containing two alcohols, and M-045, and Hatco Corporation's HATCOTM 2939 may be employed in some non-limiting embodiments.
  • Diesters may be selected, such as aliphatic diesters of a dicarboxylic acid, or a dialkyl aliphatic diester of an alkyl dicarboxylic acid, such as di-2-ethyl hexyl azelate, di-isodecyl azelate, di-tridecyl azelate, di-isodecyl adipate, di-tridecyl adipate.
  • Di-2-ethyl hexyl azelate is commercially available from Emery Chemicals under the brand name of EMERY TM 2958.
  • polyol esters such as EMERY TM 2935, 2936, and 2939 from Cognis and HATCO TM 2352, 2962, 2925, 2938, 2939, 2970, 3178, and 4322 polyol esters from Hatco Corporation, described in U.S. Pat. No. 5,344,579 , and MOBIL TM ester P 24 from Exxon-Mobil Chemical.
  • Exxon-Mobil esters such as made by reacting dicarboxylic acids, glycols, and either monobasic acids or monohydric alcohols, may be used.
  • the polyol ester for use herein may, in certain particular but non-limiting embodiments, have a pour point of -100°C or lower to -20°C and a viscosity of 10 cSt (1 x 10 -5 m 2 /s) at 100°C or lower.
  • the selected ester may be aliphatic or aromatic in nature, and may include, for example, diesters, phthalates, trimellitates, pyromellitates, dimer acid esters, polyols and polyoleates.
  • the ester is a pentaerythritol ester of certain other non-limiting embodiments, the ester is a hydrophobic ester which may be generally obtained by reacting a carboxylic acid with a polyol of formula C((CH 2 ) n OH) 4 where n is an integer between 1 and 3, inclusive. These polyols are referred to herein as pentaerythritol homologs.
  • the esters may be manufactured in any manner, such as by the process of McNeil, U.S. Pat. No. 2,961,406 , which describes the manufacture of the mono-pentaerythritol (PEOH) tetraester and the di-PEOH hexaester through a reaction between one or more alkanoic acids and a blend of mono- and di-PEOH.
  • Suitable acids described therein include acetic acid, propanoic acid, butanoic acid, 2-methylpropanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid and nonanonic acid.
  • the alkanoic acid or mixture of acids may be reacted, for example, with separate batches of the mono- and di-PEOH, the resultant batches of tetraester and hexaester being later combined.
  • the acid or mixture of acids may be selected from carboxylic acids; these acids may be normal or branched, saturated or unsaturated, aliphatic or aromatic, or any combination thereof.
  • Useful mono- and di-PEOH esters include a hydrocarbyl group, including normal and branched hydrocarbyl groups, saturated and unsaturated hydrocarbyl groups, and combinations thereof.
  • Hydrocarbyl groups include aliphatic, cycloaliphatic, and aromatic groups, such as alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, and alkaryl groups.
  • Hydrocarbyl groups also include both nonsubstituted hydrocarbyl groups and substituted hydrocarbyl groups, the latter referring to a hydrocarbyl portion bearing additional substituents, besides the carbon and hydrogen; correspondingly, aliphatic, cycloaliphatic, and aromatic groups are understood as including both nonsubstituted aliphatic, cycloaliphatic, and aromatic groups, and substituted aliphatic, cycloaliphatic, and aromatic groups, with the latter referring to the aliphatic, cycloaliphatic, and aromatic portion bearing additional substituents, besides the carbon and hydrogen.
  • Hydrocarbyl groups may include at least one hydrolytically stable heteroatom group, with "hydrolytically stable” meaning that the group does not undergo hydrolysis in the presence of an aqueous medium.
  • Suitable hydrolytically stable heteroatom groups include ether, ester, amide, sulfide, sulfone, sulfoxide, and tertiary amine linkages, as well as halogenated hydrocarbyl groups (for example, chlorinated or fluorinated alkanes).
  • a PEOH ester may comprise any combination of substituent groups, provided that a resulting mixture of PEOH ester is hydrophobic.
  • Substituent groups independently, preferably comprise hydrogen or C 1 -C 22 hydrocarbyl or alkyl groups, more preferably hydrogen or C 1 -C 14 hydrocarbyl or alkyl groups, even more preferably C 4 -C 9 hydrocarbyl or alkyl groups, and still more preferably saturate C 4 -C 9 , alkyl groups (that is, mono- and di-PEOH esters of C 5 -C 10 monobasic saturated acids, preferably a blend of monobasic C 5 - C 10 normal saturated fatty acids).
  • acids that may be reacted with the polyol include, but are not limited to, formic acid, acetic acid, propanoic acid, propenoic acid, buytric acid, isobutyric acid, malonic acid, valeric acid, glutaric acid, caproic acid, adipic acid, caprylic acid, capric acid, decandioic acid, palmitic acid, dodecandioic acid, palmitoleic acid, stearic acid, oleic acid, linolenic acid, behenic acid and erucic acid,
  • PEOH esters include those commercially available from Hercules Incorporated as HERCOLUBE TM and HERCOFLEX TM synthetic esters. These synthetic PEOH esters are essentially mixtures of mono- and di-pentaerythritol esters of C 5 -C 10 fatty acids. Tri-PEOH ester and esters of higher PEOH oligomers may also be present. Preferably, ⁇ 1 wt percent of the PEOH ester comprises impurities. Specific products include HERCOLUBE TM F, HERCOLUBE TM J, HERCOLUBE TM 202 and HERCOFLEX TM 707A, all available from Hercules Incorporated. Alternative commercially available esters include SYNATIVE TM ES TMP and TMTC unsaturated and saturated TMP esters, and saturated NPG/PE esters from Cognis.
  • the lubricant compositions include N-phenyl-1,1,3,3-tetramethylbutyl-naphthalen-1-amine as a first antioxidant.
  • the first antioxidant is commercially, available from Ciba Chemicals Corporation as IRGANOX TM L06.
  • the lubricant compositions include an alkylated diphenylamine as a second antioxidant.
  • the alkylated diphenylamine may be a reaction product of N-phenyl benzenamine and 2,4,4-trlmethylpentene, a mixture of octylated and butylated diphenylamines, or a combination thereof.
  • a commercial example of the reaction product of N-phenyl benzenamine and 2,4,4-trimethylpentene is IRGANOX TM L57, available from Ciba Chemicals Corporation.
  • a commercial example of mixed octylated and butylated diphenylamines is VANLUBE TM 961, available from R.T. Vanderbilt Company, Inc.
  • the lubricant compositions also include a phosphorus-based extreme pressure additive, examples which include isopropylated triaryl phosphates, amine-phosphates; phosphor-thionates, acid phosphates, alkyl phosphates (for example, dodecyl phosphate), and combinations thereof.
  • DURAD TM 310M commercially available from Chemtura, is a combination of isopropylated triaryl phosphates with small amounts of dodecyl phosphate and triphenyl phosphate.
  • Other extreme pressure additives include VANLUBE TM 719, 7611, 727, and 9123 from R.T. Vanderbilt Company, Inc.
  • the lubricant compositions further include a yellow metal passivator.
  • yellow metal refers to a metallurgical grouping that includes brass and bronze alloys, aluminum bronze, phosphor bronze, copper, copper nickel alloys, and beryllium copper.
  • Typical yellow metal passivators include, for example, benzotriazole, tolutriazole, tolyltriazole, mixtures of sodium tolutriazole and tolyltriazole, and combinations thereof. In one particular and non-limiting embodiment, a compound containing tolyltriazole is selected.
  • Typical commercial yellow metal deactivators include IRGAMET TM -30, and IRGAMET TM -42, available from Ciba Chemicals Corporation, and VANLUBE TM 601 and 704, and CUVAN TM 303 and 484, available from R.T. Vanderbilt Company, Inc.
  • the lubricant compositions still further include at least one corrosion inhibitor selected from. (1) an amine salt of an aliphatic phosphoric acid ester (for example, NA-LUBE TM 6110, available from King Industries); (2) an alkenyl succinic acid half ester in mineral oil (for example, IRGACOR TM L12, available from Ciba Chemicals Corporation); (3) an amine salt of an alkyl phosphoric acid combined with a dithiophosphoric acid derivative (for example, NA-LUBE TM 6330, available from King Industries); (4) a combination of barium dinonylnaphthalene sulfonate and dinonylnaphthale necarboxylate in a hydrotreated naphthenic oil (for example, NA-SUL TM BSN, available from King Industries); and (5) combinations thereof.
  • an amine salt of an aliphatic phosphoric acid ester for example, NA-LUBE TM 6110, available from King Industries
  • IRGACOR TM L17 IRGACOR TM DSSG, IRGALUBE TM 349, and SARKOSYL TM O from Ciba Chemicals Corporation
  • VANLUBE TM 601, 601 E, 704, 692 and 719 from R.T. Vanderbilt Company, Inc.
  • the lubricant compositions include each specified component, but such components may vary over a range of proportions relative to one another while providing an overall lubricant composition with desirable properties.
  • the PAG preferably ranges from 50 wt percent to 99 wt percent, preferably ⁇ 70 wt percent, more preferably ⁇ 80 wt percent.
  • the polyol ester preferably ranges from 10 wt percent to 20 wt percent, and is more preferably 15 wt percent.
  • the first antioxidant preferably ranges from 0.1 wt percent to 5.0 wt percent, more preferably ⁇ 0.5 wt percent and still more preferably ⁇ 1.0 wt percent.
  • the second antioxidant ranges from 0.5 wt percent to 5.0 wt percent, more preferably ⁇ 1.0 wt percent and still more preferably ⁇ 1.3 wt percent.
  • the extreme pressure additive preferably ranges from 0.1 wt percent to 3 wt percent, more preferably ⁇ 1.5 wt percent and still more preferably ⁇ 2 wt percent.
  • the yellow metal passivator preferably ranges from 0.01 wt percent to 0.5 wt percent, more preferably from 0.05 wt percent to 0.1 wt percent.
  • Corrosion inhibitors preferably range from 0.1 wt percent to 1.0 wt percent, more preferably from 0.2 wt percent to 0.75 wt percent, and still more preferably from 0.5 wt percent to 0.6 wt percent. Each wt percent in this paragraph is based upon total lubricant composition weight.
  • the lubricant compositions may also include one or more conventional lubricant additives in addition to components specified above.
  • additives include defoamers such as polymethylsiloxanes, demulsifiers, antioxidants (for example, phenolic antioxidants, hindered phenolic antioxidants, additional sulfurized olefins, aromatic amine antioxidants, secondary amine antioxidants, sulfurized phenolic antioxidants, oil-soluble copper compounds, and mixtures thereof), copper corrosion inhibitors, rust inhibitors, pour point depressants, detergents, dyes, metal deactivators, supplemental friction modifiers, diluents, combinations thereof, and the like.
  • the conventional lubricant additives if present, typically range from 100 parts by weight per million parts by weight (ppm) of lubricant composition to 2 wt percent, based upon total lubricant composition weight,
  • the lubricant compositions may be prepared via any method known to those skilled in the art.
  • typical blending equipment includes impeller mixers, tumble blenders, paddle and plow mixers, and single or double shaft mixers. Protocols generally prescribe charging first with a base fluid, herein a combination of PAG and polyol ester, followed by components that are used in relatively small proportion, herein antioxidants, extreme pressure additive, yellow metal passivator, corrosion inhibitor(s), and any additional additives that have been selected, in any order.
  • lubricant compositions While potential applications of the lubricant compositions appear to be unlimited, they are particularly useful for extreme conditions, including, for example, extreme environmental and mechanical conditions.
  • ASTM American Society for Testing and Materials
  • test D665B provides a means of evaluating lubricant compositions for such applications.
  • the lubricant compositions described herein may pass this test with overwhelming success, in many cases showing no significant signs of failure even at 168 hours after initiation.
  • ASTM D665 Standard Test Method for Rust-Preventing Characteristics of Inhibited Mineral Oil in the Presence of Water.
  • ASTM D665A tests with distilled water, while ASTM D6658 tests with salt water.
  • Control Composition by combining 81.1 wt percent of a 60/40 ethylene oxide/propylene oxide (weight/weight) mixed feed glycol (SYNALOX TM 40D300, The Dow Chemical Company), 1 wt percent N-phenyl-1,1,3,3-tetramethylbutylnaphthalen-1-amine as a first antioxidant (IRGANOX TM L06, Ciba Corporation), 1.3 wt percent of a reaction product between N-phenyl-benzeneamine and 2,4,4-trimethylpentene (IRGANOX TM L57, Ciba Corporation) as a second antioxidant, 15 wt percent of a pentaerythritol ester of an alkanoic acid (HERCOLUBE TM J, Hercules Incorporated),1.5 wt percent of an isopropylated triaryl phosphate (DURAD TM 310M, Chemtura) as an antiwear additive, and 0.1 wt
  • Control Composition Mix the Control Composition on a mixing plate using a stir-bar, while heating for 60 minutes at a temperature of 60°C. Test the Control Composition according to ASTM D665B, and summarize results in Table 2.
  • Example 1 also passes testing according to the SKF-Emcor Test Method DIN 51802:1990 (ISO 11 007) with distilled and with salt water (0.5 weight percent NaCl), having a rating in that test of 0 where a maximum rating of 1 is allowed to pass the test.
  • 2 SYNALOX 40D300 is a random 60/40 EO/PO copolymer having a typical kinematic viscosity of 460 cSt (4.6 x 10 -4 m 2 /s) at 40°C.
  • 3 DCF200-12500 is a polymethylsiloxane antifoam agent, available from Dow Corning Corporation. Table 2 Hours from Initiation Control Formulation Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 (Comp.) Ex. 6 (Comp.) Ex.

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  • Lubricants (AREA)

Claims (5)

  1. Composition, de lubrifiant comprenant, en quantité efficace, 1)
    au moins 50 % en poids d'un copolymère statistique ou à blocs de type polyalkylène-glycol, à base d'oxyde d'éthylène et d'oxyde de propylène, lequel polyalkylène-glycol comporte au moins 30 % en poids de motifs dérivés d'oxyde d'éthylène ;
    2) de 10 à 20 % en poids d'un ester de polyol ;
    3) de 0,1 à 5,0 % en poids de N-phényl-[(1,1,3,3-tétraméthyl-butyl)-napht-1-yl]-amine, en tant que premier anti-oxydant ;
    4) de 0,5 à 5,0 % en poids d'une diphényl-amine alkylée, formée par le produit de réaction de la N-phényl-aniline et du 2,4,4-triméthyl-pentène, ou d'un mélange de diphényl-amine octylée et de diphényl-amine butylée, en tant que deuxième anti-oxydant ;
    5) de 0,1 à 3 % en poids d'un additif extrême pression à base de phosphore ;
    6) de 0,01 à 0,5 % en poids d'un agent de passivation de métal jaune, choisi parmi les benzotriazole, tolyl-triazole, tolutriazole et les mélanges de set de sodium de tolutriazole et de sel de sodium de tolyl-triazole, ainsi que leurs combinaisons, étant entendu que le terme "métal jaune", au sens où on l'utilise ici, désigne les suivants : alliages de type laiton ou bronze, bronze à l'aluminium, bronze au phosphore, cuivre, alliages de cuivre et de nickel, et alliages de cuivre et de béryllium ;
    7) et de 0,1 à 0,75 % en poids d'au moins un inhibiteur de corrosion choisi parmi :
    a) un sel d'aminé d'un ester aliphatique d'acide phosphorique,
    b) un semi-ester d'acide alcényl-succinique, dans de l'huile minérale,
    c) un sel d'aminé d'un acide alkyl-phosphorique, en combinaison avec un dérivé d'acide dithiophosphorique,
    d) une combinaison de dinonyl-naphtalène-sulfonate et dinonylnaphtalène carboxylate de baryum, dans une huile naphténique ayant subi un hydrotraitement,
    e) et les combinaisons de tels agents.
  2. Composition de lubrifiant conforme à la revendication 1, dans laquelle le copolymère statistique ou à blocs de type polyalkylène-glycol comporte de 50 à 85 % en poids de motifs dérivés d'oxyde d'éthylène, le reste étant des motifs d'oxyde de propylène.
  3. Composition, de lubrifiant conforme à la revendication 1, dans laquelle l'ester de polyol est un ester de pentaérythritol et d'un acide alcanoïque,
  4. Composition de lubrifiant conforme à la revendication 1, pour laquelle l'additif extrême pression à base de phosphore est choisi dans l'ensemble formé par les dérivés isopropylés de phosphates de triaryle, les amine-phosphates, les phosphorothionates, les phosphates acides, les phosphates d'alkyle, et les combinaisons de tels composés.
  5. Composition de lubrifiant conforme à la revendication 1, qui comprend :
    1) 80 % en poids d'un copolymère statistique ou à blocs de type polyalkylène-glycol, à base d'oxyde d'éthylène et d'oxyde de propylène, qui comporte 60 % en poids de motifs dérivés d'oxyde d'éthylène et 40 % en poids de motifs dérivés d'oxyde de propylène, et dont le grade de viscosité ISO vaut 460 ;
    2) 15 % en poids d'un ester de pentaérythritol et d'un acide alcanoïque ;
    3) 1 % en poids de N-phényl-[(1,1,3,3,tétraméthyl-butyl)-napht-1-yl]-amine, en tant que premier anti-oxydant ;
    4) 1,3 % en poids d'une diphényl-amine alkylée, formée par le produit de réaction de la N-phényl-aniline et du 2,4,4-triméthyl-pentène, en tant que deuxième anti-oxydant ;
    5) 1,5 % en poids d'un dérivé isopropylé de phosphate de triaryle, combiné avec du phosphate de dodécyle et du phosphate de triphényle, en tant qu'additif extrême pression ;
    6) 0,1 % en poids de tolyl-triazole, en tant qu'agent de passivation de métal jaune ;
    7) et 0,6 % en poids d'au moins un sel d'aminé d'un ester aliphatique d'acide phosphorique, en tant qu'inhibiteur de corrosion.
EP09739458A 2008-04-28 2009-04-22 Composition de lubrifiant à base de polyalkylène glycol pour des éoliennes Not-in-force EP2274408B1 (fr)

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CL2009001000A1 (es) 2010-05-14
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WO2009134656A1 (fr) 2009-11-05
AR071223A1 (es) 2010-06-02
US20110039739A1 (en) 2011-02-17
CN102066537A (zh) 2011-05-18
ES2396924T3 (es) 2013-03-01

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