EP2044181A1 - Procédé pour lubrifier un appareil à engrenage renforcé - Google Patents

Procédé pour lubrifier un appareil à engrenage renforcé

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Publication number
EP2044181A1
EP2044181A1 EP07810523A EP07810523A EP2044181A1 EP 2044181 A1 EP2044181 A1 EP 2044181A1 EP 07810523 A EP07810523 A EP 07810523A EP 07810523 A EP07810523 A EP 07810523A EP 2044181 A1 EP2044181 A1 EP 2044181A1
Authority
EP
European Patent Office
Prior art keywords
lubricating oil
oil composition
kinematic viscosity
less
viscosity
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP07810523A
Other languages
German (de)
English (en)
Other versions
EP2044181A4 (fr
EP2044181B1 (fr
Inventor
Arjun K. Goyal
L. Oscar Farng
Kwasi Mitchell
Richard T. Spissel
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ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
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Publication of EP2044181A1 publication Critical patent/EP2044181A1/fr
Publication of EP2044181A4 publication Critical patent/EP2044181A4/fr
Application granted granted Critical
Publication of EP2044181B1 publication Critical patent/EP2044181B1/fr
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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
    • C10M7/00—Solid or semi-solid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single solid or semi-solid substances
    • 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
    • C10M171/02—Specified values of viscosity or viscosity index
    • 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
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
    • 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
    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • 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
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
    • C10M2207/2805—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
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C10M2207/2815—Esters of (cyclo)aliphatic monocarboxylic acids 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
    • 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
    • C10M2209/102—Polyesters
    • C10M2209/1023—Polyesters used as base material
    • 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
    • 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
    • C10N2030/54—Fuel economy
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives

Definitions

  • This invention relates to power transmitting fluids or gear oils and to a method for improving the energy efficiency of heavy duty geared machinery /apparatus by using lubricating oils of enhanced performance efficiency.
  • Heavy duty geared machinery such as manual transmissions, automatic transmissions, differentials, gear boxes, etc., operated at high temperature and high load over extended or prolonged periods of time are not adequately lubricated using current lubricating oil formulations which do not provide adequate film thickness leading to metal-to- metal contact (boundary lubrication).
  • USP 5,858,935 is directed to automotive transmission fluids comprising no less than 50 wt% of a natural mineral oil having a kinematic viscosity at 100 0 C of from 1 to 10 mm 2 /s, up to 49 wt% of a synthetic lubricating oil having a kinematic viscosity @ 100 0 C of from 1 to 10 mm 2 /s and from 1 to 25 wt% of a high viscosity polyalphaolefin having a kinematic viscosity at 100 0 C of from 40 to 500 mmVs.
  • the synthetic lubricating oil having a kinematic viscosity @ 100 0 C of from 1 to 10 mm 2 /s can be selected from hydrocarbon oils and halo-substituted hydrocarbon oils such as oligomerized, polymerized and interpolymerized olefins (e.g., polybutenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polyactenes, poly(l-hexenes) poly (1-octenes), poly (1-decenes), etc., and mixtures thereof, alkyl benzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl sulfides, preferably polyalphaolef ⁇ ns.
  • hydrocarbon oils and halo-substituted hydrocarbon oils such as oligomerized, polymerized and interpolymerized olefins (e.g., polybutene
  • Additional synthetic lubricating oils include alkylene oxidepolymers, interpolymers, copolymers and derivatives thereof, diesters which are the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimers, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol, monoethers, propylene glycol, etc.), in particular dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl se
  • Other useful synthetic lubricating oils include those made from C 5 to Ci 2 monocarboxylic acids with polyols and/or polyolester, such as neopentyl glycol, trimethylol propane, pentaerythritol, etc.
  • preferred synthetic oils are polyalphaolefins, diesters and polyol esters, having kinematic viscosities at 100 0 C of from 2 to 8 mm 2 /s, preferably 3 to 5 mm 2 /s.
  • USP 6,713,439 is directed to energy conserving power transmission fluids comprising from 1 to 49 wt% of a polyalpha olefin base stock having a kinematic viscosity at 100 0 C of from 40 to 500 mm 2 /s, from 1 to 95 wt% of a lubricant base stock having a kinematic viscosity at 100 0 C of from 2 to 10 mm 2 /s, from 1 to 49 wt% of a polyol ester of a C 5 to C30 aliphatic monocarboxylic acid and a polyol of the formula R(OH)n where n is at least 2 and an effective amount of a performance additive package, the power transmission fluid composition having a kinematic viscosity at 100 0 C of at least 4 mm 2 /s.
  • the lubricant base stock can be mineral oil, or synthetic lubricating oils, preferably polyalphaolefin or mineral oil. No viscosity range is given for the polyol ester, but the only one exemplified is Priolube 3999 from Uniquema, Gouda, Netherlands, having a kinematic viscosity at 100 0 C of 13.19 mm 2 /s.
  • USP 5,089,156 is directed to lubricating oil compositions comprising a major amount of a polyalphaolefin fluid having a kinematic viscosity @ 100 0 C of about 2 to 10 mmVs, and minor amounts of a polyalphaolefin fluid having a kinematic viscosity @ 100 0 C of about 40 to 120 mm 2 /s and antiwear/extreme pressure agent selected from phospho-dispersant and phosphorus- and boron- containing ashless dispersant, the composition being devoid of metal containing components and characterized as having a kinematic viscosity at 100 0 C of at least 5.5 mm 2 /s, a Brookfield viscosity at -40 0 C of less than 20,000 cP or a kinematic viscosity at 100 0 C of at least 6.8 mm 2 /s and a Brookfield viscosity at -40 0 C of less than 50,000 cP.
  • the formulation can also contain synthetic esters such as mixed C 9 and Cn dialkyl phthalates, trimethylol propane trioleate, di-isotridecyl-adipate, pentaerythritol tetraheptanoate and the like.
  • synthetic esters such as mixed C 9 and Cn dialkyl phthalates, trimethylol propane trioleate, di-isotridecyl-adipate, pentaerythritol tetraheptanoate and the like.
  • the Examples utilizes mixtures of PAO 6, PAO 8, PAO 110 and diisononyl adipate, dioctyl sebacate, dibutyl phthalate or di (tridecyl) phthalate along with performance additives.
  • USP 5,360,562 is directed to an automatic transmission fluid comprising a base oil composed entirely of 70 to 99% polyalpha olefin having a kinematic viscosity at 100 0 C of about 2 to 10 mm 2 /s, and 30 to 1 wt% of polyalphaolefin having a kinematic viscosity at 100 0 C of about 40 to 120 mm 2 /s and further containing 1 to 15 wt% antiwear/extreme pressure additive, other performance additives and no more than 10 wt% viscosity index improver, and essentially devoid of metal containing components, said fluid having a KV @ 100 0 C of at least 5.5 mm 2 /s and a Brookfield viscosity at -40 0 C of less than 20,000 cP or a KV at 100 0 C of at least 6.8 mm 2 /s, and a Brookfield viscosity at -40 0 C of less than 50,000 cP.
  • the fluid can also contain synthetic esters such as mixed C 9 and Cn dialkylphthalates, trimethylol propane trioleate, di (isotridecyl) adipate, pentaerythritol tetraheptanoate, and the like.
  • synthetic esters such as mixed C 9 and Cn dialkylphthalates, trimethylol propane trioleate, di (isotridecyl) adipate, pentaerythritol tetraheptanoate, and the like.
  • the Examples used mixtures of PAO 6 and/or PAO 8 plus PAO 1 10, along with diisononyl adipate, di(tridecyl) adipate, synthetic esters identified at Hatcol 2923, Hatcol 2920, Hatcol 2915, Hatcol 2970, dioctyl sebacate, dibutyl phthalate, dioctyl sebacate, Emery 2935, Emery 2939.
  • USP 6,713,438 is directed to high performance engine oil and other liquid lubricants comprising about 50 to 90 wt% of base oil selected from mineral oil, polyalpha olefin, hydroisomerized Fischer-Tropsch wax and having a KV at 100 0 C of form 1.5 to 12 mm 2 /s, about 0.1 to about 20 wt% of a first polymer and about 0.1 to about 5 wt% of a second polymers, the first polymer being of lower molecular weight than the second, and being a polyalpha olefin having a viscosity from 20 to 3000 mm 2 /s, the second polymer having a molecular weight of at least 100,000 and having viscosity thickening properties.
  • base oil selected from mineral oil, polyalpha olefin, hydroisomerized Fischer-Tropsch wax and having a KV at 100 0 C of form 1.5 to 12 mm 2 /s
  • first polymer being of lower molecular weight than the second
  • the low viscosity component can also include esters generally identified as having kinematic viscosity at 100 0 C in the range 1.5 to 12 mm 2 /s.
  • the esters are derived from dibasic acids reacted with mono alcohols and the polyol ester of monocarboxy lie acids.
  • esters include the esters of dicarboxylic acids such as phthalic acid succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc., with various alcohols such as butyl, hexyl, dodecyl, 2-ethylhexyl alcohol.
  • dicarboxylic acids such as phthalic acid succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc.
  • various alcohols such as butyl, hexyl,
  • esters include dibutyl adipate, di (2-ethylthexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecylphthalate, dilicosyl sebacate, etc.
  • Useful polyol esters include those made by reacting one or more polyhydric alcohols, preferably the hindered polyol s such as the neopentyl polyols, e.g., neopentyl glycol, trimethylol ethane, trimethylol propane, 2-methyl-2-propyl-l,3-propane diol, pentaerythritol and dipentaerythritol with alkanolic acids containing at least 4 carbon atoms, usually C 5 -C 30 acids.
  • examples of such polyol esters are Mobil P-41 and Mobil P-51 esters (Mobil Chemical Company).
  • the additive comprises an olefin oligomer of about 2,000 to 20,000 number average molecular weight and a viscosity of about 75 to 3,000 mm 2 /s at 100 0 C and a hydrocarbyl aromatic which contains at least about 5% of its weight from aromatic moieties and has a viscosity of about 3 to 50 mm 2 /s at 100 0 C.
  • Lubricating oils are described containing this additive.
  • Such lubricating oils comprise base oils which can be mineral oil, synthetic oil or mixtures thereof, synthetic oils include PAO and esters as well as other possible synthetic materials.
  • the olefin oligomer is a polymer of decene-1 having a viscosity at 100 0 C of about 150 mm 2 /s and it is employed in formulations containing PAO 4, mineral oil and an unidentified ester which has a KV at 100 0 C of 5.5 mm 2 /s, VI 131, see Examples 4.2, 4.4 and 4.6.
  • the fluid comprises a high viscosity fluid, preferably polyalpha olefin blended with a lower viscosity fluid comprising a synthetic hydrocarbon which can also be polyalphaolefin.
  • the high viscosity fluid has a KV @ 100 0 C between 40 and 3000 mm 2 /s, while the lower viscosity fluid has a KV @ 100 0 C of 40 mm 2 /s or less.
  • the formulation can also contain esters and mineral oil as well as one or more performance additives.
  • formulations comprising mixtures of additives, lower viscosity hydrocarbon fluid PAO-2 (SHFTM23), lower viscosity ester (EsterexTMMl 1) SupersynTM2150 (PAO 150); additives, PAO-25 (SHFTM23), EsterexTMMl 1, SHFTM1003 (PAO-100) (high viscosity hydrocarbon fluid) and SupersynTM2300 (PAO 300).
  • EsterexTMMl 1 is a commercially available ester which has a kinematic viscosity at 100 0 C in the range of about 1.25 to 1.45 mm 2 /s.
  • a method for improving the fuel and energy efficiency of heavy duty geared machinery under high load conditions by lubricating the heavy duty geared machinery using a lubricating oil composition comprising from about 20 to 75 wt%, preferably about 30 to about 60 wt%, more preferably about 45 to 55 wt% of a polyalpha olefin fluid having a kinematic viscosity at 100 0 C (ASTM D-445-5) of between about 2 to 10 mm 2 /s, preferably between about 3.5 to 8 mm 2 /s, most preferably 3.5 to 6 mm 2 /s, about 5 to 40 wt%, preferably about 5 to 20 wt%, more preferably about 8 to 12 wt% of a polyalpha olefin fluid having a kinematic viscosity at 100 0 C (ASTM D-445-5) between about 150 to 3000 mm 2 /s, preferably between about 150 to 1500 mm 2 /s, more
  • the base oil comprises a particular combination of polyalphaolefin base oils in combination with one or more of the recited esters to produce a formulation exhibiting unexpectedly enhanced performance characteristic.
  • PAOs Polyalphaolef ⁇ ns
  • PAOs are a hydrocarbon base stock oil well known in the lubricating oil trade. PAOs are derived by the polymerization or copolymerization of alphaolefins having from 2 to 32 carbons, more typically Q, Cio, Ci 2 , C i 4 olefins or mixtures thereof are utilized.
  • the number average molecular weight of PAOs typically vary from about 250 to about 3,000 or higher and may have viscosities at 100 0 C in the range from about 2 to about 3000 mm 2 /s or higher.
  • the PAOs are typically comprised of relatively low molecular weight hydrogenated polymers or oligomers of alphaolefms which include, but are not limited to, about C 2 to about C 32 alphaolefins with about C 8 to about Ci 6 alpha- olefins, such as 1-octene, 1-decene, 1-dodecene and the like, being preferred.
  • the preferred polyalphaolefins are poly- 1-octene, poly- 1-decene and poly-1- dodecene and mixtures thereof and mixed olefin-derived polyolefins.
  • the dimers of higher olefins in the range of about C ⁇ to Qg may be used to provide low viscosity base stocks of acceptably low volatility.
  • the PAOs may be predominantly trimers and tetramers of the starting olefins, with minor amounts of the higher oligomers.
  • PAO fluids may be conveniently made by the polymerization of an alphaolefin in the presence of a polymerization catalyst such as the Friedel- Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
  • a polymerization catalyst such as the Friedel- Crafts catalysts including, for example, aluminum trichloride, boron trifluoride or complexes of boron trifluoride with water, alcohols such as ethanol, propanol or butanol, carboxylic acids or esters such as ethyl acetate or ethyl propionate.
  • a polymerization catalyst such as the Friedel- Crafts catalysts including, for example, aluminum trichloride, boron trifluor
  • High viscosity PAOs suitable for the present invention may be prepared by the action of a reduced chromium catalyst with the alphaolefin, such PAOs are described in USP 4,827,073 (Wu); USP 4,827,064 (Wu); USP 4,967,032 (Ho et al); USP 4,926,004 (Pelrine et al); and, USP 4,914,254 (Pelrine).
  • the dimers of the C M to C )8 olefins are described in USP 4,218,330.
  • Commercially available high viscosity PAOs include SuperSynTM 2150, SuperSynTM 2300, SuperSynTM 21000, SuperSynTM 23000 (ExxonMobil Chemical Company).
  • the lubricating oil comprises a base oil consisting of a specific mixture of PAOs of different viscosities, and further containing an ester, and at least one performance additive.
  • the lubricating oil formulation comprises:
  • ester(s) selected from polyol esters, esters of mono basic or polybasic acids with monoalkanols, or mixtures of monoalkanols and polyalkanols, preferably a non-polyol ester, more preferably esters of dibasic acids with monoalkanols, most preferably esters of adipic acid, having a kinematic viscosity at 100 0 C of between about 2 to 5 mm 2 /s, preferably about 2 to 4.5 mm 2 /s, more preferably about 2.5 to 4.5 mm 2 /s; and
  • lubricant oil composition having a KV at 100 0 C of between 9 and 12.5 mm 2 /s, preferably between 10 and 12 mm 2 /s, and exhibiting a traction coefficient value (measured as the 100°C/30 SSR value) of about 0.0197 or less, preferably about 0.0195 or less, a Brookfield viscosity at -40 0 C of about 26,000 cP or less, preferably about 21 ,000 cP or less and a CCS viscosity at -25°C of about 4200 cP or less, preferably about 3,600 cP or less, more preferably about 3,400 cP or less, a NOACK volatility of 15% or less, preferably 13% or less, and a flash point of 220 0 C or higher, preferably 230 0 C or higher all weight percentages being based on the total lubricant composition.
  • the present formulations are further distinguished by the absence of viscosity index improvers, the presence of which is deterious to traction coefficient.
  • Esters of mono-basic and polybasic, especially dibasic acids with monoalkanols are exemplified by the esters of dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid, etc., with a variety of alcohols such as butyl alcohol, hexyl alcohol, dodecy 1 alcohol, 2-ethylhexyl alcohol, etc., or mixtures thereof with polyalkanols.
  • dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adip
  • esters include nonyl heptanoate, dibutyl adipate, di(2- ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, etc.
  • Other useful synthetic esters are those which are obtained by reacting one or more polyhydric alcohols (preferably the hindered polyols such as the neopentyl polyols e.g. neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl- 1,3-propanediol, trimethylol propane, pentaerythritol and dipentaerythritol) with alkanoic acids containing at least about 4 carbon atoms (preferably C 5 to C 30 acids such as saturated straight chain fatty acids including caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, and behenic acid, or the corresponding branched chain fatty acids or unsaturated fatty acids such as oleic acid).
  • polyhydric alcohols preferably the hindered polyols such as the neopentyl polyols such as the neopent
  • Suitable synthetic ester components include the esters of trimethylol propane, trimethylol butane, trimethylol ethane, pentaerythritol and/or dipentaerythritol with one or more monocarboxylic acids containing from about 5 to about 10 carbon atoms.
  • the preferred esters are the esters of dibasic acids with monoalkanols.
  • the gear oil formulation contains at least one of a gear oil performance addition in an effective amount.
  • effective amount is meant a minor amount, based on the total weight of the formulated lubricant, sufficient for the additive to produce the desired performance modification effect.
  • Effective amount is usually about 20 wt% or less, preferably about 3 to 12 wt%, more preferably about 4 to 7 wt% in total of at least one (i.e., one or more) performance additive(s).
  • Performance additives suitable for use in the present gear oil to achieve the desired lubricating oil performance are antioxidant, antiwear additives, metal corrosion inhibitors, friction modifiers, ashless dispersants, detergents, anti- foamants, seal swellant.
  • Notably absent in the present gear oil formulations are viscosity modifiers and viscosity index improvers.
  • ZDDP zinc dialkyldithio- phosphate
  • ZDDP compounds generally are of the formula Zn[SP(S)(OR 1 XOR 2 X) 2 where R 1 and R 2 are C 1 -Ci 8 alkyl groups, preferably C 2 -C i 2 alkyl groups. These alkyl groups may be straight chain or branched.
  • the ZDDP is typically used in amounts of from about 0.4 to 6 wt%, preferably about 0.8 to 4.0 wt% of the total lube oil composition, although more or less can often be used advantageously the amount of phosphorus and zinc attributable to the ZDDP being about 420-1500 ppm P and 450 to 1600 ppm Zn.
  • Sulfurized olefins are useful as antiwear and EP additives.
  • Sulfur- containing olefins can be prepared by sulftirization or various organic materials including aliphatic, arylaliphatic or alicyclic olefinic hydrocarbons containing from about 3 to 30 carbon atoms, preferably 3-20 carbon atoms.
  • the olefinic compounds contain at least one non-aromatic double bond. Such compounds are defined by the formula
  • R 3 R 4 C CR 5 R 6 [038J where each of R 3 -R 6 are independently hydrogen or a hydrocarbon radical.
  • Preferred hydrocarbon radicals are alkyl or alkenyl radicals. Any two of R 3 -R 6 may be connected so as to form a cyclic ring. Additional information concerning sulfurized olefins and their preparation can be found in USP 4,941,984.
  • alky lth iocarbamoyl compounds bis(dibutyl)thiocarbamoyl, for example
  • a molybdenum compound oxymolybdenum diisopropyl- phosphorodithioate sulfide, for example
  • a phosphorous ester dibutyl hydrogen phosphite, for example
  • USP 4,758,362 discloses use of a carbamate additive to provide improved antiwear and extreme pressure properties.
  • the use of thiocarbamate as an antiwear additive is disclosed in USP 5,693,598.
  • the use or addition of such materials should be kept to a minimum if the object is to produce low SAP formulations.
  • Esters of glycerol may be used as antiwear agents.
  • mono-, di, and tri-oleates, mono-palm itates and mono-myristates may be used.
  • ZDDP can be combined with other compositions that provide antiwear properties.
  • USP 5,034,141 discloses that a combination of a thiodixanthogen compound (octylthiodixanthogen, for example) and a metal thiophosphate (ZDDP, for example) can improve antiwear properties.
  • USP 5,034,142 discloses that use of a metal alkyoxyalkylxanthate (nickel ethoxyethylxanthate, for example) and a dixanthogen (diethoxyethyl dixanthogen, for example) in combination with ZDDP improves antiwear properties.
  • Preferred antiwear additives include phosphorus and sulfur compounds such as zinc dithiophosphates and/or sulfur, nitrogen, boron, molybdenum phosphorodithioates, molybdenum dithiocarbamates and various organo- molybdenum derivatives including heterocyclics, for example dimercaptothia- diazoles, mercaptobenzothiadiazoles, triazines, and the like, alicyclics, amines, alcohols, esters, diols, triols, fatty amides and the like can also be used.
  • Such additives may be used in an amount of about 0.01 to 6 wt%, preferably about 0.01 to 4 wt%.
  • ZDDP-like compounds provide limited hydroperoxide decomposition capability, significantly below that exhibited by compounds disclosed and claimed in this patent and can therefore be eliminated from the formulation or, if retained, kept at a minimal concentration to facilitate production of low SAP formulations.
  • Antioxidants retard the oxidative degradation of base oils during service. Such degradation may result in deposits on metal surfaces, the presence of sludge, or a viscosity increase in the lubricant.
  • One skilled in the art knows a wide variety of oxidation inhibitors that are useful in lubricating oil compositions. See, Klamann in Lubricants and Related Products, op cite, and U.S. Patents 4,798,684 and 5,084,197, for example.
  • Useful antioxidants include hindered phenols. These phenolic antioxidants may be ashless (metal-free) phenolic compounds or neutral or basic metal salts of certain phenolic compounds. Typical phenolic antioxidant compounds are the hindered phenolics which are the ones which contain a sterically hindered hydroxyl group, and these include those derivatives of dihydroxy aryl compounds in which the hydroxyl groups are in the o- or p-position to each other. Typical phenolic antioxidants include the hindered phenols substituted with C 6 + alkyl groups and the alkylene coupled derivatives of these hindered phenols.
  • phenolic materials of this type 2-t-butyl- 4-heptyl phenol; 2-t-butyl-4-octyl phenol; 2-t-butyl-4-dodecyl phenol; 2,6-di-t- butyl-4-heptyl phenol; 2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4- heptyl phenol; and 2-methyl-6-t-butyl-4-dodecyl phenol.
  • Other useful hindered mono-phenolic antioxidants may include for example hindered 2,6-di-alkyl- phenolic proprionic ester derivatives.
  • Bis-phenolic antioxidants may also be advantageously used in combination with the instant invention.
  • ortho-coupled phenols include: 2,2'-bis(4-heptyl-6-t-butyl-phenol); 2,2'-bis(4- octyl-6-t-butyl-phenol); and 2,2'-bis(4-dodecyl-6-t-butyl-phenol).
  • Para-coupled bisphenols include for example 4,4'-bis(2,6-di-t-butyl phenol) and 4,4'- methylene-bis(2,6-di-t-butyl phenol).
  • Non-phenolic oxidation inhibitors which may be used include aromatic amine antioxidants and these may be used either as such or in combination with phenolics.
  • Typical examples of non-phenolic antioxidants include: alkylated and non-alkylated aromatic amines such as aromatic monoamines of the formula R 8 R 9 R 10 N where R 8 is an aliphatic, aromatic or substituted aromatic group, R 9 is an aromatic or a substituted aromatic group, and R 10 is H, alkyl, aryl or R 11 S(O) x R 12 where R 11 is an alkylene, alkenylene, or aralkylene group, R 12 is a higher alkyl group, or an alkenyl, aryl, or alkaryl group, and x is 0, 1 or 2.
  • the aliphatic group R 8 may contain from 1 to about 20 carbon atoms, and preferably contains from about 6 to 12 carbon atoms.
  • the aliphatic group is a saturated aliphatic group.
  • both R 8 and R 9 are aromatic or substituted aromatic groups, and the aromatic group may be a fused ring aromatic group such as naphthyl.
  • Aromatic groups R 8 and R 9 may be joined together with other groups such as S.
  • Typical aromatic amines antioxidants have alkyl substituent groups of at least about 6 carbon atoms.
  • Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups will not contain more than about 14 carbon atoms.
  • the general types of amine antioxidants useful in the present compositions include diphenylamines, phenyl naphthyl- amines, phenothiazines, imidodibenzyls and diphenyl phenylene diamines. Mixtures of two or more aromatic amines are also useful. Polymeric amine antioxidants can also be used.
  • Polymeric aromatic amine antioxidants include polymeric diphenyl amine antioxidants, polymeric phenyl naphthlene amine antioxidants and polymeric diphenyl amine/phenyl naphthalene amine antioxidants.
  • aromatic amine antioxidants useful in the present invention include: p,p'-dioctyldiphenylamine; t-octy .phenyl -alpha- naphthylamine; phenyl-alphanaphthylamine; and p-octylphenyl-alpha- naphthylamine.
  • Sulf ⁇ rized alkyl phenols, alkali or alkaline earth metal salts thereof, alkyl aromatic sulfides, phosphorus compounds such as the phosphites and phosphonic acid esters and the sulfur-phosphorus compounds such as the dithiophosphates and other types such as the dialkyl dithiocarbamates and mixtures thereof also are useful antioxidants.
  • Another class of antioxidant used in lubricating oil compositions is oil- soluble copper compounds. Any oil-soluble suitable copper compound may be blended into the lubricating oil.
  • suitable copper antioxidants include copper dihydrocarbyl thio- or dithio-phosphates and copper salts of carboxylic acid (naturally occurring or synthetic).
  • suitable copper salts include copper dithiacarbamates, sulphonates, phenates, and acetylacetonates.
  • Basic, neutral, or acidic copper Cu(I) and or Cu(II) salts derived from alkenyl succinic acids or anhydrides are know to be particularly useful.
  • Preferred antioxidants include hindered phenols, arylamines. These antioxidants may be used individually by type or in combination with one another. Such additives may be used in an amount of about 0.01 to 5 wt%, preferably about 0.01 to 1.5 wt%.
  • Detergents are commonly used in lubricating compositions.
  • a typical detergent is an anionic material that contains a long chain hydrophobic portion of the molecule and a smaller anionic or oleophobic hydrophilic portion of the molecule.
  • the anionic portion of the detergent is typically derived from an organic acid such as a sulfur acid, carboxylic acid, phosphorous acid, phenol, or mixtures thereof.
  • the counterion is typically an alkaline earth or alkali metal.
  • Salts that contain a substantially stochiometric amount of the metal are described as neutral salts and have a total base number (TBN, as measured by ASTM D2896) of from 0 to 80.
  • TBN total base number
  • Many compositions are overbased, containing large amounts of a metal base that is achieved by reacting an excess of a metal compound (a metal hydroxide or oxide, for example) with an acidic gas (such as carbon dioxide).
  • a metal compound a metal hydroxide or oxide, for example
  • an acidic gas such as carbon dioxide
  • Useful detergents can be neutral, mildly overbased, or highly overbased.
  • the overbased material has a ratio of metallic ion to anionic portion of the detergent of about 1.05: 1 to 50: 1 on an equivalent basis. More preferably, the ratio is from about 4: 1 to about 25:1.
  • the resulting detergent is an overbased detergent that will typically have a TBN of about 150 or higher, often about 250 to 450 or more.
  • the overbasing cation is sodium, calcium, or magnesium.
  • a mixture of detergents of differing TBN can be used in the present invention.
  • Preferred detergents include the alkali or alkaline earth metal salts of sulfonates, phenates, carboxylates, phosphates, and salicylates.
  • Sulfonates may be prepared from sulfonic acids that are typically obtained by sulfonation of alkyl substituted aromatic hydrocarbons. Hydrocarbon examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, biphenyl and their halogenated derivatives (chlorobenzene, chloro- toluene, and chloronaphthalene, for example).
  • the alkylating agents typically have about 3 to 70 carbon atoms.
  • the alkaryl sulfonates typically contain about 9 to about 80 carbon or more carbon atoms, more typically from about 16 to 60 carbon atoms.
  • Klamann in Lubricants and Related Products, op cit discloses a number of overbased metal salts of various sulfonic acids which are useful as detergents and dispersants in lubricants.
  • Alkaline earth phenates are another useful class of detergent. These detergents can be made by reacting alkaline earth metal hydroxide or oxide (CaO, Ca(OH) 2 , BaO, Ba(OH) 2 , MgO, Mg(OH) 2 , for example) with an alkyl phenol or sulfurized alkylphenol.
  • alkaline earth metal hydroxide or oxide Ca(OH) 2 , BaO, Ba(OH) 2 , MgO, Mg(OH) 2 , for example
  • Useful alkyl groups include straight chain or branched C 1 -C 30 alkyl groups, preferably, C 4 -C 2O - Examples of suitable phenols include isobutylphenol, 2-ethylhexylphenol, nonylphenol, dodecyl phenol, and the like.
  • starting alkylphenols may contain more than one alkyl substituent that are each independently straight chain or branched.
  • the sulfurized product may be obtained by methods well known in the art. These methods include heating a mixture of alkylphenol and sulfurizing agent (including elemental sulfur, sulfur halides such as sulfur dichloride, and the like) and then reacting the sulfurized phenol with an alkaline earth metal base.
  • Metal salts of carboxylic acids are also useful as detergents. These carboxylic acid detergents may be prepared by reacting a basic metal compound with at least one carboxylic acid and removing free water from the reaction product. These compounds may be overbased to produce the desired TBN level.
  • Detergents made from salicylic acid are one preferred class of detergents derived from carboxylic acids.
  • Useful salicylates include long chain alkyl salicylates.
  • One useful family of compositions is of the formula
  • R is a hydrogen atom or an alkyl group having 1 to about 30 carbon atoms
  • n is an integer from 1 to 4
  • M is an alkaline earth metal.
  • Preferred R groups are alkyl chains of at least C M , preferably C n or greater. R may be optionally substituted with substituents that do not interfere with the detergent's function.
  • M is preferably, calcium, magnesium, or barium. More preferably, M is calcium.
  • Hydrocarbyl-substituted salicylic acids may be prepared from phenols by the Kolbe reaction. See USP 3,595,791, which is incorporated herein by reference in its entirety, for additional information on synthesis of these compounds.
  • the metal salts of the hydrocarbyl-substituted salicylic acids may be prepared by double decomposition of a metal salt in a polar solvent such as water or alcohol.
  • Alkaline earth metal phosphates are also used as detergents.
  • Detergents may be simple detergents or what is known as hybrid or complex detergents. The latter detergents can provide the properties of two detergents without the need to blend separate materials. See USP 6,034,039 for example.
  • Preferred detergents include calcium phenates, calcium sulfonates, calcium salicylates, magnesium phenates, magnesium sulfonates, magnesium salicylates and other related components (including borated detergents).
  • the total detergent concentration is about 0.01 to about 6.0 wt%, preferably, about 0.1 to 0.4 wt%.
  • Dispersants help keep these byproducts in solution, thus diminishing their deposition on metal surfaces.
  • Dispersants may be ashless or ash-forming in nature.
  • the dispersant is ashless.
  • So called ashless dispersants are organic materials that form substantially no ash upon combustion.
  • non-metal-containing or borated metal-free dispersants are considered ashless.
  • metal-containing detergents discussed above form ash upon combustion.
  • supplementary dispersants use may be made of the unborated version of any of the dispersant types previously recited. Such supplementary do non-borated dispersants can be used in amount of about 0.1 to ⁇ 20 wt% preferably about 0.1 to 8 wt% on an as received basis.
  • pour point depressants also known as lube oil flow improvers
  • pour point depressants may be added to lubricating compositions of the present invention to lower the minimum temperature at which the fluid will flow or can be poured.
  • suitable pour point depressants include polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and terpolymers of dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers.
  • 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655, 479; 2,666,746; 2,721,877; 2.721,878; and 3,250,715 describe useful pour point depressants and/or the preparation thereof.
  • Such additives may be used in an amount of about 0.01 to 5 wt%, preferably about 0.01 to 1.5 wt%.
  • Corrosion inhibitors are used to reduce the degradation of metallic parts that are in contact with the lubricating oil composition.
  • Suitable corrosion inhibitors include triazoles and thiadiazoles, succinimide derivatives such as the higher alkyl substituted amides of dodecylene succinic acid, such as the tetra- propenyl succinic mono esters, and imidazoline succinic anhydride derivatives. See, for example, USP Nos. 2,719,125; 2,719,126; and 3,087,932.
  • Such additives may be used in an amount of about 0.01 to 5 wt%, preferably about 0.01 to 1.5 wt%.
  • Seal compatibility agents help to swell elastomeric seals by causing a chemical reaction in the fluid or physical change in the elastomer.
  • Suitable seal compatibility agents for lubricating oils include organic phosphates, aromatic esters, aromatic hydrocarbons, and polybutenyl succinic anhydride. Such additives may be used in an amount of about 0.01 to 3 wt%, preferably about 0.01 to 2 wt%.
  • Anti-foam agents may advantageously be added to lubricant compositions. These agents retard the formation of stable foams. Silicones and organic polymers are typical anti-foam agents. For example, polysiloxanes, such as silicon oil or polydimethyl siloxane, provide antifoam properties. Anti-foam agents are commercially available and may be used in conventional minor amounts along with other additives such as demulsifiers; usually the amount of these additives combined is less than 1 percent and often less than 0.1 percent. Inhibitors and Antirust Additives
  • Antirust additives are additives that protect lubricated metal surfaces against chemical attack by water or other contaminants. A wide variety of these are commercially available; they are referred to in Klamann in Lubricants and Related Products, op cit.
  • antirust additive is a polar compound that wets the metal surface preferentially, protecting it with a film of oil.
  • Another type of antirust additive absorbs water by incorporating it in a water-in-oil emulsion so that only the oil touches the metal surface.
  • Yet another type of antirust additive chemically adheres to the metal to produce a non-reactive surface.
  • suitable additives include zinc dithiophosphates, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in an amount of about 0.01 to 5 wt%, preferably about 0.01 to 1.5 wt%.
  • a friction modifier is any material or materials that can alter the coefficient of friction of a surface lubricated by any lubricant or fluid containing such material(s).
  • Friction modifiers also known as friction reducers, or lubricity agents or oiliness agents, and other such agents that change the ability of base oils, formulated lubricant compositions, or functional fluids, to modify the coefficient of friction of a lubricated surface may be effectively used in combination with the base oils or lubricant compositions of the present invention if desired. Friction modifiers that lower the coefficient of friction are particularly advantageous in combination with the base oils and lube compositions of this invention. Friction modifiers may include metal-containing compounds or materials as well as ashless compounds or materials, or mixtures thereof.
  • Metal-containing friction modifiers may include metal salts or metal- ligand complexes where the metals may include alkali, alkaline earth, or transition group metals. Such metal-containing friction modifiers may also have low-ash characteristics. Transition metals may include Mo, Sb, Sn, Fe, Cu, Zn, and others.
  • Ligands may include hydrocarbyl derivative of alcohols, polyols, glycerols, partial ester glycerols, thiols, carboxylates, carbamates, thiocarba- mates, dithiocarbamates, phosphates, thiophosphates, dithiophosphates, amides, imides, amines, thiazoles, thiadiazoles, dithiazoles, diazoles, triazoles, and other polar molecular functional groups containing effective amounts of O, N, S, or P, individually or in combination.
  • Mo-containing compounds can be particularly effective such as for example Mo-dithiocarbamates, Mo(DTC), Mo-dithiophosphates, Mo(DTP), Mo-amines, Mo (Am), Mo-alcoholates, Mo- alcohol-amides, etc.
  • Ashless friction modifiers may have also include lubricant materials that contain effective amounts of polar groups, for example, hydroxyl-containing hydrocarbyl base oils, glycerides, partial glycerides, glyceride derivatives, and the like.
  • Polar groups in friction modifiers may include hydrocarbyl groups containing effective amounts of O, N, S, or P, individually or in combination.
  • Other friction modifiers that may be particularly effective include, for example, salts (both ash-containing and ashless derivatives) of fatty acids, fatty alcohols, fatty amides, fatty esters, hydroxyl-containing carboxylates, and comparable synthetic long-chain hydrocarbyl acids, alcohols, amides, esters, hydroxy carboxylates, and the like.
  • fatty organic acids, fatty amines, and sulfurized fatty acids may be used as suitable friction modifiers.
  • Useful concentrations of friction modifiers may range from about 0.01 wt% to 10-15 wt% or more, often with a preferred range of about 0.1 wt% to 5 wt%. Concentrations of molybdenum-containing materials are often described in terms of Mo metal concentration. Advantageous concentrations of Mo may range from about 10 ppm to 3000 ppm or more, and often with a preferred range of about 20-2000 ppm, and in some instances a more preferred range of about 30-1000 ppm. Friction modifiers of all types may be used alone or in mixtures with the materials of this invention. Often mixtures of two or more friction modifiers, or mixtures of friction modifier(s) with alternate surface active material(s), are also desirable.
  • Dispersants help keep these byproducts in solution, thus diminishing their deposition on metal surfaces.
  • Dispersants may be ashless or ash-forming in nature.
  • the dispersant is ashless.
  • So called ashless dispersants are organic materials that form substantially no ash upon combustion.
  • non-metal-containing or borated metal-free dispersants are considered ashless.
  • metal-containing detergents discussed above form ash upon combustion.
  • Suitable dispersants typically contain a polar group attached to a relatively high molecular weight hydrocarbon chain.
  • the polar group typically contains at least one element of nitrogen, oxygen, or phosphorus.
  • Typical hydrocarbon chains contain 50 to 400 carbon atoms.
  • dispersants may be characterized as phenates, sulfonates, sulfurized phenates, salicylates, naphthenates, stearates, carbamates, thiocarbamates, phosphorus derivatives.
  • a particularly useful class of dispersants are the alkenylsuccinic derivatives, typically produced by the reaction of a long chain substituted alkenyl succinic compound, usually a substituted succinic anhydride, with a polyhydroxy or polyamino compound.
  • the long chain group constituting the oleophilic portion of the molecule which confers solubility in the oil is normally a polyisobutylene group.
  • Exemplary U.S. patents describing such dispersants are 3,172,892; 3,2145,707; 3,219,666; 3,316,177; 3,341,542; 3,444, 170; 3,454,607; 3,541,012; 3,630,904; 3,632,511 ; 3,787,374 and 4,234,435.
  • Other types of dispersant are described in U.S.
  • a further description of dispersants may be found, for example, in European Patent Application No. 471 071 , to which reference is made for this purpose.
  • Hydrocarbyl-substituted succinic acid compounds are popular dispersants.
  • succinimide, succinate esters, or succinate ester amides prepared by the reaction of a hydrocarbon-substituted succinic acid compound preferably having at least 50 carbon atoms in the hydrocarbon substituent, with at least one equivalent of an alkylene amine are particularly useful.
  • Succinimides are formed by the condensation reaction between alkenyl succinic anhydrides and amines. Molar ratios can vary depending on the polyamine. For example, the molar ratio of alkenyl succinic anhydride to TEPA can vary from about 1 : 1 to about 5:1. Representative examples are shown in U.S. Patents 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; and 3,652,616, 3,948,800; and Canada Pat. No. 1,094,044.
  • Succinate esters are formed by the condensation reaction between alkenyl succinic anhydrides and alcohols or polyols. Molar ratios can vary depending on the alcohol or polyol used. For example, the condensation product of an alkenyl succinic anhydride and pentaerythritol is a useful dispersant.
  • Succinate ester amides are formed by condensation reaction between alkenyl succinic anhydrides and alkanol amines.
  • suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpoly- amines and polyalkenylpolyamines such as polyethylene polyamines.
  • propoxylated hexamethylenediamine Representative examples are shown in USP 4,426,305.
  • the molecular weight of the alkenyl succinic anhydrides used in the preceding paragraphs will typically range between 800 and 2,500.
  • the above products can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid, and boron compounds such as borate esters or highly borated dispersants.
  • the dispersants can be borated with from about 0.1 to about 5 moles of boron per mole of dispersant reaction product.
  • Mannich base dispersants are made from the reaction of alkylphenols, formaldehyde, and amines. See USP 4,767,551, which is incorporated herein by reference. Process aids and catalysts, such as oleic acid and sulfonic acids, can also be part of the reaction mixture. Molecular weights of the alkylphenols range from 800 to 2,500. Representative examples are shown in U.S. Patents 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; and 3,803,039.
  • Typical high molecular weight aliphatic acid modified Mannich condensation products useful in this invention can be prepared from high molecular weight alkyl-substituted hydroxyaromatics or HN(R) 2 group- containing reactants.
  • Examples of high molecular weight alkyl-substituted hydroxyaromatic compounds are polypropylphenol, polybutylphenol, and other polyalkylphenols. These polyalkylphenols can be obtained by the alkylation, in the presence of an alkylating catalyst, such as BF 3 , of phenol with high molecular weight polypropylene, polybutylene, and other polyalkylene compounds to give alkyl substituents on the benzene ring of phenol having an average 600-100,000 molecular weight.
  • Examples of HN(R) 2 group-containing reactants are alky lene polyamines, principally polyethylene polyamines.
  • HN(R) 2 group suitable for use in the preparation of Mannich condensation products are well known and include the mono- and di-amino alkanes and their substituted analogs, e.g., ethylamine and diethanol amine; aromatic diamines, e.g., phenylene diamine, diamino naphthalenes; heterocyclic amines, e.g., morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidine; melamine and their substituted analogs.
  • mono- and di-amino alkanes and their substituted analogs e.g., ethylamine and diethanol amine
  • aromatic diamines e.g., phenylene diamine, diamino naphthalenes
  • heterocyclic amines e.g., morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine, and pipe
  • alkylene polyamide reactants include ethylenediamine, diethylene triamine, triethylene tetraamine, tetraethylene pentaamine, penta- ethylene hexamine, hexaethylene heptaamine, heptaethylene octaamine, octa- ethylene nonaamine, nonaethylene decamine, and decaethylene undecamine and mixture of such amines having nitrogen contents corresponding to the alkylene polyamines, in the formula F ⁇ N-(Z -NH- ) n H, mentioned before, Z is a divalent ethylene and n is 1 to 10 of the foregoing formula.
  • propylene polyamines such as propylene diamine and di-, tri-, tetra-, pentapropylene tri-, tetra-, penta- and hexaamines are also suitable reactants.
  • the alkylene polyamines are usually obtained by the reaction of ammonia and dihalo alkanes, such as dichloro alkanes.
  • the alkylene polyamines obtained from the reaction of 2 to 11 moles of ammonia with 1 to 10 moles of dichloroalkanes having 2 to 6 carbon atoms and the chlorines on different carbons are suitable alkylene polyamine reactants.
  • Aldehyde reactants useful in the preparation of the high molecular products useful in this invention include the aliphatic aldehydes such as formaldehyde (also as paraformaldehyde and formalin), acetaldehyde and aldol ( ⁇ -hydroxybutyraldehyde). Formaldehyde or a formaldehyde-yielding reactant is preferred.
  • Hydrocarbyl substituted amine ashless dispersant additives are well known to one skilled in the art; see, for example, U.S. Patents 3,275,554; 3,438,757; 3,565,804; 3,755,433, 3,822,209, and 5,084,197, which are incorporated herein in their entirety by reference.
  • Borated dispersants can be used. Any dispersant containing either or both of nitrogen and/or oxygen atoms can be borated.
  • Preferred dispersants include borated and non-borated succinimides, including those derivatives from mono-succinimides, bis-succinimides, and/or mixtures of mono- and bis-succinimides, wherein the hydrocarbyl succinimide is derived from a hydrocarbylene group such as polyisobutylene having a Mn of from about 500 to about 5000 or a mixture of such hydrocarbylene groups.
  • Other preferred dispersants include succinic acid-esters and amides, alkylphenol- polyamine-coupled Mannich adducts, their capped derivatives, and other related components. Such additives may be used in an amount of about 0.1 to 20 wt%, preferably about 0.1 to 8 wt%.
  • lubricating oil compositions contain one or more of the additives discussed above, the additive(s) are blended into the composition in an amount sufficient for it to perform its intended function. Typical amounts of such additives useful in the present invention are shown in Table 1 below.
  • Anti-wear Additive 0.01-6 0.01-4
  • Anti-foam Agent 0.001-3 0.001-0.15
  • Traction coefficient is determined using the Mini Traction Machine which is a computer controlled, precision traction measurement system. A small sample of fluid is placed in the test cell and the machine automatically runs through a range of speeds, slide/roll ratios, temperatures and loads to produce a comprehensive traction map for the test fluid without any operator intervention.
  • the MTM can be used with different specimen configuration but the standard test specimens used herein are a polished 19.05 mm (3/4 inch) ball and a 50.0 mm diameter disc manufactured from AISI 52100 bearing steel. The specimens are designed to be single use, throw away items. The specimens are independently driven by DC servo motors and drives to allow high precision speed control, particularly at low slide/roll ratios. Each specimen is end mounted on shafts in a small stainless steel test fluid bath.
  • the vertical shaft and rive system which supports the 50 mm diameter test specimen, is fixed.
  • the shaft and drive system which supports the 19.05 mm diameter test specimen is supported by a gimbal arrangement such that it can rotate around two orthogonal axes. One axis is normal to the load application direction, the other to the traction force direction.
  • Application of the load and restraint of the traction force is made through high stiffness force transducers appropriately mounted in the gimbal arrangement to minimize the overall support system deflections.
  • the output from these force transducers is monitored directly by a personal computer (PC).
  • the test conditions used herein are: 16 newton load, 100 0 C temperature, and 30% slide to roll ratio (16N/100°C/30 SSR).
  • Comparative Examples 1 , 2 and 3 use of an adipate ester of KV @ 100 0 C of between 5.1 to 5.5 mm 2 /s, while Comparative Example 4 differed in using a different additive package while still employing the adipate ester of KV @ 100 0 C of between 5.1 to 5.5 mm 2 /s.
  • Example 1 using a polyolester of KV @ 100 0 C of 4.2 to 4.5 mm 2 /s, pour point below -45°C
  • Example 2 using an adipate (a di ester) of KV @ 100 0 C of 2.7 mm 2 /s, pour point below -45°C.
  • Comparative Example 5 was similar to Comparative Example 4 but substituted Emoline 2958 (believed to be a di-2-hexyl adipate) which has a reported of KV @ 100 0 C of 2.8-2.9 mm 2 /s pour point below -45°C for the 5.1- 5.5 mm 2 /s adipate.
  • Comparative Examples 6 and 7 were similar to Comparative Examples 1 , 2, 3 but substituted EsterexTM M31 (ethyl hexyl polmitate a mono ester, KV @ 100 0 C of 2.7 mm 2 /s pour point 3°C) and EstererTM Ml 1 (nonyl heptanoate a mono ester literature value KV @ 100 0 C of 1.25-1.45 mm 2 /s pour point, below - 45°C) respectively for the 5.1-5.5 mm 2 /s adipate (di ester).
  • EsterexTM M31 ethyl hexyl polmitate a mono ester, KV @ 100 0 C of 2.7 mm 2 /s pour point 3°C
  • EstererTM Ml 1 nonyl heptanoate a mono ester literature value KV @ 100 0 C of 1.25-1.45 mm 2 /s pour point, below - 45°C
  • Comparative Examples 6 and 7 While the formulation of Comparative Examples 6 and 7 exhibited CCS viscosities and traction coefficients, and in the case of Comparative Example 7 a Brookfield viscosity meeting the specification targets of the present invention, they would prove to be undesirable and insufficient from a practical stand point if employed in an actual working environment.
  • the formulation of Comparative Example 6 exhibited a totally unsatisfactory high Brookfield viscosity while the formulation of Comparative Example 7 exhibited unsatisfactory flash point and NOACK volatility.
  • Comparative Example 5 demonstrates that even when a diester of desirable KV is employed, if the combination of PAO base stocks does not correspond to that recited in the present application, the resulting formulated oil having a KV outside the target of between 9 to 12.5 mm 2 /s exhibits an unacceptable Brookfield viscosity, an unacceptable CCS viscosity and does not achieve the desired traction coefficient.

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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)
  • Lubricants (AREA)
  • General Details Of Gearings (AREA)

Abstract

L'invention concerne un procédé permettant d'augmenter l'intervalle entre les vidanges d'huile, améliorent ainsi le rendement en carburant et en énergie de la machine à engrenage renforcé par lubrification dudit appareil à l'aide d'une composition d'huile lubrifiante comprenant, comme huile de base, environ 20 à 75 % en poids de PAO 2 à 10, environ 5 à 40 % en poids de PAO 150-1000, environ 10 à 40 % en poids de PAO 20-100, environ 5 à 20 % en poids d'au moins un ester de polyol ou ester d'acide dibasique dont une viscosité cinématique est située entre environ 2 à 5 mm2/sec à 100 °C et contenant en outre une quantité efficace d'au moins un additif d'huile pour engrenage, ladite composition d'huile lubrifiante présentant une viscosité cinématique à 100 °C entre 9 et 12,5 mm2/sec, et une valeur de coefficient de traction (100 °C/valeur SSR 30) de 0,0197 ou moins, une viscosité Brookfield à -40 °C d'environ 26 000 cP ou moins, une viscosité CSS à -25 °C de 4200 cP ou moins, un point d'inflammation de 220 °C ou plus et une volatilité NOACK de 15 % ou moins.
EP07810523.6A 2006-07-21 2007-07-17 Procédé pour lubrifier un appareil à engrenage renforcé Not-in-force EP2044181B1 (fr)

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US83269206P 2006-07-21 2006-07-21
PCT/US2007/016173 WO2008013698A1 (fr) 2006-07-21 2007-07-17 Procédé pour lubrifier un appareil à engrenage renforcé

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EP2044181A4 EP2044181A4 (fr) 2011-07-13
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EP2104728B1 (fr) * 2006-12-27 2018-10-24 Shell International Research Maatschappij B.V. Composition d'huile lubrifiante

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JP5396628B2 (ja) * 2008-02-28 2014-01-22 東燃ゼネラル石油株式会社 潤滑油組成物
US8476205B2 (en) * 2008-10-03 2013-07-02 Exxonmobil Research And Engineering Company Chromium HVI-PAO bi-modal lubricant compositions
JP5398218B2 (ja) * 2008-10-06 2014-01-29 Ｊｘ日鉱日石エネルギー株式会社 潤滑油組成物
CN102272083B (zh) * 2009-01-08 2015-01-21 埃克森美孚化学专利公司 醇或者与醇有关的改进
JP5731435B2 (ja) * 2012-03-30 2015-06-10 住友重機械工業株式会社 冷凍倉庫用の減速機
US11434447B2 (en) 2013-11-22 2022-09-06 Valvoline Licensing and Intellectual Property, LLC Silicone modified lubricant
WO2015077461A1 (fr) 2013-11-22 2015-05-28 Ashland Licensing And Intellectual Property, Llc Huile pour engrenage ou pour moteur à tension superficielle réduite
WO2016152229A1 (fr) * 2015-03-20 2016-09-29 Ｊｘエネルギー株式会社 Composition d'huile lubrifiante pour boîte de vitesses
GB2543731A (en) 2015-06-12 2017-05-03 Elekta ltd Improvements in dosimetry techniques for radiotherapy
KR20180080820A (ko) * 2017-01-05 2018-07-13 유니버셜오일 주식회사 윤활성 및 저온특성이 우수한 엔진오일 조성물
CN107033997B (zh) * 2017-04-26 2019-11-26 中国石油化工股份有限公司 一种高温抗腐蚀润滑油组合物及其制备方法
WO2019173427A1 (fr) 2018-03-06 2019-09-12 Valvoline Licensing And Intellectual Property Llc Composition de fluide de traction
CA3130106C (fr) 2019-03-13 2023-05-02 Valvoline Licensing And Intellectual Property Llc Nouveau fluide de traction presentant des proprietes ameliorees a basse temperature
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Also Published As

Publication number Publication date
EP2044181A4 (fr) 2011-07-13
KR20090033397A (ko) 2009-04-02
JP2009544767A (ja) 2009-12-17
WO2008013698A1 (fr) 2008-01-31
CA2658208A1 (fr) 2008-01-31
EP2044181B1 (fr) 2015-07-08
US20080248983A1 (en) 2008-10-09

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