US20120245065A1 - Lubricating Composition Containing an Antiwear Agent - Google Patents

Lubricating Composition Containing an Antiwear Agent Download PDF

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Publication number
US20120245065A1
US20120245065A1 US13/390,711 US201013390711A US2012245065A1 US 20120245065 A1 US20120245065 A1 US 20120245065A1 US 201013390711 A US201013390711 A US 201013390711A US 2012245065 A1 US2012245065 A1 US 2012245065A1
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Prior art keywords
lubricating composition
detergent
lubricating
alkali
earth metal
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US13/390,711
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English (en)
Inventor
Mark C. Davies
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Lubrizol Corp
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Lubrizol Corp
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Application filed by Lubrizol Corp filed Critical Lubrizol Corp
Priority to US13/390,711 priority Critical patent/US20120245065A1/en
Assigned to THE LUBRIZOL CORPORATION reassignment THE LUBRIZOL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DAVIES, MARK C.
Publication of US20120245065A1 publication Critical patent/US20120245065A1/en
Abandoned legal-status Critical Current

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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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • 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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027—Neutral salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/042—Epoxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C10M2215/224—Imidazoles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—Neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/043—Ammonium or amine salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol fueled engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/26—Two-strokes or two-cycle engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/10—Chemical after-treatment of the constituents of the lubricating composition by sulfur or a compound containing sulfur

Definitions

  • the invention provides a method of lubricating an aluminium-alloy surface of an internal combustion engine comprising supplying to the aluminium-alloy surface a lubricating composition comprising an oil of lubricating viscosity and an alkali or alkaline earth metal phenate detergent.
  • the phenate disclosed herein may further provide antiwear performance on the aluminium-alloy surface.
  • lubricating oils It is well known for lubricating oils to contain a number of surface active additives (including antiwear agents, dispersants, or detergents) used to protect internal combustion engines from corrosion, wear, soot deposits and acid build up. Often, such surface active additives can have harmful effects on engine component wear (in both iron and aluminium based components), bearing corrosion or fuel economy.
  • a common antiwear additive for engine lubricating oils is zinc dialkyldithiophosphate (ZDDP). It is believed that ZDDP antiwear additives protect the engine by forming a protective film on metal surfaces. ZDDP may also have a detrimental impact on fuel economy and efficiency and copper corrosion. Consequently, engine lubricants may also contain a friction modifier to obviate the detrimental impact of ZDDP on fuel economy and corrosion inhibitors to obviate the detrimental impact of ZDDP on copper corrosion. Other additives may also increase lead corrosion.
  • non-ferric engine components are based on aluminium-alloy, silicates, oxides, or other ceramic materials.
  • Antiwear additives such as ZDDP are believed to result in poorer engine wear performance in aluminium-alloy based engine compared with ferric based engines.
  • engine lubricants containing phosphorus compounds and sulphur have been shown to contribute in part to particulate emissions and emissions of other pollutants.
  • sulphur and phosphorus tend to poison the catalysts used in catalytic converters, resulting in a reduction in performance of said catalysts.
  • EP 624 044 A1 discloses a method of lubricating an aluminium alloy surface with a lubricating composition containing an effective friction reducing amount of an oil soluble tri-nuclear organo-molybdenum compound.
  • WO2008/144701 discloses lubricating an aluminium-alloy surface by supplying to the aluminium-alloy surface a lubricating composition comprising an oil of lubricating viscosity and an ashless antiwear agent.
  • a lubricating composition comprising an oil of lubricating viscosity and an ashless antiwear agent.
  • the examples disclosed therein also indicate 1.5 wt % of detergent. However, there is no specific disclosure of the type of detergent utilised.
  • the present invention provides a method of lubricating an aluminium-alloy surface of an internal combustion engine comprising supplying to the aluminium-alloy surface a lubricating composition comprising an oil of lubricating viscosity and an alkali or alkaline earth metal (including lithium, sodium, calcium, magnesium, or barium) phenate detergent.
  • a lubricating composition comprising an oil of lubricating viscosity and an alkali or alkaline earth metal (including lithium, sodium, calcium, magnesium, or barium) phenate detergent.
  • the phenate detergent may be a calcium sulphurised-phenate, in particular an overbased calcium sulphurised-phenate.
  • the present invention provides a method of lubricating an aluminium-alloy surface of an internal combustion engine comprising supplying to the aluminium-alloy surface a lubricating composition comprising (a) an oil of lubricating viscosity, (b) an overbased alkali or alkaline earth metal (including lithium, sodium, calcium, magnesium, or barium, typically calcium) phenate (typically a sulphurised-phenate) detergent having a TBN of 200 to 400 (or 200 to 350), and (c) a neutral phenate (typically a non-sulphur containing calcium phenate) with a TBN of 20 to 170 (such as 155).
  • the non-sulphur containing calcium phenate may include detergents described in European Patent applications EP 1 680 491 A, or EP 1 778 824 A.
  • the present invention provides a method of lubricating an aluminium-alloy surface of an internal combustion engine comprising supplying to the aluminium-alloy surface a lubricating composition comprising an oil of lubricating viscosity and an alkali or alkaline earth metal phenate detergent (typically a calcium sulphurised-phenate).
  • a lubricating composition comprising an oil of lubricating viscosity and an alkali or alkaline earth metal phenate detergent (typically a calcium sulphurised-phenate).
  • the invention provides a method of controlling wear of an aluminium-alloy surface in an internal combustion engine comprising supplying to the aluminium-alloy surface a lubricating composition comprising an oil of lubricating viscosity and an alkali or alkaline earth metal phenate detergent (typically a calcium sulphurised-phenate).
  • a lubricating composition comprising an oil of lubricating viscosity and an alkali or alkaline earth metal phenate detergent (typically a calcium sulphurised-phenate).
  • the invention provides for the use of the lubricating composition disclosed herein to mitigate wear on an aluminium alloy surface of an internal combustion engine.
  • the invention provides for the use of an alkali or alkaline earth metal phenate detergent (typically a calcium sulphurised-phenate) as an antiwear agent for an aluminium alloy surface of an internal combustion engine.
  • the invention provides a method of lubricating an internal combustion engine as disclosed herein, wherein the aluminium alloy is an eutectic or hyper-eutectic aluminium alloy (such as those derived from aluminium silicates, aluminium oxides, or other ceramic materials).
  • the aluminium alloy is an eutectic or hyper-eutectic aluminium alloy (such as those derived from aluminium silicates, aluminium oxides, or other ceramic materials).
  • the invention provides a method of lubricating an internal combustion engine as disclosed herein, wherein the internal combustion engine has part or all of a cylinder bore, cylinder block, or piston ring composed of an aluminium alloy, or aluminium composite.
  • the present invention provides a lubricating composition and a method for lubricating an engine as disclosed above.
  • the alkali or alkaline earth metal phenate detergent may be described as an overbased material.
  • Overbased materials otherwise referred to as overbased or superbased salts, are generally single phase, homogeneous Newtonian systems characterised by an amount of excess metal beyond that which would be necessary for neutralisation according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal.
  • the amount of excess metal is commonly expressed in terms of substrate to metal ratio.
  • substrate to metal ratio alternatively expressed as the metal to substrate ratio, or simply “metal ratio,” is the ratio of the total equivalents of the metal to the equivalents of the substrate.
  • metal ratio is provided in “Chemistry and Technology of Lubricants”, Second Edition, Edited by R. M. Mortier and S. T. Orszulik, pages 85 and 86, 1997.
  • the overbased alkali or alkaline earth metal phenate detergent may have a metal ratio of 0.8 to 10, or 1 to 10, or 3 to 9, or 4 to 8, or 5 to 7.
  • the alkali or alkaline earth metal phenate detergent may have a total base number (TBN) 50 to 400, or 200 to 350, or 220 to 300. In one embodiment the alkali or alkaline earth metal phenate detergent may have a TBN of about 255.
  • TBN total base number
  • a more detailed description of the alkali or alkaline earth metal phenate detergent is described in for example, U.S. Pat. No. 6,551,965, or European Patent applications EP 1 903 093 A and EP 0 601 721 A.
  • the alkali or alkaline earth metal phenate detergent additive may be derived from a hydrocarbyl-substituted phenol, wherein the hydrocarbyl-substituted phenol may be present in range from 10 wt % to 70 wt %, or 25 wt % to 65 wt %, or 30 wt % to 60 wt % of the phenate detergent.
  • the overall percentage reduces due to diluent effect of all the base oil and presence of other additives in the overall lubricating composition.
  • the alkali or alkaline earth metal phenate detergent may be derived from a hydrocarbyl-substituted phenol, wherein the alkaline earth metal phenate detergent delivers 0.75 wt % to 2 wt %, or 0.9 wt % to 1.75 wt %, or 1 wt % to 1.5 wt % of hydrocarbyl-substituted phenol to the lubricating composition.
  • the hydrocarbyl-substituted phenol content (this includes the phenol and anions thereof) delivered by the alkali or alkaline earth metal phenate detergent may vary from 0.75 wt % to 2 wt %, or 0.9 wt % to 1.75 wt %, or 1 wt % to 1.5 wt % of the lubricating composition.
  • the alkali or alkaline earth metal phenate detergent hydrocarbyl-substituted phenol content and sulphated ash may vary.
  • the hydrocarbyl-substituted phenol content delivered by the phenate may be 0.9 wt % to 1.75 wt %; and the sulphated ash content may be at least 0.4 wt % to 1.3 wt % of the lubricating composition.
  • the hydrocarbyl-substituted phenol content delivered by the phenate may be 0.9 wt % to 1.75 wt %; and the sulphated ash content may be at least 0.4 wt % to 1.2 wt % of the lubricating composition.
  • the hydrocarbyl-substituted phenol content delivered by the phenate may be 1 wt % or higher to 1.5 wt %; and the sulphated ash content may be at least 0.6 wt % to 1.1 wt % of the lubricating composition.
  • Each hydrocarbyl group of hydrocarbyl-substituted phenol may contain on average 6 or more, 8 or more, or 10 or more carbon atoms.
  • the maximum number of carbon atoms per hydrocarbyl group may be up to 300, or up to 100, or up to 70, or up to 50, or up to 20.
  • each hydrocarbyl group may 8 to 20, or 10 to 12 carbon atoms (typically each hydrocarbyl group may be dodecyl).
  • the amount of sulphated ash delivered by the overbased alkali or alkaline earth metal phenate detergent may be 0.4 wt % to 1.2 wt %, or 0.6 wt % to 1.1 wt % of the lubricating composition.
  • the lubricant composition for an internal combustion engine may be suitable for any engine lubricant irrespective of the sulphur, phosphorus or sulphated ash (ASTM D-874) content.
  • the sulphur content of the engine oil lubricant may be 1 wt % or less, or 0.8 wt % or less, or 0.5 wt % or less, or 0.3 wt % or less. In one embodiment the sulphur content may be in the range of 0.001 wt % to 0.5 wt %, or 0.01 wt % to 0.3 wt %.
  • the phosphorus content may be 0.2 wt % or less, or 0.12 wt % or less, or 0.1 wt % or less, or 0.085 wt % or less, or 0.08 wt % or less, or even 0.06 wt % or less, 0.055 wt % or less, or 0.05 wt % or less.
  • the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm.
  • the sulphated ash content of the lubricating composition may be at least 0.3 wt %, or at least 0.4 wt %, at least 0.6 wt % up to 2 wt %, or 1.5 wt %, or 1.3 wt %, or 1.1 wt % of the lubricating composition.
  • the sulphated ash content may in different embodiments range from 0.3 wt % to 2 wt %, or 0.4 wt % to 1.5 wt %, or 0.6 wt % to 1.3 wt %, or 0.6 wt % to 1.1 wt % of the lubricating composition.
  • the lubricating composition may be characterised as having (i) a sulphur content of 0.5 wt % or less, (ii) a phosphorus content of 0.06 wt % or less, and (iii) a sulphated ash content of 1.3 wt % or less.
  • the lubricating composition comprises an oil of lubricating viscosity.
  • oils 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 International Publication WO2008/147704, paragraphs [0054] to [0056].
  • a more detailed description of natural and synthetic lubricating oils is described in paragraphs [0058] to [0059] respectively of WO2008/147704.
  • Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerised 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 oils.
  • Oils of lubricating viscosity may also be defined as specified in April 2008 version of “Appendix E—API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils”, section 1.3 Sub-heading 1.3. “Base Stock Categories”.
  • the oil of lubricating viscosity may be an API Group I, or Group II, or Group III, or Group IV oil.
  • the oil of lubricating viscosity may be an API Group II or Group III oil.
  • the amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 wt % the sum of the amount of the compound of the invention and the other performance additives.
  • the lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating composition of the invention (comprising the additives disclosed herein) is 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 the 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 composition optionally comprises other performance additives.
  • the other performance additives include at least one of metal deactivators, viscosity modifiers, detergents (in addition to the phenate previously described as part of the invention), friction modifiers, antiwear agents, corrosion inhibitors, dispersants, dispersant viscosity modifiers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, pour point depressants, seal swelling agents and mixtures thereof.
  • metal deactivators include at least one of metal deactivators, viscosity modifiers, detergents (in addition to the phenate previously described as part of the invention), friction modifiers, antiwear agents, corrosion inhibitors, dispersants, dispersant viscosity modifiers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, pour point depressants, seal swelling agents and mixtures thereof.
  • fully-formulated lubricating oil will contain one or more of these performance additives.
  • the lubricating composition further includes other additives.
  • the invention provides a lubricating composition further comprising at least one of a dispersant, an antiwear agent, a dispersant viscosity modifier, a friction modifier, a viscosity modifier, an antioxidant, a detergent (in addition to the phenate previously described as part of the invention), or mixtures thereof.
  • the dispersant of the present invention may be a succinimide dispersant, or mixtures thereof. In one embodiment the dispersant may be present as a single dispersant. In one embodiment the dispersant may be present in a mixture of two or three different dispersants, wherein at least one may be a succinimide dispersant.
  • the succinimide dispersant may be derived from an aliphatic polyamine, or mixtures thereof.
  • the aliphatic polyamine may be aliphatic polyamine such as an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or mixtures thereof.
  • the aliphatic polyamine may be ethylenepolyamine.
  • the aliphatic polyamine may be selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.
  • the dispersant may be a N-substituted long chain alkenyl succinimide.
  • N-substituted long chain alkenyl succinimide include polyisobutylene succinimide.
  • the polyisobutylene from which the polyisobutylene succinic anhydride is derived has a number average molecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500.
  • Succinimide dispersants and their preparation are disclosed, for instance in U.S. Pat. Nos.
  • the dispersant may also be post-treated by conventional methods by a reaction with any of a variety of agents.
  • agents include boron compounds, urea, thiourea, dimercaptothiadiazoles, carbon disulphide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds.
  • the dispersant may be present at 0.01 wt % to 20 wt %, or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 6 wt % of the lubricating composition.
  • the lubricating composition of the invention further comprises a dispersant viscosity modifier.
  • the dispersant viscosity modifier may be present at 0 wt % to 5 wt %, or 0 wt % to 4 wt %, or 0.05 wt % to 2 wt % of the lubricating composition.
  • the dispersant viscosity modifier may include functionalised polyolefins, for example, ethylene-propylene copolymers that have been functionalized with an acylating agent such as maleic anhydride and an amine; polymethacrylates functionalised with an amine, or styrene-maleic anhydride copolymers reacted with an amine. More detailed description of dispersant viscosity modifiers are disclosed in International Publication WO2006/015130 or U.S. Pat. Nos. 4,863,623; 6,107,257; 6,107,258; and 6,117,825. In one embodiment the dispersant viscosity modifier may include those described in U.S. Pat. No. 4,863,623 (see column 2, line 15 to column 3, line 52) or in International Publication WO2006/015130 (see page 2, paragraph [0008] and preparative examples are described paragraphs [0065] to [0073]).
  • an acylating agent such as maleic anhydride and an amine
  • fatty has at least 6 or at least 8 to 30, or 20 carbon atoms.
  • the friction modifier may be selected from the group consisting of fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric acids.
  • the friction modifier may be present at 0 wt % to 6 wt %, or 0.05 wt % to 4 wt %, or 0.1 wt % to 2 wt % of the lubricating composition
  • the invention provides a lubricating composition which further includes a zinc dialkyldithiophosphate, or mixtures thereof.
  • Zinc dialkyldithiophosphates are known in the art.
  • the zinc dialkyldithiophosphate may be present at 0 wt % to 5 wt %, or 0.1 wt % to 3 wt %, or 0.5 wt % to 2 wt % of the lubricating composition.
  • the invention provides a lubricating composition further comprising a molybdenum compound.
  • the molybdenum compound may be selected from the group consisting of molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine salts of molybdenum compounds, and mixtures thereof.
  • the molybdenum compound may provide the lubricating composition with 0 to 1000 ppm, or 5 to 1000 ppm, or 10 to 750 ppm 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum.
  • the invention provides a lubricating composition further comprising a neutral or an overbased detergent in addition to the phenate previously described as part of the invention.
  • the neutral or overbased detergent may be selected from the group consisting of sulphonates, salixarates, salicylates, saligenins and mixtures thereof.
  • the neutral or overbased detergent may be a sodium, calcium or magnesium salt of the sulphonates, salixarates and salicylates.
  • Neutral detergents may have a TBN of less than 200, or typically less than 170.
  • a “neutral” or “slightly overbased” sulphonate detergent may have a TBN of 0 to 100 or 20 to 100 (such as 80 or 85).
  • the lubricating composition may contain 0 wt % to 5 wt % or 0.5 to 3 wt % of a neutral sulphonate detergent (typically calcium sulphonate) with a TBN of 80 or 85.
  • the lubricating composition may contain 0 wt % to 3 wt %, or 0.5 to 2 wt % of a calcium phenate detergent with a TBN of 155. (A neutral phenate detergent, i.e., not overbased, will typically still exhibit a measurable TBN.)
  • Overbased phenates and salicylates typically have a total base number of 200 to 450 TBN. Overbased sulphonates typically have a total base number of 250 to 600, or 300 to 500 (typically 300 or 400).
  • Overbased detergents are known in the art.
  • the sulphonate detergent may be a predominantly linear alkylbenzene sulphonate detergent having a metal ratio of at least 8 to 40 as is described in paragraphs [0026] to [0037] of US Patent Application 2005065045 (and granted as U.S. Pat. No. 7,407,919) having a TBN of 400.
  • the predominantly linear alkylbenzene sulphonate detergent may be particularly useful for assisting in improving fuel economy.
  • the total amount of neutral and overbased detergent in addition to the claimed phenate may be present at 0 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 0.2 wt % to 8 wt % of the lubricating composition (including amounts of diluent oil known to be conventionally associated with detergents. This may for instance be 30 to 50 wt % of the ranges quoted).
  • the lubricating composition includes an antioxidant, or mixtures thereof.
  • the antioxidant may be present at 0 wt % to 15 wt 5, or 0.1 wt % to 10 wt %, or 0.5 wt % to 5 wt % of the lubricating composition.
  • Antioxidants include sulphurised olefins, alkylated diphenylamines (typically dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine), hindered phenols, molybdenum compounds (such as molybdenum dithiocarbamates), or mixtures thereof.
  • the hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
  • the phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and/or a bridging group linking to a second aromatic group.
  • hindered phenol antioxidants examples include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol.
  • the hindered phenol antioxidant may be an ester and may include, e.g., IrganoxTM L-135 from Ciba.
  • IrganoxTM L-135 from Ciba
  • Suitable friction modifiers include 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; or fatty di-alkyl tartramides.
  • Friction modifiers may also encompass materials such as sulphurised fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil or monoester of a polyol and an aliphatic carboxylic acid.
  • the friction modifier may be selected from the group consisting of fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty alkyl tartrates; fatty alkyl tartrimides; and fatty alkyl tartramides.
  • the fatty alkyl tartrates; fatty alkyl tartrimides; and fatty alkyl tartramides may be the same or different to the amide, ester or imide derivative of a hydroxy-carboxylic acid described above.
  • the friction modifier may be a fatty acid ester.
  • the fatty acid ester may be a mono-ester and in another embodiment the fatty acid ester may be a (tri)glyceride.
  • corrosion inhibitors include those described in paragraphs 5 to 8 of US Application US05/038319, published as WO2006/047486, octylamine octanoate, or condensation products of dodecenyl succinic acid or anhydride and a fatty acid such as oleic acid with a polyamine.
  • the corrosion inhibitors include the Synalox® corrosion inhibitor.
  • the Synalox® corrosion inhibitor may be a homopolymer or copolymer of propylene oxide.
  • the Synalox® corrosion inhibitor is described in more detail in a product brochure with Form No. 118-01453-0702 AMS, published by The Dow Chemical Company.
  • the product brochure is entitled “SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications.”
  • Metal deactivators including derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides may be useful.
  • benzotriazoles typically tolyltriazole
  • dimercaptothiadiazole derivatives 1,2,4-triazoles
  • benzimidazoles 2-alkyldithiobenzimidazoles
  • Foam inhibitors that may be useful in the compositions of the invention include copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers.
  • Pour point depressants that may be useful in the compositions of the invention include polyalphaolefins, esters of maleic anhydride-styrene, poly(meth)acrylates, polyacrylates or polyacrylamides.
  • Embodiments (wt %) Additive A B C Phenate of the Invention 0.01 to 5 0.1 to 3 0.25 to 1.5 Dispersant 0.05 to 12 0.75 to 8 0.5 to 6 Dispersant Viscosity Modifier 0 to 5 0 to 4 0.05 to 2 Additional Overbased Detergent 0 to 15 0.1 to 10 0.2 to 8 Antioxidant 0 to 15 0.1 to 10 0.5 to 5 Antiwear Agent 0 to 15 0.1 to 10 0.3 to 5 Friction Modifier 0 to 6 0.05 to 4 0.1 to 2 Viscosity Modifier 0 to 10 0.5 to 8 1 to 6 Any Other Performance Additive 0 to 10 0 to 8 0 to 6 Oil of Lubricating Viscosity Balance to Balance to Balance to 100% 100% 100% Footnote: Ranges quoted above are on an oil free basis i.e., amount of active ingredient with diluent oil factored out.
  • the lubricating composition may be utilised in an internal combustion engine.
  • the internal combustion engine may or may not have an Exhaust Gas Recirculation system.
  • the internal combustion engine may be fitted with an emission control system or a turbocharger. Examples of the emission control system include diesel particulate filters (DPF), or systems employing selective catalytic reduction (SCR).
  • DPF diesel particulate filters
  • SCR selective catalytic reduction
  • the internal combustion engine may be a diesel fuelled engine (typically a heavy duty diesel engine), a gasoline fuelled engine, a natural gas fuelled engine or a mixed gasoline/alcohol fuelled engine.
  • the internal combustion engine may be a diesel fuelled engine and in another embodiment a gasoline fuelled engine.
  • the internal combustion engine may be a 2-stroke or 4-stroke engine.
  • Suitable internal combustion engines include marine diesel engines, aviation piston engines, low-load diesel engines, and automobile and truck engines.
  • Comparative Lubricant Examples 1 to 5 are prepared by blending a mixture of succinimide dispersants (total amount of succinimide dispersants 8.3 wt % including 40 wt % diluent oil), 3 wt % of a dispersant viscosity modifier commercially sold as Hitec®5777 (including diluent oil), 4 wt % of a mixture of antioxidants (including amine and phenolic antioxidants), and 1.2 wt % of glycerol monooleate friction modifier.
  • CE1 to CE5 contain overbased detergent as is described in the table below. Also included is the charactisation data for each lubricant indicating sulphated ash content and total base number (TBN mg KOH/g).
  • Amount of each detergent quoted includes conventional amounts of diluent oil (typically ranging from 30 to 50 wt %).
  • Comparative Lubricant Examples 6 to 7 are prepared by blending a mixture of succinimide dispersants (total amount of succinimide dispersants 7.9 wt % including 40 wt % diluent oil), a mixture of antioxidants (including amine and phenolic antioxidants), and 0.57 wt % of a zinc dialkyldithiophosphate.
  • CE6 and CE7 contain 2 wt % (including diluent oil) and 2.7 wt % (including diluent oil) of overbased calcium sulphonate respectively.
  • EX1 and EX2 are similar to CE6 and CE7, except EX1 contains 1.9 wt % (including 39 wt % diluent oil) and 2.75 wt % (including 39 wt % diluent oil) of overbased calcium sulphurised-phenate respectively in place of overbased calcium sulphonate.
  • CE6, CE7, EX1 and EX2 are characterised as follows:
  • the lubricants are evaluated for wear in a programmed temperature high frequency reciprocating rig (HFRR) available from PCS Instruments.
  • HFRR conditions for the evaluations were 500 g load, 75 minute duration, 1000 micrometer stroke, 20 Hertz frequency, and temperature profile of 15 minutes at 40° C. followed by an increase in temperature to 160° C. at a rate of 2° C. per minute.
  • the upper test piece was a 6 mm diameter aluminium silicate piece cut from a commercially available engine. Both the upper and lower specimens are available together from PCS Instruments (Part Number HFRSSP).
  • Part Number HFRSSP Part Number HFRSSP
  • the lubricating composition containing overbased calcium sulphurised-phenate has reduced wear on aluminium components compared with similar lubricants containing overbased calcium sulphonate.
  • the data indicates that the lubricating composition containing overbased calcium sulphurised-phenate has at least 20% less wear than the lubricating composition containing overbased calcium sulphonate.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include: hydrocarbon substituents, including aliphatic, alicyclic, and aromatic substituents; substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent; and hetero substituents, that is, substituents which similarly have a predominantly hydrocarbon character but contain other than carbon in a ring or chain.

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BR112012003694A2 (pt) 2016-03-29
EP2467456B1 (en) 2014-10-22

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