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
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/06—Well-defined aromatic compounds
  • C10M2203/065—Well-defined aromatic 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
  • 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
  • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers 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
  • 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
  • C10M2205/022—Ethene
  • C10M2205/0225—Ethene 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
  • 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
  • C10M2205/026—Butene
• • 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
  • C10M2205/026—Butene
  • C10M2205/0265—Butene 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
  • 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
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/027—Neutral salts thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/028—Overbased salts thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
  • C10M2209/084—Acrylate; Methacrylate
• • 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
  • C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether 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
  • C10M2217/00—Organic macromolecular compounds containing nitrogen 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
  • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
  • C10M2217/023—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group the amino group containing an ester bond
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
• • 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—Overbased sulfonic 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
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/045—Metal containing thio derivatives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/02—Viscosity; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/43—Sulfur free or low sulfur content compositions
• • 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
  • C10N2030/50—Emission or smoke controlling 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/72—Extended drain
• • 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
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines
• • 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
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines
  • C10N2040/253—Small diesel engines
• • 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
  • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
  • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

• the present invention relates to synthetic based lubricants which are particularly useful for lubricating heavy duty diesel engines.
• a heavy duty diesel lubricant has now been formulated using a selection of synthetic base oils, a dispersant-viscosity modifier, and a sulfur-free functionalized alkyl phenol detergent.
• the preferred lubricant also exhibits good emissions performance.
• U.S. Patent 5,719,107, Outten et al., February 17, 1998 discloses a crankcase lubricant for diesel engines, comprising an admixture of a major amount of an oil of lubricating viscosity, at least 4 mass % dispersant, at least 0.3 mass % of a metal phenate, which may be neutral or overbased, and various other components.
• the oil can be any of the synthetic or natural oils, or mixtures.
• the oil has a viscosity of about 2.5 to about 12 mm 2 /sec. Multifunctional viscosity modifiers that also function as dispersants are also disclosed.
• Suitable metal phenates include calcium, magnesium, and mixtures of the two.
• Metal salts and condensates are prepared from the following ingredients: an aromatic compound containing a polar radical or radicals (e.g., phenols), and aldehydes such as formaldehyde.
• a polar radical or radicals e.g., phenols
• aldehydes such as formaldehyde.
• the Ca, Mg, Sr, Cu, Zn,Al, and Sn salts of certain of these condensation products are disclosed.
• SUMMARY OF THE INVENTION The present invention provides a lubricant suitable for use in a diesel engine, comprising:
• the invention also provides a method for lubricating a crankcase-lubricated diesel engine comprising supplying such a lubricant to the crankcase thereof.
• the first component of the present lubricants is a selected synthetic base oil or mixture of base oils. Synthetic oils in general include hydrocarbon oils such as polymerized and interpolymerized olefins, e.g., polyalphaolefins (PAOs).
• polyalphaolefins are derived from monomers having from about 4 to about 30, or from about 4 to about 20, or from about 6 to about 16 carbon atoms.
• PAOs are hydrogenated. Examples of useful PAOs polybutylenes, polypropylenes, propylene-isobutylene copolymers, poly(l-hexenes, poly(l- octenes), poly(l-decenes), and mixtures thereof).
• Alkylbenzenes are another species of synthetic hydrocarbon oil.
• Alkylbenzenes include generally C 1 0-1 3 alkyl-substituted benzenes, including dodecylbenzenes and bisdodecylbenzenes such as m-bisdodecylbenzene; tetradecylbenzenes; dinonylbenzenes; and di(2-ethylhexyl)-benzenes;
• Group III base oils are also sometimes considered to be synthetic base oils, and for the purposes of this invention they can be considered to be included within the definition of "synthetic base oils.”
• Group III base oils are defined by the API Base Oil Interchange Guidelines as having the following minimum characteristics: ⁇ 0.03 % sulfur, > 90 % saturates, and > 120 viscosity index.. These are generally oils which are derived from natural stocks (as opposed to being derived from synthetic sources), but are so highly refined that they can exhibit the performance and viscosity parameters of other synthetic base oils.
• Another class of synthetic base oils includes alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, or similar reaction constitute. These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methylpolyisopropylene glycol ether having an average molecular weight of 1,000 diphenyl ether of polyethylene glycol having a molecular weight of 500-1,000, diethyl ether of polypropylene glycol having a molecular weight of 1,000-1,500) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3 -C 8 fatty acid esters, or the C 13 Oxo acid diester of tetraethylene glycol.
• the oils prepared through polymerization of ethylene oxide or propylene oxide the alkyl and aryl ethers of these
• Another suitable class of synthetic lubricating oils comprises synthetic esters, including the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, dodecanedioic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, and alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, and propylene glycol).
• dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid
• esters include dibutyl adipate, di(2-ethylhexyl sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
• Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol.
• Examples of synthetic monoester oils which are commercially available include EmeryTM 2935, EmeryTM2971, PriolubeTM 1976, PriolubeTM 3999, NycobaseTM 8311, NycobaseTM 8885, and NycobaseTM 8886.
• a useful synthetic base oil composition is selected from one or more polyalphaolefin oils, one or more synthetic esters, and one or more alkylbenzenes, or mixtures thereof.
• the base oil is a mixture of a polyalphaolefin oil having a viscosity of 4 to 8 x 10 "6 m 2 /s (4-8 cSt) at 100°C, alternatively in an amount of 60 to 95% by weight, a C ⁇ 0 - ⁇ 3 alkyl-substituted benzene, or in an amount of 5 to 20 percent by weight, and optionally a synthetic monoester, for instance, in an amount of 0 to 20 percent by weight.
• the synthetic base oil composition used in the present lubricant should exhibit a kinematic viscosity (ASTM 445) of at least 4.8 x 10 "6 m 2 /s (4.8 cSt) at 100°C and alternatively at least 5.0, 5.1 or 5.3, and optionally up to 7.0 x 10 "6 m 2 /s at 100°C.
• the base oil composition overall should also exhibit a viscosity index (ASTM 2270) of at least 110, such as at least 120, or in the range of 120 to 160.
• Viscosity Index or "N.I.” is an arbitrary number which indicates the resistance of a lubricant to viscosity change with temperature.
• the Dean and Davis viscosity index calculated from the observed viscosities of a lubricant at 40°C and 100°C gives N.I. values ranging from 0 or negative values to values of 200 or more. The higher its V.I. value, the greater the resistance of a lubricant to thicken at low temperatures and thin out at high temperatures. These parameters are intended to apply the base oil composition as such, without the benefit of any viscosity index modifiers (which may, however, also be present).
• any components of the oil which individually have a viscosity index of less than 120 can optionally comprise in total no more than 20 percent, and in one embodiment no more than 10 percent by weight of the base oil composition.
• at most a small portion of the overall base oil composition will comprise a natural (i.e., non-synthetic) oil. This option may be desired because natural oils generally do not exhibit the desirable viscosity or viscosity index properties.
• the base oil composition can contain 1 to 25 percent by weight of natural base oil components, or less than 20 percent, or less than 10 percent, and in one embodiment can contain substantially no natural base oil components (e.g., less than 5% or less than 1%).
• the amount of natural base oils present as diluent oils normally present in the various additives is to be taken into account. These materials can typically contribute 5 to 10 percent or more of oil to the overall composition.
• a second component of the lubricant of the present invention is a dispersant viscosity index modifier.
• Multifunctional additives that provide both viscosity improving properties and dispersant properties are known in the art and are commercially available. Such products are described in numerous publications including Dieter Klamann, “Lubricants and Related Products", Verlag Chemie Gmbh (1984), pp 185-193; C.N. Smalheer and R.K. Smith “Lubricant Additives”, Lezius- Hiles Co. (1967); M.W. Ranney, “Lubricant Additives", Noyes Data Corp. (1973), pp 92-145, M.W.
• Dispersant viscosity index modifiers are generally one or a mixture of polymers which perform several functions. They serve first as a viscosity index (“VI”) modifier, sometimes referred to as a viscosity index improver. This is the well-known function of controlling the rate or amount of viscosity change of a lubricant as a function of temperature. These are materials which have comparatively little thickening effect at low temperatures but significant thickening at high temperatures. This behavior extends the temperature range over which a lubricant can be used.
• VI viscosity index
• a viscosity index improver This is the well-known function of controlling the rate or amount of viscosity change of a lubricant as a function of temperature. These are materials which have comparatively little thickening effect at low temperatures but significant thickening at high temperatures. This behavior extends the temperature range over which a lubricant can be used.
• the VI modifiers for which the present invention is particularly useful further contain functional groups which provide dispersant functionality (and sometimes other functionality, such as antioxidation properties) to the lubricant composition.
• Dispersant functionality serves to prevent particulate contamination in an oil or other lubricant from agglomerating into larger particles which can settle out as sludge or varnish.
• dispersant additives can also be used in the present invention, the presence of one or more comonomers on the VI modifier entity which serve this function is desirable.
• the dispersant viscosity index modifiers can be functionalized versions of polymers which are generally used as viscosity index modifiers.
• polymers which are generally used as viscosity index modifiers.
• common classes of such polymers are olefin copolymers and acrylate or methacrylate copolymers.
• Functionalized olefin copolymers can be, for instance, interpolymers of ethylene and propylene which are grafted with an active monomer such as maleic anhydride and then derivatized with an alcohol or an amine, as described in U.S. Patent 4,089,794.
• Other such copolymers are copolymers of ethylene and propylene which are reacted or grafted with nitrogen compounds, as described in U.S. Patent 4,068,056.
• Vinyl pyridine, N-vinyl pyrrolidone and N,N'-dimethylaminoethyl methacrylate are examples of typical nitrogen-containing monomers.
• Dispersant viscosity index modifier additives are well-known as dispersant viscosity index modifier additives.
• Dispersant acrylate or polymethacrylate viscosity modifiers such as AcryloidTM 985, ViscoplexTM 6-054, or ViscoplexTM 2-500, from RohMax, or LZ ® 7720C, from The Lubrizol Corporation, are particularly useful.
• the amount of the dispersant viscosity modifier should be an amount suitable to provide a desirable overall viscosity index as well as to impart dispersancy to the formulation.
• the desired degree of dispersancy (which can also be provided in part by conventional dispersants) is that which will permit the oil formulation to meet the requirements of soot handling, such as that measured in the Mack T8-E test for Mack EO-M+ specification, while maintaining good piston cleanliness and seal compatibility, in accordance with the Mercedes Benz 228.5 specifications.
• the amount of the dispersant viscosity modifier is typically 0.5 to 3 weight percent of the lubricant, such as 1 to 2 percent by weight, or 0.3 to 1.6 percent by weight.
• the final required component of the present invention is a sulfur-free functionalized alkyl phenol detergent.
• Detergents in general are extremely well known additives for engine oil lubricants. They are generally salts of organic acids, which are often overbased.
• Metal overbased salts of organic acids are widely known to those of skill in the art and generally include metal salts wherein the amount of metal present exceeds the stoichiometric amount. Such salts are said to have conversion levels in excess of 100% (i.e., they comprise more than 100% of the theoretical amount of metal needed to convert the acid to its "normal” or “neutral” salt). They are commonly referred to as overbased, hyperbased or superbased salts and are usually salts of organic sulfur acids, organic phosphorus acids, carboxylic acids, phenols or mixtures of these.
• metal ratio is used to designate the ratio of the total chemical equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the salt which would be expected to result in the reaction between the organic acid to be overbased and the basic reacting metal compound according to the known chemical reactivity and stoichiometry of the two reactants.
• metal ratio in a normal or neutral salt the metal ratio is one and, in an overbased salt, the metal ratio is greater than one.
• the overbased salts usually have metal ratios of at least 1.1:1. Typically they have ratios of 2:1 or 3:1 to 40:1. Salts having ratios of 12:1 to 20:1 are often used.
• the basically reacting metal compounds used to make the overbased salts are usually an alkali or alkaline earth metal compound (i.e., the Group IA, IIA, and IIB metals, but normally excluding francium and radium and typically also excluding rubidium, cesium and beryllium), although other basically reacting metal compounds can be used.
• alkali or alkaline earth metal compound i.e., the Group IA, IIA, and IIB metals, but normally excluding francium and radium and typically also excluding rubidium, cesium and beryllium
• Compounds of Ca, Ba, Mg, Na and Li, such as their hydroxides and alkoxides of lower alkanols are usually used as basic metal compounds in preparing these overbased salts but others can be used as shown by the prior art referred to herein.
• Overbased salts containing a mixture of ions of two or more of these metals can be used in the present invention.
• Overbased materials are generally prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid, such as carbon dioxide) with a mixture comprising an acidic organic compound, a reaction medium comprising at least one inert, organic solvent (mineral oil, naphtha, toluene, xylene, etc.) for said acidic organic material, a stoichiometric excess of a metal base, and a promoter.
• the acidic organic compound will, in the present instance, be the functionalize alkyl phenol.
• the acidic material used in preparing the overbased material can be a liquid such as formic acid, acetic acid, nitric acid, or sulfuric acid. Acetic acid is particularly useful.
• Inorganic acidic materials can also be used, such as HC1, SO 2 , SO 3 , CO 2 , or H 2 S, and in one embodiment, CO 2 or mixtures thereof, e.g., mixtures of CO 2 and acetic acid.
• a promoter is a chemical employed to facilitate the incorporation of metal into the basic metal compositions. The promoters are diverse and are well known in the art and includes lower alcohols. A discussion of suitable promoters is found in U.S. Patents 2,777,874, 2,695,910, and 2,616,904. Patents specifically describing techniques for maldng basic salts of acidic organic compounds generally include U.S.
• the detergents useful in the present invention are sulfur-free functionalized alkyl phenol detergents (phenates).
• phenol and "phenate” is not intended to imply that the aromatic moiety is limited to alkyl phenol per se, that is, a single benzene ring substituted with an OH group and an alkyl group, although, in fact, this is a particularly useful species upon which the substituted phenol is constructed.
• aromatic species which are encompassed within the scope of the present invention include those containing more than one OH group, such as catechols; phenolic species containing multiple alkyl or hydrocarbyl substituents; multiple ring structures including fused ring structures, comprising both unsaturated fused rings (e.g., naphthalene-based) and saturated rings (e.g., tetrahydronaphthalene); and non-condensed multiple ring structures including phenyl substitution and phenylalkyl substitution.
• catechols phenolic species containing multiple alkyl or hydrocarbyl substituents
• multiple ring structures including fused ring structures comprising both unsaturated fused rings (e.g., naphthalene-based) and saturated rings (e.g., tetrahydronaphthalene); and non-condensed multiple ring structures including phenyl substitution and phenylalkyl substitution.
• the functionalization of the alkyl phenol can comprise the addition of any functional group to the phenolic compound, other than an additional hydroxy group or an additional hydrocarbyl group, at least one such alkyl or hydrocarbyl group already being present in sufficient amount to provide oil solubility to the detergent.
• Typical functional groups include t-butyl groups, methylene coupling groups, ester-substituted alkyl groups, and aldehyde groups.
• the functionalization is by addition of carboxy functionality, in which case the detergent can be an alkyl salicylate or a derivative thereof.
• Salicylate detergents are well known; see, for instance, U.S. Patent 5,688,751 or 4,627,928.
• the substituent can be based on a glyoxylic acid condensation.
• a typical glyoxylate condensation product is
• the R groups are alkyl groups.
• the material shown would be the condensation of 2 moles of alkyl phenol with 1 mole of glyoxylic acid or derivative thereof. Other molar ratios are also possible; when a 1:1 ratio is approached, the condensation product becomes oligomeric or polymeric.
• the functionalized alkyl phenol can be a condensation product of the alkyl phenol with formaldehyde or other lower aldehydes.
• the acidic substituent in this case, would be considered to be the one or more additional phenolic groups.
• the simplest such condensation product would be
• oligomeric structures can be formed when the molar ratio of formaldehyde:phenol increases.
• examples of such type of oligomeric species are the calixarates, which are cyclic materials containing 4 to 8 phenol-formaldehye repeat units. Calixarates and methods of their preparation are disclosed in greater detail in U.S. Patent 5,114,601. As will be apparent, mixtures of formaldehyde, other aldehydes, and glyoxylic acid can also be employed in such condensation reactions.
• Saligenin itself, also known as salicyl alcohol and o- hydroxybenzyl alcohol, is represented by the structure
• Useful saligenin derivatives include certain metal saligenin derivative which function as detergents.
• X comprises -CHO or -CH 2 OH
• Y comprises -CH 2 - or -CH OCH?-
• -CHO groups comprise at least about 10 mole percent of the X and Y groups
• M is hydrogen, ammonium, or a valence of a metal ion
• R 1 is a hydrocarbyl group containing 1 to about 60 carbon atoms
• m is 0 to about 10
• each p is independently 0, 1, 2, or 3, provided that at least one aromatic ring contains an R 1 substituent and that the total number of carbon atoms in all R 1 groups is at least 7.
• m is 1 or greater, one of the X groups can be hydrogen.
• the expression "represented by the formula” indicates that the formula presented is generally representative of the structure of the chemical in question. However, it is well known that minor variations can occur, including in particular positional isomerization, that is, location of the X, Y, and R groups at different position on the aromatic ring from those shown in the structure. The expression “represented by the formula” is expressly intended to encompass such variations.
• Mg represents a valence of a magnesium ion, and n, in each instance, is 0 or 1. (When n is zero the Mg is typically replaced by H to form an -OH group.)
• the value for "m” is typically 0 to 10, so number of such rings will be 1 to 11, although it is to be understood that the upper limit of "m” is not a critical variable. In one embodiment m is 2 to 9, such as 3 to 8 or 4 to 6.
• Other metals include alkali metals such as lithium, sodium, or potassium; alkaline earth metals such as calcium or barium; and other metals such as copper, zinc, and tin.
• R 1 which is the aforementioned hydrocarbyl group, such as alkyl group.
• R 1 can contain 1 to 60 carbon atoms, such as 7 to 28 carbon atoms or 9 to 18 carbon atoms.
• R 1 will normally comprise a mixture of various chain lengths, so that the foregoing numbers will normally represent an average number of carbon atoms in the R groups (number average).
• Each ring in the structure will be substituted with 0, 1, 2, or 3 such R 1 groups (that is, p is 0, 1, 2, or 3), most typically 1, and of course different rings in a given molecule may contain different numbers of such substituents.
• At least one aromatic ring in the molecule must contain at least one R 1 group, and the total number of carbon atoms in all the R 1 groups in the molecule should be at least 7, such as at least 12.
• the X and Y groups may be seen as groups derived from formaldehyde or a formaldehyde source, by condensative reaction with the aromatic molecule.
• the relative amounts of the various X and Y groups depends to a certain extent on the conditions of synthesis of the molecules. While various species of X and Y may be present in the molecules in question, the commonest species comprising X are -CHO (aldehyde functionality) and -CH 2 OH (hydroxymethyl functionality); similarly the commonest species comprising Y are -CH 2 - (methylene bridge) and -CH 2 OCH 2 - (ether bridge).
• the relative molar amounts of these species in a sample of the above material can be determined by ⁇ C NMR as each carbon and hydrogen nucleus has a distinctive environment and produces a distinctive signal.
• the signal for the ether linkage, -CH 2 OCH 2 - must be corrected for the presence of two carbon atoms, in order to arrive at a correct calculation of the molar amount of this material. Such a correction is well within the abilities of the person skilled in the art.
• X is at least in part -CHO and such -CHO groups comprise at least 10, 12, or 15 mole percent of the X and Y groups. In another embodiment the -CHO groups comprise 20 to 60 mole percent of the X and Y groups, such as 25 to 40 mole percent of the X and Y groups.
• X is at least in part -CH 2 OH and such -CH 2 OH groups comprise 10 to 50 mole percent of the X and Y groups, such as 15 to 30 mole percent of the X and Y groups.
• Y is at least in part -CH - and such -CH 2 - groups comprise 10 to 55 mole percent of the X and Y groups, such as 25 to 45 or 32 to 45 mole percent of the X and Y groups.
• Y is at least in part -CH 2 OCH 2 - and such -CH 2 OCH 2 - groups comprise 5 to 20 mole percent of the X and Y groups, such as 10 to 16 mole percent of the X and Y groups.
• the above-described compound is, as mentioned, typically a magnesium salt and, indeed, the presence of magnesium during the preparation of the condensed product is believed to be useful in achieving the desired ratios of X and Y components described above.
• the number of Mg ions in the compound is characterized by an average value of "n" of 0.1 to 1 throughout the composition, such as 0.2 or 0.3 to 0.4 or 0.5, or 0.35 to 0.45.
• Mg is normally a divalent ion
• the average value of n in the composition will be 0.5, that is, each Mg ion neutralizes 2 phenolic hydroxy groups. Those two hydroxy groups may be on the same or on different molecules. If the value of n is less than 0.5, this indicates that the hydroxy groups are less than completely neutralized by Mg ions. If the value of n is greater than 0.5, this indicates that a portion of the valence of the Mg ions is satisfied by an anion other than the phenolic structure shown.
• each Mg ion could be associated with one phenolic anion and one hydroxy (OH) ion, to provide an n value of 1.0.
• n is 0.1 to 1.0 is not directly applicable to overbased versions of this material (described below and also a part of the present invention) in which an excess of Mg or another metal can be present.
• the above-described component can be prepared by combining a phenol substituted by the above-described R 1 group with formaldehyde or a source of formaldehyde and magnesium oxide or magnesium hydroxide under reactive conditions, in the presence of a catalytic amount of a strong base.
• formaldehyde includes paraformaldehyde, trixoane, formalin and methal.
• paraformaldehyde is can be used.
• the relative molar amounts of the substituted phenol and the formaldehyde can be important in providing products with the desired structure and properties.
• the substituted phenol and formaldehyde are reacted in equivalent ratios of 1:1 to 1:3 or 1.4, such as 1:1.1 to 1:2.9 or 1: 1.4 to 1:2.6, or 1:1.7 to 1:2.3.
• One equivalent of formaldehyde is considered to correspond to one H 2 CO unit; one equivalent of phenol is considered to be one mole of phenol.
• the strong base is can be sodium hydroxide or potassium hydroxide, and can be supplied in an aqueous solution.
• the process can be conducted by combining the above components with an appropriate amount of magnesium oxide or magnesium hydroxide with heating and stirring.
• a diluent such as mineral oil or other diluent oil can be included to provide for suitable mobility of the components.
• An additional solvent such as an alcohol can be included if desired, although it is believed that the reaction may proceed more efficiently in the absence of additional solvent.
• the reaction can be conducted at room temperature or at a slightly elevated temperature such as 35-120°C, 70-110°C, or 90-100°C, and of course the temperature can be increased in stages. When water is present in the reaction mixture it is convenient to maintain the mixture at or below the normal boiling point of water.
• the mixture can be heated to a higher temperature, typically under reduced pressure, to strip off volatile materials.
• a suitable time e.g., 30 minutes to 5 hours or 1 to 3 hours
• the mixture can be heated to a higher temperature, typically under reduced pressure, to strip off volatile materials.
• the final temperature of this stripping step is 100 to about 150°C, such as 120 to about 145°C.
• Reaction under the conditions described above typically leads to a product which has a relatively high content of -CHO substituent groups, that is, 10%, 12%, and even 15% and greater.
• Such materials when used as detergents in lubricating compositions, exhibit good upper piston cleanliness performance, low Cu/Pb corrosion, and good compatibility with seals.
• Use of metals other than magnesium in the synthesis typically leads to a reduction in the content of -CHO substituent groups.
• a second increment of 58 g MgO is added and the batch further heated and maintained at 95-100°C for 1 hour. Thereafter the mixture is heated to 120°C under a flow of nitrogen at 28 L/hr (1.0 std. ft 3 /hr.). When 120°C is reached, 252 g diluent oil is added, and the mixtures is stripped for 1 hour at a pressure of 2.7 kPa (20 torr) at 120°C for 1 hour and then filtered.
• the resulting product is analyzed and contains 1.5% by weight magnesium and has a Total Base Number (TBN) of 63.
• TBN Total Base Number
• Analysis of the product by ID and 2D l ⁇ J 13 C NMR reveals an aldehyde content of 29 mole %, a methylene bridge content of 38 mole %, an ether bridge content of 12 mole %, and a hydroxymethyl content of 21 mole %.
• Borated compositions are prepared by reaction of the above- described saligenin derivative one or more boron compounds.
• Suitable boron compounds include boric acid, borate esters, and alkali or mixed alkali metal and alkaline earth metal borates. These metal borates are generally a hydrated particulate metal borate and they, as well as the other borating agents, are known in the art and are available commercially.
• the saligenin derivative is heated with boric acid at 50-100°C.
• the material can also be overbased. Overbased salts of organic acids generally, and methods of their synthesis, have been described above and are widely known to those of skill in the art.
• the magnesium saligenin derivative can be overbased using additional Mg metal or using a different metal.
• Example 2 Into a 2 L four-necked flask equipped with stirrer, thermowell, reflux condenser, and a subsurface tube, is charged 1000 g of the product of Example 2 (Mg saligenin derivative in diluent oil), 50 g of a mixture of isobutyl and amyl alcohols, 100 g of methanol, and 74 g of Ca(OH) 2 . A solution of 1 g acetic acid in 4 g water is added to the flask and the contents are held, with stirring, at 44°C for 30 minutes. Carbon dioxide is blown through the mixture for 1 hour or longer, at 14 L/hr (0.5 std. ftVhr.) until a direct base number of 15 is obtained.
• Mg saligenin derivative in diluent oil 50 g of a mixture of isobutyl and amyl alcohols, 100 g of methanol, and 74 g of Ca(OH) 2 .
• the mixture is heated to 120°C under a nitrogen flow of 28 L/hr (1.0 std. ft 3 /hr.) for 1 hour, to strip volatiles.
• the resulting mixture is filtered and determined to have a TBN of 142 and to contain 3% Ca and 1.4 % Mg by weight.
• NMR analysis reveals 30% aldehyde functionality, 39% methylene coupling, 17% ether coupling, and 14% hydroxymethyl functionality.
• Example 3 Mg overbased saligenin derivative.
• Carbon dioxide is blown through the mixture for over 3 hours at 28 L/hr (0.5 std. ft 3 /hr) until a direct base number of less than 5 is obtained for the mixture.
• the mixture is stripped to 120°C under a carbon dioxide flow of 28 L/hr (0.5 std. ft 3 /hr) and held at this temperature for 1 hour under nitrogen flow at 14 L/hr (0.5 std. ft 3 /hr)..
• the product is filtered and determined to have a TBN of 130 and to contain 2.8 weight % magnesium. Analysis reveals 32% aldehyde functionality, 41% methylene coupling, 12% ether coupling, and 15% hydroxymethyl functionality.
• the detergents generally can also be borated by treatment with a borating agent such as boric acid.
• a borating agent such as boric acid.
• Typical conditions include heating the detergent with boric acid at 100 to 150°C, the number of equivalents of boric acid being roughly equal to the number of equivalents of metal in the salt.
• U.S. Patent No. 3,929,650 discloses borated complexes and their preparation.
• the functionalized hydrocarbyl-substituted phenol detergent should be sulfur free. This requirement excludes all but small, incidental amounts of sulfur introduced as, for instance, small amounts of linking or bridging groups, or in the form of sulfonic acid groups. These are not substantially sulfurized materials.
• the presence of sulfur in the phenol detergent is generally undesirable because it can lead to decreased compatibility with diesel aftertreament devices and worsened corrosion.
• the amount of S present in the phenol detergent is typically less than 0.5% by weight, such as less than 0.25%, or less than 0.1%, or even completely sulfur free.
• the amount of the detergent component in a completely formulated lubricant will depend, to some extent, on the specific detergent which is selected.
• the amount will typically be 0.5 to 4 percent by weight of the lubricant composition, such as 1 to 2 or 3 percent by weight, or 1.2 to 1.7 percent by weight. Its concentration in a concentrate will be correspondingly increased, to, e.g., 5 to 65 weight percent.
• antioxidants include alkyl phenols, especially hindered alkyl phenols.
• a favored structure, when the alkyl groups are t- butyl groups, is represented by the following formula:
• antioxidants include aromatic amines.
• the antioxidant comprises an alkylated diphenylamine such as nonylated diphenylamine:
• optional components include corrosion inhibitors and rust inhibitors such as various acid-containing compounds.
• Other optional components are extreme pressure and anti-wear agents, which include chlorinated aliphatic hydrocarbons, boron-containing compounds including borate esters and molybdenum compounds.
• Well known classes of antiwear agents include zinc dialkyldithiophosphates and dithiocarbamates.
• Detergents other than the sulfur-free functionalized hydrocarbyl-substituted phenol detergent can also be included.
• Such other detergents are extremely well known and will be based on other acidic materials such as sulfonic acids, carboxylic acids, phosphorus acids, and other phenolic materials.
• Such detergents have been described in detail in numerous references, including U.S. Patents 2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284; and 3,629,109.
• the lubricant will also contain a calcium phenate detergent or a calcium sulfonate detergent, or both.
• viscosity improvers beside the dispersant viscosity improvers described above, can also be present. They include polyisobutenes, polymethacrylate acid esters, polyacrylate acid esters, hydrogenated diene polymers, polyalkyl styrenes, hydrogenated alkenyl aryl conjugated diene copolymers, and polyolefins.
• Pour point depressants are a particularly useful type of additive sometimes included in the lubricating oils described herein. See for example, page 8 of "Lubricant Additives” by C. V. Smalheer and R. Kennedy Smith (Lesius-Hiles Company Publishers, Cleveland, Ohio, 1967).
• Anti-foam agents used to reduce or prevent the formation of stable foam include silicones or organic polymers. Examples of these and additional anti-foam compositions are described in "Foam Control Agents", by Henry T. Kerner (Noyes Data Corporation, 1976), pages 125-162.
• a lubricant composition containing a very low amount of chlorine due to environmental concerns.
• Such lubricants can contain less than 50 parts per million, or less than 40 parts per million chlorine, or even lower amounts.
• Chlorine is often introduced into lubricants along with one or more additive components which may have been prepared using chlorine during the manufacturing process. Removal of residual amounts of chlorine from the additive may be less than complete.
• Recently various approaches have been reported for preparing dispersants and other products with very low chlorine levels. Among those which may be suitable for preparing dispersants for use in the present compositions are those disclosed in U.S. Patent 6,077,909 and references cited therein.
• hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
• hydrocarbyl groups include:
• hydrocarbon substituents that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic- substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
• aliphatic e.g., alkyl or alkenyl
• alicyclic e.g., cycloalkyl, cycloalkenyl
• aromatic-, aliphatic-, and alicyclic- substituted aromatic substituents as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
• substituted hydrocarbon substituents that is, substituents containing non- hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);
• hetero substituents that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms.
• Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
• no more than two, or no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group. It is known that some of the materials described above may interact in the final formulation, so that the components of the final formulation may be different from those that are initially added.
• metal ions of, e.g., a detergent
• the products formed thereby, including the products formed upon employing the composition of the present invention in its intended use, may not susceptible of easy description. Nevertheless, all such modifications and reaction products are included within the scope of the present invention; the present invention encompasses the composition prepared by admixing the components described above.
• Example 4 A lubricant formulation is prepared containing the following components:
• Example 5 A lubricant formulation is prepared containing the following components:
• Examples 6-10 are prepared and evaluated for their wear performance.
• a modified version of the CH-4 Cummins M-11 engine test is used to determine heavy duty diesel valve train wear performance.
• the CH-4 Cummins M- 11 is a turbocharged in-line 6-cylinder, 11 L engine.
• the engine test duration is 200 hours, which is divided into four 50-hour stages. During the first and third stage, the engine is over-fueled and is operated with retarded timing to generate excessive soot, such that the reference oil and test oil produce more than 5% and 4.5% soot, respectively, at 150 hours.
• the second and fourth stages are run at lower speed and higher torque, to induce wear.
• the test used is modified somewhat to provide a shorter duration test with more severe conditions. The results of the test are presented in terms of mg weight loss due to wear at the crossheads. Normal criteria for passing this test include an average weight loss of 6.5 mg or less at 4.5% soot.
• Example 6 is a comparative ("C") example in that it does not contain a dispersant viscosity modifier. While it formally passes the modified Cummins M-11 test, it (as well as the material of Example 7, but unlike the material of Example 10) may not be fully satisfactory in single engine deposit tests designed for low emission engines. Examples 6 and 7 may be compared, however, and it is observed that Example 7 provides significantly improved antiwear performance on the modified Cummins M-11 test. This improvement is observed even though Example 7 has a significantly higher sulfated ash content, a feature which is known to con-elate with diminished antiwear performance. Examination of Examples 8 and 9 illustrates an advantage of another aspect of the present invention.
• Example 9 a significant proportion of the detergent is the overbased magnesium saligenin derivative, while in Example 8 the Mg saligenin salt is not present, although a calcium phenate salt is present.
• the wear results for Example 9 are significantly improved compared with Example 8, illustrating the benefit of using the overbased magnesium saligenin compound. It is noted that the wear performance of these two examples is diminished compared to that of some of the other materials, presumably due to the presence of the fatty friction modifier.
• Example 11 which does not contain the fatty friction modifier, shows excellent antiwear performance.
• Examples 12-17 Emissions data.
• VTEC Variable Temperature Emissions Chamber
• CVS Constant Volume Sample
• CMV Critical Flow Venturi
• FIGE cycle is selected, which is considered to be the most representative European all-round cycle for general truck operations.
• the FIGE cycle is a real world test cycle which was developed from a study of 17 different goods vehicles from small delivery vans to 40 ton articulated vehicles and 3 local public transport buses. From the study a transient driven test cycle was developed in order to allow emission levels to be determined under dynamic operating conditions.
• the FIGE cycle consists of three distinct operating phases:
• Oil formulations are tested in two different vehicle types, both containing heavy duty diesel engine meeting Euro 2 emissions regulations.
• the engine is filled with the test oil and conditioned the evening before the test day, making it necessary only to warm the vehicle to an axle temperature of 75°C before hot start tests.
• the test vehicle is warmed up for 25 minutes between tests or 40 minutes from a cold start, by running at 75 km/h in 8L gear to allow the engine temperature to stabilize.
• Each vehicle is tested using the FIGE cycle three times on each oil.
• the ambient temperature is 22°C.
• Example 4 The formulation of Example 4, above. (A 5W-30 formulation in Synthetic poly- ⁇ - olefin oil.)

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)

Priority Applications (4)

Applications Claiming Priority (4)

Publications (2)

Family

ID=27119952

Family Applications (1)

Country Status (6)

Cited By (1)

Families Citing this family (13)

Family Cites Families (14)

• 2001
  • 2001-10-16 US US09/981,057 patent/US6610637B2/en not_active Expired - Fee Related
• 2002
  • 2002-01-22 WO PCT/US2002/001788 patent/WO2002064709A2/en not_active Ceased
  • 2002-01-22 JP JP2002565027A patent/JP2004524402A/ja active Pending
  • 2002-01-22 AU AU2002237907A patent/AU2002237907B2/en not_active Ceased
  • 2002-01-22 CA CA002437624A patent/CA2437624A1/en not_active Abandoned
  • 2002-01-22 EP EP02704212.6A patent/EP1362088B1/en not_active Expired - Lifetime

Also Published As

Similar Documents

Legal Events