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
  • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
  • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
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  • 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
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  • 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
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  • 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
  • C10M2215/28—Amides; Imides
• • 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
• • 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
  • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
  • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
• • 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
  • C10M2219/046—Overbasedsulfonic acid 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/06—Thio-acids; Thiocyanates; Derivatives 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
  • C10M2219/085—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
  • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
• • 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/62—Food grade properties
• • 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
• • 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
  • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
• • 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
  • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
• • 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
  • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/12—Gas-turbines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/30—Refrigerators lubricants or compressors lubricants
• • 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
  • C10N2070/00—Specific manufacturing methods for lubricant compositions
  • C10N2070/02—Concentrating of additives

Definitions

• the present invention relates to lubricating oil compositions. More specifically to lubricating oil compositions comprising additive packages for reducing oxidative deterioration.
• Lubricants such as those used in a variety of machinery, are susceptible to oxidative deterioration during storage, transportation, and usage, particularly when such lubricants are exposed to high temperatures and iron catalytic environments, which greatly promote the oxidation of the lubricant.
• This oxidation if not controlled, contributes to the formation of corrosive acidic products, sludge, varnishes, resins, and other oil-insoluble products and may lead to a loss of designated physical and tribological properties of the lubricants.
• These oxidation products may lead to the formation of harmful deposits on critical engine parts, such as the pistons, piston liners, valves, and valve lifters.
• ADPA alkylated diphenylamine
• Lubricant compositions containing various antioxidants are widely known in the art.
• U.S. Patent No. 6,326,336 to Gatto, et al . discloses a turbine lubricating oil comprising (A) an amine antioxidant selected from the group consisting of alkylated diphenylamines, phenylnaphthylamines and mixtures thereof; (B) sulfur-containing additives selected from the group consisting of sulfurized olefins, sulfurized fatty acids, ashless dithiocarbamates, tertaalkylthiuram disulfides and mixtures thereof, and (C) a base oil.
• amine antioxidant selected from the group consisting of alkylated diphenylamines, phenylnaphthylamines and mixtures thereof
• sulfur-containing additives selected from the group consisting of sulfurized olefins, sulfurized fatty acids, ashless dithiocarbamates, tertaalkylthiuram
• Gatto such a composition provides superior oxidation protection and acceptable sludge control in turbine oils formulated with Group II or higher base oils.
• An important criterion for selecting the concentration of sulfur-containing additive is the sulfur content of the additive package.
• the sulfur-containing additive should deliver between 0.005 wt. % and 0.07 wt. % of sulfur to the finished turbine oil.
• Gatto utilizes only sulfurized olefins, sulfurized fatty acids, ashless dithiocarbamates, tetraalkylthiuram disulfides and mixtures thereof.
• Gatto states that there are a number of problems that may be associated with the use of hindered phenols.
• Gatto states that hindered phenols under high temperatures can dealkylate and produce free phenol and that water extractablility of certain water soluble phenols is another potential problem.
• Gatto states a phenol-free formulation may be desired.
• U.S. Patent No. 5,091,099 discloses to a phosphite-free lubricating oil composition which comprises a) a mineral oil or a synthetic oil or a mixture thereof; and b) a mixture containing at least one aromatic amine of the formula (I), and at least one phenol of the formula (II) and the compounds are present in the mixture in a ratio of 2 to 6 parts by weight of the aromatic amine(s) of the formula (I) to 1 part by weight of the phenol(s) of the formula II.
• U.S. Patent No. 5,523,007 discloses a lubricating oil composition
• a lubricating oil composition comprising a diesel engine oil and, as antioxidant, a compound of formula I wherein X is and R is a straight chain or branched alkyl radical of the formula C n H 2n+1 , wherein n is an integer from 8 to 22.
• a phenol may contain sulfur, but weight percentages and relationships to other components are not taught.
• PNA phenyl naphthylamine
• EP 1 006 173 discloses the use, in a lubricant composition comprising a hydraulic antiwear component and a base oil, of an additive comprising an amine antioxidant and a t least one additional antioxidant selected from ashless dithiocarbamate, sulphurised olefin and phenolic antioxidants to provide a lubricant having improved thermal and oxidation stability.
• US 2006/0128574 discloses a lubricant composition comprising at least two antioxidants: a secondary diarylamine and a para phenylenediamine.
• the present invention generally relates to lubricating oil compositions that may be utilized in high temperature environments. Typically, such high temperature environments promote oxidative deterioration of the lubricants.
• the lubricating oil compositions of the present invention are less susceptible to such oxidative deterioration, i.e., they are more stable, and, as such, provide improved physical and tribological properties at high temperatures.
• the composition comprises a liquid additive package essentially consisting of at least 5 wt%, at least 7 wt%, at least 10 wt%, or at least 15 wt%, of a phenyl naphthylamine (PNA), e.g., phenyl- ⁇ -naphthylamine, and a base stock.
• PNA phenyl naphthylamine
• the PNA may be present in amounts ranging from 1 wt% to 50 wt%, e.g., from 2 wt% to 50 wt%, from 3 wt% to 40 wt%, from 5 wt% to 30 wt %, or from 5 wt% to 30 wt%.
• Such additive packages when combined with a suitable base stock, reduces the amount of harmful deposits resulting from oxidation of the lubricating oil composition as compared to additive packages with less than 5 wt% PNA.
• the liquid additive package e.g., liquid antioxidant additive package, comprises a diphenylamine, e.g., an alkylated diphenylamine (ADPA), and at least 5 wt% PNA.
• the PNA is solid at room temperature and is difficult to dissolve in liquids, e.g., ADPA or base stocks.
• the PNA is combined with ADPA, e.g., under heat, e.g. at about 150°C, about 100°C, about 65°C, or about 50°C, and/or under nitrogen or a similar inert atmosphere until a homogeneous mixture is achieved.
• the mixture is a stable liquid at room temperature.
• the ADPA and the PNA may be mixed for 10 to 20 minutes, e.g. 12 to 18 minutes, or 14 to 16 minutes. It should be noted that the time periods listed above are merely exemplary and that the time will vary as the quantities of each of the materials vary.
• the resultant composition is dark reddish in color and has a viscosity of less than 50 Pa ⁇ s (50,000 cP), e.g., less than 30 Pa ⁇ s (30,000 cP) or less than 20 Pa ⁇ s (20,000 cP), as measured at 25°C.
• the viscosity of the composition ranges from 0,1 to 100 Pa ⁇ s (100 to 100,000 cP), e.g., from 0,1 to 50 Pa ⁇ s (100 to 50,000 cP), or from 1 to 25 Pa ⁇ s (1,000 to 25,000 cP), as measured at 25° C.
• the lubricant oil composition when combined with a poly- ⁇ -olefin base stock at a weight ratio of 99:1, base stock to additive package, shows an oxidation induction time (OIT), as tested under the pressurized differential scanning calorimeter (PDSC) conditions shown in TABLE 1, of at least 25 minutes, e.g., at least 38 minutes, at least 40 minutes, at least 50 minutes or at least 75 minutes.
• OIT oxidation induction time
• PDSC pressurized differential scanning calorimeter
• the a sample tested at 160°C may have a longer OIT than a similar sample tested at 185°C.
• TABLE 1 Test Parameters PDSC Test Conditions Isothermal Temperature 185 °C O 2 Gas Pressure 3,45 ⁇ 10 6 Pa (500 psi) O 2 Gas Flow Rate Through Cell 100 ml/min, continuous Catalyst 50 ppm of Iron Sample Holder Open Aluminum Pan Sample size 1.0 - 2.0 mg Induction Time Enthalpy Change
• the additive package essentially consists of ADPA, PNA and a sulfur-containing phenol.
• the sulfur-containing phenol is solid at room temperature.
• sulfur-containing phenols that are liquids at room temperature may be utilized as well.
• the combination of the ADPA, PNA and sulfur-containing phenol forms a clear liquid.
• the combination of the ADPA, PNA and sulfur-containing phenol produces an additive package that significantly improves the oxidative stability and reduces the amount of Mid-High Temperature Thermo-Oxidation Engine Oil Simulation Test (TEOST MHT, ASTM D 7097) deposits (see below) over that of ADPA alone.
• TEOST MHT Mid-High Temperature Thermo-Oxidation Engine Oil Simulation Test
• the lubricant oil composition has a TEOST MHT value of less than 50 mg, less than 40 mg or less than 20 mg. It should be noted that an additive package of pure ADPA yields a TEOST MHT value of about 55 mg, pure PNA yields a TEOST MHT value of about 80 mg, and pure sulfur-containing phenol yields a TEOST MHT value of about 63 mg. Hence, a TEOST MHT value of less than 55 mg, for the lubricant composition, is surprising and unexpected.
• the ADPA is present in an amount of at least 50 wt%, e.g., at least 60 wt%, or at least 70 wt%, based on the weight of the additive package. In terms of ranges, preferably, the ADPA is present in an amount ranging from 50 to 99 wt%, e.g., from 60 to 99 wt%, from 70 to 95 wt%, or from 70 to 90 wt%, based on the weight of the additive package.
• the PNA is present in an amount of at least 5 wt%, at least 7 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, or at least 50 wt%, based on the weight of the additive package. In terms of ranges, the PNA is present in an amount ranging from 1 wt% to 50 wt%, e.g., from 2 wt% to 50 wt%, from 5 wt% to 50 wt%, from 3 wt% to 40 wt%, from 5 wt% to 30 wt %, or from 5 wt% to 30 wt%, based on the weight of the additive package.
• Additive packages having the above-mentioned amounts of PNA demonstrate results that are surprising and unexpected when compared to the results of additive packages utilizing less than 50 wt%, e.g., less than 25 wt%, less than 20 wt %, less than 15 wt%, less than 10 wt%, less than 5 wt% or less than 1 wt%.
• the sulfur-containing phenol is present in an amount of at least 1 wt% e.g., at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%. In terms of ranges, the sulfur-containing phenol is present in an amount ranging from 5 to 25 wt%, e.g., from 10 wt% to 25 wt%, from 10 wt% to 20 wt% or from 10 wt% to 15 wt%, based on the weight of the additive package.
• the ADPA is present in an amount of at least 50 wt%, e.g., at least 60 wt%, or at least 70 wt
• the PNA is present in an amount of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%
• the sulfur-containing phenol is present in an amount of at least 1 wt% e.g., at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, all wt% being based on the weight of the additive package.
• the ADPA is present in an amount of about 70 wt% +/- 10 wt%, e.g., +/- 5 wt %, +/- 3 wt% or +/- 1 wt%;
• the PNA is present in an amount of about 15 wt% +/- 14 wt%, e.g., +/- 10 wt%, +/- 5 wt %, +/- 3 wt% or +/- 1 wt%;
• the sulfur-containing phenol is present in an amount of about 15 wt% +/- 10 wt%, e.g., +/- 5 wt %, +/- 3 wt% or +/- 1 wt%; all wt% being based on the weight of the additive package.
• Additional preferred embodiments utilize the wt% combinations of ADPA, PNA and sulfur-containing phenol listed in TABLE 2.
• Each of the weight percentages listed for these embodiments can vary by +/- 10 wt%, e.g., +/- 5 wt %, +/- 3 wt%, +/- 2 wt% or +/- 1 wt%.
• TABLE 2 Exemplary Combination Wt% ADPA Wt% PNA Wt% Sulfur-containing phenol 1 60 20 20 2 60 10 30 3 60 30 10 4 60 15 25 5 60 25 15 6 70 10 20 7 70 20 10 8 70 5 25 9 70 25 5 10 80 10 10 11 80 5 15 12 80 15 5 13 90 5 5 5
• the weight ratio of ADPA to sulfur-containing phenol in the additive package is at least 3:1, e.g., at least 6:1 or at least 10:1.
• the weight ratio of PNA to sulfur-containing phenol in the additive package ranges from 1:10 to 10:1, e.g., from 1:8 to 8:1, from 1:5 to 5:1 or from 1:3 to 3:1.
• the weight ratio of ADPA and PNA, combined to sulfur-containing phenol is at least 2:1, e.g., at least 3:1, at least 4:1, at least 5:1 or at least 10:1.
• the weight ratio of ADPA to PNA in the additive package is at least 2:1, e.g., at least 3:1, at least 4:1, at least 5:1 or at least 10:1. In terms of ranges, the weight ratio ranges e.g. from 3:1 to 15:1 or from 3:1 to 10:1.
• the base stock is present in an amount of at least 50 wt%, e.g. at least 75 wt%, at least 95 wt% or at least 99 wt%, based on the weight of the lubricating oil composition (including the additive package).
• the additive package is present in an amount of at least 0.5 wt%, at least 1 wt% or at least 10 wt%, based on the weight of the lubricating oil composition.
• the lubricating oil composition comprises 99 wt% of the base stock combined with 1 wt% of the additive package based on the total weight of the lubricating oil.
• the additive packages of the present invention are especially useful as components in combination with many potential base stocks.
• the additive packages may be included in a variety of oils with lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof.
• the additive packages are included in crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines.
• the additive packages can also be used, for example, with gas engine lubricants, turbine lubricants, automatic transmission fluids, gear lubricants, compressor lubricants, metal-working lubricants, hydraulic fluids, and other lubricating oil and grease compositions.
• the additive package is utilized in the preparation of lubricants that may have food contact e.g., incidental food contact. More specifically, the additive package may be utilized with an H1 food grade base stock.
• the additive packages are combined with a grease or a combination of greases.
• Greases are often used in applications having high pressures and slow speed. Such applications include, but are not limited to, continuous casting operations.
• the ADPA of the present invention comprises ADPAs of the Formula I: wherein R 1 and R 2 are independently selected from the group consisting of linear or branched C 1 C 20 alkyl, substituted or unsubstituted C 3 -C 20 cycloalkyl.
• R 1 and R 2 may be the same substituent. In one embodiment of the invention, R 1 or R 2 are both not hydrogen.
• cycloalkyl groups for use herein for R 1 and R 2 include, for example, substituted or unsubstituted rings containing from about 5 to about 20 carbon atoms, e.g., cyclopentyl, cyclohexyl, n-methyl-cyclohexyl, n-dimethyl-cyclohexyl, n-ethyl-cyclohexyl, cycloheptyl, cyclooctyl, etc., mixtures and thereof, and the like.
• the ADPA is further alkylated with more than two substituent groups. In another embodiment of the invention, the ADPA is alkylated with only one substituent group.
• Preferred ADPAs that can be employed in the practice of the present invention include, for example, nonylated diphenylamine, octylated diphenylamine (e.g., di(octylphenyl)amine), styrenated diphenylamine, octylated styrenated diphenylamine, butylated octylated diphenylamine, diphenylamine, butyldiphenylamine, dibutyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine, nonyldiphenylamine, dinonyldiphenylamine, heptyldiphenylamine, diheptyldiphenylamine, mixed butyl/octyl alkylated diphenylamines, mixed nonyl/ethyl alkylated diphenylamines, tert-butyl diphenylamine,
• the additive package comprises a mixture of two or more ADPAs selected from the structures and compounds identified above.
• exemplary mixtures are mixed mono- and di-octyl diphenylamines (DPAs), mixed mono and di-nonyl DPAs, and mixed butyl/octyl alkylated DPAs.
• the PNA comprises phenyl- ⁇ -naphthylamine. In another embodiment of the invention, the PNA comprises phenyl- ⁇ -naphthlyamine.
• the PNA comprises one or more PNAs of formula II:
• the PNA comprises one or more PNAs of Formula III:
• the PNA comprises a blend of PNAs of the previous two formulae.
• the PNA is substituted. e.g., alkylated, with one or more substituent groups.
• the potential substituent groups include, for example, the substituents mentioned above as candidates for R 1 and R 2 .
• the phenyl rings of Formula II or Formula III are substituted at the ortho, para or meta positions.
• Preferred PNAs that can be employed in the present invention include, for example, octyl) alkylated phenyl- ⁇ -naphthylamine, docecyl phenyl- ⁇ -naphthylamines and mixed alkylated phenyl- ⁇ -naphthylamines.
• Examples of commercially produced substituted PNAs are Naugalube® PANA and Irganox® L06.
• Preferred commercially produced PNAs that can be utilized in the present invention include, for example, Naugard® PANA.
• composition comprising a mixture of two or more PNAs selected from the structures and compounds identified above.
• the sulfur-containing phenol comprises sulfur-containing phenols of Formula IV wherein R 3 is a sulfur-containing alkyl or aryl group, or a sulfur-containing alkene or carboxylic acid; and wherein R 4 and R 5 are alkyl or aryl.
• Preferred sulfur-containing phenols that can employed in the present invention include, for example, 2,2'-thiodiethylene bis (3,5,-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-thiobis(4-methyl-6-t-butyl-phenol), 4,4'-thiobis(2-t-butyl-5-methylphenol) and iso(C10-C14)alkyl (3,5-di-tert-butyl-4-hydroxyphenyl)methylthioacetate.
• Preferred commercially produced sulfur-containing phenols that can be utilized in the present invention include, for example, Naugalube® 15, Naugalube®16 and Naugalube® 18 from Chemtura Corporation; Irganox®L115, Irganox®L118, Irganox®L1035, Irganox®L 1081 and Irganox®L415 for Ciba Specialty chemicals.
• the additive package is prepared by mixing Naugalube® 438L with Naugard® PNA and a sulfur-containing phenol. Mixing is carried out at 65°C and under nitrogen protection.
• the mixing may be carried out for at least 5 minutes, e.g., at least 10 minutes, at least 15 minutes, at least 25 minutes, or at least 60 minutes. It should be appreciated by those of ordinary skill in the art that the mixing time will vary based on the quantities of each of the materials.
• the resultant mixture was a free-flowing liquid at room temperature having a viscosity, measured at 40°C, of less than 100 Pa ⁇ s (100,000 cP), e.g., less than 50 Pa ⁇ s (50,000 cP), less than 40 Pa ⁇ s (40,000 cP), less than 25 Pa ⁇ s (25,000 cP) or less than 10 Pa ⁇ s (10,000 cP). In other embodiments, the resultant mixture was dark reddish in color.
• the additive package comprises nonylated diphenylamine, octyl phenyl-alpha-naphthylamine and 2,2'-thiodiethylene bis (3,5,-di-t-butyl-4-hydroxyphenyl)propionate.
• the additive package comprises butyl and octylated diphenylamine, octyl alkylated phenyl-alpha-naphthylamine and 2,2'-thiobis(4-methyl-6-t-butyl-phenol).
• the additive package comprises octyl and styrenated diphenylamine, mixed alkylated phenyl- ⁇ -naphthylamines and 2,2'-thiodiethylene bis (3,5,-di-t-butyl-4-hydroxyphenyl)propionate.
• Additional embodiments utilize the combinations of ADPA, PNA and sulfur-containing phenol listed in TABLE 3. This listing is not exclusive of all preferred embodiments.
• TABLE 3 Exemplary Combination ADPA PNA Sulfur-containing Phenol 14 Mixed mono- and di-octyl DPAs Octyl alkylated phenyl- ⁇ -naphthylamine 2,2'-thiodiethylene bis (3,5,-di-t-butyl-4-hydroxyphenyl)propionate 15 Mixed mono- and di ⁇ octyl DPAs Dodecyl phenyl- ⁇ -naphthylamine 2,2'-thiodiethylene bis (3,5,-di-t-butyl-4-hydroxyphenyl)propionate 16 Mixed mono- and di-nonyl DPAs Octyl alkylated phenyl- ⁇ -naphthylamine 2,2'-thiodiethylene bis (3,5,-di-t-butyl-4-hydroxyphen
• ADPA Exemplary ADPA, PNA and sulfur-containing phenol candidates are listed in TABLE 4 This listing is not exclusive TABLE 4
• ADPA PNA Sulfur-containing Phenol Mixed mono and di-octyl DPAs Phenyl- ⁇ -naphthylamine 2,2'-thiodiethylene bis (3,5, ⁇ di-t-butyl-4-hydroxyphenyl)propionate Mixed mono and di-nonyl DPAs Octyl phenyl- ⁇ -naphthylamine 2,2'-thiobis(4-methyl-6-t-butylphenol Dodecyl phenyl- ⁇ -naphthylamine 4,4' thiobis(2-t-butyl-5-methylphenol Iso(C10-C14)alkyl(3,5-di-tert-butyl-4-hydroxyphenyl) methylthioacetate Mixed butyl/octyl alkylated DPAs
• additives may be incorporated in the compositions of the invention to enable them to meet particular requirements.
• additives that may be included in the lubricating, oil compositions are dispersants, detergents, metal rust inhibitors, viscosity index improvers, corrosion inhibitors, oxidation inhibitors, friction modifiers, other dispersants, anti-foaming agents, anti-wear agents and pour point depressants. Some are discussed in further detail below.
• Lubricating oil compositions of the present invention can further contain one or more ashless dispersants which effectively reduce formation of deposits upon use in gasoline and diesel engines, when added to lubricating oils.
• Ashless dispersants useful in the compositions of the present invention comprise an oil soluble polymeric long chain backbone having functional groups capable of associating with particles to be dispersed.
• such dispersants comprise amine alcohol, amide or ester polar moieties attached to the polymer backbone, often via a bridging group.
• the ashless dispersant can be, for example selected from oil soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon substituted mono- and polycarboxylic, acids or anhydrides thereof; thiocarboxylate derivatives of long chain hydrocarbons; long chain aliphatic hydrocarbons having polyamine moieties attached directly thereto; and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine.
• Preferred dispersants include polyamine-derivatized poly alpha-olefin, dispersants, particularly ethylene/butene alpha-olefin and polyisobutylene-based dispersants.
• Particularly preferred are ashless dispersants derived from polyisobutylene substituted with succinic anhydride groups and reacted with polyethylene amines, e.g., polyethylene diamine, tetraethylene pentamine; or a polyoxyalkylene polyamine, e.g., polyoxypropylene diamine, trimethylolaminomethane; a hydroxy compound, e.g., pentaerythritol; and combinations thereof.
• One particularly preferred dispersant combination is a combination of (A) polyisobutylene substituted with succinic anhydride groups and reacted with (B) a hydroxy compound, e.g., pentaerythritol; (C) a polyoxyalkylene polyamine, e.g., polyoxypropylene diamine, or (D) a polyalkylene diamine, e.g., polyethylene diamine and tetraethylene pentamine using 0.3 to 2 moles of (B), (C) and/or (D) per mole of (A).
• Another preferred dispersant combination comprises a combination of (A) polyisobutenyl succinic anhydride with (B) a polyalkylene polyamine, e.g., tetraethylene pentamine, and (C) a polyhydric alcohol or polyhydroxy-substituted aliphatic primary amine, e.g., pentaerythritol or trismethylolaminomethane, as described in U.S. Patent No. 3,632,511 .
• Mannich base condensation products Another class of ashless dispersants comprises Mannich base condensation products. Generally, these products are prepared by condensing about one mole of an alkyl-substituted mono- or polyhydroxy benzene with about 1 to 2.5 moles of carbonyl compound(s) (e.g., formaldehyde and paraformaldehyde) and about 0.5 to 2 moles of polyalkylene polyamine, as disclosed, for example, in U.S. Patent No. 3,442,808 .
• carbonyl compound(s) e.g., formaldehyde and paraformaldehyde
• Such Mannich base condensation products can include a polymer product of a metallocene catalyzed polymerization as a substituent on the benzene group, or can be reacted with a compound containing such a polymer substituted on a succinic anhydride in a manner similar to that described in U.S. Patent No. 3,442,808 .
• Examples of functionalized and/or derivatized olefin polymers synthesized using metallocene catalyst systems are described in the publications identified supra.
• the dispersant can be further post treated by a variety of conventional post treatments such as boration, as generally taught in U.S. Patent Nos. 3,087,936 and 3,254,025 .
• Boration of the dispersant is readily accomplished by treating an acyl nitrogen-containing dispersant with a boron compound, such as boron oxide, boron halide boron acids, and esters of boron acids, in an amount sufficient to provide from 0.1 to 20 atomic proportions of boron for each mole of acylated nitrogen composition.
• Useful dispersants contain from 0.05 to 2.0 wt. %, e.g., from 0.05 to 0.7 wt. % boron.
• the boron which appears in the product as dehydrated boric acid polymers (primarily (HBO 2 ) 3 ), is believed to attach to the dispersant imides and diimides as amine salts, e.g., the metaborate salt of the diimide.
• Boration can be performed by adding from 0.5 to 4 wt. %, e.g., from 1 to 3 wt % (based on the mass of acyl nitrogen compound) of a boron compound, preferably boric acid, usually as a slurry, to the acyl nitrogen compound and heating with stirring at from 135°C to 190°C, e.g., 140°C to 170°C, for from about one to about five hours, followed by nitrogen stripping.
• the boron treatment can be conducted by adding boric acid to a hot reaction mixture of the dicarboxylic acid material and amine, while removing water. Other post reaction processes commonly known in the art can also be applied.
• the dispersant can also be further post treated by reaction with a so-called “capping agent.”
• a so-called "capping agent” nitrogen-containing dispersants have been “capped” to reduce the adverse effect such dispersants have on the fluoroelastomer engine seals.
• Numerous capping agents and methods are known. Of the known “capping agents,” those that convert basic dispersant amino groups to non-basic moieties (e.g., amido or imido groups) are most suitable.
• alkyl acetoacetate e.g., ethyl acetoacetate (EAA)
• a nitrogen-containing dispersant can be added in an amount providing the lubricating oil composition with from 0.03 wt % to 0.15 wt %, preferably from 0.07 to 0.12 wt %, of nitrogen.
• Metal-containing or ash-forming detergents function both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life.
• Detergents generally comprise a polar head with a long hydrophobic tail, with the polar head comprising a metal salt of an acidic organic compound.
• the salts can contain a substantially stoichiometric amount of the metal, in which case they are usually described as normal or neutral salts, and would typically have a total base number or TBN (as can be measured by ASTM D2896) of from 0 to 80.
• a large amount of a metal base can be incorporated by reacting excess metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide).
• the resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base (e.g. carbonate) micelle.
• Such overbased detergents can have a TBN of 150 or greater and typically will have a TBN of from 250 to 450 or more.
• Detergents that can be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, naphthenates, and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g., sodium, potassium, lithium, calcium, and magnesium.
• the most commonly used metals are calcium and magnesium, which can both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium.
• Particularly convenient metal detergents are neutral and overbased calcium sulfonates having TBN of from 20 to 450 TBN, and neutral and overbased calcium phenates and sulfurized phenates having TBN of from 50 to 450. Combinations of detergents, whether overbased or neutral or both, can be used.
• Sulfonates can be prepared from sulfonic acids which are typically obtained by the sulfonation of alkyl substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum or by the alkylation of aromatic hydrocarbons. Examples included those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl, or their halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene.
• the alkylation can be performed in the presence of a catalyst with alkylating agents having from 3 to more than 70 carbon atoms.
• the alkaryl sulfonates usually contain from 9 to 80 or more carbon atoms, preferably from 16 to 60 carbon atoms, per alkyl substituted aromatic moiety.
• the oil soluble sulfonates or alkaryl sulfonic acids can be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylate, sulfides, hydrosulfides, nitrates, borates, and ethers of the metal.
• the amount of metal compound is chosen having regard to the desired TBN of the final product but typically ranges from 100 to 220 wt. % (preferably at least 125 wt. %) of that stoichiometrically required.
• Metal salts of phenols and sulfurized phenols are prepared by reaction with an appropriate metal compound such as an oxide or hydroxide, and neutral or overbased products can be obtained by methods well known in the art.
• Sulfurized phenols can be prepared by reacting a phenol with sulfur or a sulfur containing compound such as hydrogen sulfide, sulfur monohalide, or sulfur dihalide, to form products which are generally mixtures of compounds in which two or more phenols are bridged by sulfur containing bridges.
• Dihydrocarbyl dithiophosphate metal salts are frequently used as antiwear and antioxidant agents.
• the metal can be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper.
• the zinc salts are most commonly used in lubricating oil in amounts of 0.1 to 10 wt %, preferably 0.2 to 2 wt %, based upon the total weight of the lubricating oil composition. They can be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohols or a phenol with P 2 S 5 and then neutralizing the formed DDPA with a zinc compound.
• DDPA dihydrocarbyl dithiophosphoric acid
• a dithiophosphoric acid can be made by reacting mixtures of primary and secondary alcohols.
• multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character.
• any basic or neutral zinc compound could be used, but the oxides, hydroxides, and carbonates are most generally employed. Commercial additives frequently contain an excess of zinc due to the use of an excess of the basic zinc compound in the neutralization reaction.
• the preferred zinc dihydrocarbyl dithiophosphates are oil soluble salts of dihydrocarbyl dithiophosphoric acids and can comprise zinc dialkyl dithiophosphates.
• the present invention can be particularly useful when used with passenger car diesel engine lubricant compositions containing phosphorus levels of from 0.02 to 0.12 wt %, such as from 0.03 to 0.10 wt %, or from 0.05 to 0.08 wt %, based on the total mass of the composition and heavy duty diesel engine lubricant compositions containing phosphorus levels of from 0.02 to 0.16 wt %, such as from 0.05 to 0.14 wt %, or from 0.08 to 0.12 wt %, based on the total mass of the composition.
• lubricating oil compositions of the present invention contain zinc dialkyl dithiophosphate derived predominantly (e.g., over 50 mol. %, such as over 60 mol. %) from secondary alcohols.
• Oxidation inhibitors or antioxidants reduce the tendency of mineral oils to deteriorate in service. Oxidative deterioration can be evidenced by sludge in the lubricant, varnish-like deposits on the metal surfaces, and by viscosity growth.
• Oxidative deterioration can be evidenced by sludge in the lubricant, varnish-like deposits on the metal surfaces, and by viscosity growth.
• Such oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkylphenolthioesters having preferably C 5 to C 12 alkyl side chains, calcium nonylphenol sulfide, oil soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons, phosphorous esters, metal thiocarbamates, oil soluble copper compounds as described in U.S. Patent No. 4,867,890 , and molybdenum-containing compounds.
• Typical oil soluble aromatic amines having at least two aromatic groups attached directly to one amine nitrogen contain from 6 to 16 carbon atoms.
• the amines can contain more than two aromatic groups.
• Compounds having a total of at least three aromatic groups, in which two aromatic groups are linked by a covalent bond or by an atom or group (e.g., an oxygen or sulfur atom, or a -CO-, -SO 2 - or alkylene group) and two are directly attached to one amine nitrogen, are also considered aromatic amines having at least two aromatic groups attached directly to the nitrogen.
• the aromatic rings are typically substituted by one or more substituents selected from alkyl, cycloalkyl, alkoxy, aryloxy, acyl, acylamino, hydroxy, and nitro groups.
• lubricating oil compositions useful in the practice of the present invention particularly lubricating oil compositions useful in the practice of the present invention that are required to contain no greater than 1200 ppm of phosphorus, contain ashless antioxidants other than benzenediamines, in an amount of from 0.1 to 5 wt. %, preferably from 0.3 wt. % to 4 wt. %, more preferably from 0.5 wt. % to 3 wt. %.
• the amount of ashless antioxidant other than benzenediamine will preferably increase accordingly.
• suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene, polymethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, interpolymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/isoprene, styrenelbutadiene, and isoprene/butadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene.
• a viscosity index improver dispersant functions both as a viscosity index improver and as a dispersant.
• examples of viscosity index improver dispersants include reaction products of amines, for example, polyamines, with a hydrocarbyl-substituted mono- or dicarboxylic acid in which the hydrocarbyl substituent comprises a chain of sufficient length to impart viscosity index improving properties to the compounds.
• the viscosity index improver dispersant can be, for example, a polymer of a C 4 to C 24 unsaturated ester of vinyl alcohol or a C 3 to C 10 unsaturated mono-carboxylic acid or a C 4 to C 10 di-carboxylic acid with an unsaturated nitrogen-containing monomer having 4 to 20 carbon atoms; a polymer of a C 2 to C 20 olefin with an unsaturated C 3 to C 10 mono- or di-carboxylic acid neutralized with an amine, hydroxyamine or an alcohol; or a polymer of ethylene with a C 3 to C 20 olefin further reacted either by grafting a C 4 to C 20 unsaturated nitrogen-containing monomer thereon or by grafting an unsaturated acid onto the polymer backbone and then reacting carboxylic acid groups of the grafted acid with an amine, hydroxy amine, or alcohol.
• Friction modifiers and fuel economy agents that arc compatible with the other ingredients of the final oil can also be included.
• examples of such materials include glyceryl monoesters of higher fatty acids, for example, glyceryl mono-oleate; esters of long chain polycarboxylic acids with diols, for example, the butane diol ester of a dimerized unsaturated fatty acid; oxazoline compounds; and alkoxylated alkyl-substituted mono-amines, diamines and alkyl ether amines, for example, ethoxylated tallow amine and ethoxylated tallow ether amine.
• organo-molybdenum friction modifiers comprise oil-soluble organo-molybdenum compounds.
• organo-molybdenum friction modifiers also provide antioxidant and antiwear credits to a lubricating oil composition.
• examples of such.oil soluble organo-molybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof.
• molybdenum dithiocarbamates, dialkyldithiophosphates, alkyl xanthates, and alkylthioxanthates are particularly preferred.
• the molybdenum compound can be an acidic molybdenum compound. These compounds will react with a basic nitrogen compound as measured by ASTM test D-664 or D-2896 titration procedure and are typically hexavalent. Included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkaline metal molybdates and other molybdenum salts, e.g., hydrogen sodium molybdate, MoOCl 4 , MoO 2 Br 2 , Mo 2 O 3 Cl 6 , molybdenum trioxide or similar acidic molybdenum compounds.
• organo-molybdenum compounds useful in the lubricating compositions of this invention are trinuclear molybdenum compounds, especially those of the formula Mo 3 S k L n Q z and mixtures thereof wherein the L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 through 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. At least 21 total carbon atoms should be present among all the ligand organo groups, such as at least 25, at least 30, or at least 35 carbon atoms.
• Pour point depressants otherwise known as lube oil flow improvers (LOFI)
• LOFI lube oil flow improvers
• Such additives are well known. Typical of those additives that improve the low temperature fluidity of the fluid are C 8 to C 18 dialkyl fumarate/vinyl acetate copolymers, and polymethacrylates.
• Foam control can he provided by an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
• additives can provide a multiplicity of effects; thus, for example, a single additive can act as a dispersant-oxidation inhibitor. This approach is well known and need not be further elaborated herein.
• additives that maintains the stability of the viscosity of the blend.
• polar group-containing additives achieve a suitably low viscosity in the pre-blending stage, it has been observed that some compositions increase in viscosity when stored for prolonged periods.
• Additives which are effective in controlling this viscosity increase include the long chain hydrocarbons functionalized by reaction with mono- or dicarboxylic acids or anhydrides which are used in the preparation of the ashless dispersants as hereinbefore disclosed.
• each additive is typically blended into the base stock in an amount that enables the additive to provide its desired function.
• Representative effect amounts of such additives, when used in crankcase lubricants, are listed below in TABLE 5. All the values listed are exemplary and are stated as weight percent active ingredient.
• Fully formulated passenger car diesel engine lubricating oil (PCDO) compositions of the present invention preferably have a sulfur content of less than 0.4 wt %, such as less than 0.35 wt %, more preferably less than 0.03 wt %, such as less than 0.15 wt %.
• the Noack volatility of the fully formulated PCDO (oil of lubricating viscosity plus all additives) will be no greater than 13, such as no greater than 12, preferably no greater than 10.
• Fully formulated PCDOs of the present invention preferably have no greater than 1200 ppm of phosphorus, such as no greater than 1000 ppm of phosphorus, or no greater than 800 ppm of phosphorus.
• Fully formulated PCDOs of the present invention preferably have a sulfated ash (SASH) content of 1.0 wt % or less.
• Fully formulated heavy duty diesel engine (HDD) lubricating oil compositions of the present invention preferably have a sulfur content of less than 1.0 wt %, such as less than 0.6 wt %, more preferably less than 0.4 wt %, such as less than 0.15 wt %.
• the Noack volatility of the fully formulated HDD lubricating oil composition will be no greater than 20, such as no greater than 15, preferably no greater than 12.
• Fully formulated HDD lubricating oil compositions of the present invention preferably have no greater than 1600 ppm of phosphorus, such as no greater than 1400 ppm of phosphorus, or no greater than 1200 ppm of phosphorus.
• Fully formulated HDD lubricating oil compositions of the present invention preferably have a sulfated ash (SASH) content of 1.0 wt % or less.
• phenol anti-oxidants examples include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-iso-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, o-tert-butylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, o-tert-butylphenol, 2,6-d
• aminic anti-oxidanis examples include, N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-di(2-naphthyl)-p-phenylenediamine, 4-(p-toluenesulfonamido)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, 4-n-butylaminophenol,
• esters of thiodipropionic acid or of thiodiacetic acid examples include esters of thiodipropionic acid or of thiodiacetic acid and salts of dithiocarbamide acid or dithiophosphoric acid
• metal deactivators examples include triazoles, benzotriazoles and their derivatives, tolutriazoles and their derivatives, 2-mercaptobenzothiazole, 2-mercaptobenzotriazole, 2,5-dimercaptobenzotriazole, 2,5-dimercaptobenzothiadiazole, 5,5'-methylenebisbenzotriazole, 4,5,6,7-tetrahydrobenzotriazole, salicylidenepropylenediamine, salicylaminoguanidine and their salts
• rust inhibitors include a) organic acids and esters, metal salts and anhydrides thereof, for example: N-oleoylsarcosine, sorbitol monooleate, lead naphthenate, alkenylsuccinic anhydride, for example dodecenylsuccinic anhydride, alkenylsuccinic acid hemiester and hemi-amides, und 4-nonylphenoxyacetic acid; b) Nitrogenous compounds, for example, primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, for example oil-soluble alkylammonium carboxylates; heterocyclic compounds, for example, substituted imidazolines and oxazolines, c) Phosphorus compounds, for example, amine salts of partial esters of phosphoric acid or partial esters of phosphonic acid, zinc dialkyldithiophosphates, d) Sulf
• viscosity index improvers examples include polyacrylates, polymethacrylates, vinylpyrrolidone/methacrylate copolymers, polyvinylpyrrolidones, polybutenes, olefin copolymers, styrene/acrylate copolymers, polyethers.
• pour-point depressants examples include polymethacrylate and alkylated napltlhalene derivatives.
• dispersants/surfactants examples include polybutenylsuccinamides or -imides, polybutenylphosphonic acid derivatives, basic magnesium, calcium and barium sulfonates, and phenolates.
• anti-wear additives include compounds containing sulfur and/or phosphorus and/or halogen, such as sulfurized vegetable oils, zinc dialkyldithiophosphates, tritolylphosphate, chlorinated paraffins, alkyl sulfides, aryl disulfides and aryl trisulfides, triphenylphosphorothionates, and diethanolaminomethyltolyltriazole, di(2-ethylhexyl)aminomethyltolyltriazole.
• sulfur and/or phosphorus and/or halogen such as sulfurized vegetable oils, zinc dialkyldithiophosphates, tritolylphosphate, chlorinated paraffins, alkyl sulfides, aryl disulfides and aryl trisulfides, triphenylphosphorothionates, and diethanolaminomethyltolyltriazole, di(2-ethylhexyl)aminomethyltolyltriazole.
• the lubricating oil compositions of the present invention improve the oxidative stability of materials that are subject to oxidative, thermal, and/or light-induced degradation.
• These organic materials can be natural or synthetic.
• These organic materials can include "functional fluids," lubricating oils, greases, and fuels, as well as automatic and manual transmission fluids, power steering fluid, hydraulic fluids, gas turbine oils, compressor lubricants, automotive and industrial gear lubricants and heat transfer oils.
• H1 food grade lubricants are used as base stocks.
• Such base stocks are those that could have incidental food contact. These are sometimes referred to as "above the line" lubricants.
• Such stocks may be used on food-processing equipment as a protective antirust film, as a release agent on gaskets or seals of tank closures and as a lubricant for machine parts and equipment in locations where the lubricated part is potentially exposed to food.
• the amount used is the smallest needed to accomplish the desired technical effect on the equipment.
• the ADPA is Naugalube® 640 and the base stock is such a H1 food grade base stock.
• H1 food grade lubricants that can be utilized in the present invention include Tri-Flow® and Spray-on®711® from Krylon Products Group and NEVASTANE® lubricants from TOTAL Lubricants USA, Inc.
• base stocks of lubricating viscosity useful in the context of the present invention are selected from natural lubricating oils, synthetic lubricating oils, and mixtures thereof.
• the lubricating oil can range in viscosity from light distillate mineral oils to heavy lubricating oils, such as gasoline engine oils, mineral lubricating oils, and heavy duty diesel oils.
• the viscosity of the oil ranges from 2 centistokes to 40 centistokes, especially from 4 centistokes to 20 centistokes, as measured at 100°C.
• the diesel fuel is a petroleum-based fuel oil, especially a middle distillate fuel oil.
• distillate fuel oils generally boil within the range of from 110°C to 500°C, e.g. 150°C to 400°C.
• the fuel oil may comprise atmospheric distillate or vacuum distillate, cracked gas oil, or a blend in any proportion of straight run and thermally and/or refinery streams such as catalytically cracked and hydro-cracked distillates.
• Fischer-Tropsch fuels also known as FT fuels
• FT fuels include those described as gas-to-liquid (GTL) fuels, biomass-to-liquid (BTL) fuels and coal conversion fuels.
• GTL gas-to-liquid
• BTL biomass-to-liquid
• coal conversion fuels coal conversion fuels.
• syngas (CO + H 2 ) is first generated and then converted to normal paraffins by a Fischer-Tropsch process.
• the normal paraffins can then be modified by processes such as catalytic cracking/reforming or isomerization, hydrocracking and hydroisomerization to yield a variety of hydrocarbons such as iso-paraffins, cyclo-paraffins and aromatic compounds.
• the resulting FT fuel can be used as such or in combination with other fuel components and fuel types.
• diesel fuels derived from plant or animal sources These can be used alone or in combination with other types of fuel.
• Oils and fats derived from plant or animal materials are increasingly finding application as fuels and, in particular, as partial or complete replacements for petroleum derived middle distillate fuels such as diesel.
• fuels are known as “biofuels” or “biodiesels.”
• Biofuels may be derived from many sources. Among the most common are the alkyl, often methyl, esters of fatty acids extracted from plants, such as rapeseed, sunflower, and the like. These types of fuel are often referred to as FAME (fatty acid methyl esters).
• Base stocks may include natural oils including animal oils and vegetable oils, e.g.. lard oil, castor oil, liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral oils of the paraffinic, naphthenic, and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale also serve as useful base oils.
• oils and fats derived from animal or vegetable material are rapeseed oil, coriander oil, soya bean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, maize oil, almond oil, canola oil, jojoba oil, palm kernel oil, coconut oil, mustard seed oil, jatropha oil, beef tallow, and fish oils.
• oils derived from corn, jute, sesame, shea nut, ground nut, and linseed oil may be derived therefrom by methods known in the art.
• Rapeseed oil which is a mixture uf fatty acids partially esterified with glycerol. is available in large quantities and can be obtained in a simple way by pressing from rapeseed.
• Recycled oils such as used kitchen oils are also suitable.
• Useful base stocks are, for example, alkyl esters of fatty acids, which include commercial mixtures of the ethyl, propyl, butyl and especially methyl esters of fatty acids with 12 to 22 carbon atoms.
• alkyl esters of fatty acids which include commercial mixtures of the ethyl, propyl, butyl and especially methyl esters of fatty acids with 12 to 22 carbon atoms.
• lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselic acid, ricinoleic acid, clacostearic acid, linoleic acid, linolenic acid, cicosanoic acid, gadoleic acid, docosanoic acid, or erucic acid are useful and have an iodine number from 50 to 150, especially 90 to 125.
• Mixtures with particularly advantageous properties are those which contain mainly, i.e., at least 50 wt. %, methyl esters of fatty acids with 16 to 22 carbon atoms and 1, 2, or 3 double bonds.
• the preferred lower alkyl esters of fatty acids are the methyl esters of oleic acid, linoleic acid, linolenic acid, and erucic acid.
• alkyl esters of fatty acids are obtained for example by cleavage and esterification of animal and vegetable fats and oils by their transesterification with lower aliphatic alcohols.
• For production of alkyl esters of fatty acids it is advantageous to start from fats and oils which contain low levels of saturated acids, less than 20%, and which have an iodine number of less than 130.
• Blends of the following esters or oils are suitable, e.g., rapeseed, sunflower, coriander, castor, soya bean, peanut, cotton seed, beef tallow, and the like.
• Alkyl esters of fatty acids based on a new variety of rapeseed oil, the fatty acid component of which comprises more than 80 wt. % unsaturated fatty acids with 18 carbon atoms, are preferred.
• Particularly preferred base stocks arc oils capable of being utilized as biofuels.
• Biofuels i.e., fuels derived from animal or vegetable material, are believed to be less damaging to the environment on combustion and are obtained from a renewable source. It has been reported that on combustion less carbon dioxide is formed by the equivalent quantity of petroleum distillate fuel, e.g., diesel fuel, and very little sulfur dioxide is formed.
• Certain derivatives of vegetable oil e.g., those obtained by saponification and re-esterification with a monohydric alkyl alcohol, can be used as a substitute for diesel fuel.
• Preferred biofuels are vegetable oil derivatives, of which particularly preferred biofuels are alkyl ester derivatives of rapeseed oil, cottonseed oil, soya bean oil, sunflower oil, olive oil, or palm oil, rapeseed oil methyl ester being especially preferred, either alone or in admixture with other vegetable oil derivatives, e.g., mixtures in any proportion of rapeseed oil methyl ester and palm oil methyl ester.
• biofuels arc most commonly used in combination with petroleum-derived oils.
• the present invention is applicable to mixtures of biofuel and petroleum-derived fuels in any ratio.
• at least 5%, preferably at least 25%, more preferably at least 50%, and most preferably at least 95% by weight of the oil may be derived from a plant or animal source.
• Synthetic base stock lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1 octenes), poly(1-decenes)), alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethy)hexyl)henzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and derivative, analogs. and homologs thereof. Also useful are synthetic oils derived from a gas to
• Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having a molecular weight of 1000 or diphenyl ether of polyethylene glycol having a molecular weight of 1000 to 1500), and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3 -C 8 fatty acid esters, and C 13 oxo acid diester of tetraethylene glycol.
• polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g.
• Another suitable class of synthetic base stock lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
• dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, lin
• esters includes dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, dodecyl phthalate, dielcosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2 ethylhexanoic acid.
• Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
• Silicon-based oils (such as the polyalhyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils.
• Other synthetic lubricating oils include liquid esters of phosphorus-containing acids, polymeric tetrahydrofurans, poly- ⁇ -olefins, and the like.
• Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils comprise another useful class of synthetic base stock lubricants; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes.
• oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhe
• Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
• the lubricating oil may be derived from unrefined, refined, rerefined oils, or mixtures thereof.
• Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar and bitumen) without further purification or treatment.
• Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment.
• Refined oils are similar to unrefined oils, except that refined oils have been treated in one or more purification steps to improve one or more properties.
• Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, percolation, and the like, all of which are well-known to those skilled in the art.
• Rerefined oils are obtained by treating refined oils in processes similar to those used to obtain the refined oils. These rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
• Lubricating oil base stocks derived from the hydroisomerization of wax may also be used, either alone or in combination with the aforesaid natural and/or synthetic base stocks.
• Such wax isomerate oil is produced by the hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst.
• Natural waxes are typically the slack waxes recovered by the solvent dewaxing of mineral oils; synthetic waxes are typically the wax produced by the Fischer-Tropsch process.
• the resulting isomerate product is typically subjected to solvent dewaxing and fractionation to recover various fractions having a specific viscosity range.
• Wax isomerate is also characterized by possessing very high viscosity indices, generally having a viscosity index of at least 130, preferably at least 135 or higher and, following dewaxing, a pour point of about -20°C. or lower.
• the base stock of lubricating viscosity can comprise a Group I, Group II, or Group III base stock or base oil blends of the aforementioned base stocks.
• the oil of lubricating viscosity is a Group II or Group III base stock, or a mixture thereof, or a mixture of a Group I base stock and one or more of a Group II and Group III.
• a major amount of the oil of lubricating viscosity is a Group II, Group III, Group IV, or Group V base stock, or a mixture thereof.
• the base stock, or base stock blend preferably has a saturate content of at least 65%, e.g., at least 75% or at least 85%. Most preferably, the base stock, or base stock blend, has a saturate content of greater than 90%.
• the volatility of the oil or oil blend is less than or equal to 30%, preferably less than or equal to 25%, more preferably less than or equal to 20%, most preferably less than or equal to 16%.
• the viscosity index (VI) of the oil or oil blend is at least 85, preferably at least 100, most preferably from 105 to 140.
• the additive package is added to the base stock in the form of an additive package concentrate.
• the total amount of additive components in the concentrates generally varies from 20 to 95 wt. % or more, with the balance being diluent oil.
• the diluent oil may be the base stocks of the invention, as defined above, or a hydrocarbon, preferably aromatic, solvent or mixtures thereof.
• the concentrates may contain other additives, as listed below.
• the additive package concentrates are added to the base stock in an amount sufficient to provide the proper weight % of ADPA, PNA and/or sulfur-containing phenol to the finished lubricating oil composition.
• ASTM D7097 is the "Standard Test Method for Determination of Moderately High Temperature Piston Deposits by Thermo-oxidation Engine Oil Simulation Tests," approved December 2004.
• ASTM D7097 is a new standard lubricant industry test for the evaluation of the oxidation and carbonaceous deposit-forming characteristics of engine oils. The test is designed to simulate high temperature deposit formation in the piston ring belt area of modem engines.
• the test is also a useful tool for studying the formation of volatile organic molecules upon oxidation of an engine oil. It is generally understood that the formation of volatile organic molecules upon oxidation of a lubricant are detrimental because they lead to an increase in emissions, and can also promote further polymerization of the lubricant. Polymerization of the lubricant leads to viscosity increase, which is also undesirable.
• the additive combination of this invention is effective at controlling both deposit formation and the formation of volatile organic molecules.
• polar volatile organic molecules are formed by decomposition of an organic peroxide in the lubricant. This decomposition produces an organic alkoxy radical that can react with another oil molecule to produce an alcohol, or that can degrade to form aldehydes and ketones.
• the degradation to aldehydes and ketones generally reduces molecular weight and thus produces more volatile fragments, which are pollutants and are also active precursors to oligomers and polymers that thicken the lubricant. It is therefore highly desirable to prevent or eliminate the formation of these polar volatile organic molecules.
• the TEOST MHT determines the mass of deposit formed on a specially constructed, pre-weighed steel depositor rod.
• the fully formulated lubricant (8.4 g) and an organometallic catalyst (about 0.1 g) are added to a flask equipped with a Teflon stirring bar and stirred for 20-60 minutes without heating.
• the depositor rod, sample flask, oil inlet, air inlet, and volatiles collection vial arc fitted to the TEOST apparatus according to manufacturers specifications.
• the pump is started at a high flow rate and run until the test oil reaches the connection of the pump and oil feed tube, at which point the pump flow is turned to zero.
• the heater switch is turned on and when the depositor rod temperature controller is between 200-210° C..
• the pump speed increased to achieve a sample delivery of 0.25 ⁇ 0.02 g/min, making sure that the oil is flowing down the depositor rod and is not leaking.
• the temperature is allowed to stabilize at 285 ⁇ 2° C. and the test is run under these conditions for 24 hrs.
• Three test tubes arc prepared with cyclohexane or another suitable hydrocarbon solvent for extraction of oil from the depositor rod.
• the test instrument is disassembled as per manufacturer's instructions and the depositor rod is transferred to a weighing boat and kept under cover.
• the depositor rod is placed successively for 10 minutes each in each of the three test tubes prepared with a hydrocarbon solvent.
• the rod is placed in tared weighing boat and allowed to sit for 10 minutes to insure evaporation of the hydrocarbon solvent.
• the rod and the boat are weighed, verifying that a constant mass has been achieved.
• the contents of the three test tubes, along with the lower-end cap deposits and glass mantle deposits are washed into a common container which is then filtered using a glass funnel equipped with a filter cartridge. After completing the filtering, the filter cartridge is dried under vacuum and weighed, until a constant mass is achieved. The total mass of the deposits from the depositor rod and filter deposits is then determined.
• the volatile compounds in the formulated oil that are there originally or those formed during the test are flashed off the depositor rod. These volatiles condense on the glass mantle and are collected on a continuous basis in a small, weighed vial. The vial and volatiles are measured at the end of the 24 hour test period and the amount of volatiles is calculated by subtracting the original weight of the vial.
• PDSC testing can be used to measure of the oxidation induction time (OIT) of materials.
• OIT oxidation induction time
• the samples discussed in this application were tested in accordance with the parameters listed in TABLE I (displayed above).
• the PDSC instrument used was a Mettler DSC27HP manufactured by Mettler-Toledo, Inc.
• the PDSC method employs a steel cell under constant oxygen pressure throughout each run. The instrument has a typical repeatability of ⁇ 5.0 minutes with 95 percent confidence for an OIT of 200 minutes.
• the PDSC steel cell is pressurized with oxygen and heated at a rate of 40°C per minute to the isothermal temperature listed in TABLE 1.
• the induction time is measured from the time the sample reaches its isothermal temperature until the enthalpy change is observed.
• the longer the oxidation induction time the better the oxidation stability of the oil, i.e., longer OITs indicate more stable compositions.
• 40 ⁇ L of oil soluble ferric naphthenate (6 weight pcrccnt in mineral oil) was added, prior to PDSC testing, to facilitate 50 ppm of iron in oil.
• the antioxidant effect of the present invention may preferably be demonstrated in, for example, a low phosphorus-containing SAE 5W20 fully formulated engine oil.
• a low phosphorus-containing SAE 5W20 fully formulated engine oil was used in the PDSC testing discussed herein.
• the SAE 5W20 engine oil formulation was pre-blended with the components shown in TABLE 6, all of which are commercially available.
• the antioxidant package was subsequently added to the engine oil pre-blend.
• the PDSC testing was carried out at 185°C.
• TABLE 6 SAE 20 Engine oil Pre-blend Formula Composition Amounts in composition, wt% Overbased Calcium Sulfonate Detergents 2.5 ZDDP 0.5 Succinimide Dispersant 6.4 Pour Point Depressant 0.1 OCP VI Improver 5.0 Base oil, API Group II Balance
• Additive package blends 1-6 and A-C were prepared according to the proportions shown in TABLE 7.
• TABLE 7 ADPA- Naugalube 438L PNA-Naugard PNA Sulfur- containing phenol- Naugalube-15 OIT, minutes Expected OIT, minutes TEOST MHT, mg Expected TEOST MHT, mg
• Examples 1-6 1 0.7 0.15 0.15 39 34.3 37.4 57.6 2 0.8 0.1 0.1 39.8 35.2 44.9 56.7 3 0.75 0.2 0.05 45.5 38.3 43.0 57.2 4 0.7 0.1 0.2 34.9 31.9 39.1 57.5 5 0.9 0.05 0.05 39.6 36.1 43.3 56.9 6 0.75 0.05 0.2 40.3 31.1 47.3 57.1
• Comparative Examples A-C A 1.0 0 0 37 -- 55 -- B 0 1 0 52.0 -- 63.7 -- C 0 0 1 3.8 -- 63.0 --
• Example blends 1-6 are representative embodiments of the invention.
• Example blends A-C are comparative.
• the lubricant oil compositions were tested for OIT and TEOST MHT. The results arc shown in TABLE 7.
• Comparative Examples A, B, and C represent pure ADPA, PNA and sulfur-containing phenol, respectively. These blends demonstrated OIT values of 37.0, 52.0, and 3.8 minutes, respectively, and TEOST MHT values of 55.0, 63.7 and 63 grams of deposits, respectively.
• the expected OITs for additive packages may be calculated by adding the OlTs of pure ADPA, PNA and sulfur-containing phenol according to the appropriate weight percentages of the respective mixture.
• the expected TEOST MHT values for additive packages may be calculated in a similar manner.
• the expected OITs and the expected TEOST MHT values are also shown in TABLE 7.
• the lubricating oil blend 1 which is representative of the present invention, demonstrates TEOST MHT values below 40.
• the additive packages of the embodiments of the invention demonstrate OIT values that are greater than 38 minutes, when tested according to the parameters mentioned above.
• additive packages of the embodiments of the invention surprisingly and unexpectedly demonstrate superior OITs when compared to the expected values-in most cases, greater than 13% increases. Further, these additive packages show superior TEOST MHT values when compared to the expected values-in most cases, greater than 20% decreases, which are also surprising and unexpected.

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