WO2024019952A1 - Deposit control compounds for lubricating compositions - Google Patents

Deposit control compounds for lubricating compositions Download PDF

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Publication number
WO2024019952A1
WO2024019952A1 PCT/US2023/027863 US2023027863W WO2024019952A1 WO 2024019952 A1 WO2024019952 A1 WO 2024019952A1 US 2023027863 W US2023027863 W US 2023027863W WO 2024019952 A1 WO2024019952 A1 WO 2024019952A1
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Prior art keywords
composition
lubricating
weight
alkaline earth
earth metal
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PCT/US2023/027863
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French (fr)
Inventor
Edward P. SAMPLER
Alexandra Mayhew
Thomas Derevjanik
Gary M. Walker
John-Louis Diflavio
Yanshi Zhang
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The Lubrizol Corporation
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Publication of WO2024019952A1 publication Critical patent/WO2024019952A1/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/24—Polyethers
    • C10M145/26—Polyoxyalkylenes
    • C10M145/36—Polyoxyalkylenes etherified
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
    • 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
    • C10N2030/04—Detergent property or dispersant property
    • 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
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy

Definitions

  • the disclosed technology relates to lubricating compositions for internal combustion engines, such as diesel engines (such as heavy-duty diesel engines) or gasoline direct injection engines (such as with turbocharging) and methods of lubricating such engines by supplying the engines with the lubricating composition(s).
  • the lubricating compositions disclosed herein may improve fuel economy and/or wear protection.
  • Lubricating compositions are used for the smooth operation of internal combustion engines.
  • the engine oils for internal combustion engines in particular serve to, for example: (i) lubricate various sliding interfaces between the piston ring and cylinder liner, in bearings of the crank shaft and the connecting rod, and in the valve driving mechanism including cams and valve lifters; (ii) cool the engine; (iii) clean and disperse the combustion products; and/or (iv) prevent corrosion and consequent rust formation.
  • the stringent requirements for high performance engines in recent years has meant greater demand from improved lubricants used in such engines.
  • the disclosed technology provides a compound which may provide deposit control in lubricating compositions, while maintaining adequate viscosity.
  • a lubricating composition comprising: (a) an oil of lubricating viscosity; (b) a compound according to formula I: wherein, independently for each molecule of the compound: R 1 is an aliphatic hydrocarbyl group having from 10 to 24 carbon atoms; R 2 is CH3 or C2H5; and n is an integer from 3 to 8; and (c) an alkaline earth metal alkyl detergent.
  • R 1 is an aliphatic hydrocarbyl group having from 10 to 24 carbon atoms
  • R 2 is CH3 or C2H5
  • n is an integer from 3 to 8
  • an alkaline earth metal alkyl detergent provided is a deposit control additive according to formula I as described above.
  • a lubricating composition comprising: (a) an oil of lubricating viscosity; (b) a compound according to formula I: wherein, independently for each molecule of the compound: R 1 is an aliphatic hydrocarbyl group having from 10 to 24 carbon atoms; R 2 is CH3 or C2H5; and n is an integer from 3 to 8; and (c) an alkaline earth metal alkyl detergent.
  • alkaline earth metal alkyl detergent comprises a surfactant portion which is at least one of phenate, salicylate, sulfonate, saligenin, or salixarate.
  • at least one additional additive comprising at least one of antioxidants, detergents, dispersants, antiwear agent, corrosion inhibitors, viscosity modifiers, metal passivators, pour point depressants, seal compatibility agents, antifoam agents, extreme pressure agents, or friction modifiers.
  • a method of lubricating a heavy duty diesel engine comprising supplying the composition of any one of embodiments 1 to 30 to the engine.
  • a method of lubricating a compression-ignition internal combustion engine having a laden mass over 2,700 kg comprising supplying the composition of any one of embodiments 1 to 30 to the engine.
  • a method of lubricating the crankcase of a compression-ignition or spark- ignited engine comprising supplying the composition of any one of embodiments 1 to 30 to the crankcase.
  • condensation product is intended to encompass esters, amides, imides and other such materials that may be prepared by a condensation reaction of an acid or a reactive equivalent of an acid (e.g., an acid halide, anhydride, or ester) with an alcohol or amine, irrespective of whether a condensation reaction is actually performed to lead directly to the product.
  • an acid e.g., an acid halide, anhydride, or ester
  • a particular ester may be prepared by a transesterification reaction rather than directly by a condensation reaction.
  • the resulting product is still considered a condensation product.
  • each chemical component described herein is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, that is, on a 100% active chemical basis, unless otherwise indicated. Unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.
  • hydrocarbyl refers to a group having a carbon atom directly attached to the remainder of the molecule, where the group includes at least carbon and hydrogen atoms. If the hydrocarbyl group comprises more than one carbon atom, then those carbons need not necessarily be linked to each other. For example, at least two of the carbons may be linked via a suitable element or group.
  • hydrocarbyl refers to a group having a carbon atom directly attached to the remainder of the molecule, where the group consists of carbon, hydrogen, optionally one or more heteroatoms provided the heteroatoms do not alter the predominantly hydrocarbon nature of the substituent.
  • the heteroatom may to link at least two of the carbons in the hydrocarbyl group, and optionally no more than two non-hydrocarbon substituents.
  • Suitable heteroatoms will be apparent to those skilled in the art and include, for instance, sulphur, nitrogen, oxygen, phosphorus and silicon.
  • the hydrocarbyl contains heteroatoms, optionally, no more than two heteroatoms will be present for every ten carbon atoms in the hydrocarbyl group.
  • Suitable non-hydrocarbon substituents will also be apparent to those skilled in the art and include, for instance, halo, hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulphoxy.
  • hydrocarbyl s within the context of the present technology therefore include: (i) hydrocarbon groups selected from aliphatic (e.g. alkyl or alkenyl), alicyclic (e.g. cycloalkyl, cycloalkenyl, cycloalkadienyl), and aromatic groups; (ii) substituted hydrocarbon groups, selected from hydrocarbon groups defined in (i) substituted with no more than two nonhydrocarbon substituents and/or one or more hydrocarbon substituents, the non-hydrocarbon substituents being selected from the group consisting of halo, hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulphoxy; and/or (iii) hetero-containing hydrocarbon groups, selected from hydrocarbon groups defined in (i) containing one or more heteroatom in the ring or chain, provided that the group has no more than two heteroatoms present for every ten carbon atoms in the group, the heteroatoms being
  • hetero-containing hydrocarbon groups may be substituted with no more than two non-hydrocarbon substituents and/or one or more hydrocarbon substituents.
  • hydrocarbyl refers to a group having a carbon atoms directly attached to the remainder of the molecule, where the group consists of carbon and hydrogen atoms.
  • the indefinite article “a”/“an” is intended to mean one or more than one.
  • the phrase “at least one” means one or more than one of the following terms.
  • “a”/“an” and “at least one” may be used interchangeably.
  • “at least one of A, B or C” means that just one of A, B or C may be included, and any mixture of two or more of A, B and C may be included, in alternative embodiments.
  • the term “substantially free of’ means that a component does not include any intentional addition of the material which the component is “substantially free of’.
  • the component may include a material which the component is “substantially free of’ at no more than impurity levels, which may be the result of incomplete chemical reactions and/or unintended/undesired (but perhaps unavoidable) reaction products.
  • the transitional term “comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps.
  • the term also encompass, as alternative embodiments, the phrases “consisting essentially of’ and “consisting of,” where “consisting of’ excludes any element or step not specified and “consisting essentially of’ permits the inclusion of additional un-recited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.
  • a lubricating composition comprising: (a) an oil of lubricating viscosity; (b) a compound according to formula I: wherein, independently for each molecule of the compound: R 1 is an aliphatic hydrocarbyl group having from 10 to 24 (such as from 12 to 24, from 14 to 24, from 16 to 24, from 18 to 24, from 20 to 24, from 22 to 24, from 10 to 22, from 12 to 22, from 14 to 22, from 16 to 22, from 18 to 22, from 20 to 22, from 10 to 20, from 12 to 20, from 14 to 20, from 16 to 20, from 18 to 20, from 10 to 18, from 12 to 18, from 14 to 18, from 16 to 18, from 10 to 16, from 12 to 16, from 14 to 16, from 10 to 14, from 12 to 14, or from 10 to 12) carbon atoms; R 2 is CH3 or C2H5; and n is an integer from 3 to 8 (such as from 4 to 8, from 5 to 8, from 6 to 8, from 7 to 8, from 3 to 7, from 4 to 7, from 5 to 7, from 6 to 7, from 3 to 6, from 4 to 6, from 5 to 6,
  • the lubricating compositions described herein may find use in various applications as a lubricant composition for: internal combustion engines, including gasoline engines and/or spark-ignited engines, such as passenger car engines diesel engines, or compression-ignited engines, such as heavy duty diesel truck engines, natural gas fueled engines, such as stationary power engines, two-cycle engines, aviation piston engines and turbine engines, marine and railroad diesel engines; and hydrocarbon fuels for an internal combustion engine such as middle distillate fuels such as jet fuel, kerosene and diesel fuels.
  • internal combustion engines including gasoline engines and/or spark-ignited engines, such as passenger car engines diesel engines, or compression-ignited engines, such as heavy duty diesel truck engines, natural gas fueled engines, such as stationary power engines, two-cycle engines, aviation piston engines and turbine engines, marine and railroad diesel engines; and hydrocarbon fuels for an internal combustion engine such as middle distillate fuels such as jet fuel, kerosene and diesel fuels.
  • the lubricating compositions disclosed herein comprise an oil of lubricating viscosity.
  • oils may include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils, or mixtures thereof.
  • a more detailed description of unrefined, refined and re-refined oils is provided in WO 2008/147704 Al, paragraphs [0054] to [0056], A more detailed description of natural and synthetic lubricating oils is described in paragraphs [0058] to [0059] respectively of WO 2008/147704 Al.
  • Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes.
  • oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure, as well as other gas-to-liquid procedures.
  • Suitable oils may be produced from biological (i.e., natural) sources or by bioengineered processes. This includes both naturally-occurring oils, such as vegetable oils and triglyceride oils, which may be further refined or purified by standard processes, and those oils that may be derived by biological conversion of a natural chemical into oil directly or by bioformation of building block pre-cursor molecules capable of being further converted into oil by known processes.
  • Oils of lubricating viscosity may also be defined as specified in the April 2008 version of “Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils”, section 1.3, “Base Stock Categories”. The API Guidelines are also summarized in US 7,285,516 B2 see column 11, line 64 to column 12, line 10).
  • the oil of lubricating viscosity may be an API Group I base oil, Group II base oil, Group III base oil, or Group IV base oil (e.g., mineral oil), an ester or other synthetic oil, a Group V base oil, or any mixtures thereof.
  • the amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 percent by weight the sum of the amount of the additives of the disclosed compositions and the other performance additives. Illustrative amounts may include 50 to 99 percent by weight, or 60 to 98, or 70 to 95, or 80 to 94, or 85 to 93 percent by weight, based on the total weight of the composition.
  • the lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant.
  • the lubricating compositions described herein are in the form of a concentrate (which may be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of these additives to the oil of lubricating viscosity and/or to diluent oil include the ranges of 1 :99 to 99: 1 by weight, or 80:20 to 10:90 by weight.
  • the lubricating composition described herein include at least 50, or at least 60, or at least 70, or at least 80 percent by weight of an oil of lubricating viscosity.
  • the composition has a high temperature high shear viscosity of from 1.5 to 4.5 (such as from 1.6 to 4.5, from 1.7 to 4.5, from 1.8 to 4.5, from 1.9 to 4.5, from 2 to 4.5, from 2.1 to 4.5, from 2.2 to 4.5, from 2.3 to 4.5, from 2.4 to 4.5, from 2.5 to 4.5, from 2.6 to 4.5, from 2.7 to 4.5, from 2.8 to 4.5, from 2.9 to 4.5, from 3 to 4.5, from 3.1 to 4.5, from 3.2 to 4.5, from 3.3 to 4.5, from 3.4 to 4.5, from 3.5 to 4.5, from 3.6 to 4.5, from 3.7 to 4.5, from 3.8 to 4.5, from 3.9 to 4.5, from 4 to 4.5, from 4.
  • 1.5 to 4.5 such as from 1.6 to 4.5, from 1.7 to 4.5, from 1.8 to 4.5, from 1.9 to 4.5, from 2 to 4.5, from 2.1 to 4.5, from 2.2 to 4.5, from
  • 3.6 from 3.1 to 3.6, from 3.2 to 3.6, from 3.3 to 3.6, from 3.4 to 3.6, from 3.5 to 3.6, from 1.5 to 3.5, from 1.6 to 3.5, from 1.7 to 3.5, from 1.8 to 3.5, from 1.9 to 3.5, from 2 to 3.5, from 2.1 to 3.5, from 2.2 to 3.5, from 2.3 to 3.5, from 2.4 to 3.5, from 2.5 to 3.5, from 2.6 to 3.5, from
  • 2.3 to 2.4 from 1.5 to 2.3, from 1.6 to 2.3, from 1.7 to 2.3, from 1.8 to 2.3, from 1.9 to 2.3, from 2 to 2.3, from 2.1 to 2.3, from 2.2 to 2.3, from 1.5 to 2.2, from 1.6 to 2.2, from 1.7 to 2.2, from 1.8 to 2.2, from 1.9 to 2.2, from 2 to 2.2, from 2.1 to 2.2, from 1.5 to 2.1, from 1.6 to 2.1, from 1.7 to 2.1, from 1.8 to 2.1, from 1.9 to 2.1, from 2 to 2.1, from 1.5 to 2, from 1.6 to 2, from
  • the alkaline earth metal alkyl detergent contributes from 2 to 7 (such as from 2 to 6, from 2 to 5, from 2 to 4, from 2 to 3, from 3 to 7, from 3 to 6, from 3 to 5, from 3 to 4, from 4 to 7, from 4 to 6, from 4 to 5, from 5 to 7, from 5 to 6, or from 6 to 7) TBN to the composition as measured by ASTM D4739.
  • TBN refers to total base number, as is known to those of skill in the art When referring to ASTM D4739 herein, what is meant is version 11 published February 7, 2018.
  • the composition has a sulfated ash level of less than or equal to 1 percent (such as less than or equal to 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1) by weight, based on the total weight of the composition, as measured by ASTM D874.
  • ASTM D874 When referring to ASTM D874 herein, what is meant is version 13a published June 1, 2018.
  • the alkaline earth metal alkyl detergent contributes from 6 to 7 TBN to the composition as measured by ASTM D4739.
  • the alkaline earth metal alkyl detergent contributes from 2 to 3.5 TBN to the composition as measured by ASTM D4739.
  • the compound according to formula I is present in the composition in an amount of from 1 to 10 (such as from 2 to 10, from 3 to 10, from 4 to 10, from 5 to 10, from 6 to 10, from 7 to 10, from 8 to 10, from 9 to 10, from 1 to 9, from 2 to 9, from 3 to 9, from 4 to 9, from 5 to 9, from 6 to 9, from 7 to 9, from 8 to 9, from 1 to 8, from 2 to 8 from 3 to 8, from 4 to 8, from 5 to 8, from 6 to 8, from 7 to 8, from 1 to 7, from 2 to 7, from 3 to 7, from 4 to 7, from 5 to 7, from 6 to 7, from 1 to 6, from 2 to 6, from 3 to 6, from 4 to 6, from 5 to 6, from 1 to 5, from 2 to 5, from 3 to 5, from 4 to 5, from 1 to 4, from 2 to 4, from 3 to 4, from 1 to 3, from 2 to 3, or from 1 to 2) percent by weight, based on the total weight of the composition.
  • 1 to 10 such as from 2 to 10, from 3 to 10, from 4 to 10, from 5 to 10, from 6 to 10, from 7 to 10, from 8 to 10, from 9 to 10, from 1
  • the composition has a TBN of from 2 to 12 (such as from
  • the alkaline earth metal alkyl detergent is present in the composition in an amount less than 3.5 (such as less than 3.4, 3.3, 3.2, 3.1, 3, 2.9, 2.8, 2.7, 2.6,
  • the alkaline earth metal alkyl detergent is present in the composition in an amount from greater than 0 to 3.5 (such as from 0.1 to 3.5, from 0.2 to 3.5, from 0.3 to 3.5, from 0.4 to 3.5, from 0.5 to 3.5, from 0.6 to 3.5, from 0.7 to 3.5, from 0.8 to 3.5, from 0.9 to 3.5 (such as from 0.1 to 3.5, from 0.2 to 3.5, from 0.3 to 3.5, from 0.4 to 3.5, from 0.5 to 3.5, from 0.6 to 3.5, from 0.7 to 3.5, from 0.8 to 3.5, from 0.9 to
  • 1.3 to 1.4 from greater than 0 to 1.3, from 0.1 to 1.3, from 0.2 to 1.3, from 0.3 to 1.3, from 0.4 to 1.3, from 0.5 to 1.3, from 0.6 to 1.3, from 0.7 to 1.3, from 0.8 to 1.3, from 0.9 to 1.3, from 1 to 1.3, from 1.1 to 1.3, from 1.2 to 1.3, from greater than 0 to 1.2, from 0.1 to 1.2, from 0.2 to 1.2, from 0.3 to 1.2, from 0.4 to 1.2, from 0.5 to 1.2, from 0.6 to 1.2, from 0.7 to 1.2, from 0.8 to 1.2, from 0.9 to 1.2, from 1 to 1.2, from 1.1 to 1.2, from greater than 0 to 1.1, from 0.1 to 1.1, from 0.2 to 1.1, from 0.3 to 1.1, from 0.4 to 1.1, from 0.5 to 1.1, from 0.6 to 1.1, from 0.7 to 1.1, from 0.8 to 1.2, from 0.9 to 1.2,
  • the alkaline earth metal alkyl detergent comprises an alkaline earth metal which is at least one of magnesium or calcium. In certain embodiments, the alkaline earth metal alkyl detergent comprises a surfactant portion which is at least one of phenate, salicylate, sulfonate, saligenin, or salixarate. In certain embodiments, the alkaline earth metal alkyl detergent comprises a surfactant portion which is at least one of salicylate or sulfonate.
  • the composition comprises less than 200 (such as less than 190, less than 180, less than 170, less than 160, less than 150, less than 140, less than 130, less than 120, less than 110, less than 100, less than 90, less than 80, less than 70, less than 60, less than 50, less than 40, less than 30, less than 20, or less than 10) ppm by weight magnesium, based on the total weight of the composition.
  • the composition may be substantially free of magnesium-containing material.
  • the composition will not include any intentionally-added, magnesium-containing material.
  • the composition further comprises an aromatic amine, maleic anhydride, ethylene-propylene copolymer dispersant in an amount of from 0.1 to 5 (such as from 0.5 to 5, from 1 to 5, from 1.5 to 5, from 2 to 5, from 2.5 to 5, from 3 to 5, from 3.5 to 5, from 4 to 5, from 4.5 to 5, from 0.1 to 4.5, from 0.5 to 4.5, from 1 to 4.5, from 1.5 to 4.5, from 2 to 4.5, from 2.5 to 4.5, from 3 to 4.5, from 3.5 to 4.5, from 4 to 4.5, from 0.1 to 4, from 0.5 to 4, from 1 to 4, from 1.5 to 4, from 2 to 4, from 2.5 to 4, from 3 to 4, from 3.5 to 4, from 0.1 to 3.5, from 0.5 to 3.5, from 1 to 3.5, from 1.5 to 3.5, from 2 to 3.5, from 2.5 to 3.5, from 3 to 3.5, from 0.1 to 3, from 0.5 to 3, from 1 to 3, from 1.5 to 3, from 2 to 3, from 2.5 to 3, from 0.1 to 2.5
  • the composition further comprises at least one additional additive comprising at least one of antioxidants, detergents (other than the alkaline earth metal alkyl detergent described herein), dispersants, antiwear agent, corrosion inhibitors, viscosity modifiers (other than the DVM discussed above), metal passivators, pour point depressants, seal compatibility agents, antifoam agents, extreme pressure agents, or friction modifiers.
  • additional additive comprising at least one of antioxidants, detergents (other than the alkaline earth metal alkyl detergent described herein), dispersants, antiwear agent, corrosion inhibitors, viscosity modifiers (other than the DVM discussed above), metal passivators, pour point depressants, seal compatibility agents, antifoam agents, extreme pressure agents, or friction modifiers.
  • Antioxidants encompass phenolic antioxidants, which may comprise a butyl substituted phenol containing 2 or 3 t-butyl groups. The para position may also be occupied by a hydrocarbyl group, an ester-containing group, or a group bridging two aromatic rings. Antioxidants also include aromatic amines, such as nonylated diphenylamines or alkylated phenylnaphthylamine. Other antioxidants include sulfurized olefins, titanium compounds, and molybdenum compounds.
  • US 4,285,822 discloses lubricating oil compositions containing a molybdenum and sulfur containing composition.
  • US 2006/0217271 Al discloses a variety of titanium compounds, including titanium alkoxides and titanated dispersants, which materials may also impart improvements in deposit control and fdterability.
  • Other titanium compounds include titanium carboxylates such as neodecanoate. If a titanium compound is present, its amount may be such as to provide 15 to 1000 or 25 to 200 parts per million titanium.
  • antioxidants will, of course, depend on the specific antioxidant and its individual effectiveness, but illustrative total amounts can be 0.01 to 5 (such as from 0.15 to 4.5, or from 0.2 to 4) percent by weight, based on the total weight of the composition. Additionally, more than one antioxidant may be present, and certain combinations of these can be synergistic in their combined overall effect.
  • the detergent may comprise an overbased metal detergent.
  • Overbased detergents are generally homogeneous Newtonian systems having a metal content in excess of that which would be present for neutralization according to the stoichiometry of the metal and the detergent anion. The amount of excess metal is commonly expressed in terms of metal ratio, that is, the ratio of the total equivalents of the metal to the equivalents of the acidic organic compound.
  • Overbased materials are prepared by reacting an acidic material (such as carbon dioxide) with an acidic organic compound, an inert reaction medium (such as mineral oil), a stoichiometric excess of a metal base, and a promoter (such as a phenol or alcohol).
  • an acidic material such as carbon dioxide
  • an inert reaction medium such as mineral oil
  • a promoter such as a phenol or alcohol
  • Overbased detergents may be characterized by TBN (ASTM D4739), the amount of strong acid needed to neutralize all of the material's basicity, expressed as mg KOH per gram of sample. Since overbased detergents are commonly provided in a form which contains diluent oil, for the purpose of this document, TBN is to be recalculated to an oil-free basis by dividing by the fraction of the detergent (as supplied) that is not oil. Some suitable detergents may have a TBN of 100 to 800, or 150 to 750, or 400 to 700.
  • the metal compounds suitable in making the basic metal salts are generally any Group 1 or Group 2 metal compounds (CAS version of the Periodic Table of the Elements). Examples include alkali metals such as sodium, potassium, lithium, copper, magnesium, calcium, barium, zinc, and cadmium. In certain embodiments, the metals are sodium, magnesium, or calcium; or calcium or magnesium; or calcium.
  • the anionic portion of the salt may be hydroxide, oxide, carbonate, borate, or nitrate.
  • the lubricant can contain an overbased sulfonate detergent.
  • Suitable sulfonic acids include sulfonic and thiosulfonic acids, including mono- or polynuclear aromatic or cycloaliphatic compounds.
  • Certain oil-soluble sulfonates can be represented by R 2 - T- (SO3')a or R 3 -(SO3')b, where a and b are each at least one; T is a cyclic nucleus such as benzene or toluene; R 2 is an aliphatic group such as alkyl, alkenyl, alkoxy, or alkoxyalkyl; (R 2 )- T typically contains a total of at least 15 carbon atoms; and R 3 is an aliphatic hydrocarbyl group typically containing at least 15 carbon atoms.
  • the groups T, R 2 , and R 3 can also contain other inorganic or organic substituents.
  • the sulfonate detergent may be a predominantly linear alkylbenzenesulfonate detergent having a metal ratio of at least 8 as described in paragraphs [0026] to [0037] of US 2005/0065045 Al.
  • the linear alkyl group may be attached to the benzene ring anywhere along the linear chain of the alkyl group, but often in the 2, 3 or 4 position of the linear chain, and in some instances predominantly in the 2 position.
  • Another overbased material is an overbased phenate detergent.
  • the phenols suitable in making phenate detergents can be represented by (R x ) a — Ar — (OH)b, where R 1 is an aliphatic hydrocarbyl group of 4 to 400, or 6 to 80, or 6 to 30, or 8 to 25, or 8 to 15 carbon atoms; Ar is an aromatic group such as benzene, toluene or naphthalene; a and b are each at least one, the sum of a and b being up to the number of displaceable hydrogens on the aromatic nucleus of Ar, such as 1 to 4, or 1 to 2. There is typically an average of at least 8 aliphatic carbon atoms provided by the R 1 groups for each phenol compound. Phenate detergents are also sometimes provided as sulfur-bridged species.
  • Alkylphenols are often used as constituents in and/or building blocks for overbased detergents.
  • Alkylphenols may be used to prepare phenate, salicylate, salixarate, or saligenin detergents or mixtures thereof.
  • Suitable alkylphenols may include para-substituted hydrocarbyl phenols.
  • the hydrocarbyl group may be linear or branched aliphatic groups of 1 to 60 carbon atoms, 8 to 40 carbon atoms, 10 to 24 carbon atoms, 12 to 20 carbon atoms, or 16 to 24 carbon atoms.
  • the alkylphenol overbased detergent is prepared from an alkylphenol or mixture thereof that is free of or substantially free of p-dodecylphenol.
  • the lubricating composition of the invention contains less than 0.3 weight percent of alkylphenol, less than 0 1 weight percent of alkylphenol, or less than 0.05 weight percent of alkylphenol.
  • the overbased material is an overbased saligenin detergent.
  • Overbased saligenin detergents are commonly overbased magnesium salts which are based on saligenin derivatives.
  • a general example of such a saligenin derivative can be represented by the formula where X is — CHO or — CH2OH, Y is — CH2 — or — CH2OCH2 — , and the — CHO groups typically comprise at least 10 mole percent of the X and Y groups;
  • M is hydrogen, ammonium, or a valence of a metal ion (that is, if M is multivalent, one of the valences is satisfied by the illustrated structure and other valences are satisfied by other species such as anions or by another instance of the same structure),
  • Ri is a hydrocarbyl group of 1 to 60 carbon atoms, m is 0 to 10, and 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
  • one of the X groups can be hydrogen.
  • M is a valence of a Mg ion or a mixture of Mg and hydrogen.
  • Saligenin detergents are disclosed in greater detail in US 6,310,009 Bl, with special reference to their methods of synthesis (column 8 and Example 1) and preferred amounts of the various species of X and Y (column 6).
  • Salixarate detergents are overbased materials that can be represented by a compound comprising at least one unit of formula (A) and/or formula (B) and each end of the compound having a terminal group of formula (C) and/or (D):
  • R 3 is hydrogen, a hydrocarbyl group, or a valence of a metal ion;
  • R 2 is hydroxyl or a hydrocarbyl group, and j is 0, 1, or 2;
  • R 6 is hydrogen, a hydrocarbyl group, or a hetero- substituted hydrocarbyl group; either R 4 is hydroxyl and R 5 and R 7 are independently either hydrogen, a hydrocarbyl group, or hetero-substituted hydrocarbyl group, or else R 5 and R 7 are both hydroxyl and R 4 is hydrogen, a hydrocarbyl group, or a hetero-substituted hydrocarbyl group; provided that at least one of R 4 , R 5 , R 6 and R 7 is hydrocarbyl containing at least 8 carbon atoms; and wherein the molecules on average contain at least one of unit (A) or (C) and at least one of unit (B) or (
  • formaldehyde or a formaldehyde equivalent e.g., paraformaldehyde, formalin.
  • Glyoxylate detergents are similar overbased materials which are based on an anionic group which, in certain embodiments, may have the structure wherein each R is independently an alkyl group containing at least 4, or at least 8 carbon atoms, provided that the total number of carbon atoms in all such R groups is at least 12, or at least 16, or at least 24. Alternatively, each R can be an olefin polymer substituent.
  • the acidic material from which the overbased glyoxylate detergent is prepared is the condensation product of a hydroxyaromatic material such as a hydrocarbyl-substituted phenol with a carboxylic reactant such as glyoxylic acid or another omega-oxoalkanoic acid.
  • a hydroxyaromatic material such as a hydrocarbyl-substituted phenol
  • carboxylic reactant such as glyoxylic acid or another omega-oxoalkanoic acid.
  • the overbased detergent can also be an overbased salicylate, e.g., an alkali metal or alkaline earth metal salt of a substituted salicylic acid.
  • the salicylic acids may be hydrocarbyl- substituted wherein each substituent contains an average of at least 8 carbon atoms per substituent and 1 to 3 substituents per molecule.
  • the substituents can be polyalkene substituents.
  • the hydrocarbyl substituent group contains 7 to 300 carbon atoms and can be an alkyl group having a molecular weight of 150 to 2000.
  • Overbased salicylate detergents and their methods of preparation are disclosed in US 4,719,023 and US 3,372,116.
  • Salicylate detergents and overbased salicylate detergents may be prepared in at least two different manners. Carbonylation (also referred to as carboxylation) of a p-alkylphenol is described in many references, including US 8,399,388 B2. Carbonylation may be followed by overbasing to form overbased salicylate detergent. Suitable p-alkylphenols include those with linear and/or branched hydrocarbyl groups of 1 to 60 carbon atoms. Salicylate detergents may also be prepared by alkylation of salicylic acid, followed by overbasing, as described in US 7,009,072 B2.
  • Salicylate detergents prepared in this manner may be prepared from linear and/or branched alkylating agents (usually 1-olefins) containing 6 to 50 carbon atoms, 10 to 30 carbon atoms, or 14 to 24 carbon atoms.
  • the overbased detergent of the invention is a salicylate detergent.
  • the salicylate detergent of the invention may be substantially free of, or free of unreacted p-alkylphenol.
  • the salicylate detergent of the invention is prepared by alkylation of salicylic acid.
  • overbased detergents can include overbased detergents having a Mannich base structure, as disclosed in US 6,569,818 B2.
  • the hydrocarbyl substituents on hydroxy-substituted aromatic rings in the above detergents are free of or substantially free of C12 aliphatic hydrocarbyl groups. In some embodiments such hydrocarbyl substituents contain at least 14, or at least 18 carbon atoms.
  • Any suitable dispersants may be used, as would be understood by one of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable dispersants. In certain embodiments, the dispersant(s) may be succinimide dispersants.
  • the succinimide dispersants may be present in the lubricating composition in an amount of from 0.25 to 5 (such as from 0.25 to 4.5, from 0.25 to 4.25, from 0.5 to 4, from 1 to 3.5, from 0.35 to 1.8, from 0.5 to 1.5, or from 1 to 1.45) percent by weight, based on the total weight of the composition.
  • Suitable succinimide dispersants include, without limitation, N-substituted long chain alkenyl succinimides, having a variety of chemical structures, such as where each R x is independently an alkyl group, such as a polyisobutylene group, and the R 1 groups may have a number average molecular weight (Mn) of 1000 to 3,500.
  • the R 2 groups are alkylene groups, such as ethylene (C2H4) groups.
  • the Mn of the R 1 groups may alternatively be 1500 to 3000, or 2800 to 2500.
  • Such molecules may be derived from reaction of an alkenyl acylating agent with a polyamine, and a wide variety of linkages between the two moieties is possible beside the simple imide structure shown above, including a variety of amides and quaternary ammonium salts.
  • the amine portion is shown as an alkylene polyamine, although other aliphatic and aromatic mono- and polyamines may also be used. Also, a variety of modes of linkage of the R 1 groups onto the imide structure are possible, including various cyclic linkages.
  • the ratio of the carbonyl groups of the acylating agent to the nitrogen atoms of the amine may be 1 :0.5 to 1:3, and in other instances 1 : 1 to 1 :2.75, or 1: 1.5 to 1 :2.5.
  • Succinimide dispersants are more fully described in US 4,234,435, US 3,172,892, and EP 0 355 895 Bl .
  • Succinimides made by the so-called conventional (or chlorine) route as well as by the thermal or direct alkylation or “ene” route are included, as disclosed in the abovereferenced patent documents.
  • Succinimide dispersants made by the different routes may be characterized by differences in the detailed structures, whereby the R 1 groups are attached.
  • Dispersants may also be post-treated with various agents such as borating agents (e.g., boric acid) to make borated dispersants.
  • TBN of the dispersant will depend on the amount of amine functionality contained therein, and may be 10 to 60, or 12 to 50, or 15 to 40, or 20 to 35, or 30 to 35. Other embodiments may include 10 to 30, or 12 to 25, or 20 to 60, or 30 to 50 mg KOH/g (all calculated on an oil-free basis).
  • Succinimide dispersants can also be post-treated by reaction with any of a variety of agents. Among these are urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, and phosphorus compounds. References detailing such treatment are listed in US 4,654,403.
  • the dispersant may be or comprise a dispersant viscosity modifier (because the material may have both dispersant and viscosity modifying properties, e.g., as described below, the olefin polymer may serve to impart viscosity modifier performance and the reacted amine may provide nitrogen or other polar functionality that may impart dispersant performance).
  • the dispersant viscosity modifier may comprise an olefin polymer that has been modified by the addition of a polar moiety.
  • the dispersant viscosity modifier may comprise an ashless condensation reaction product of an olefin polymer with grafted carboxylic acid (or equivalent) functionality, reacted with a monoamine or a polyamine which may have a single primary amino group. If the olefin polymer is an ethyl ene/propylene copolymer, then said polyamine is not a poly(ethyleneamine).
  • Various dispersant viscosity modifiers have been used in the lubrication of heavy-duty diesel engines, where they perform the role of dispersing soot arising from the combustion of the diesel fuel.
  • Gasoline (spark-ignited) engines generally do not generate soot and thus such dispersant viscosity modifiers may not be used in gasoline engines for the dispersion of soot.
  • the use of the present dispersant viscosity modifiers in a non-sooted engine environment permits reduction in the amount of conventional dispersant, such as succinimide dispersant, while retaining dispersant performance and permitting greater flexibility in formulation of the lubricant composition to meet performance targets.
  • the olefin polymer is an ethylene-a-olefin copolymer.
  • the functionalized ethylene-a-olefin copolymer may include those described in US 4,863,623 (column 2, line 15, to column 3, line 52) or in WO 2006/015130 Al (paragraph [0008] and paragraphs [0065] to [0073]).
  • the olefm polymers may be functionalized by modifying the polymer by the addition of a polar moiety.
  • the functionalized copolymer is the reaction product of an olefm polymer grafted with an acylating agent.
  • the acylating agent may be an ethylenically unsaturated acylating agent.
  • Suitable acylating agents are typically a, p-un saturated compounds having at least one ethylenic bond (prior to reaction) and at least one, for example two, carboxylic acid (or its anhydride) groups or a polar group which is convertible into said carboxyl groups by oxidation or hydrolysis.
  • the acylating agent grafts onto the olefm polymer to give two carboxylic acid functionalities.
  • suitable acylating agents include maleic anhydride, chlormaleic anhydride, itaconic anhydride, or the reactive equivalents thereof, for example, the corresponding dicarboxylic acids, such as maleic acid, fumaric acid, cinnamic acid, (meth)acrylic acid, the esters of these compounds and the acid chlorides of these compounds.
  • the functionalized ethylene-a-olefin copolymer comprises an olefm copolymer grafted with the acyl group, which is further functionalized with a hydrocarbyl amine, a hydrocarbyl alcohol group, amino- or hydroxy- terminated polyether compounds, and mixtures thereof.
  • the hydrocarbyl amine may be selected from aromatic amines, aliphatic amines, and mixtures thereof.
  • corrosion inhibitors include those described in WO 2006/047486 Al, octyl octanamide, condensation products of dodecenyl succinic acid or anhydride and a fatty acid (such as oleic acid) with a polyamine may be present in the lubricating compositions described herein.
  • the corrosion inhibitors include Synalox® (a registered trademark of The Dow Chemical Company) corrosion inhibitors. Synalox® corrosion inhibitors may be a homopolymer or copolymer of propylene oxide. The Synalox®. corrosion inhibitors are described in more detail in a product brochure with Form No. 118-01453-0702 AMS, published by The Dow Chemical Company, entitled “SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications”.
  • the lubricating compositions described herein may further comprise: metal deactivators, including derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles, benzimidazoles, 2- alkyldithiobenzimidazoles, and/or 2-alkyldithiobenzothiazoles; foam inhibitors, including copolymers of ethyl acrylate and 2-ethylhexylacrylate, and/or copolymers of ethyl acrylate and 2-ethylhexylacrylate and vinyl acetate; demulsifiers, including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides, and/or (ethylene oxide/propylene oxide) polymers; and pour point depressants, including esters of maleic anhydride- styrene, polymethacrylates, polyacrylates, and/or polyacrylamides.
  • any other suitable viscosity modifiers may be used, as would be understood by one of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable viscosity modifiers.
  • the oil of lubricating viscosity will generally be selected so as to provide, among other properties, an appropriate viscosity (kinematic viscosity and/or high temperature high shear viscosity) and viscosity index.
  • a viscosity modifier other than the dispersant viscosity modifier as described above, that is to say, a supplemental viscosity modifier. While the viscosity modifier is sometimes considered a part of the base oil, it may be considered as a separate component, the selection of which is within the abilities of the person skilled in the art.
  • Viscosity modifiers may be polymeric materials which may be hydrocarbon-based polymers generally having number average molecular weights from 25,000 to 500,000, e.g., from 50,000 to 300,000, or from 50,000 to 200,000.
  • Hydrocarbon polymers can be used as viscosity index improvers.
  • examples include homopolymers and polymers of two or more monomers of C2 to C30, e.g., C2 to Cs olefins, including both alphaolefins and internal olefins, which may be straight or branched, aliphatic, aromatic, alkyl-aromatic, or cycloaliphatic.
  • Examples include ethylene-propylene copolymers, generally referred to as OCP's, prepared by copolymerizing ethylene and propylene by known processes.
  • Hydrogenated styrene-conjugated diene copolymers or hydrogenated conjugated diene polymers are other classes of viscosity modifiers. These polymers include polymers which are hydrogenated or partially hydrogenated homopolymers, and also include random, tapered, star, and block interpolymers.
  • the term “styrene” includes various substituted styrenes.
  • the conjugated diene may contain four to six carbon atoms and may include, e.g., piperylene, 2,3-dimethyl-l,3-butadiene, chloroprene, isoprene, and 1,3 -butadiene. Mixtures of such conjugated dienes are suitable.
  • the styrene content of these copolymers may be 20% to 70% by weight or 40% to 60%, and the aliphatic conjugated diene content may be 30% to 80% or 40% to 60%.
  • These copolymers can be prepared by methods well known in the art and are typically hydrogenated to remove a substantial portion of their olefinic double bonds.
  • esters obtained by copolymerizing styrene and maleic anhydride in the presence of a free radical initiator and thereafter esterifying the copolymer with a mixture of C4-18 alcohols also are suitable as viscosity modifying additives in motor oils.
  • poly(meth)acrylates (PMA) may be used as viscosity modifiers.
  • (meth)acrylate” and its cognates means either methacrylate or acrylate, as will be readily understood. These materials are typically prepared from mixtures of (meth)acrylate monomers having different alkyl groups, which may be either straight chain or branched chain groups containing 1 to 18 carbon atoms.
  • Certain viscosity modifiers may be multi-armed polymers. These may include (meth)acrylate-containing polymers comprising a multiplicity of arms which contain at least 20, or at least 50, or at least 100, or at least 200, or at least 350, or at least 500, or at least 1000, carbon atoms, said arms being attached to a multivalent organic moiety.
  • the multi-armed polymer may thus be characteristic of a “star” polymer, a “comb” polymer, or a polymer otherwise having multiple arms or branches as described herein.
  • the amount of the viscosity modifier component may be from 0.02 to 5 (such as from 0.1 to 2, or from 0.2 to 1, or from 0.3 to 0.6) percent by weight, based on the total weight of the composition.
  • Any suitable metal passivators may be used, as would be understood by one of ordinary skill in the art.
  • Suitable pour point depressants may be used, as would be understood by one of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable pour point depressants.
  • suitable pour point depressants may include polyalphaolefins, esters of maleic anhydride-styrene, poly(meth)acrylates, polyacrylates, and/or polyacrylamides.
  • Suitable antifoam agents may include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxidepropylene oxide) polymers.
  • EP agents that are soluble in oil include sulfur- and chlorosulfur-containing EP agents, dimercaptothiadiazole or CS2 derivatives of dispersants (typically succinimide dispersants), derivatives of chlorinated hydrocarbon EP agents and phosphorus EP agents.
  • EP agents include chlorinated wax; sulfurized olefins (such as sulfurized isobutylene), a hydrocarbyl-substituted 2,5-dimercapto-l,3,4-thiadiazole, or oligomers thereof, organic sulphides and polysulphides such as dibenzyldisulphide, bis-(chlorobenzyl) disulphide, dibutyl tetrasulphide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons such as the reaction product of phosphorus sulphide with turpentine or methyl oleate; phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphites, e.g., dibutyl phosphite, diheptyl phosphite, dicyclo
  • Friction modifiers that may be suitable in an exemplary lubricating composition include fatty acid derivatives such as amines, esters, epoxides, fatty imidazolines, condensation products of carboxylic acids and polyalkylenepolyamines and amine salts of alkylphosphoric acids.
  • Ashless friction modifiers are those which typically do not produce any sulfated ash when subjected to the conditions of ASTM D 874.
  • An additive is referred to as “non-metal containing” if it does not contribute metal content to the lubricant composition.
  • the term “fatty alkyl” or “fatty” in relation to friction modifiers means a carbon chain having 8 to 30 carbon atoms, typically a straight carbon chain.
  • the ash-free friction modifier is a fatty ester, amide, or imide of various hydroxy-carboxylic acids, such as tartaric acid, malic acid lactic acid, glycolic acid, and mandelic acid.
  • suitable materials include tartaric acid di(2-ethylhexyl) ester (e.g., di(2-ethylhexyl)tartrate), di(Cs-Cio)tartrate, di(Ci2-is)tartrate, di-oleyltartrate, oleyltartrimide, and oleyl maleimide.
  • the ash-free friction modifier may be chosen from long chain fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty phosphonates; fatty phosphites; borated phospholipids, borated fatty epoxides; glycerol esters; borated glycerol esters; fatty amines; alkoxylated fatty amines; borated alkoxylated fatty amines; hydroxyl and polyhydroxy fatty amines including tertiary hydroxy fatty amines; hydroxy alkyl amides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines;
  • Suitable friction modifiers may also encompass materials such as sulfurized fatty compounds and olefins, sunflower oil or soybean oil monoester of a polyol and an aliphatic carboxylic acid.
  • the friction modifier may be a long chain fatty acid ester.
  • the long chain fatty acid ester may be a mono-ester and in another embodiment the long chain fatty acid ester may be a triglyceride.
  • the ashless friction modifier is one or more of an ester, an amide, or an imide of an alpha-hydroxy carbonyl compound, and mixtures thereof.
  • the ashless friction modifier may be present in the lubricating composition in an amount of from 0.01 to 6, or from 0.05 to 4, or from 0.1 to 2, or from 0.01 to 1.1, or from 0.1 to 0.5, or from 0.2 to 0.4 percent by weight, based on the total weight of the composition.
  • the composition comprises less than 200 (such as less than 190, less than 180, less than 170, less than 160, less than 150, less than 140, less than 130, less than 120, less than 110, less than 100, less than 90, less than 80, less than 70, less than 60, less than 50, less than 40, less than 30, less than 20, or less than 10) ppm by weight molybdenum, based on the total weight of the composition.
  • the composition may be substantially free of molybdenum-containing material.
  • the composition will not include any intentionally-added, molybdenum-containing material. Any suitable molybdenum-containing material may be used, as would be understood by one of ordinary sill in the art.
  • molybdenum-containing materials also referred to as a molybdenum compound.
  • Molybdenum compounds as lubricant additives are known in the art and may serve in various functions, such as antiwear agents, friction modifiers and antioxidants.
  • the use of molybdenum- and sulfur-containing compositions in lubricating oil compositions as antiwear agents and antioxidants is known.
  • Such materials may be a molybdenum hydrocarbyldithiocarbamate.
  • US 4,285,822 discloses lubricating oil compositions containing a molybdenum and sulfur containing composition prepared by (1) combining a polar solvent, an acidic molybdenum compound and an oil-soluble basic nitrogen compound to form a molybdenum-containing complex and (2) contacting the complex with carbon disulfide to form the molybdenum and sulfur containing composition.
  • molybdenum-containing materials include molybdenum dihydrocarbyldithio-phosphates.
  • molybdenum-containing materials include molybdenum-amine compounds as described in US 6,329,327 Bl; organomolybdenum compounds made from the reaction of a molybdenum source, fatty oil, and a diamine as described in US 6,914,037 B2; and trinuclear molybdenum- sulfur complexes as described in US 6,232,276 B2.
  • the molybdenum compound is a molybdenum dithiocarbamate complex, a molybdenum dithiocarbamate dimer complex, or a tri-nuclear molybdenum compound.
  • the lubricant formulation contains a molybdenum- containing material in an amount to provide 40 to 1200 parts per million by weight molybdenum to the lubricant, or alternatively 50 to 250, 50 to 500, 60 to 200, 300 to 1000, or 400 to 800 parts per million.
  • the actual amount of the molybdenum-containing material will depend in part on the nature and formula weight of the anion or complexing agent associated with the molybdenum, in a way that may be readily calculated.
  • the molybdenum-containing compound is present in the lubricating composition in an amount of from 0 to 1.1, or from 0.01 to 0.5, or from 0.03 to 0.35, or from 0.02 to 0.2, or from 0.07 to 0.18, or from 0.04 to 0.18 percent by weight, based on the total weight of the lubricating composition.
  • the composition further comprises an antiwear agent, wherein the anti wear agent contributes from 300 to 900 (such as from 350 to 900, from 400 to 900, from 450 to 900, from 500 to 900, from 550 to 900, from 600 to 900, from 650 to 900, from 700 to 900, from 750 to 900, from 800 to 900, from 850 to 900, from 300 to 850, from 350 to 850, from 400 to 850, from 450 to 850, from 500 to 850, from 550 to 850, from 600 to 850, from 650 to 850, from 700 to 850, from 750 to 850, from 800 to 850, from 300 to 800, from 350 to 800, from 400 to 800, from 450 to 800, from 500 to 800, from 550 to 800, from 600 to 800, from 650 to 800, from 700 to 800, from 750 to 800, from 300 to 750, from 350 to 750, from 400 to 750 to 800, from 500 to 800, from 550 to 800, from 600 to
  • any suitable antiwear agents may be used, as would be understood by one of ordinary sill in the art. Without limitation, the following description provides certain embodiments of suitable antiwear agents.
  • anti-wear agents include phosphorus- containing anti-wear/extreme pressure agents (such as metal thiophosphates), phosphoric acid esters and salts thereof, phosphorus-containing carboxylic acids, phosphorus-containing esters, phosphorus-containing ethers, phosphorus-containing amides, and phosphites Tn certain embodiments, a phosphorus anti-wear agent may be present in an amount to deliver from 0.01 to 0.2 weight percent, or from 0.015 to 0.15 weight percent, or from 0.02 to 0.1 weight percent, or from 0.025 to 0.08 weight percent, or from 0.01 to 0.05 weight percent phosphorus to the total lubricating composition.
  • the anti-wear agent is a zinc dialkyldithiophosphate.
  • Zinc dialkyldithiophosphates may be described as primary zinc dialkyldithiophosphates or as secondary zinc dialkyldithiophosphates, depending on the structure of the alcohol used in its preparation.
  • the lubricating compositions described herein may comprise primary zinc dialkyldithiophosphates.
  • the lubricating compositions described herein may comprise secondary zinc dialkyldithiophosphates.
  • the lubricating compositions described herein may comprise a mixture of primary and secondary zinc dialkyldithiophosphates, optionally wherein the ratio of primary zinc dialkyldithiophosphates to secondary zinc dialkyldithiophosphates (one a weight basis) is at least 1 : 1, or at least 1: 1.2, or at least 1 : 1.5, or at least 1 :2, or at least 1: 10.
  • the lubricating compositions described herein may comprise a mixture of primary and secondary zinc dialkyldithiophosphates which is at least 50 (such as at least 60, at least 70, at least 80, or at least 90) percent by weight primary zinc dialkyldithiophosphate.
  • the lubricating compositions described herein are substantially free of primary zinc dialkyldithiophosphates, or free of primary zinc di alkyl dithi ophosphates .
  • antiwear agents include tartrate esters, tartramides, and tartrimides.
  • examples include oleyl tartrimide (the imide formed from oleylamine and tartaric acid) and oleyl diesters (from, e.g., mixed C12-16 alcohols).
  • Other related materials that may be suitable include esters, amides, and imides of other hydroxycarboxylic acids in general, including hydroxy-polycarboxylic acids, for instance, acids such as tartaric acid, citric acid, lactic acid, glycolic acid, hydroxy -propionic acid, hydroxy glutaric acid, and mixtures thereof. These materials may also impart additional functionality to a lubricant beyond antiwear performance.
  • Such derivatives of (or compounds derived from) a hydroxy-carboxylic acid may typically be present in the lubricating composition in an amount of 0.1 weight % to 5 weight %, or 0.2 weight % to 3 weight %, or greater than 0.2 weight % to 3 weight %.
  • the composition comprises from 700 to 1,000 (such as from 750 to 1,000, from 800 to 1,000, from 850 to 1,000, from 900 to 1,000, from 950 to 1,000, from 700 to 950, from 750 to 950, from 800 to 950, from 850 to 950, from 900 to 950, from 700 to 900, from 750 to 900, from 800 to 900, from 850 to 900, from 700 to 850, from 750 to 850, from 800 to 850, from 700 to 800, from 750 to 800, or from 700 to 750) ppm by weight zinc, based on the total weight of the composition.
  • 700 to 1,000 such as from 750 to 1,000, from 800 to 1,000, from 850 to 1,000, from 900 to 1,000, from 950 to 1,000, from 700 to 950, from 750 to 950, from 800 to 950, from 850 to 950, from 900 to 950, from 700 to 900, from 750 to 900, from 800 to 900, from 700 to 850, from 750 to 850, from
  • a method of lubricating a heavy duty diesel engine comprising supplying a lubricating composition as described herein to the engine.
  • a method of lubricating a compression-ignition internal combustion engine having a laden mass over 2,700 kg comprising supplying a lubricating composition as described herein to the engine.
  • a method of lubricating the crankcase of a compression-ignition or spark-ignited engine comprising supplying a lubricating composition as described herein to the crankcase.
  • the spark-ignited engine may be a gasoline direct-injection engine.
  • the gasoline direct-injection engine comprises a turbocharger.
  • a lubricating composition as described herein may have a composition as disclosed in Table 1:
  • a series of engine lubricants having low HTHS (2.5) suitable for use in a passenger car diesel engine were prepared in a Group III base oil of lubricating viscosity containing the additives described herein, including a deposit control additive according to formula I, polymeric viscosity modifiers, ashless succinimide dispersants, over-based detergents, antioxidants, zinc dialkyldithiophosphate (ZDDP), as well as other performance additives in the amounts (percent by weight based on the total weight of the lubricant) shown in Table 4:
  • ’Other additives include antifoam agents, pourpoint depressants, sulfurized alkylene ester, and metal deactivators

Abstract

The subject matter disclosed herein provides a lubricating composition including: (a) an oil of lubricating viscosity; (b) a compound according to formula I: wherein, independently for each molecule of the compound: R1 is an aliphatic hydrocarbyl group having from 10 to 24 carbon atoms; R2 is CH3 or C2H5; and n is an integer from 3 to 8; and (c) an alkaline earth metal alkyl detergent.

Description

DEPOSIT CONTROL COMPOUNDS FOR LUBRICATING COMPOSITIONS
[00011 The disclosed technology relates to lubricating compositions for internal combustion engines, such as diesel engines (such as heavy-duty diesel engines) or gasoline direct injection engines (such as with turbocharging) and methods of lubricating such engines by supplying the engines with the lubricating composition(s). The lubricating compositions disclosed herein may improve fuel economy and/or wear protection.
[0002] Lubricating compositions are used for the smooth operation of internal combustion engines. The engine oils for internal combustion engines in particular serve to, for example: (i) lubricate various sliding interfaces between the piston ring and cylinder liner, in bearings of the crank shaft and the connecting rod, and in the valve driving mechanism including cams and valve lifters; (ii) cool the engine; (iii) clean and disperse the combustion products; and/or (iv) prevent corrosion and consequent rust formation. The stringent requirements for high performance engines in recent years has meant greater demand from improved lubricants used in such engines.
[0003] There is increasing interest in improving the fuel efficiency of internal combustion engines. Vehicle manufacturers have improved fuel economy through engine design, improvements which take advantage of advances in lubricating compositions which provide better oxidative stability, wear protection, and reduced friction, for example. In particular, operators of heavy-duty diesel vehicles have been reluctant to adopt low viscosity grade engine oils to improve fuel economy; durability, or the ability to maintain vehicles on the road for extended periods of time and mileage, has been and remains a primary concern. Thus, the most widely used viscosity grades for on-highway heavy duty diesel vehicles have been SAE 15W- 40, 10W-30, and 5W-30. In recent years, there is a growing push to improve the fuel efficiency of heavy-duty diesel vehicles. Consequently, there is a need to improve the fuel economy of diesel engines without compromising the durability of the engines or otherwise negatively impacting the lubricant performance, including deposit and soot control, and oxidation and corrosion resistance. This is particularly relevant for viscosity grades lighter than SAE 5W-30, such as 0W-20, OW-16, and OW-12.
[0004] Additionally, with recent changes to engine specifications, there is an increasing demand on the lubricant to reduce deposits. For instance, Caterpillar IN (ASTM D6750) requirements in APT CK-4, CJ-4 and FA-4 requires weighted piston demerits maximum of 286.2 after 252 hrs. API FA-4 oils are blended to a high temperature high shear (“HTHS”) viscosity range of 2.9 cP to 3.2 cP to assist in reducing greenhouse gas (“GHG”) emissions. These oils are especially effective at sustaining emission control system durability where particulate fdters and other advanced after-treatment systems are used. Lower HTHS viscosity ranges oils, such as 2.0 to 2.9 cP, will improve fuel economy, but still also require special attention to soot deposits, since accumulation of soot deposits may lead to higher viscosities. [0005] The disclosed technology provides a compound which may provide deposit control in lubricating compositions, while maintaining adequate viscosity.
[0006] The subject matter disclosed herein provides a lubricating composition comprising: (a) an oil of lubricating viscosity; (b) a compound according to formula I:
Figure imgf000003_0001
wherein, independently for each molecule of the compound: R1 is an aliphatic hydrocarbyl group having from 10 to 24 carbon atoms; R2 is CH3 or C2H5; and n is an integer from 3 to 8; and (c) an alkaline earth metal alkyl detergent. In certain embodiments, provided is a deposit control additive according to formula I as described above.
[0007] The following embodiments of the present subject matter are contemplated:
[0008] 1. A lubricating composition comprising: (a) an oil of lubricating viscosity; (b) a compound according to formula I:
Figure imgf000003_0002
wherein, independently for each molecule of the compound: R1 is an aliphatic hydrocarbyl group having from 10 to 24 carbon atoms; R2 is CH3 or C2H5; and n is an integer from 3 to 8; and (c) an alkaline earth metal alkyl detergent.
[0009] 2. The lubricating composition of embodiment 1, having a high temperature high shear viscosity of from 1.5 to 4.5 mPa s, as measured at 150 °C according to ASTM D4683.
[0010] 3. The lubricating composition of either embodiment 1 or embodiment 2, having a high temperature high shear viscosity of from 1.5 to 3.5 mPa s, as measured at 150 °C according to ASTM D4683.
[0011] 4. The lubricating composition of any one of embodiments 1 to 3, wherein the alkaline earth metal alkyl detergent contributes from 2 to 7 TBN to the composition as measured by ASTM D4739.
[0012] 5. The lubricating composition of any one of embodiments 1 to 3, wherein the alkaline earth metal alkyl detergent contributes from 2 to 6 TBN to the composition as measured by ASTM D4739.
[0013] 6. The lubricating composition of any one of embodiments 1 to 3, wherein the alkaline earth metal alkyl detergent contributes from 2 to 4 TBN to the composition as measured by ASTM D4739.
[0014] 7. The lubricating composition of any one of embodiments 1 to 6, having a sulfated ash level of less than or equal to 1 percent by weight, based on the total weight of the composition, as measured by ASTM D874.
[0015] 8. The lubricating composition of embodiment 7, wherein the alkaline earth metal alkyl detergent contributes from 6 to 7 TBN to the composition as measured by ASTM D4739. [0016] 9. The lubricating composition of any one of embodiments 1 to 6, having a sulfated ash level of less than or equal to 0.5 percent by weight, based on the total weight of the composition, as measured by ASTM D874.
[0017] 10. The lubricating composition of embodiment 9, wherein the alkaline earth metal alkyl detergent contributes from 2 to 3.5 TBN to the composition as measured by ASTM D4739.
[0018] 11. The lubricating composition of any one of embodiments 1 to 10, wherein the compound according to formula I is present in the composition in an amount of from 1 to 10 percent by weight, based on the total weight of the composition. [0019] 12. The lubricating composition of any one of embodiments 1 to 1 1, wherein R1 is an aliphatic hydrocarbyl group having from 14 to 20 carbon atoms.
[0020] 13. The lubricating composition of any one of embodiments 1 to 12, having a TBN of from 2 to 12 as measured by ASTM D2896.
[0021] 14. The lubricating composition of any one of embodiments 1 to 12, having a TBN of from 2 to 8 as measured by ASTM D2896.
[0022] 15. The lubricating composition of any one of embodiments 1 to 12, having a TBN of from 2 to 7 as measured by ASTM D2896.
[0023] 16. The lubricating composition of any one of embodiments 1 to 12, having a TBN of from 2 to 6 as measured by ASTM D2896.
[0024] 17. The lubricating composition of any one of embodiments 1 to 16, wherein the alkaline earth metal alkyl detergent is present in the composition in an amount less than 3.5 percent by weight, based on the total weight of the composition.
[0025] 18. The lubricating composition of any one of embodiments 1 to 16, wherein the alkaline earth metal alkyl detergent is present in the composition in an amount less than 1 percent by weight, based on the total weight of the composition.
[0026] 19. The lubricating composition of any one of embodiments 1 to 18, wherein the alkaline earth metal alkyl detergent comprises an alkaline earth metal which is at least one of magnesium or calcium.
[0027] 20. The lubricating composition of any one of embodiments 1 to 19, wherein the alkaline earth metal alkyl detergent comprises a surfactant portion which is at least one of phenate, salicylate, sulfonate, saligenin, or salixarate.
[0028] 21. The lubricating composition of any one of embodiments 1 to 20, wherein the alkaline earth metal alkyl detergent comprises a surfactant portion which is at least one of salicylate or sulfonate.
[0029] 22. The lubricating composition of any one of embodiments 1 to 21, further comprising at least one additional additive comprising at least one of antioxidants, detergents, dispersants, antiwear agent, corrosion inhibitors, viscosity modifiers, metal passivators, pour point depressants, seal compatibility agents, antifoam agents, extreme pressure agents, or friction modifiers. [0030] 23. The lubricating composition of any one of embodiments 1 to 22, having less than 200 ppm by weight molybdenum, based on the total weight of the composition.
[0031] 24. The lubricating composition of any one of embodiments 1 to 23, having less than 120 ppm by weight molybdenum, based on the total weight of the composition.
[0032] 25. The lubricating composition of any one of embodiments 1 to 24, further comprising at least one of a metal-based antiwear agent or an amine-based antiwear agent.
[0033] 26. The lubricating composition of any one of embodiments 1 to 25, further comprising an anti wear agent, wherein the antiwear agent contributes from 300 to 900 ppm by weight phosphorus to the composition, based on the total weight of the composition.
[0034] 27. The lubricating composition of any one of embodiments 1 to 25, further comprising an antiwear agent, wherein the antiwear agent contributes from 300 to 800 ppm by weight phosphorus to the composition, based on the total weight of the composition.
[0035] 28. The lubricating composition of any one of embodiments 1 to 27, having from
700 to 1,000 ppm by weight zinc, based on the total weight of the composition.
[0036] 29. The lubricating composition of any one of embodiments 1 to 27, having from
700 to 900 ppm by weight zinc, based on the total weight of the composition.
[0037] 30. The lubricating composition of any one of embodiments 1 to 29, further comprising an aromatic amine, maleic anhydride, ethylene-propylene copolymer dispersant in an amount of from 0.1 to 5 percent by weight, based on the total weight of the composition.
[0038] 31. A method of lubricating a heavy duty diesel engine comprising supplying the composition of any one of embodiments 1 to 30 to the engine.
[0039] 32. A method of lubricating a compression-ignition internal combustion engine having a laden mass over 2,700 kg comprising supplying the composition of any one of embodiments 1 to 30 to the engine.
[0040] 33. A method of lubricating the crankcase of a compression-ignition or spark- ignited engine comprising supplying the composition of any one of embodiments 1 to 30 to the crankcase.
[0041] 34. The method of embodiment 33, wherein the spark-ignited engine is a gasoline direct-injection engine.
[0042] 35. The method of embodiment 34, wherein the gasoline direct-injection engine comprises a turbocharger. [0043] Various features and embodiments of the present subject matter will be described below by way of non-limiting illustration.
[0044] As used herein, the term “condensation product” is intended to encompass esters, amides, imides and other such materials that may be prepared by a condensation reaction of an acid or a reactive equivalent of an acid (e.g., an acid halide, anhydride, or ester) with an alcohol or amine, irrespective of whether a condensation reaction is actually performed to lead directly to the product. Thus, for example, a particular ester may be prepared by a transesterification reaction rather than directly by a condensation reaction. The resulting product is still considered a condensation product.
[0045] The amount of each chemical component described herein is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, that is, on a 100% active chemical basis, unless otherwise indicated. Unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.
[0046] As used herein, the term “hydrocarbyl” refers to a group having a carbon atom directly attached to the remainder of the molecule, where the group includes at least carbon and hydrogen atoms. If the hydrocarbyl group comprises more than one carbon atom, then those carbons need not necessarily be linked to each other. For example, at least two of the carbons may be linked via a suitable element or group. In various embodiments, the term “hydrocarbyl” refers to a group having a carbon atom directly attached to the remainder of the molecule, where the group consists of carbon, hydrogen, optionally one or more heteroatoms provided the heteroatoms do not alter the predominantly hydrocarbon nature of the substituent. The heteroatom may to link at least two of the carbons in the hydrocarbyl group, and optionally no more than two non-hydrocarbon substituents. Suitable heteroatoms will be apparent to those skilled in the art and include, for instance, sulphur, nitrogen, oxygen, phosphorus and silicon. Where the hydrocarbyl contains heteroatoms, optionally, no more than two heteroatoms will be present for every ten carbon atoms in the hydrocarbyl group. Suitable non-hydrocarbon substituents will also be apparent to those skilled in the art and include, for instance, halo, hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulphoxy. [0047] Examples of hydrocarbyl s within the context of the present technology therefore include: (i) hydrocarbon groups selected from aliphatic (e.g. alkyl or alkenyl), alicyclic (e.g. cycloalkyl, cycloalkenyl, cycloalkadienyl), and aromatic groups; (ii) substituted hydrocarbon groups, selected from hydrocarbon groups defined in (i) substituted with no more than two nonhydrocarbon substituents and/or one or more hydrocarbon substituents, the non-hydrocarbon substituents being selected from the group consisting of halo, hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulphoxy; and/or (iii) hetero-containing hydrocarbon groups, selected from hydrocarbon groups defined in (i) containing one or more heteroatom in the ring or chain, provided that the group has no more than two heteroatoms present for every ten carbon atoms in the group, the heteroatoms being selected from sulphur, nitrogen, oxygen, phosphorus and silicon. The hetero-containing hydrocarbon groups may be substituted with no more than two non-hydrocarbon substituents and/or one or more hydrocarbon substituents. In certain embodiments, the term “hydrocarbyl” refers to a group having a carbon atoms directly attached to the remainder of the molecule, where the group consists of carbon and hydrogen atoms.
[0048] It is known that some of the materials described herein may interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. For instance, metal ions (of, e.g., a detergent) may migrate to other acidic or anionic sites of other molecules. The products formed thereby, including the products formed upon employing the composition of the present subject matter in its intended use, may not be susceptible of easy description. Nevertheless, all such modifications and reaction products are included within the scope of the present subject matter; the present subject matter encompasses the composition prepared by admixing the components described herein.
[0049] As used herein, the indefinite article “a”/“an” is intended to mean one or more than one. As used herein, the phrase “at least one” means one or more than one of the following terms. Thus, “a”/“an” and “at least one” may be used interchangeably. For example “at least one of A, B or C” means that just one of A, B or C may be included, and any mixture of two or more of A, B and C may be included, in alternative embodiments.
[0050] As used herein, the term “substantially free of’ means that a component does not include any intentional addition of the material which the component is “substantially free of’. For example, the component may include a material which the component is “substantially free of’ at no more than impurity levels, which may be the result of incomplete chemical reactions and/or unintended/undesired (but perhaps unavoidable) reaction products.
[00511 As used herein, the transitional term “comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps. However, in each recitation of “comprising” herein, it is intended that the term also encompass, as alternative embodiments, the phrases “consisting essentially of’ and “consisting of,” where “consisting of’ excludes any element or step not specified and “consisting essentially of’ permits the inclusion of additional un-recited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.
[0052] A lubricating composition comprising: (a) an oil of lubricating viscosity; (b) a compound according to formula I:
Figure imgf000009_0001
wherein, independently for each molecule of the compound: R1 is an aliphatic hydrocarbyl group having from 10 to 24 (such as from 12 to 24, from 14 to 24, from 16 to 24, from 18 to 24, from 20 to 24, from 22 to 24, from 10 to 22, from 12 to 22, from 14 to 22, from 16 to 22, from 18 to 22, from 20 to 22, from 10 to 20, from 12 to 20, from 14 to 20, from 16 to 20, from 18 to 20, from 10 to 18, from 12 to 18, from 14 to 18, from 16 to 18, from 10 to 16, from 12 to 16, from 14 to 16, from 10 to 14, from 12 to 14, or from 10 to 12) carbon atoms; R2 is CH3 or C2H5; and n is an integer from 3 to 8 (such as from 4 to 8, from 5 to 8, from 6 to 8, from 7 to 8, from 3 to 7, from 4 to 7, from 5 to 7, from 6 to 7, from 3 to 6, from 4 to 6, from 5 to 6, from 3 to 5, from 4 to 5, or from 3 to 4); and (c) an alkaline earth metal alkyl detergent.
[0053] The lubricating compositions described herein may find use in various applications as a lubricant composition for: internal combustion engines, including gasoline engines and/or spark-ignited engines, such as passenger car engines diesel engines, or compression-ignited engines, such as heavy duty diesel truck engines, natural gas fueled engines, such as stationary power engines, two-cycle engines, aviation piston engines and turbine engines, marine and railroad diesel engines; and hydrocarbon fuels for an internal combustion engine such as middle distillate fuels such as jet fuel, kerosene and diesel fuels.
[0054] The lubricating compositions disclosed herein comprise an oil of lubricating viscosity. Such oils may include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils, or mixtures thereof. A more detailed description of unrefined, refined and re-refined oils is provided in WO 2008/147704 Al, paragraphs [0054] to [0056], A more detailed description of natural and synthetic lubricating oils is described in paragraphs [0058] to [0059] respectively of WO 2008/147704 Al. Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In certain embodiments, oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure, as well as other gas-to-liquid procedures.
[0055] Suitable oils may be produced from biological (i.e., natural) sources or by bioengineered processes. This includes both naturally-occurring oils, such as vegetable oils and triglyceride oils, which may be further refined or purified by standard processes, and those oils that may be derived by biological conversion of a natural chemical into oil directly or by bioformation of building block pre-cursor molecules capable of being further converted into oil by known processes.
[0056] Oils of lubricating viscosity may also be defined as specified in the April 2008 version of “Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils”, section 1.3, “Base Stock Categories”. The API Guidelines are also summarized in US 7,285,516 B2 see column 11, line 64 to column 12, line 10). In certain embodiments, the oil of lubricating viscosity may be an API Group I base oil, Group II base oil, Group III base oil, or Group IV base oil (e.g., mineral oil), an ester or other synthetic oil, a Group V base oil, or any mixtures thereof.
[0057] The amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 percent by weight the sum of the amount of the additives of the disclosed compositions and the other performance additives. Illustrative amounts may include 50 to 99 percent by weight, or 60 to 98, or 70 to 95, or 80 to 94, or 85 to 93 percent by weight, based on the total weight of the composition. [0058] The lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating compositions described herein (comprising the additives disclosed herein) are in the form of a concentrate (which may be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of these additives to the oil of lubricating viscosity and/or to diluent oil include the ranges of 1 :99 to 99: 1 by weight, or 80:20 to 10:90 by weight. Typically, the lubricating composition described herein include at least 50, or at least 60, or at least 70, or at least 80 percent by weight of an oil of lubricating viscosity.
[0059] In certain embodiments, the composition has a high temperature high shear viscosity of from 1.5 to 4.5 (such as from 1.6 to 4.5, from 1.7 to 4.5, from 1.8 to 4.5, from 1.9 to 4.5, from 2 to 4.5, from 2.1 to 4.5, from 2.2 to 4.5, from 2.3 to 4.5, from 2.4 to 4.5, from 2.5 to 4.5, from 2.6 to 4.5, from 2.7 to 4.5, from 2.8 to 4.5, from 2.9 to 4.5, from 3 to 4.5, from 3.1 to 4.5, from 3.2 to 4.5, from 3.3 to 4.5, from 3.4 to 4.5, from 3.5 to 4.5, from 3.6 to 4.5, from 3.7 to 4.5, from 3.8 to 4.5, from 3.9 to 4.5, from 4 to 4.5, from 4. 1 to 4.5, from 4.2 to 4.5, from 4.3 to 4.5, from 4.4 to 4.5, from 1.5 to 4.4, from 1.6 to 4.4, from 1.7 to 4.4, from 1.8 to 4.4, from 1.9 to 4.4, from 2 to 4.4, from 2.1 to 4.4, from 2.2 to 4.4, from 2.3 to 4.4, from 2.4 to 4.4, from 2.5 to 4.4, from 2.6 to 4.4, from 2.7 to 4.4, from 2.8 to 4.4, from 2.9 to 4.4, from 3 to 4.4, from 3.1 to 4.4, from 3.2 to 4.4, from 3.3 to 4.4, from 3.4 to 4.4, from 3.5 to 4.4, from 3.6 to 4.4, from
3.7 to 4.4, from 3.8 to 4.4, from 3.9 to 4.4, from 4 to 4.4, from 4.1 to 4.4, from 4.2 to 4.4, from
4.3 to 4.4, from 1.5 to 4.3, from 1.6 to 4.3, from 1.7 to 4.3, from 1.8 to 4.3, from 1.9 to 4.3, from 2 to 4.3, from 2.1 to 4.3, from 2.2 to 4.3, from 2.3 to 4.3, from 2.4 to 4.3, from 2.5 to 4.3, from 2.6 to 4.3, from 2.7 to 4.3, from 2.8 to 4.3, from 2.9 to 4.3, from 3 to 4.3, from 3.1 to 4.3, from 3.2 to 4.3, from 3.3 to 4.3, from 3.4 to 4.3, from 3.5 to 4.3, from 3.6 to 4.3, from 3.7 to
4.3, from 3.8 to 4.3, from 3.9 to 4.3, from 4 to 4.3, from 4.1 to 4.3, from 4.2 to 4.3, from 1.5 to
4.2, from 1.6 to 4.2, from 1.7 to 4.2, from 1.8 to 4.2, from 1.9 to 4.2, from 2 to 4.2, from 2.1 to
4.2, from 2.2 to 4.2, from 2.3 to 4.2, from 2.4 to 4.2, from 2.5 to 4.2, from 2.6 to 4.2, from 2.7 to 4.2, from 2.8 to 4.2, from 2.9 to 4.2, from 3 to 4.2, from 3.1 to 4.2, from 3.2 to 4.2, from 3.3 to 4.2, from 3.4 to 4.2, from 3.5 to 4.2, from 3.6 to 4.2, from 3.7 to 4.2, from 3.8 to 4.2, from 3.9 to 4.2, from 4 to 4.2, from 4.1 to 4.2, from 1.5 to 4.1, from 1.6 to 4.1, from 1.7 to 4.1, from
1.8 to 4.1, from 1.9 to 4.1, from 2 to 4.1, from 2.1 to 4.1, from 2.2 to 4.1, from 2.3 to 4.1, from
2.4 to 4.1, from 2.5 to 4.1, from 2.6 to 4.1, from 2.7 to 4.1, from 2.8 to 4.1, from 2.9 to 4.1, from 3 to 4.1 , from 3.1 to 4.1, from 3.2 to 4.1, from 3.3 to 4.1, from 3.4 to 4.1, from 3.5 to 4.1 , from 3.6 to 4.1, from 3.7 to 4.1, from 3.8 to 4.1, from 3.9 to 4.1, from 4 to 4.1, from 1.5 to 4, from 1.6 to 4, from 1.7 to 4, from 1.8 to 4, from 1.9 to 4, from 2 to 4, from 2.1 to 4, from 2.2 to 4, from 2.3 to 4, from 2.4 to 4, from 2.5 to 4, from 2.6 to 4, from 2.7 to 4, from 2.8 to 4, from 2.9 to 4, from 3 to 4, from 3.1 to 4, from 3.2 to 4, from 3.3 to 4, from 3.4 to 4, from 3.5 to 4, from 3.6 to 4, from 3.7 to 4, from 3.8 to 4, from 3.9 to 4, from 1.5 to 3.9, from 1.6 to 3.9, from
1.7 to 3.9, from 1.8 to 3.9, from 1.9 to 3.9, from 2 to 3.9, from 2.1 to 3.9, from 2.2 to 3.9, from
2.3 to 3.9, from 2.4 to 3.9, from 2.5 to 3.9, from 2.6 to 3.9, from 2.7 to 3.9, from 2.8 to 3.9, from 2.9 to 3.9, from 3 to 3.9, from 3.1 to 3.9, from 3.2 to 3.9, from 3.3 to 3.9, from 3.4 to 3.9, from 3.5 to 3.9, from 3.6 to 3.9, from 3.7 to 3.9, from 3.8 to 3.9, from 1.5 to 3.8, from 1.6 to 3.8, from 1.7 to 3.8, from 1.8 to 3.8, from 1.9 to 3.8, from 2 to 3.8, from 2.1 to 3.8, from 2.2 to 3.8, from 2.3 to 3.8, from 2.4 to 3.8, from 2.5 to 3.8, from 2.6 to 3.8, from 2.7 to 3.8, from 2.8 to 3.8, from 2.9 to 3.8, from 3 to 3.8, from 3.1 to 3.8, from 3.2 to 3.8, from 3.3 to 3.8, from 3.4 to 3.8, from 3.5 to 3.8, from 3.6 to 3.8, from 3.7 to 3.8, from 1.5 to 3.7, from 1.6 to 3.7, from
1.7 to 3.7, from 1.8 to 3.7, from 1.9 to 3.7, from 2 to 3.7, from 2.1 to 3.7, from 2.2 to 3.7, from
2.3 to 3.7, from 2.4 to 3.7, from 2.5 to 3.7, from 2.6 to 3.7, from 2.7 to 3.7, from 2.8 to 3.7, from 2.9 to 3.7, from 3 to 3.7, from 3.1 to 3.7, from 3.2 to 3.7, from 3.3 to 3.7, from 3.4 to 3.7, from 3.5 to 3.7, from 3.6 to 3.7, from 1.5 to 3.6, from 1.6 to 3.6, from 1.7 to 3.6, from 1.8 to
3.6, from 1.9 to 3.6, from 2 to 3.6, from 2.1 to 3.6, from 2.2 to 3.6, from 2.3 to 3.6, from 2.4 to
3.6, from 2.5 to 3.6, from 2.6 to 3.6, from 2.7 to 3.6, from 2.8 to 3.6, from 2.9 to 3.6, from 3 to
3.6, from 3.1 to 3.6, from 3.2 to 3.6, from 3.3 to 3.6, from 3.4 to 3.6, from 3.5 to 3.6, from 1.5 to 3.5, from 1.6 to 3.5, from 1.7 to 3.5, from 1.8 to 3.5, from 1.9 to 3.5, from 2 to 3.5, from 2.1 to 3.5, from 2.2 to 3.5, from 2.3 to 3.5, from 2.4 to 3.5, from 2.5 to 3.5, from 2.6 to 3.5, from
2.7 to 3.5, from 2.8 to 3.5, from 2.9 to 3.5, from 3 to 3.5, from 3.1 to 3.5, from 3.2 to 3.5, from
3.3 to 3.5, from 3.4 to 3.5, from 1.5 to 3.4, from 1.6 to 3.4, from 1.7 to 3.4, from 1.8 to 3.4, from 1.9 to 3.4, from 2 to 3.4, from 2.1 to 3.4, from 2.2 to 3.4, from 2.3 to 3.4, from 2.4 to 3.4, from 2.5 to 3.4, from 2.6 to 3.4, from 2.7 to 3.4, from 2.8 to 3.4, from 2.9 to 3.4, from 3 to 3.4, from 3.1 to 3.4, from 3.2 to 3.4, from 3.3 to 3.4, from 1.5 to 3.3, from 1.6 to 3.3, from 1.7 to 3.3, from 1.8 to 3.3, from 1.9 to 3.3, from 2 to 3.3, from 2.1 to 3.3, from 2.2 to 3.3, from 2.3 to 3.3, from 2.4 to 3.3, from 2.5 to 3.3, from 2.6 to 3.3, from 2.7 to 3.3, from 2.8 to 3.3, from 2.9 to 3.3, from 3 to 3.3, from 3.1 to 3.3, from 3.2 to 3.3, from 1.5 to 3.2, from 1.6 to 3.2, from 1.7 to 3.2, from 1 .8 to 3.2, from 1 .9 to 3.2, from 2 to 3.2, from 2.1 to 3.2, from 2.2 to 3.2, from 2.3 to 3.2, from 2.4 to 3.2, from 2.5 to 3.2, from 2.6 to 3.2, from 2.7 to 3.2, from 2.8 to 3.2, from 2.9 to 3.2, from 3 to 3.2, from 3.1 to 3.2, from 1.5 to 3.1, from 1.6 to 3.1, from 1.7 to 3.1, from 1.8 to 3.1, from 1.9 to 3.1, from 2 to 3.1, from 2.1 to 3.1, from 2.2 to 3.1, from 2.3 to 3.1, from
2.4 to 3.1, from 2.5 to 3.1, from 2.6 to 3.1, from 2.7 to 3.1, from 2.8 to 3.1, from 2.9 to 3.1, from 3 to 3.1, from 1.5 to 3, from 1.6 to 3, from 1.7 to 3, from 1.8 to 3, from 1.9 to 3, from 2 to 3, from 2.1 to 3, from 2.2 to 3, from 2.3 to 3, from 2.4 to 3, from 2.5 to 3, from 2.6 to 3, from
2.7 to 3, from 2.8 to 3, from 2.9 to 3, from 1.5 to 2.9, from 1.6 to 2.9, from 1.7 to 2.9, from 1.8 to 2.9, from 1.9 to 2.9, from 2 to 2.9, from 2.1 to 2.9, from 2.2 to 2.9, from 2.3 to 2.9, from 2.4 to 2.9, from 2.5 to 2.9, from 2.6 to 2.9, from 2.7 to 2.9, from 2.8 to 2.9, from 1.5 to 2.8, from
1.6 to 2.8, from 1.7 to 2.8, from 1.8 to 2.8, from 1.9 to 2.8, from 2 to 2.8, from 2.1 to 2.8, from
2.2 to 2.8, from 2.3 to 2.8, from 2.4 to 2.8, from 2.5 to 2.8, from 2.6 to 2.8, from 2.7 to 2.8, from 1.5 to 2.7, from 1.6 to 2.7, from 1.7 to 2.7, from 1.8 to 2.7, from 1.9 to 2.7, from 2 to 2.7, from 2. 1 to 2.7, from 2.2 to 2.7, from 2.3 to 2.7, from 2.4 to 2.7, from 2.5 to 2.7, from 2.6 to 2.7, from 1.5 to 2.6, from 1.6 to 2.6, from 1.7 to 2.6, from 1.8 to 2.6, from 1.9 to 2.6, from 2 to 2.6, from 2.1 to 2.6, from 2.2 to 2.6, from 2.3 to 2.6, from 2.4 to 2.6, from 2.5 to 2.6, from 1.5 to 2.5, from 1.6 to 2.5, from 1.7 to 2.5, from 1.8 to 2.5, from 1.9 to 2.5, from 2 to 2.5, from 2.1 to 2.5, from 2.2 to 2.5, from 2.3 to 2.5, from 2.4 to 2.5, from 1.5 to 2.4, from 1.6 to 2.4, from
1.7 to 2.4, from 1.8 to 2.4, from 1.9 to 2.4, from 2 to 2.4, from 2.1 to 2.4, from 2.2 to 2.4, from
2.3 to 2.4, from 1.5 to 2.3, from 1.6 to 2.3, from 1.7 to 2.3, from 1.8 to 2.3, from 1.9 to 2.3, from 2 to 2.3, from 2.1 to 2.3, from 2.2 to 2.3, from 1.5 to 2.2, from 1.6 to 2.2, from 1.7 to 2.2, from 1.8 to 2.2, from 1.9 to 2.2, from 2 to 2.2, from 2.1 to 2.2, from 1.5 to 2.1, from 1.6 to 2.1, from 1.7 to 2.1, from 1.8 to 2.1, from 1.9 to 2.1, from 2 to 2.1, from 1.5 to 2, from 1.6 to 2, from
1.7 to 2, from 1.8 to 2, from 1.9 to 2, from 1.5 to 1.9, from 1.6 to 1.9, from 1.7 to 1.9, from 1.8 to 1.9, from 1.5 to 1.8, from 1.6 to 1.8, from 1.7 to 1.8, from 1.5 to 1.7, from 1.6 to 1.7, or from
1.5 to 1.6) mPa s, as measured at 150 °C according to ASTM D4683. When referring to ASTM D4683 herein, what is meant is version 20 published June 10, 2020.
[0060] In certain embodiments, the alkaline earth metal alkyl detergent contributes from 2 to 7 (such as from 2 to 6, from 2 to 5, from 2 to 4, from 2 to 3, from 3 to 7, from 3 to 6, from 3 to 5, from 3 to 4, from 4 to 7, from 4 to 6, from 4 to 5, from 5 to 7, from 5 to 6, or from 6 to 7) TBN to the composition as measured by ASTM D4739. The acronym “TBN” refers to total base number, as is known to those of skill in the art When referring to ASTM D4739 herein, what is meant is version 11 published February 7, 2018.
[00611 In certain embodiments, the composition has a sulfated ash level of less than or equal to 1 percent (such as less than or equal to 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1) by weight, based on the total weight of the composition, as measured by ASTM D874. When referring to ASTM D874 herein, what is meant is version 13a published June 1, 2018. In certain embodiments, such as when the composition has a sulfated ash level of less than or equal to 1 percent by weight, based on the total weight of the composition, the alkaline earth metal alkyl detergent contributes from 6 to 7 TBN to the composition as measured by ASTM D4739. In certain embodiments, such as when the composition has a sulfated ash level of less than or equal to 0.5 percent by weight, based on the total weight of the composition, the alkaline earth metal alkyl detergent contributes from 2 to 3.5 TBN to the composition as measured by ASTM D4739.
[0062] In certain embodiments, the compound according to formula I is present in the composition in an amount of from 1 to 10 (such as from 2 to 10, from 3 to 10, from 4 to 10, from 5 to 10, from 6 to 10, from 7 to 10, from 8 to 10, from 9 to 10, from 1 to 9, from 2 to 9, from 3 to 9, from 4 to 9, from 5 to 9, from 6 to 9, from 7 to 9, from 8 to 9, from 1 to 8, from 2 to 8 from 3 to 8, from 4 to 8, from 5 to 8, from 6 to 8, from 7 to 8, from 1 to 7, from 2 to 7, from 3 to 7, from 4 to 7, from 5 to 7, from 6 to 7, from 1 to 6, from 2 to 6, from 3 to 6, from 4 to 6, from 5 to 6, from 1 to 5, from 2 to 5, from 3 to 5, from 4 to 5, from 1 to 4, from 2 to 4, from 3 to 4, from 1 to 3, from 2 to 3, or from 1 to 2) percent by weight, based on the total weight of the composition.
[0063] In certain embodiments, the composition has a TBN of from 2 to 12 (such as from
3 to 12, from 4 to 12, from 5 to 12, from 6 to 12, from 7 to 12, from 8 to 12, from 9 to 12, from 10 to 12, from 11 to 12, from 2 to 11, from 3 to 11, from 4 to 11, from 5 to 11, from 6 to 11, from 7 to 11, from 8 to 11, from 9 to 11, from 10 to 11, from 2 to 10, from 3 to 10, from 4 to 10, from 5 to 10, from 6 to 10, from 7 to 10, from 8 to 10, from 9 to 10, from 2 to 9, from 3 to 9, from 4 to 9, from 5 to 9, from 6 to 9, from 7 to 9, from 8 to 9, from 2 to 8, from 3 to 8, from
4 to 8, from 5 to 8, from 6 to 8, from 7 to 8, from 2 to 7, from 3 to 7, from 4 to 7, from 5 to 7, from 6 to 7, from 2 to 6, from 3 to 6, from 4 to 6, from 5 to 6, from 2 to 5, from 3 to 5, from 4 to 5, from 2 to 4, from 3 to 4, or from 2 to 3) as measured by ASTM D2896. [0064] Tn certain embodiments, the alkaline earth metal alkyl detergent is present in the composition in an amount less than 3.5 (such as less than 3.4, 3.3, 3.2, 3.1, 3, 2.9, 2.8, 2.7, 2.6,
2.5, 2.4, 2.3, 2.2, 2.1, 2., 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1) percent by weight, based on the total weight of the composition. In certain embodiments, the alkaline earth metal alkyl detergent is present in the composition in an amount from greater than 0 to 3.5 (such as from 0.1 to 3.5, from 0.2 to 3.5, from 0.3 to 3.5, from 0.4 to 3.5, from 0.5 to 3.5, from 0.6 to 3.5, from 0.7 to 3.5, from 0.8 to 3.5, from 0.9 to
3.5, from 1 to 3.5, from 1.1 to 3.5, from 1.2 to 3.5, from 1.3 to 3.5, from 1.4 to 3.5, from 1.5 to
3.5, from 1.6 to 3.5, from 1.7 to 3.5, from 1.8 to 3.5, from 1.9 to 3.5, from 2 to 3.5, from 2.1 to
3.5, from 2.2 to 3.5, from 2.3 to 3.5, from 2.4 to 3.5, from 2.5 to 3.5, from 2.6 to 3.5, from 2.7 to 3.5, from 2.8 to 3.5, from 2.9 to 3.5, from 3 to 3.5, from 3.1 to 3.5, from 3.2 to 3.5, from 3.3 to 3.5, from 3.4 to 3.5, from greater than 0 to 3.4, from 0.1 to 3.4, from 0.2 to 3.4, from 0.3 to 3.4, from 0.4 to 3.4, from 0.5 to 3.4, from 0.6 to 3.4, from 0.7 to 3.4, from 0.8 to 3.4, from 0.9 to 3.4, from 1 to 3.4, from 1.1 to 3.4, from 1.2 to 3.4, from 1.3 to 3.4, from 1.4 to 3.4, from 1.5 to 3.4, from 1.6 to 3.4, from 1.7 to 3.4, from 1.8 to 3.4, from 1.9 to 3.4, from 2 to 3.4, from 2.1 to 3.4, from 2.2 to 3.4, from 2.3 to 3.4, from 2.4 to 3.4, from 2.5 to 3.4, from 2.6 to 3.4, from 2.7 to 3.4, from 2.8 to 3.4, from 2.9 to 3.4, from 3 to 3.4, from 3.1 to 3.4, from 3.2 to 3.4, from 3.3 to 3.4, from greater than 0 to 3.3, from 0.1 to 3.3, from 0.2 to 3.3, from 0.3 to 3.3, from 0.4 to 3.3, from 0.5 to 3.3, from 0.6 to 3.3, from 0.7 to 3.3, from 0.8 to 3.3, from 0.9 to 3.3, from 1 to 3.3, from 1.1 to 3.3, from 1.2 to 3.3, from 1.3 to 3.3, from 1.4 to 3.3, from 1.5 to 3.3, from 1.6 to 3.3, from 1.7 to 3.3, from 1.8 to 3.3, from 1.9 to 3.3, from 2 to 3.3, from 2.1 to 3.3, from 2.2 to 3.3, from 2.3 to 3.3, from 2.4 to 3.3, from 2.5 to 3.3, from 2.6 to 3.3, from 2.7 to 3.3, from 2.8 to 3.3, from 2.9 to 3.3, from 3 to 3.3, from 3.1 to 3.3, from 3.2 to 3.3, from greater than 0 to 3.2, from 0.1 to 3.2, from 0.2 to 3.2, from 0.3 to 3.2, from 0.4 to 3.2, from 0.5 to 3.2, from 0.6 to 3.2, from 0.7 to 3.2, from 0.8 to 3.2, from 0.9 to 3.2, from 1 to 3.2, from 1.1 to 3.2, from 1.2 to 3.2, from 1.3 to 3.2, from 1.4 to 3.2, from 1.5 to 3.2, from 1.6 to 3.2, from 1.7 to 3.2, from 1.8 to 3.2, from 1.9 to 3.2, from 2 to 3.2, from 2.1 to 3.2, from 2.2 to 3.2, from 2.3 to 3.2, from 2.4 to 3.2, from 2.5 to 3.2, from 2.6 to 3.2, from 2.7 to 3.2, from 2.8 to 3.2, from 2.9 to 3.2, from 3 to 3.2, from 3.1 to 3.2, from greater than 0 to 3.1, from 0.1 to 3.1, from 0.2 to 3.1, from 0.3 to 3.1, from 0.4 to 3.1, from 0.5 to 3.1, from 0.6 to 3.1, from 0.7 to 3.1, from 0.8 to 3.1, from 0.9 to 3.1, from 1 to 3.1, from 1.1 to 3.1, from 1.2 to 3.1, from 1.3 to 3.1, from 1.4 to 3.1, from 1 .5 to 3.1, from 1 .6 to 3.1, from 1 .7 to 3.1, from 1 .8 to 3.1, from 1 .9 to 3.1, from 2 to 3.1, from 2.1 to 3.1, from 2.2 to 3.1, from 2.3 to 3.1, from 2.4 to 3.1, from 2.5 to 3.1, from 2.6 to 3.1, from 2.7 to 3.1, from 2.8 to 3.1, from 2.9 to 3.1, from 3 to 3.1, from greater than 0 to 3, from 0.1 to 3, from 0.2 to 3, from 0.3 to 3, from 0.4 to 3, from 0.5 to 3, from 0.6 to 3, from 0.7 to 3, from 0.8 to 3, from 0.9 to 3, from 1 to 3, from 1.1 to 3, from 1.2 to 3, from 1.3 to 3, from
1.4 to 3, from 1.5 to 3, from 1.6 to 3, from 1.7 to 3, from 1.8 to 3, from 1.9 to 3, from 2 to 3, from 2.1 to 3, from 2.2 to 3, from 2.3 to 3, from 2.4 to 3, from 2.5 to 3, from 2.6 to 3, from 2.7 to 3, from 2.8 to 3, from 2.9 to 3, from greater than 0 to 2.9, from 0.1 to 2.9, from 0.2 to 2.9, from 0.3 to 2.9, from 0.4 to 2.9, from 0.5 to 2.9, from 0.6 to 2.9, from 0.7 to 2.9, from 0.8 to
2.9, from 0.9 to 2.9, from 1 to 2.9, from 1.1 to 2.9, from 1.2 to 2.9, from 1.3 to 2.9, from 1.4 to
2.9, from 1.5 to 2.9, from 1.6 to 2.9, from 1.7 to 2.9, from 1.8 to 2.9, from 1.9 to 2.9, from 2 to
2.9, from 2.1 to 2.9, from 2.2 to 2.9, from 2.3 to 2.9, from 2.4 to 2.9, from 2.5 to 2.9, from 2.6 to 2.9, from 2.7 to 2.9, from 2.8 to 2.9, from greater than 0 to 2.8, from 0.1 to 2.8, from 0.2 to 2.8, from 0.3 to 2.8, from 0.4 to 2.8, from 0.5 to 2.8, from 0.6 to 2.8, from 0.7 to 2.8, from 0.8 to 2.8, from 0.9 to 2.8, from 1 to 2.8, from 1.1 to 2.8, from 1.2 to 2.8, from 1.3 to 2.8, from 1.4 to 2.8, from 1.5 to 2.8, from 1.6 to 2.8, from 1.7 to 2.8, from 1.8 to 2.8, from 1.9 to 2.8, from 2 to 2.8, from 2.1 to 2.8, from 2.2 to 2.8, from 2.3 to 2.8, from 2.4 to 2.8, from 2.5 to 2.8, from 2.6 to 2.8, from 2.7 to 2.8, from greater than 0 to 2.7, from 0.1 to 2.7, from 0.2 to 2.7, from 0.3 to 2.7, from 0.4 to 2.7, from 0.5 to 2.7, from 0.6 to 2.7, from 0.7 to 2.7, from 0.8 to 2.7, from 0.9 to 2.7, from 1 to 2.7, from 1.1 to 2.7, from 1.2 to 2.7, from 1.3 to 2.7, from 1.4 to 2.7, from
1.5 to 2.7, from 1.6 to 2.7, from 1.7 to 2.7, from 1.8 to 2.7, from 1.9 to 2.7, from 2 to 2.7, from
2.1 to 2.7, from 2.2 to 2.7, from 2.3 to 2.7, from 2.4 to 2.7, from 2.5 to 2.7, from 2.6 to 2.7, from greater than 0 to 2.6, from 0.1 to 2.6, from 0.2 to 2.6, from 0.3 to 2.6, from 0.4 to 2.6, from 0.5 to 2.6, from 0.6 to 2.6, from 0.7 to 2.6, from 0.8 to 2.6, from 0.9 to 2.6, from 1 to 2.6, from
1.1 to 2.6, from 1.2 to 2.6, from 1.3 to 2.6, from 1.4 to 2.6, from 1.5 to 2.6, from 1.6 to 2.6, from 1.7 to 2.6, from 1.8 to 2.6, from 1.9 to 2.6, from 2 to 2.6, from 2.1 to 2.6, from 2.2 to 2.6, from 2.3 to 2.6, from 2.4 to 2.6, from 2.5 to 2.6, from greater than 0 to 2.5, from 0.1 to 2.5, from 0.2 to 2.5, from 0.3 to 2.5, from 0.4 to 2.5, from 0.5 to 2.5, from 0.6 to 2.5, from 0.7 to 2.5, from 0.8 to 2.5, from 0.9 to 2.5, from 1 to 2.5, from 1.1 to 2.5, from 1.2 to 2.5, from 1.3 to 2.5, from 1.4 to 2.5, from 1.5 to 2.5, from 1.6 to 2.5, from 1.7 to 2.5, from 1.8 to 2.5, from 1.9 to 2.5, from 2 to 2.5, from 2.1 to 2.5, from 2.2 to 2.5, from 2.3 to 2.5, from 2.4 to 2.5, from greater than 0 to 2.4, from 0.1 to 2.4, from 0.2 to 2.4, from 0.3 to 2.4, from 0.4 to 2.4, from 0.5 to 2.4, from 0.6 to 2.4, from 0.7 to 2.4, from 0.8 to 2.4, from 0.9 to 2.4, from 1 to 2.4, from 1.1 to 2.4, from 1.2 to 2.4, from 1.3 to 2.4, from 1.4 to 2.4, from 1.5 to 2.4, from 1.6 to 2.4, from 1.7 to 2.4, from 1.8 to 2.4, from 1.9 to 2.4, from 2 to 2.4, from 2.1 to 2.4, from 2.2 to 2.4, from 2.3 to 2.4, from greater than 0 to 2.3, from 0.1 to 2.3, from 0.2 to 2.3, from 0.3 to 2.3, from 0.4 to 2.3, from 0.5 to 2.3, from 0.6 to 2.3, from 0.7 to 2.3, from 0.8 to 2.3, from 0.9 to 2.3, from 1 to 2.3, from 1.1 to 2.3, from 1.2 to 2.3, from 1.3 to 2.3, from 1.4 to 2.3, from 1.5 to 2.3, from 1.6 to 2.3, from 1.7 to 2.3, from 1.8 to 2.3, from 1.9 to 2.3, from 2 to 2.3, from 2.1 to 2.3, from 2.2 to 2.3, from greater than 0 to 2.2, from 0.1 to 2.2, from 0.2 to 2.2, from 0.3 to 2.2, from 0.4 to 2.2, from 0.5 to 2.2, from 0.6 to 2.2, from 0.7 to 2.2, from 0.8 to 2.2, from 0.9 to 2.2, from 1 to 2.2, from 1.1 to 2.2, from 1.2 to 2.2, from 1.3 to 2.2, from 1.4 to 2.2, from 1.5 to 2.2, from 1.6 to 2.2, from 1.7 to 2.2, from 1.8 to 2.2, from 1.9 to 2.2, from 2 to 2.2, from 2.1 to 2.2, from greater than 0 to 2.1, from 0.1 to 2.1, from 0.2 to 2.1, from 0.3 to 2.1, from 0.4 to 2.1, from 0.5 to 2.1, from 0.6 to 2.1, from 0.7 to 2.1, from 0.8 to 2.1, from 0.9 to 2.1, from 1 to 2.1, from 1.1 to 2. 1, from 1.2 to 2.1, from 1.3 to 2.1, from 1.4 to 2.1, from 1.5 to 2.1, from 1.6 to 2.1, from 1.7 to 2.1, from 1.8 to 2.1, from 1.9 to 2.1, from 2 to 2.1, from greater than 0 to 2, from 0.1 to 2, from 0.2 to 2, from 0.3 to 2, from 0.4 to 2, from 0.5 to 2, from 0.6 to 2, from 0.7 to 2, from 0.8 to 2, from 0.9 to 2, from 1 to 2, from 1.1 to 2, from 1.2 to 2, from 1.3 to 2, from 1.4 to 2, from 1.5 to 2, from 1.6 to 2, from 1.7 to 2, from 1.8 to 2, from 1.9 to 2, from greater than 0 to 1.9, from 0.1 to 1.9, from 0.2 to 1.9, from 0.3 to 1.9, from 0.4 to 1.9, from 0.5 to 1.9, from 0.6 to 1.9, from 0.7 to 1.9, from 0.8 to 1.9, from 0.9 to 1.9, from 1 to 1.9, from 1.1 to 1.9, from 1.2 to 1.9, from 1.3 to 1.9, from 1.4 to 1.9, from 1.5 to 1.9, from 1.6 to 1.9, from 1.7 to 1.9, from 1.8 to 1.9, from greater than 0 to 1.8, from 0.1 to 1.8, from 0.2 to 1.8, from 0.3 to 1.8, from 0.4 to 1.8, from 0.5 to 1.8, from 0.6 to 1.8, from 0.7 to 1.8, from 0.8 to 1.8, from 0.9 to 1.8, from 1 to 1.8, from 1.1 to 1.8, from 1.2 to 1.8, from 1.3 to 1.8, from 1.4 to 1.8, from 1.5 to 1.8, from 1.6 to 1.8, from 1.7 to 1.8, from greater than 0 to 1.7, from 0.1 to 1.7, from 0.2 to 1.7, from 0.3 to 1.7, from 0.4 to 1.7, from 0.5 to 1.7, from 0.6 to 1.7, from 0.7 to 1.7, from 0.8 to 1.7, from 0.9 to 1.7, from 1 to 1.7, from 1.1 to 1.7, from 1.2 to 1.7, from 1.3 to 1.7, from 1.4 to 1.7, from 1.5 to 1.7, from 1.6 to 1.7, from greater than 0 to 1.6, from 0.1 to 1.6, from 0.2 to 1.6, from 0.3 to 1.6, from 0.4 to 1.6, from 0.5 to 1.6, from 0.6 to 1.6, from 0.7 to 1.6, from 0.8 to 1.6, from 0.9 to 1.6, from 1 to 1.6, from 1.1 to 1.6, from 1.2 to 1.6, from 1.3 to 1.6, from 1.4 to 1.6, from 1.5 to 1.6, from greater than 0 to 1 .5, from 0.1 to 1 .5, from 0.2 to 1 .5, from 0 3 to 1.5, from 0.4 to 1 .5, from 0.5 to 1.5, from 0.6 to 1.5, from 0.7 to 1.5, from 0.8 to 1.5, from 0.9 to 1.5, from 1 to 1.5, from
1.1 to 1.5, from 1.2 to 1.5, from 1.3 to 1.5, from 1.4 to 1.5, from greater than 0 to 1.4, from 0.1 to 1.4, from 0.2 to 1.4, from 0.3 to 1.4, from 0.4 to 1.4, from 0.5 to 1.4, from 0.6 to 1.4, from 0.7 to 1.4, from 0.8 to 1.4, from 0.9 to 1.4, from 1 to 1.4, from 1.1 to 1.4, from 1.2 to 1.4, from
1.3 to 1.4, from greater than 0 to 1.3, from 0.1 to 1.3, from 0.2 to 1.3, from 0.3 to 1.3, from 0.4 to 1.3, from 0.5 to 1.3, from 0.6 to 1.3, from 0.7 to 1.3, from 0.8 to 1.3, from 0.9 to 1.3, from 1 to 1.3, from 1.1 to 1.3, from 1.2 to 1.3, from greater than 0 to 1.2, from 0.1 to 1.2, from 0.2 to 1.2, from 0.3 to 1.2, from 0.4 to 1.2, from 0.5 to 1.2, from 0.6 to 1.2, from 0.7 to 1.2, from 0.8 to 1.2, from 0.9 to 1.2, from 1 to 1.2, from 1.1 to 1.2, from greater than 0 to 1.1, from 0.1 to 1.1, from 0.2 to 1.1, from 0.3 to 1.1, from 0.4 to 1.1, from 0.5 to 1.1, from 0.6 to 1.1, from 0.7 to 1.1, from 0.8 to 1.1, from 0.9 to 1.1, from 1 to 1.1, from greater than 0 to 1, from 0.1 to 1, from 0.2 to 1, from 0.3 to 1, from 0.4 to 1, from 0.5 to 1, from 0.6 to 1, from 0.7 to 1, from 0.8 to 1, from 0.9 to 1, from greater than 0 to 0.9, from 0.1 to 0.9, from 0.2 to 0.9, from 0.3 to 0.9, from 0.4 to 0.9, from 0.5 to 0.9, from 0.6 to 0.9, from 0.7 to 0.9, from 0.8 to 0.9, from greater than 0 to 0.8, from 0.1 to 0.8, from 0.2 to 0.8, from 0.3 to 0.8, from 0.4 to 0.8, from 0.5 to 0.8, from 0.6 to 0.8, from 0.7 to 0.8, from greater than 0 to 0.7, from 0.1 to 0.7, from 0.2 to 0.7, from 0.3 to 0.7, from 0.4 to 0.7, from 0.5 to 0.7, from 0.6 to 0.7, from greater than 0 to 0.6, from 0.1 to 0.6, from 0.2 to 0.6, from 0.3 to 0.6, from 0.4 to 0.6, from 0.5 to 0.6, from greater than 0 to 0.5, from 0.1 to 0.5, from 0.2 to 0.5, from 0.3 to 0.5, from 0.4 to 0.5, from greater than 0 to 0.4, from 0.1 to 0.4, from 0.2 to 0.4, from 0.3 to 0.4, from greater than 0 to 0.3, from 0.1 to 0.3, from 0.2 to 0.3, from greater than 0 to 0.2, from 0.1 to 0.2, or from greater than 0 to 0.1) percent by weight, based on the total weight of the composition. In certain embodiments, the alkaline earth metal alkyl detergent comprises an alkaline earth metal which is at least one of magnesium or calcium. In certain embodiments, the alkaline earth metal alkyl detergent comprises a surfactant portion which is at least one of phenate, salicylate, sulfonate, saligenin, or salixarate. In certain embodiments, the alkaline earth metal alkyl detergent comprises a surfactant portion which is at least one of salicylate or sulfonate.
[0065] In certain embodiments, the composition comprises less than 200 (such as less than 190, less than 180, less than 170, less than 160, less than 150, less than 140, less than 130, less than 120, less than 110, less than 100, less than 90, less than 80, less than 70, less than 60, less than 50, less than 40, less than 30, less than 20, or less than 10) ppm by weight magnesium, based on the total weight of the composition. In certain embodiments, the composition may be substantially free of magnesium-containing material. In certain embodiments, the composition will not include any intentionally-added, magnesium-containing material.
[0066] In certain embodiments, the composition further comprises an aromatic amine, maleic anhydride, ethylene-propylene copolymer dispersant in an amount of from 0.1 to 5 (such as from 0.5 to 5, from 1 to 5, from 1.5 to 5, from 2 to 5, from 2.5 to 5, from 3 to 5, from 3.5 to 5, from 4 to 5, from 4.5 to 5, from 0.1 to 4.5, from 0.5 to 4.5, from 1 to 4.5, from 1.5 to 4.5, from 2 to 4.5, from 2.5 to 4.5, from 3 to 4.5, from 3.5 to 4.5, from 4 to 4.5, from 0.1 to 4, from 0.5 to 4, from 1 to 4, from 1.5 to 4, from 2 to 4, from 2.5 to 4, from 3 to 4, from 3.5 to 4, from 0.1 to 3.5, from 0.5 to 3.5, from 1 to 3.5, from 1.5 to 3.5, from 2 to 3.5, from 2.5 to 3.5, from 3 to 3.5, from 0.1 to 3, from 0.5 to 3, from 1 to 3, from 1.5 to 3, from 2 to 3, from 2.5 to 3, from 0.1 to 2.5, from 0.5 to 2.5, from 1 to 2.5, from 1.5 to 2.5, from 2 to 2.5, from 0.1 to 2, from 0.5 to 2, from 1 to 2, from 1.5 to 2, from 0.1 to 1.5, from 0.5 to 1.5, from 1 to 1.5, from 0.1 to 1, from 0.5 to 1, or from 0.1 to 0.5) percent by weight, based on the total weight of the composition.
[0067] In certain embodiments, the composition further comprises at least one additional additive comprising at least one of antioxidants, detergents (other than the alkaline earth metal alkyl detergent described herein), dispersants, antiwear agent, corrosion inhibitors, viscosity modifiers (other than the DVM discussed above), metal passivators, pour point depressants, seal compatibility agents, antifoam agents, extreme pressure agents, or friction modifiers.
[0068] Any suitable antioxidants may be used, as would be understood by one of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable antioxidants. Antioxidants encompass phenolic antioxidants, which may comprise a butyl substituted phenol containing 2 or 3 t-butyl groups. The para position may also be occupied by a hydrocarbyl group, an ester-containing group, or a group bridging two aromatic rings. Antioxidants also include aromatic amines, such as nonylated diphenylamines or alkylated phenylnaphthylamine. Other antioxidants include sulfurized olefins, titanium compounds, and molybdenum compounds. US 4,285,822, for instance, discloses lubricating oil compositions containing a molybdenum and sulfur containing composition. US 2006/0217271 Al discloses a variety of titanium compounds, including titanium alkoxides and titanated dispersants, which materials may also impart improvements in deposit control and fdterability. Other titanium compounds include titanium carboxylates such as neodecanoate. If a titanium compound is present, its amount may be such as to provide 15 to 1000 or 25 to 200 parts per million titanium. Typical amounts of antioxidants will, of course, depend on the specific antioxidant and its individual effectiveness, but illustrative total amounts can be 0.01 to 5 (such as from 0.15 to 4.5, or from 0.2 to 4) percent by weight, based on the total weight of the composition. Additionally, more than one antioxidant may be present, and certain combinations of these can be synergistic in their combined overall effect.
[0069] In addition to the alkaline earth metal alkyl detergent described above, any other suitable detergents may be used, as would be understood be one of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable additional detergents. In certain embodiments, the detergent may comprise an overbased metal detergent. Overbased detergents are generally homogeneous Newtonian systems having a metal content in excess of that which would be present for neutralization according to the stoichiometry of the metal and the detergent anion. The amount of excess metal is commonly expressed in terms of metal ratio, that is, the ratio of the total equivalents of the metal to the equivalents of the acidic organic compound. Overbased materials are prepared by reacting an acidic material (such as carbon dioxide) with an acidic organic compound, an inert reaction medium (such as mineral oil), a stoichiometric excess of a metal base, and a promoter (such as a phenol or alcohol). The acidic organic material will normally have a sufficient number of carbon atoms to provide oil-solubility.
[0070] Overbased detergents may be characterized by TBN (ASTM D4739), the amount of strong acid needed to neutralize all of the material's basicity, expressed as mg KOH per gram of sample. Since overbased detergents are commonly provided in a form which contains diluent oil, for the purpose of this document, TBN is to be recalculated to an oil-free basis by dividing by the fraction of the detergent (as supplied) that is not oil. Some suitable detergents may have a TBN of 100 to 800, or 150 to 750, or 400 to 700.
[0071] The metal compounds suitable in making the basic metal salts are generally any Group 1 or Group 2 metal compounds (CAS version of the Periodic Table of the Elements). Examples include alkali metals such as sodium, potassium, lithium, copper, magnesium, calcium, barium, zinc, and cadmium. In certain embodiments, the metals are sodium, magnesium, or calcium; or calcium or magnesium; or calcium. The anionic portion of the salt may be hydroxide, oxide, carbonate, borate, or nitrate.
[00721 In certain embodiments, the lubricant can contain an overbased sulfonate detergent. Suitable sulfonic acids include sulfonic and thiosulfonic acids, including mono- or polynuclear aromatic or cycloaliphatic compounds. Certain oil-soluble sulfonates can be represented by R2- T- (SO3')a or R3-(SO3')b, where a and b are each at least one; T is a cyclic nucleus such as benzene or toluene; R2 is an aliphatic group such as alkyl, alkenyl, alkoxy, or alkoxyalkyl; (R2)- T typically contains a total of at least 15 carbon atoms; and R3 is an aliphatic hydrocarbyl group typically containing at least 15 carbon atoms. The groups T, R2, and R3 can also contain other inorganic or organic substituents. In certain embodiments, the sulfonate detergent may be a predominantly linear alkylbenzenesulfonate detergent having a metal ratio of at least 8 as described in paragraphs [0026] to [0037] of US 2005/0065045 Al. In some embodiments the linear alkyl group may be attached to the benzene ring anywhere along the linear chain of the alkyl group, but often in the 2, 3 or 4 position of the linear chain, and in some instances predominantly in the 2 position.
[0073] Another overbased material is an overbased phenate detergent. The phenols suitable in making phenate detergents can be represented by (Rx)a — Ar — (OH)b, where R1 is an aliphatic hydrocarbyl group of 4 to 400, or 6 to 80, or 6 to 30, or 8 to 25, or 8 to 15 carbon atoms; Ar is an aromatic group such as benzene, toluene or naphthalene; a and b are each at least one, the sum of a and b being up to the number of displaceable hydrogens on the aromatic nucleus of Ar, such as 1 to 4, or 1 to 2. There is typically an average of at least 8 aliphatic carbon atoms provided by the R1 groups for each phenol compound. Phenate detergents are also sometimes provided as sulfur-bridged species.
[0074] Alkylphenols are often used as constituents in and/or building blocks for overbased detergents. Alkylphenols may be used to prepare phenate, salicylate, salixarate, or saligenin detergents or mixtures thereof. Suitable alkylphenols may include para-substituted hydrocarbyl phenols. The hydrocarbyl group may be linear or branched aliphatic groups of 1 to 60 carbon atoms, 8 to 40 carbon atoms, 10 to 24 carbon atoms, 12 to 20 carbon atoms, or 16 to 24 carbon atoms. In certain embodiments, the alkylphenol overbased detergent is prepared from an alkylphenol or mixture thereof that is free of or substantially free of p-dodecylphenol. In certain embodiments, the lubricating composition of the invention contains less than 0.3 weight percent of alkylphenol, less than 0 1 weight percent of alkylphenol, or less than 0.05 weight percent of alkylphenol.
[00751 In certain embodiments, the overbased material is an overbased saligenin detergent. Overbased saligenin detergents are commonly overbased magnesium salts which are based on saligenin derivatives. A general example of such a saligenin derivative can be represented by the formula
Figure imgf000022_0001
where X is — CHO or — CH2OH, Y is — CH2 — or — CH2OCH2 — , and the — CHO groups typically comprise at least 10 mole percent of the X and Y groups; M is hydrogen, ammonium, or a valence of a metal ion (that is, if M is multivalent, one of the valences is satisfied by the illustrated structure and other valences are satisfied by other species such as anions or by another instance of the same structure), Ri is a hydrocarbyl group of 1 to 60 carbon atoms, m is 0 to 10, and each p is independently 0, 1, 2, or 3, provided that at least one aromatic ring contains an R1 substituent and that the total number of carbon atoms in all R1 groups is at least 7. When m is 1 or greater, one of the X groups can be hydrogen. In certain embodiments, M is a valence of a Mg ion or a mixture of Mg and hydrogen. Saligenin detergents are disclosed in greater detail in US 6,310,009 Bl, with special reference to their methods of synthesis (column 8 and Example 1) and preferred amounts of the various species of X and Y (column 6).
[0076] Salixarate detergents are overbased materials that can be represented by a compound comprising at least one unit of formula (A) and/or formula (B) and each end of the compound having a terminal group of formula (C) and/or (D):
Figure imgf000022_0002
Figure imgf000023_0001
such groups being linked by divalent bridging groups A, which may be the same or different. In formulas (A)-(D) R3 is hydrogen, a hydrocarbyl group, or a valence of a metal ion; R2 is hydroxyl or a hydrocarbyl group, and j is 0, 1, or 2; R6is hydrogen, a hydrocarbyl group, or a hetero- substituted hydrocarbyl group; either R4is hydroxyl and R5 and R7 are independently either hydrogen, a hydrocarbyl group, or hetero-substituted hydrocarbyl group, or else R5 and R7 are both hydroxyl and R4 is hydrogen, a hydrocarbyl group, or a hetero-substituted hydrocarbyl group; provided that at least one of R4, R5, R6 and R7 is hydrocarbyl containing at least 8 carbon atoms; and wherein the molecules on average contain at least one of unit (A) or (C) and at least one of unit (B) or (D) and the ratio of the total number of units (A) and (C) to the total number of units of (B) and (D) in the composition is 0.1 : 1 to 2: 1. The divalent bridging group “A,” which may be the same or different in each occurrence, includes — CH2 — and — CH2OCH2 — , either of which may be derived from formaldehyde or a formaldehyde equivalent (e.g., paraformaldehyde, formalin). Salixarate derivatives and methods of their preparation are described in greater detail in US 6,200,936 Bl and WO 01/56968 Al. It is believed that the salixarate derivatives have a predominantly linear, rather than macrocyclic, structure, although both structures are intended to be encompassed by the term “salixarate.” [0077] Glyoxylate detergents are similar overbased materials which are based on an anionic group which, in certain embodiments, may have the structure
Figure imgf000023_0002
wherein each R is independently an alkyl group containing at least 4, or at least 8 carbon atoms, provided that the total number of carbon atoms in all such R groups is at least 12, or at least 16, or at least 24. Alternatively, each R can be an olefin polymer substituent. The acidic material from which the overbased glyoxylate detergent is prepared is the condensation product of a hydroxyaromatic material such as a hydrocarbyl-substituted phenol with a carboxylic reactant such as glyoxylic acid or another omega-oxoalkanoic acid. Overbased glyoxylic detergents and their methods of preparation are disclosed in greater detail in US 6,310,011 Bl .
[0078] The overbased detergent can also be an overbased salicylate, e.g., an alkali metal or alkaline earth metal salt of a substituted salicylic acid. The salicylic acids may be hydrocarbyl- substituted wherein each substituent contains an average of at least 8 carbon atoms per substituent and 1 to 3 substituents per molecule. The substituents can be polyalkene substituents. In certain embodiments, the hydrocarbyl substituent group contains 7 to 300 carbon atoms and can be an alkyl group having a molecular weight of 150 to 2000. Overbased salicylate detergents and their methods of preparation are disclosed in US 4,719,023 and US 3,372,116. Salicylate detergents and overbased salicylate detergents may be prepared in at least two different manners. Carbonylation (also referred to as carboxylation) of a p-alkylphenol is described in many references, including US 8,399,388 B2. Carbonylation may be followed by overbasing to form overbased salicylate detergent. Suitable p-alkylphenols include those with linear and/or branched hydrocarbyl groups of 1 to 60 carbon atoms. Salicylate detergents may also be prepared by alkylation of salicylic acid, followed by overbasing, as described in US 7,009,072 B2. Salicylate detergents prepared in this manner, may be prepared from linear and/or branched alkylating agents (usually 1-olefins) containing 6 to 50 carbon atoms, 10 to 30 carbon atoms, or 14 to 24 carbon atoms. In certain embodiments, the overbased detergent of the invention is a salicylate detergent. In certain embodiments, the salicylate detergent of the invention may be substantially free of, or free of unreacted p-alkylphenol. In certain embodiments, the salicylate detergent of the invention is prepared by alkylation of salicylic acid.
[0079] Other overbased detergents can include overbased detergents having a Mannich base structure, as disclosed in US 6,569,818 B2.
[0080] In certain embodiments, the hydrocarbyl substituents on hydroxy-substituted aromatic rings in the above detergents (e.g., phenate, saligenin, salixarate, glyoxylate, or salicylate) are free of or substantially free of C12 aliphatic hydrocarbyl groups. In some embodiments such hydrocarbyl substituents contain at least 14, or at least 18 carbon atoms. [0081] Any suitable dispersants may be used, as would be understood by one of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable dispersants. In certain embodiments, the dispersant(s) may be succinimide dispersants. In certain embodiments, the succinimide dispersants may be present in the lubricating composition in an amount of from 0.25 to 5 (such as from 0.25 to 4.5, from 0.25 to 4.25, from 0.5 to 4, from 1 to 3.5, from 0.35 to 1.8, from 0.5 to 1.5, or from 1 to 1.45) percent by weight, based on the total weight of the composition. Suitable succinimide dispersants include, without limitation, N-substituted long chain alkenyl succinimides, having a variety of chemical structures, such as
Figure imgf000025_0001
where each Rx is independently an alkyl group, such as a polyisobutylene group, and the R1 groups may have a number average molecular weight (Mn) of 1000 to 3,500. The R2 groups are alkylene groups, such as ethylene (C2H4) groups. The Mn of the R1 groups may alternatively be 1500 to 3000, or 2800 to 2500. Such molecules may be derived from reaction of an alkenyl acylating agent with a polyamine, and a wide variety of linkages between the two moieties is possible beside the simple imide structure shown above, including a variety of amides and quaternary ammonium salts. In the above structure, the amine portion is shown as an alkylene polyamine, although other aliphatic and aromatic mono- and polyamines may also be used. Also, a variety of modes of linkage of the R1 groups onto the imide structure are possible, including various cyclic linkages. The ratio of the carbonyl groups of the acylating agent to the nitrogen atoms of the amine may be 1 :0.5 to 1:3, and in other instances 1 : 1 to 1 :2.75, or 1: 1.5 to 1 :2.5. Succinimide dispersants are more fully described in US 4,234,435, US 3,172,892, and EP 0 355 895 Bl . Succinimides made by the so-called conventional (or chlorine) route as well as by the thermal or direct alkylation or “ene” route are included, as disclosed in the abovereferenced patent documents. Succinimide dispersants made by the different routes may be characterized by differences in the detailed structures, whereby the R1 groups are attached. Dispersants may also be post-treated with various agents such as borating agents (e.g., boric acid) to make borated dispersants. [0082] TBN of the dispersant will depend on the amount of amine functionality contained therein, and may be 10 to 60, or 12 to 50, or 15 to 40, or 20 to 35, or 30 to 35. Other embodiments may include 10 to 30, or 12 to 25, or 20 to 60, or 30 to 50 mg KOH/g (all calculated on an oil-free basis).
[0083] Succinimide dispersants can also be post-treated by reaction with any of a variety of agents. Among these are urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, and phosphorus compounds. References detailing such treatment are listed in US 4,654,403.
[0084] In certain embodiments, the dispersant may be or comprise a dispersant viscosity modifier (because the material may have both dispersant and viscosity modifying properties, e.g., as described below, the olefin polymer may serve to impart viscosity modifier performance and the reacted amine may provide nitrogen or other polar functionality that may impart dispersant performance). In certain embodiments, the dispersant viscosity modifier may comprise an olefin polymer that has been modified by the addition of a polar moiety. In certain embodiments, the dispersant viscosity modifier may comprise an ashless condensation reaction product of an olefin polymer with grafted carboxylic acid (or equivalent) functionality, reacted with a monoamine or a polyamine which may have a single primary amino group. If the olefin polymer is an ethyl ene/propylene copolymer, then said polyamine is not a poly(ethyleneamine). Various dispersant viscosity modifiers have been used in the lubrication of heavy-duty diesel engines, where they perform the role of dispersing soot arising from the combustion of the diesel fuel. Gasoline (spark-ignited) engines generally do not generate soot and thus such dispersant viscosity modifiers may not be used in gasoline engines for the dispersion of soot. The use of the present dispersant viscosity modifiers in a non-sooted engine environment permits reduction in the amount of conventional dispersant, such as succinimide dispersant, while retaining dispersant performance and permitting greater flexibility in formulation of the lubricant composition to meet performance targets. In certain embodiments, the olefin polymer is an ethylene-a-olefin copolymer. The formation of functionalized ethylene-a-olefin copolymer is well known in the art, for instance those described in US 7,790,661 B2, column 2, line 48, to column 10, line 38. Additional detailed descriptions of similar functionalized ethylene-a-olefin copolymers may be found in WO 2006/015130 Al, US 4,863,623, US 6,107,257, US 6,107,258, US 6,117,825, and US 7,790,661 B2. Tn certain embodiments, the functionalized ethylene-a-olefin copolymer may include those described in US 4,863,623 (column 2, line 15, to column 3, line 52) or in WO 2006/015130 Al (paragraph [0008] and paragraphs [0065] to [0073]).
[0085] The olefm polymers may be functionalized by modifying the polymer by the addition of a polar moiety. In certain embodiments, the functionalized copolymer is the reaction product of an olefm polymer grafted with an acylating agent. In certain embodiments, the acylating agent may be an ethylenically unsaturated acylating agent. Suitable acylating agents are typically a, p-un saturated compounds having at least one ethylenic bond (prior to reaction) and at least one, for example two, carboxylic acid (or its anhydride) groups or a polar group which is convertible into said carboxyl groups by oxidation or hydrolysis. The acylating agent grafts onto the olefm polymer to give two carboxylic acid functionalities. Examples of suitable acylating agents include maleic anhydride, chlormaleic anhydride, itaconic anhydride, or the reactive equivalents thereof, for example, the corresponding dicarboxylic acids, such as maleic acid, fumaric acid, cinnamic acid, (meth)acrylic acid, the esters of these compounds and the acid chlorides of these compounds.
[0086] In certain embodiments, the functionalized ethylene-a-olefin copolymer comprises an olefm copolymer grafted with the acyl group, which is further functionalized with a hydrocarbyl amine, a hydrocarbyl alcohol group, amino- or hydroxy- terminated polyether compounds, and mixtures thereof.
[0087] In certain embodiments, the hydrocarbyl amine may be selected from aromatic amines, aliphatic amines, and mixtures thereof. In certain embodiments, the hydrocarbyl amine component may comprise at least one aromatic amine containing at least one amino group capable of condensing with said acyl group to provide a pendant group and at least one additional group comprising at least one nitrogen, oxygen, or sulfur atom, wherein said aromatic amine is selected from the group consisting of (i) a nitro- substituted aniline, (ii) an amine comprising two aromatic moieties linked by a -(C=O)NR- group, a -C=O- group, an -O- group, an -N=N- group, or an -CH2- group where R is hydrogen or hydrocarbyl, one of said aromatic moieties bearing said condensable amino group, (iii) an aminoquinoline, (iv) an aminobenzimidazole, (v) an N,N- dialkylphenylenediamine, (vi), an aminodiphenyl amine (also N-phenylphenylenediamine), (vii) a ring-substituted benzylamine, and (viii) a methylene- coupled dimer of aminodiphenyl amine.
[00881 Any suitable corrosion inhibitors may be used, as would be understood by one of ordinary skill in the art.
[0089] Other performance additives, such as corrosion inhibitors, include those described in WO 2006/047486 Al, octyl octanamide, condensation products of dodecenyl succinic acid or anhydride and a fatty acid (such as oleic acid) with a polyamine may be present in the lubricating compositions described herein. In certain embodiments, the corrosion inhibitors include Synalox® (a registered trademark of The Dow Chemical Company) corrosion inhibitors. Synalox® corrosion inhibitors may be a homopolymer or copolymer of propylene oxide. The Synalox®. corrosion inhibitors are described in more detail in a product brochure with Form No. 118-01453-0702 AMS, published by The Dow Chemical Company, entitled “SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications”.
[0090] The lubricating compositions described herein may further comprise: metal deactivators, including derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles, benzimidazoles, 2- alkyldithiobenzimidazoles, and/or 2-alkyldithiobenzothiazoles; foam inhibitors, including copolymers of ethyl acrylate and 2-ethylhexylacrylate, and/or copolymers of ethyl acrylate and 2-ethylhexylacrylate and vinyl acetate; demulsifiers, including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides, and/or (ethylene oxide/propylene oxide) polymers; and pour point depressants, including esters of maleic anhydride- styrene, polymethacrylates, polyacrylates, and/or polyacrylamides.
[0091] Instead of or in addition to the optional dispersants (such as dispersant viscosity modifiers) describe above, any other suitable viscosity modifiers may be used, as would be understood by one of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable viscosity modifiers. The oil of lubricating viscosity will generally be selected so as to provide, among other properties, an appropriate viscosity (kinematic viscosity and/or high temperature high shear viscosity) and viscosity index. Many modern engine lubricants are multigrade lubricants which contain viscosity index improvers to provide suitable viscosity at both low and high temperatures, that is, a viscosity modifier other than the dispersant viscosity modifier as described above, that is to say, a supplemental viscosity modifier. While the viscosity modifier is sometimes considered a part of the base oil, it may be considered as a separate component, the selection of which is within the abilities of the person skilled in the art.
[0092] Viscosity modifiers may be polymeric materials which may be hydrocarbon-based polymers generally having number average molecular weights from 25,000 to 500,000, e.g., from 50,000 to 300,000, or from 50,000 to 200,000.
[0093] Hydrocarbon polymers can be used as viscosity index improvers. Examples include homopolymers and polymers of two or more monomers of C2 to C30, e.g., C2 to Cs olefins, including both alphaolefins and internal olefins, which may be straight or branched, aliphatic, aromatic, alkyl-aromatic, or cycloaliphatic. Examples include ethylene-propylene copolymers, generally referred to as OCP's, prepared by copolymerizing ethylene and propylene by known processes.
[0094] Hydrogenated styrene-conjugated diene copolymers or hydrogenated conjugated diene polymers are other classes of viscosity modifiers. These polymers include polymers which are hydrogenated or partially hydrogenated homopolymers, and also include random, tapered, star, and block interpolymers. The term “styrene” includes various substituted styrenes. The conjugated diene may contain four to six carbon atoms and may include, e.g., piperylene, 2,3-dimethyl-l,3-butadiene, chloroprene, isoprene, and 1,3 -butadiene. Mixtures of such conjugated dienes are suitable. The styrene content of these copolymers may be 20% to 70% by weight or 40% to 60%, and the aliphatic conjugated diene content may be 30% to 80% or 40% to 60%. These copolymers can be prepared by methods well known in the art and are typically hydrogenated to remove a substantial portion of their olefinic double bonds.
[0095] Esters obtained by copolymerizing styrene and maleic anhydride in the presence of a free radical initiator and thereafter esterifying the copolymer with a mixture of C4-18 alcohols also are suitable as viscosity modifying additives in motor oils. Likewise, poly(meth)acrylates (PMA) may be used as viscosity modifiers. As used herein, the term “(meth)acrylate” and its cognates means either methacrylate or acrylate, as will be readily understood. These materials are typically prepared from mixtures of (meth)acrylate monomers having different alkyl groups, which may be either straight chain or branched chain groups containing 1 to 18 carbon atoms. [0096] Certain viscosity modifiers may be multi-armed polymers. These may include (meth)acrylate-containing polymers comprising a multiplicity of arms which contain at least 20, or at least 50, or at least 100, or at least 200, or at least 350, or at least 500, or at least 1000, carbon atoms, said arms being attached to a multivalent organic moiety. The multi-armed polymer may thus be characteristic of a “star” polymer, a “comb” polymer, or a polymer otherwise having multiple arms or branches as described herein.
[0097] The amount of the viscosity modifier component (other than the dispersant viscosity modifier described above) may be from 0.02 to 5 (such as from 0.1 to 2, or from 0.2 to 1, or from 0.3 to 0.6) percent by weight, based on the total weight of the composition.
[0098] Any suitable metal passivators may be used, as would be understood by one of ordinary skill in the art.
[0099] Any suitable pour point depressants may be used, as would be understood by one of ordinary skill in the art. Without limitation, the following description provides certain embodiments of suitable pour point depressants. Suitable our point depressants may include polyalphaolefins, esters of maleic anhydride-styrene, poly(meth)acrylates, polyacrylates, and/or polyacrylamides.
[0100] Any suitable seal compatibility agents may be used, as would be understood by one of ordinary skill in the art.
[0101] Any suitable antifoam agents may be used, as would be understood by one of ordinary sill in the art. Without limitation, the following description provides certain embodiments of suitable antifoam agents. Suitable antifoam agents may include polysiloxanes, copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxidepropylene oxide) polymers.
[0102] Any suitable extreme pressure agents may be used, as would be understood by one of ordinary sill in the art. Without limitation, the following description provides certain embodiments of suitable extreme pressure agents. Extreme Pressure (EP) agents that are soluble in oil include sulfur- and chlorosulfur-containing EP agents, dimercaptothiadiazole or CS2 derivatives of dispersants (typically succinimide dispersants), derivatives of chlorinated hydrocarbon EP agents and phosphorus EP agents. Examples of such EP agents include chlorinated wax; sulfurized olefins (such as sulfurized isobutylene), a hydrocarbyl-substituted 2,5-dimercapto-l,3,4-thiadiazole, or oligomers thereof, organic sulphides and polysulphides such as dibenzyldisulphide, bis-(chlorobenzyl) disulphide, dibutyl tetrasulphide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons such as the reaction product of phosphorus sulphide with turpentine or methyl oleate; phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphites, e.g., dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite; dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite and polypropylene substituted phenol phosphite; metal thiocarbamates such as zinc dioctyldithiocarbamate and barium heptylphenol diacid; amine salts of alkyl and dialkylphosphoric acids or derivatives including, for example, the amine salt of a reaction product of a dialkyldithiophosphoric acid with propylene oxide and subsequently followed by a further reaction with P2O5; and mixtures thereof (as described in US 3,197,405).
[0103] Any suitable friction modifiers may be used, as would be understood by one of ordinary sill in the art. Without limitation, the following description provides certain embodiments of suitable friction modifiers. Friction modifiers that may be suitable in an exemplary lubricating composition include fatty acid derivatives such as amines, esters, epoxides, fatty imidazolines, condensation products of carboxylic acids and polyalkylenepolyamines and amine salts of alkylphosphoric acids. Ashless friction modifiers are those which typically do not produce any sulfated ash when subjected to the conditions of ASTM D 874. An additive is referred to as “non-metal containing” if it does not contribute metal content to the lubricant composition. As used herein the term “fatty alkyl” or “fatty” in relation to friction modifiers means a carbon chain having 8 to 30 carbon atoms, typically a straight carbon chain. In certain embodiments, the ash-free friction modifier may be represented by the formula:
Figure imgf000031_0001
where, D and D' are independently selected from -O-, -NH, -NR23, an imide group formed by taking together both D and D' groups and forming a R21-N- group between two -C=O groups; E is selected from -R24-O-R25-, -CH2, -CHR26, -CR26R27, -C(OH)(CO2R22), -C(CO2R22)2, and -CHOR28; where R24 and R25 are independently selected from -CH2, -CHR26, -CR26R27, - C(OH)(CO2R22), and -CHOR28; q is 0 to 10, with the proviso that when q is 1, E is not -CH2, and when n is 2, both Es are not -CH2; p is 0 or 1 ; R21 is independently hydrogen or a hydrocarbyl group, optionally containing 1 to 150 carbon atoms, with the proviso that when R21 is hydrogen, p is 0, and q is more than or equal to 1; R22 is a hydrocarbyl group, typically containing 1 to 150 carbon atoms; R23, R24, R25, R26 and R27 are independently hydrocarbyl groups; and R28 is hydrogen or a hydrocarbyl group, optionally containing 1 to 150 carbon atoms, or 4 to 32 carbon atoms, or 8 to 24 carbon atoms. In certain embodiments, the hydrocarbyl groups R23, R24, and R25, may be linear or predominantly linear alkyl groups.
[0104] In certain embodiments, the ash-free friction modifier is a fatty ester, amide, or imide of various hydroxy-carboxylic acids, such as tartaric acid, malic acid lactic acid, glycolic acid, and mandelic acid. Examples of suitable materials include tartaric acid di(2-ethylhexyl) ester (e.g., di(2-ethylhexyl)tartrate), di(Cs-Cio)tartrate, di(Ci2-is)tartrate, di-oleyltartrate, oleyltartrimide, and oleyl maleimide.
[0105] In certain embodiments, the ash-free friction modifier may be chosen from long chain fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty phosphonates; fatty phosphites; borated phospholipids, borated fatty epoxides; glycerol esters; borated glycerol esters; fatty amines; alkoxylated fatty amines; borated alkoxylated fatty amines; hydroxyl and polyhydroxy fatty amines including tertiary hydroxy fatty amines; hydroxy alkyl amides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty oxazolines; fatty ethoxylated alcohols; condensation products of carboxylic acids and polyalkylene polyamines; or reaction products from fatty carboxylic acids with guanidine, aminoguanidine, urea, or thiourea and salts thereof.
[0106] Suitable friction modifiers may also encompass materials such as sulfurized fatty compounds and olefins, sunflower oil or soybean oil monoester of a polyol and an aliphatic carboxylic acid.
[0107] In certain embodiments, the friction modifier may be a long chain fatty acid ester. In certain embodiments, the long chain fatty acid ester may be a mono-ester and in another embodiment the long chain fatty acid ester may be a triglyceride. In certain embodiments, the ashless friction modifier is one or more of an ester, an amide, or an imide of an alpha-hydroxy carbonyl compound, and mixtures thereof. [0108] The ashless friction modifier may be present in the lubricating composition in an amount of from 0.01 to 6, or from 0.05 to 4, or from 0.1 to 2, or from 0.01 to 1.1, or from 0.1 to 0.5, or from 0.2 to 0.4 percent by weight, based on the total weight of the composition.
[0109] In certain embodiments, the composition comprises less than 200 (such as less than 190, less than 180, less than 170, less than 160, less than 150, less than 140, less than 130, less than 120, less than 110, less than 100, less than 90, less than 80, less than 70, less than 60, less than 50, less than 40, less than 30, less than 20, or less than 10) ppm by weight molybdenum, based on the total weight of the composition. In certain embodiments, the composition may be substantially free of molybdenum-containing material. In certain embodiments, the composition will not include any intentionally-added, molybdenum-containing material. Any suitable molybdenum-containing material may be used, as would be understood by one of ordinary sill in the art. Without limitation, the following description provides certain embodiments of suitable molybdenum-containing materials (also referred to as a molybdenum compound). Molybdenum compounds as lubricant additives are known in the art and may serve in various functions, such as antiwear agents, friction modifiers and antioxidants. The use of molybdenum- and sulfur-containing compositions in lubricating oil compositions as antiwear agents and antioxidants is known. Such materials may be a molybdenum hydrocarbyldithiocarbamate. US 4,285,822, for instance, discloses lubricating oil compositions containing a molybdenum and sulfur containing composition prepared by (1) combining a polar solvent, an acidic molybdenum compound and an oil-soluble basic nitrogen compound to form a molybdenum-containing complex and (2) contacting the complex with carbon disulfide to form the molybdenum and sulfur containing composition. Other molybdenum-containing materials include molybdenum dihydrocarbyldithio-phosphates. Yet other molybdenum- containing materials include molybdenum-amine compounds as described in US 6,329,327 Bl; organomolybdenum compounds made from the reaction of a molybdenum source, fatty oil, and a diamine as described in US 6,914,037 B2; and trinuclear molybdenum- sulfur complexes as described in US 6,232,276 B2. In certain embodiments, the molybdenum compound is a molybdenum dithiocarbamate complex, a molybdenum dithiocarbamate dimer complex, or a tri-nuclear molybdenum compound.
[0110] In certain embodiments, the lubricant formulation contains a molybdenum- containing material in an amount to provide 40 to 1200 parts per million by weight molybdenum to the lubricant, or alternatively 50 to 250, 50 to 500, 60 to 200, 300 to 1000, or 400 to 800 parts per million. The actual amount of the molybdenum-containing material will depend in part on the nature and formula weight of the anion or complexing agent associated with the molybdenum, in a way that may be readily calculated. In certain embodiments, the molybdenum-containing compound is present in the lubricating composition in an amount of from 0 to 1.1, or from 0.01 to 0.5, or from 0.03 to 0.35, or from 0.02 to 0.2, or from 0.07 to 0.18, or from 0.04 to 0.18 percent by weight, based on the total weight of the lubricating composition.
[OHl] In certain embodiments, the composition further comprises an antiwear agent, wherein the anti wear agent contributes from 300 to 900 (such as from 350 to 900, from 400 to 900, from 450 to 900, from 500 to 900, from 550 to 900, from 600 to 900, from 650 to 900, from 700 to 900, from 750 to 900, from 800 to 900, from 850 to 900, from 300 to 850, from 350 to 850, from 400 to 850, from 450 to 850, from 500 to 850, from 550 to 850, from 600 to 850, from 650 to 850, from 700 to 850, from 750 to 850, from 800 to 850, from 300 to 800, from 350 to 800, from 400 to 800, from 450 to 800, from 500 to 800, from 550 to 800, from 600 to 800, from 650 to 800, from 700 to 800, from 750 to 800, from 300 to 750, from 350 to 750, from 400 to 750, from 450 to 750, from 500 to 750, from 550 to 750, from 600 to 750, from 650 to 750, from 700 to 750, from 300 to 700, from 350 to 700, from 400 to 700, from 450 to 700, from 500 to 700, from 550 to 700, from 600 to 700, from 650 to 700, from 300 to 650, from 350 to 650, from 400 to 650, from 450 to 650, from 500 to 650, from 550 to 650, from 600 to 650, from 300 to 600, from 350 to 600, from 400 to 600, from 450 to 600, from 500 to 600, from 550 to 600, from 300 to 550, from 350 to 550, from 400 to 550, from 450 to 550, from 500 to 550, from 300 to 500, from 350 to 500, from 400 to 500, from 450 to 500, from 300 to 450, from 350 to 450, from 400 to 450, from 300 to 400, from 350 to 400, or from 300 to 350) ppm by weight phosphorus to the composition, based on the total weight of the composition.
[0112] Any suitable antiwear agents may be used, as would be understood by one of ordinary sill in the art. Without limitation, the following description provides certain embodiments of suitable antiwear agents. Examples of anti-wear agents include phosphorus- containing anti-wear/extreme pressure agents (such as metal thiophosphates), phosphoric acid esters and salts thereof, phosphorus-containing carboxylic acids, phosphorus-containing esters, phosphorus-containing ethers, phosphorus-containing amides, and phosphites Tn certain embodiments, a phosphorus anti-wear agent may be present in an amount to deliver from 0.01 to 0.2 weight percent, or from 0.015 to 0.15 weight percent, or from 0.02 to 0.1 weight percent, or from 0.025 to 0.08 weight percent, or from 0.01 to 0.05 weight percent phosphorus to the total lubricating composition. In certain embodiments, the anti-wear agent is a zinc dialkyldithiophosphate.
[0113] Zinc dialkyldithiophosphates may be described as primary zinc dialkyldithiophosphates or as secondary zinc dialkyldithiophosphates, depending on the structure of the alcohol used in its preparation. In certain embodiments, the lubricating compositions described herein may comprise primary zinc dialkyldithiophosphates. In certain embodiments, the lubricating compositions described herein may comprise secondary zinc dialkyldithiophosphates. In certain embodiments, the lubricating compositions described herein may comprise a mixture of primary and secondary zinc dialkyldithiophosphates, optionally wherein the ratio of primary zinc dialkyldithiophosphates to secondary zinc dialkyldithiophosphates (one a weight basis) is at least 1 : 1, or at least 1: 1.2, or at least 1 : 1.5, or at least 1 :2, or at least 1: 10. In certain embodiments, the lubricating compositions described herein may comprise a mixture of primary and secondary zinc dialkyldithiophosphates which is at least 50 (such as at least 60, at least 70, at least 80, or at least 90) percent by weight primary zinc dialkyldithiophosphate. In certain embodiments, the lubricating compositions described herein are substantially free of primary zinc dialkyldithiophosphates, or free of primary zinc di alkyl dithi ophosphates .
[0114] Other materials that may be used as antiwear agents include tartrate esters, tartramides, and tartrimides. Examples include oleyl tartrimide (the imide formed from oleylamine and tartaric acid) and oleyl diesters (from, e.g., mixed C12-16 alcohols). Other related materials that may be suitable include esters, amides, and imides of other hydroxycarboxylic acids in general, including hydroxy-polycarboxylic acids, for instance, acids such as tartaric acid, citric acid, lactic acid, glycolic acid, hydroxy -propionic acid, hydroxy glutaric acid, and mixtures thereof. These materials may also impart additional functionality to a lubricant beyond antiwear performance. These materials are described in greater detail in US 2006/0079413 Al and WO 2010/077630 Al. Such derivatives of (or compounds derived from) a hydroxy-carboxylic acid, if present, may typically be present in the lubricating composition in an amount of 0.1 weight % to 5 weight %, or 0.2 weight % to 3 weight %, or greater than 0.2 weight % to 3 weight %.
[01151 In certain embodiments, the composition comprises from 700 to 1,000 (such as from 750 to 1,000, from 800 to 1,000, from 850 to 1,000, from 900 to 1,000, from 950 to 1,000, from 700 to 950, from 750 to 950, from 800 to 950, from 850 to 950, from 900 to 950, from 700 to 900, from 750 to 900, from 800 to 900, from 850 to 900, from 700 to 850, from 750 to 850, from 800 to 850, from 700 to 800, from 750 to 800, or from 700 to 750) ppm by weight zinc, based on the total weight of the composition.
[0116] A method of lubricating a heavy duty diesel engine comprising supplying a lubricating composition as described herein to the engine.
[0117] A method of lubricating a compression-ignition internal combustion engine having a laden mass over 2,700 kg comprising supplying a lubricating composition as described herein to the engine.
[0118] A method of lubricating the crankcase of a compression-ignition or spark-ignited engine comprising supplying a lubricating composition as described herein to the crankcase. In certain embodiments, the spark-ignited engine may be a gasoline direct-injection engine. In certain embodiments, the gasoline direct-injection engine comprises a turbocharger.
[0119] Without limitation, a lubricating composition as described herein may have a composition as disclosed in Table 1:
Table 1
Figure imgf000036_0001
[0120] The subject matter disclosed herein may be better understood with reference to the following examples, which are set forth merely to further illustrate the subject matter disclosed herein. The illustrative examples should not be construed as limiting the subject matter in any manner. [0121] A series of engine lubricants having low HTHS (2.4) suitable for use in a heavy duty diesel engine were prepared in a Group III base oil of lubricating viscosity containing the additives described herein, including a deposit control additive according to formula I, polymeric viscosity modifiers, ashless succinimide dispersants, over-based detergents, antioxidants, zinc dialkyldithiophosphate (ZDDP), as well as other performance additives in the amounts (percent by weight based on the total weight of the lubricant) shown in Table 2:
Table 2
Figure imgf000038_0001
lrTBN = 300 via ASTM D4739
2TBN = 170 via ASTM D4739
3TBN = 690 via ASTM D4739 4Reaction product of an olefin polymer comprising a carboxylic acid functionality with 3 -nitroaniline
5Amine functionalized aromatic maleic anhydride-styrene copolymer
6 Succinimide dispersant derived from poly isobutylene
’Combination of phenolic and arylamine antioxidants
^Combination of primary and secondary ZDDP derived from C3 and C6 alcohols ’Other additives include antifoam agents, pourpoint depressants, extreme pressure agents and metal deactivators [0122] Table 3 shows results of certain tests performed on the lubricants of Examples 1 through 4:
Table 3
Figure imgf000039_0001
[0123] A series of engine lubricants having low HTHS (2.5) suitable for use in a passenger car diesel engine were prepared in a Group III base oil of lubricating viscosity containing the additives described herein, including a deposit control additive according to formula I, polymeric viscosity modifiers, ashless succinimide dispersants, over-based detergents, antioxidants, zinc dialkyldithiophosphate (ZDDP), as well as other performance additives in the amounts (percent by weight based on the total weight of the lubricant) shown in Table 4:
Table 4
Figure imgf000040_0001
'TBN = 300 via ASTM D4739
Example F from US 2017/0026794 Al (US Patent/Pub. No.)
3TBN = 690 via ASTM D4739 4Styrene/Butadiene block copolymer
6Borated Succinimide dispersant derived from polyisobutylene
’Combination of phenolic and arylamine antioxidants
^Combination of primary and secondary ZDDP derived from C3 and C6 alcohols
’Other additives include antifoam agents, pourpoint depressants, sulfurized alkylene ester, and metal deactivators
[0124] The lubricating compositions of examples 5 through 7 were tested in a Panel
Coker heated to 325 °C, with a sump temperature of 105 °C, and a splash/bake cycle of 120 s/45s. The airflow is 350 ml/min, with a spindle speed of 1000 rpm and the test lasts for 4 hours. The oil is splashed onto an aluminum panel. Panel weights are recorded before and after exposure with the difference being reported as the Deposit Gain. The results obtained are summarized in Table 5.
Table 5
Figure imgf000041_0001
[0125] Except in the Examples, or where otherwise explicitly indicated or required by context, all numerical quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word “about”. As used herein, the term “about” means that a value of a given quantity is within ±20% of the stated value. In other embodiments, the value is within ±15% of the stated value. In other embodiments, the value is within ±10% of the stated value. In other embodiments, the value is within ±5% of the stated value. In other embodiments, the value is within ±2.5% of the stated value. In other embodiments, the value is within ±1% of the stated value. In other embodiments, the value is within a range of the explicitly-described value which would be understood by those of ordinary skill, based on the disclosures provided herein, to perform substantially similarly to compositions including the literal amounts described herein.
[0126] It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined, and that any amount within a disclosed range is contemplated to provide a minimum or maximum of a narrower range in alternative embodiments (with the proviso, of course, that the minimum amount of a range must be lower than the maximum amount of the same range). Similarly, the ranges and amounts for each element of the subject matter disclosed herein may be used together with ranges or amounts for any of the other elements.
[0127] While certain representative embodiments and details have been shown for the purpose of illustrating the subject matter disclosed herein, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the scope of the subject matter. In this regard, the scope of the invention is to be limited only by the following claims.

Claims

What is claimed is:
1. A lubricating composition comprising: a. an oil of lubricating viscosity; b. a compound according to formula I:
Figure imgf000042_0001
wherein, independently for each molecule of the compound:
R1 is an aliphatic hydrocarbyl group having from 10 to 24 carbon atoms;
R2 is CH3 or C2H5; and n is an integer from 3 to 8; and c. an alkaline earth metal alkyl detergent.
2. The lubricating composition of claim 1, having a high temperature high shear viscosity of from 1.5 to 4.5 mPa s, as measured at 150 °C according to ASTM D4683.
3. The lubricating composition of either claim 1 or claim 2, wherein the alkaline earth metal alkyl detergent contributes from 2 to 7 TBN to the composition as measured by ASTM D4739.
4. The lubricating composition of any one of claims 1 to 3, having a sulfated ash level of less than or equal to 1 percent by weight, based on the total weight of the composition, as measured by ASTM D874.
5. The lubricating composition of claim 4, wherein the alkaline earth metal alkyl detergent contributes from 6 to 7 TBN to the composition as measured by ASTM D4739.
6. The lubricating composition of any one of claims 1 to 5, wherein the compound according to formula I is present in the composition in an amount of from 1 to 10 percent by weight, based on the total weight of the composition.
7. The lubricating composition of any one of claims 1 to 6, having a TBN of from 2 to 12 as measured by ASTM D2896.
8. The lubricating composition of any one of claims 1 to 7, wherein the alkaline earth metal alkyl detergent is present in the composition in an amount less than 3.5 percent by weight, based on the total weight of the composition.
9. The lubricating composition of any one of claims 1 to 8, wherein the alkaline earth metal alkyl detergent comprises an alkaline earth metal which is at least one of magnesium or calcium.
10. The lubricating composition of any one of claims 1 to 9, wherein the alkaline earth metal alkyl detergent comprises a surfactant portion which is at least one of phenate, salicylate, sulfonate, saligenin, or salixarate.
11. The lubricating composition of any one of claims 1 to 10, having less than 200 ppm by weight molybdenum, based on the total weight of the composition.
12. The lubricating composition of any one of claims 1 to 11 , further comprising an antiwear agent, wherein the antiwear agent contributes from 300 to 900 ppm by weight phosphorus to the composition, based on the total weight of the composition.
13. The lubricating composition of any one of claims 1 to 12, having from 700 to 1,000 ppm by weight zinc, based on the total weight of the composition.
14. The lubricating composition of any one of claims 1 to 13, further comprising an aromatic amine, maleic anhydride, ethylene-propylene copolymer dispersant in an amount of from 0.1 to 5 percent by weight, based on the total weight of the composition.
15. A method of lubricating a heavy duty diesel engine comprising supplying the composition of any one of claims 1 to 14 to the engine.
16. A method of lubricating a compression-ignition internal combustion engine having a laden mass over 2,700 kg comprising supplying the composition of any one of claims 1 to 14 to the engine.
17. A method of lubricating the crankcase of a compression-ignition or spark-ignited engine comprising supplying the composition of any one of claims 1 to 14 to the crankcase.
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Citations (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3172892A (en) 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
US3197405A (en) 1962-07-09 1965-07-27 Lubrizol Corp Phosphorus-and nitrogen-containing compositions and process for preparing the same
US3372116A (en) 1965-10-05 1968-03-05 Lubrizol Corp Preparation of basic metal phenates and salicylates
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
US4285822A (en) 1979-06-28 1981-08-25 Chevron Research Company Process for preparing a sulfurized molybdenum-containing composition and lubricating oil containing the composition
US4654403A (en) 1985-03-25 1987-03-31 The Lubrizol Corporation Polymeric compositions comprising olefin polymer and nitrogen containing ester of a carboxy interpolymer
US4719023A (en) 1985-12-23 1988-01-12 Shell Oil Company Grease composition
US4863623A (en) 1988-03-24 1989-09-05 Texaco Inc. Novel VI improver, dispersant, and anti-oxidant additive and lubricating oil composition containing same
EP0355895B1 (en) 1988-08-05 1994-12-14 Shell Internationale Researchmaatschappij B.V. Process for the preparation of succinic anhydride derivatives
US6107257A (en) 1997-12-09 2000-08-22 Ethyl Corporation Highly grafted, multi-functional olefin copolymer VI modifiers
US6107258A (en) 1997-10-15 2000-08-22 Ethyl Corporation Functionalized olefin copolymer additives
US6117825A (en) 1992-05-07 2000-09-12 Ethyl Corporation Polyisobutylene succinimide and ethylene-propylene succinimide synergistic additives for lubricating oils compositions
US6200936B1 (en) 1997-11-13 2001-03-13 The Lubrizol Corporation Salicyclic calixarenes and their use as lubricant additives
US6232276B1 (en) 1996-12-13 2001-05-15 Infineum Usa L.P. Trinuclear molybdenum multifunctional additive for lubricating oils
WO2001056968A1 (en) 2000-02-07 2001-08-09 Bp Oil International Limited Calixarenes and their use as lubricant additives
US6310011B1 (en) 1994-10-17 2001-10-30 The Lubrizol Corporation Overbased metal salts useful as additives for fuels and lubricants
US6310009B1 (en) 2000-04-03 2001-10-30 The Lubrizol Corporation Lubricating oil compositions containing saligenin derivatives
US6329327B1 (en) 1999-09-30 2001-12-11 Asahi Denka Kogyo, K.K. Lubricant and lubricating composition
US6569818B2 (en) 2000-06-02 2003-05-27 Chevron Oronite Company, Llc Lubricating oil composition
US20050065045A1 (en) 2001-11-05 2005-03-24 Wilk Melody A. Sulfonate detergent system for improved fuel economy
US6914037B2 (en) 2002-02-08 2005-07-05 Ethyl Corporation Molybdenum-containing lubricant additive compositions and processes for making and using same
WO2006015130A1 (en) 2004-07-30 2006-02-09 The Lubrizol Corporation Dispersant viscosity modifiers containing aromatic amines
US7009072B2 (en) 2002-10-31 2006-03-07 Crompton Corporation Method for producing lubricant detergents
US20060079413A1 (en) 2004-10-12 2006-04-13 The Lubrizol Corporation, A Corporation Of The State Of Ohio Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof
WO2006047486A1 (en) 2004-10-25 2006-05-04 The Lubrizol Corporation Corrosion inhibition
US20060217271A1 (en) 2005-03-28 2006-09-28 The Lubrizol Corporation Titanium compounds and complexes as additives in lubricants
US7285516B2 (en) 2002-11-25 2007-10-23 The Lubrizol Corporation Additive formulation for lubricating oils
WO2008147704A1 (en) 2007-05-24 2008-12-04 The Lubrizol Corporation Lubricating composition containing ashfree antiwear agent based on hydroxypolycarboxylic acid derivative and a molybdenum compound
WO2010077630A1 (en) 2008-12-09 2010-07-08 The Lubrizol Corporation Lubricating composition containing a compound derived from a hydroxy-carboxylic acid
US8399388B2 (en) 2009-07-01 2013-03-19 Chevron Oronite Company Llc Low temperature performance lubricating oil detergents and method of making the same
US20170267941A1 (en) * 2014-12-03 2017-09-21 The Lubrizol Corporation Lubricating composition containing an oxyalkylated hydrocarbyl phenol
WO2021158757A1 (en) * 2020-02-04 2021-08-12 The Lubrizol Corporation Lubricating compositions and methods of operating an internal combustion engine

Patent Citations (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3172892A (en) 1959-03-30 1965-03-09 Reaction product of high molecular weight succinic acids and succinic anhydrides with an ethylene poly- amine
US3197405A (en) 1962-07-09 1965-07-27 Lubrizol Corp Phosphorus-and nitrogen-containing compositions and process for preparing the same
US3372116A (en) 1965-10-05 1968-03-05 Lubrizol Corp Preparation of basic metal phenates and salicylates
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
US4285822A (en) 1979-06-28 1981-08-25 Chevron Research Company Process for preparing a sulfurized molybdenum-containing composition and lubricating oil containing the composition
US4654403A (en) 1985-03-25 1987-03-31 The Lubrizol Corporation Polymeric compositions comprising olefin polymer and nitrogen containing ester of a carboxy interpolymer
US4719023A (en) 1985-12-23 1988-01-12 Shell Oil Company Grease composition
US4863623A (en) 1988-03-24 1989-09-05 Texaco Inc. Novel VI improver, dispersant, and anti-oxidant additive and lubricating oil composition containing same
EP0355895B1 (en) 1988-08-05 1994-12-14 Shell Internationale Researchmaatschappij B.V. Process for the preparation of succinic anhydride derivatives
US6117825A (en) 1992-05-07 2000-09-12 Ethyl Corporation Polyisobutylene succinimide and ethylene-propylene succinimide synergistic additives for lubricating oils compositions
US6310011B1 (en) 1994-10-17 2001-10-30 The Lubrizol Corporation Overbased metal salts useful as additives for fuels and lubricants
US6232276B1 (en) 1996-12-13 2001-05-15 Infineum Usa L.P. Trinuclear molybdenum multifunctional additive for lubricating oils
US6107258A (en) 1997-10-15 2000-08-22 Ethyl Corporation Functionalized olefin copolymer additives
US6200936B1 (en) 1997-11-13 2001-03-13 The Lubrizol Corporation Salicyclic calixarenes and their use as lubricant additives
US6107257A (en) 1997-12-09 2000-08-22 Ethyl Corporation Highly grafted, multi-functional olefin copolymer VI modifiers
US6329327B1 (en) 1999-09-30 2001-12-11 Asahi Denka Kogyo, K.K. Lubricant and lubricating composition
WO2001056968A1 (en) 2000-02-07 2001-08-09 Bp Oil International Limited Calixarenes and their use as lubricant additives
US6310009B1 (en) 2000-04-03 2001-10-30 The Lubrizol Corporation Lubricating oil compositions containing saligenin derivatives
US6569818B2 (en) 2000-06-02 2003-05-27 Chevron Oronite Company, Llc Lubricating oil composition
US20050065045A1 (en) 2001-11-05 2005-03-24 Wilk Melody A. Sulfonate detergent system for improved fuel economy
US6914037B2 (en) 2002-02-08 2005-07-05 Ethyl Corporation Molybdenum-containing lubricant additive compositions and processes for making and using same
US7009072B2 (en) 2002-10-31 2006-03-07 Crompton Corporation Method for producing lubricant detergents
US7285516B2 (en) 2002-11-25 2007-10-23 The Lubrizol Corporation Additive formulation for lubricating oils
WO2006015130A1 (en) 2004-07-30 2006-02-09 The Lubrizol Corporation Dispersant viscosity modifiers containing aromatic amines
US7790661B2 (en) 2004-07-30 2010-09-07 The Lubrizol Corporation Dispersant viscosity modifiers containing aromatic amines
US20060079413A1 (en) 2004-10-12 2006-04-13 The Lubrizol Corporation, A Corporation Of The State Of Ohio Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof
WO2006047486A1 (en) 2004-10-25 2006-05-04 The Lubrizol Corporation Corrosion inhibition
US20060217271A1 (en) 2005-03-28 2006-09-28 The Lubrizol Corporation Titanium compounds and complexes as additives in lubricants
WO2008147704A1 (en) 2007-05-24 2008-12-04 The Lubrizol Corporation Lubricating composition containing ashfree antiwear agent based on hydroxypolycarboxylic acid derivative and a molybdenum compound
WO2010077630A1 (en) 2008-12-09 2010-07-08 The Lubrizol Corporation Lubricating composition containing a compound derived from a hydroxy-carboxylic acid
US8399388B2 (en) 2009-07-01 2013-03-19 Chevron Oronite Company Llc Low temperature performance lubricating oil detergents and method of making the same
US20170267941A1 (en) * 2014-12-03 2017-09-21 The Lubrizol Corporation Lubricating composition containing an oxyalkylated hydrocarbyl phenol
WO2021158757A1 (en) * 2020-02-04 2021-08-12 The Lubrizol Corporation Lubricating compositions and methods of operating an internal combustion engine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications", THE DOW CHEMICAL COMPANY, article "Form No. 118-01453-0702 AMS"

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