EP2374866B1 - A lubricating oil composition comprising alkoxylated phenol-formaldehyde condensate - Google Patents

A lubricating oil composition comprising alkoxylated phenol-formaldehyde condensate Download PDF

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Publication number
EP2374866B1
EP2374866B1 EP11155213A EP11155213A EP2374866B1 EP 2374866 B1 EP2374866 B1 EP 2374866B1 EP 11155213 A EP11155213 A EP 11155213A EP 11155213 A EP11155213 A EP 11155213A EP 2374866 B1 EP2374866 B1 EP 2374866B1
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EP
European Patent Office
Prior art keywords
oxyalkylated
oil
composition
mole
additive component
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EP11155213A
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German (de)
English (en)
French (fr)
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EP2374866A1 (en
Inventor
Jesse Dambacher
Tushar Bera
Jacob Emert
Philip Skinner
Richard Severt
Adam Marsh
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Infineum International Ltd
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Infineum International Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C10M145/20—Condensation polymers of aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • 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
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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

Definitions

  • the present invention relates to lubricating oil compositions, more especially to automotive lubricating oil compositions for use in piston engines, especially gasoline (spark-ignited) and diesel (compression-ignited) crankcase lubrication, such compositions being referred to as crankcase lubricants.
  • the present invention relates to use of ashless detergent additives with good copper corrosion properties in lubricating oil compositions where corrosion is a concern.
  • crankcase lubricant is an oil used for general lubrication in an internal combustion engine where an oil sump is situated generally below the crankshaft of the engine and to which circulated oil returns. It is well known to include additives in crankcase lubricants for several purposes.
  • metal-containing detergents are additives that reduce formation of piston deposits, for example high-temperature varnish and lacquer deposits, in engines; they have acid-neutralising properties and are capable of keeping finely-divided solids in suspension. They are based on metal salts of acidic organic compounds, sometimes referred to as soaps.
  • a metal detergent comprises a polar head with a long hydrophobic tail, the polar head comprising the metal salt.
  • Lubricant specifications are becoming, or have become, more exacting such as in limiting the amount of metal, expressed as sulfated ash. There is therefore considerable incentive to provide detergents that are free of metal, so-called “ashless" detergents.
  • RD 417045 describes ethoxylated methylene-bridged alkyl phenols as detergents that are metal free, which may for example be represented by the structural formula: wherein the "n" of the ethoxylated groups is an integer such as in the range of 1 to 20.
  • the compounds are described as being made by the acid-catalysed reaction of an alkylated phenol with paraformaldehyde to give a methylene-bridged phenol, with subsequent ethoxylation using ethylene oxide.
  • EP-B-0 032 617 describes lubricants that contain similar additives to those described in RD 417045 (including an additive marketed under the trade name "Prochinor GR77") for controlling or eliminating emulsion-sludge formation.
  • n is from 2 to 10, which is most preferably obtained by ethoxylation using ethylene oxide, and also prefers a molecular weight of 4,000 to 6,000.
  • the present invention provides a lubricating oil composition that exhibits superior deposit control properties whilst minimising copper corrosion.
  • the value of n in the oil-soluble oxyalkylated detergent is controlled.
  • the present invention provides a lubricating oil composition comprising or made by admixing
  • the present invention provides a method of making an additive component (B) as defined in the first aspect, the method including the steps of forming an oxyalkylated hydrocarbyl phenol-aldehyde condensate via the steps of (1) oxyalkylating a hydrocarbyl phenol in the presence of a base catalyst, preferably a sodium salt, with 0.5 to 3, preferably to less than 2.5, preferably less than 2.0, equivalents of ethylene carbonate, propylene carbonate or butylene carbonate and (2) condensation in the presence of an acid or base catalyst of said oxyalkylated hydrocarbyl phenol with an aldehyde.
  • a base catalyst preferably a sodium salt
  • the present invention provides the use of additive component (B) as defined in the first aspect to improve the deposit control properties whilst not adversely affecting the copper corrosion properties of the lubricant.
  • the oil of lubricating viscosity (sometimes referred to as “base stock” or “base oil”) is the primary liquid constituent of a lubricant, into which additives and possibly other oils are blended, for example to produce a final lubricant (or lubricant composition). Also, a base oil is useful for making concentrates as well as for making lubricants therefrom.
  • a base oil may be selected from natural (vegetable, animal or mineral) and synthetic lubricating oils and mixtures thereof. It may range in viscosity from light distillate mineral oils to heavy lubricating oils such as gas engine oil, mineral lubricating oil, motor vehicle oil and heavy duty diesel oil. Generally the viscosity of the oil ranges from 2 to 30, especially 5 to 20, mm 2 s -1 at 100°C.
  • Natural oils include animal and vegetable oils (e.g. castor and lard oil), liquid petroleum oils and hydrorefined, solvent-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
  • Synthetic lubricating oils include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g. polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes)); alkylbenzenes (e.g. dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenols (e.g. biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogues and homologues thereof.
  • hydrocarbon oils such as polymerized and interpolymerized olefins (e.g. polybut
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g. phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g. butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
  • dicarboxylic acids e.g. phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dim
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
  • Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
  • Unrefined, refined and re-refined oils can be used in the compositions of the present invention.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • a shale oil obtained directly from retorting operations a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be unrefined oil.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art.
  • Re-refined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such re-refined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for approval of spent additive and oil breakdown products.
  • base oil examples include gas-to-liquid (“GTL”) base oils, i.e. the base oil may be an oil derived from Fischer-Tropsch synthesised hydrocarbons made from synthesis gas containing H 2 and CO using a Fischer-Tropsch catalyst. These hydrocarbons typically require further processing in order to be useful as a base oil. For example, they may, by methods known in the art, be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed.
  • GTL gas-to-liquid
  • Base oil may be categorised in Groups I to V according to the API EOLCS 1509 definition.
  • the oil of lubricating viscosity When used to make a concentrate, it is present in a concentrate-forming amount (e.g., from 30 to 70, such as 40 to 60, mass %) to give a concentrate containing for example 1 to 90, such as 10 to 80, preferably 20 to 80, more preferably 20 to 70, mass % active ingredient of an additive or additives, being component (B) above, optionally with one or more co-additives.
  • the oil of lubricating viscosity used in a concentrate is a suitable oleaginous, typically hydrocarbon, carrier fluid, e.g. mineral lubricating oil, or other suitable solvent. Oils of lubricating viscosity such as described herein, as well as aliphatic, naphthenic, and aromatic hydrocarbons, are examples of suitable carrier fluids for concentrates.
  • Concentrates constitute a convenient means of handling additives before their use, as well as facilitating solution or dispersion of additives in lubricants.
  • additive components typically include more than one type of additive (sometime referred to as “additive components")
  • each additive may be incorporated separately, each in the form of a concentrate.
  • additive packages also referred to as an "adpack” comprising one or more co-additives, such as described hereinafter, in a single concentrate.
  • the oil of lubricating viscosity may be provided in a major amount, in combination with a minor amount of additive component (B) as defined herein and, if necessary, one or more co-additives, such as described hereinafter, constituting a lubricant.
  • This preparation may be accomplished by adding the additive directly to the oil or by adding it in the form of a concentrate thereof to disperse or dissolve the additive.
  • Additives may be added to the oil by any method known to those skilled in the art, either before, at the same time as, or after addition of other additives.
  • the oil of lubricating viscosity is present in the lubricant in an amount of greater than 55 mass %, more preferably greater than 60 mass %, even more preferably greater than 65 mass %, based on the total mass of the lubricant.
  • the oil of lubricating viscosity is present in an amount of less than 98 mass %, more preferably less than 95 mass %, even more preferably less than 90 mass %, based on the total mass of the lubricant.
  • the lubricants of the invention may be used to lubricate mechanical engine components, particularly in internal combustion engines, e.g. spark-ignited or compression-ignited two- or four-stroke reciprocating engines, by adding the lubricant thereto.
  • they are crankcase lubricants.
  • the lubricating oil compositions of the invention comprise defined components that may or may not remain the same chemically before and after mixing with an oleaginous carrier.
  • This invention encompasses compositions which comprise the defined components before mixing, or after mixing, or both before and after mixing.
  • concentrates When concentrates are used to make the lubricants, they may for example be diluted with 3 to 100, e.g. 5 to 40, parts by mass of oil of lubricating viscosity per part by mass of the concentrate.
  • the lubricants of the present invention may contain low levels of phosphorus, namely not greater than 0.12 mass %, preferably up to 0.08 mass %, more preferably up to 0.06 mass % of phosphorus, expressed as atoms of phosphorus, based on the total mass of the lubricant.
  • the lubricants may contain low levels of sulfur.
  • the lubricant contains up to 0.4, more preferably up to 0.3, most preferably up to 0.2, mass % sulfur, expressed as atoms of sulfur, based on the total mass of the lubricant.
  • the lubricant may contain low levels of sulfated ash.
  • the lubricant contains less than 1.0, preferably less than 0.8, more preferably less than 0.5, mass % sulfated ash, based on the total mass of the lubricant.
  • the lubricant may have a total base number (TBN) of 5 or more, preferably 7 or more, such as up to 16, preferably 8 to 16.
  • TBN total base number
  • This basicity may originate from metal bases such as overbased detergents or non-metal bases such as nitrogen bases, examples of which are dispersants, anti-oxidants (e.g. alkylated diphenylamine and phenylene diamine) and quaternary ammonium salts, or combinations thereof.
  • up to 30%, preferably up to 40%, more preferably up to 50%, even more preferably up to 60% of the TBN in the lubricant originates from non-metal bases.
  • the oxyalkylated condensates in (B) are preferably represented by the following general structural formula: wherein x is 1 to 50, preferably 1 to 40, more preferably 1 to 30; R 1 and R 2 are H, hydrocarbyl groups having 1 to 12 carbon atoms, or hydrocarbyl groups having 1 to 12 carbon atoms and at least one heteroatom; and R is a hydrocarbyl group having 9 to 100, preferably 9 to 70, preferably 9 to 50, preferably 9 to 30, preferably 9 to 20 and most preferably 9 to 15 carbon atoms.
  • R is preferably in the para position in relation to the ⁇ O-[CH 2 CH 2 O] n H group.
  • oxyalkylated condensates in (B) less than 5 mole % of the phenolic functional groups of the condensates are poly-oxyalkylated (i.e. n ⁇ 2), which includes di-oxyalkylation, tri-oxyalkylation, tetra-oxyalkylation etc.
  • the mixture has a number average molecular weight (M n ), as measured by GPC, in the range of 1000 to less than 4000, such as to 3000.
  • the mixture has a weight average molecular weight (M w ), as measured by GPC, in the range of 1100 to less than 6000, preferably less than 4000, such as 3500; advantageously, M w /M n is in the range of 1.10-1.60.
  • the mixture has a number average degree of polymerization of 4-20, such as 5-15, and more preferred 6-10.
  • R is preferably, independently, a branched chain alkyl group having 9 to 30 carbon atoms, preferably 9 to 15 carbon atoms, more preferably 12 to 15 carbon atoms.
  • the oxyalkylated condensate mixtures of the invention are preferably made by oxyalkylating a hydrocarbyl phenol condensate with ethylene carbonate (which is preferred), propylene carbonate or butylene carbonate.
  • steric factors inhibit reaction with central units and then further reaction can occur with terminal units to confer the di- and poly-oxyalkyl (i.e. n ⁇ 2) content.
  • Additive component (B) is present in the amount of 0.1 to 10, such as 0.1 to 5, such as 0.1 to 2, mass % based on the total lubricant mass.
  • Co-additives with representative effective amounts in lubricants that may also be present, different from additive component (B), are listed below. All the values listed are stated as mass percent active ingredient.
  • Ashless Dispersant 0.1 - 20 1 - 8 Metal Detergents 0.1 - 15 0.2 - 9 Friction modifier 0 - 5 0 - 1.5 Corrosion Inhibitor 0 - 5 0 - 1.5 Metal Dihydrocarbyl Dithiophosphate 0 - 10 0 - 4 Anti-Oxidants 0 - 5 0.01 - 3 Pour Point Depressant 0.01 - 5 0.01 - 1.5 Anti-Foaming Agent 0 - 5 0.001 - 0.15 Supplement Anti-Wear Agents 0 - 5 0 - 2 Viscosity Modifier (1) 0 - 6 0.01 - 4 Mineral or Synthetic Base Oil Balance Balance (1) Viscosity modifiers are used only in multi-graded oils
  • the final lubricant typically made by blending the or each additive into the base oil, may contain from 5 to 25, preferably 5 to 18, typically 7 to 15, mass % of the co-additives, the remainder being oil of lubricating viscosity.
  • additives can provide a multiplicity of effects, for example, a single additive may act as a dispersant and as an oxidation inhibitor.
  • a dispersant is an additive whose primary function is to hold solid and liquid contaminations in suspension, thereby passivating them and reducing engine deposits at the same time as reducing sludge depositions.
  • a dispersant maintains in suspension oil-insoluble substances that result from oxidation during use of the lubricant, thus preventing sludge flocculation and precipitation or deposition on metal parts of the engine.
  • Dispersants are usually "ashless", as mentioned above, being non-metallic organic materials that form substantially no ash on combustion, in contrast to metal-containing, and hence ash-forming materials. They comprise a long hydrocarbon chain with a polar head, the polarity being derived from inclusion of e.g. an O, P, or N atom.
  • the hydrocarbon is an oleophilic group that confers oil-solubility, having, for example 40 to 500 carbon atoms.
  • ashless dispersants may comprise an oil-soluble polymeric backbone.
  • a preferred class of olefin polymers is constituted by polybutenes, specifically polyisobutenes (PIB) or poly-n-butenes, such as may be prepared by polymerization of a C 4 refinery stream.
  • PIB polyisobutenes
  • poly-n-butenes such as may be prepared by polymerization of a C 4 refinery stream.
  • Dispersants include, for example, derivatives of long chain hydrocarbon-substituted carboxylic acids, examples being derivatives of high molecular weight hydrocarbyl-substituted succinic acid.
  • a noteworthy group of dispersants is constituted by hydrocarbon-substituted succinimides, made, for example, by reacting the above acids (or derivatives) with a nitrogen-containing compound, advantageously a polyalkylene polyamine, such as a polyethylene polyamine.
  • reaction products of polyalkylene polyamines with alkenyl succinic anhydrides such as described in US-A-3,202,678 ; - 3,154,560 ; - 3,172,892 ; - 3,024,195 ; - 3,024,237 , - 3,219,666 ; and - 3,216,936 , that may be post-treated to improve their properties, such as borated (as described in US-A-3,087,936 and - 3,254,025 ) fluorinated and oxylated.
  • boration may be accomplished by treating an acyl nitrogen-containing dispersant with a boron compound selected from boron oxide, boron halides, boron acids and esters of boron acids.
  • the dispersant if present, is a succinimide dispersant derived from a polyisobutene of number average molecular weight in the range of 1000 to 3000, preferably 1500 to 2500, and of moderate functionality.
  • the succinimide is preferably derived from highly reactive polyisobutene.
  • Metal detergents are metal salts as mentioned above.
  • the salts may contain a substantially stoichiometric amount of the metal when they are usually described as normal or neutral salts and would typically have a total base number or TBN (as may be measured by ASTM D2896) of from 0 to 80.
  • TBN total base number
  • Large amounts of a metal base can be included by reaction of an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide.
  • the resulting overbased detergent comprises neutralised detergent as an outer layer of a metal base (e.g. carbonate) micelle.
  • Such overbased detergents may have a TBN of 150 or greater, and typically of from 250 to 500 or more.
  • Detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g. sodium, potassium, lithium, calcium and magnesium.
  • a metal particularly the alkali or alkaline earth metals, e.g. sodium, potassium, lithium, calcium and magnesium.
  • the most commonly-used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium.
  • Particularly preferred metal detergents are neutral and overbased alkali or alkaline earth metal detergents having a TBN of from 50 to 450, preferably a TBN of 50 to 250.
  • Highly preferred detergents include alkaline earth metal salicylates, particularly magnesium and calcium, especially, calcium salicylates.
  • the weight ratio of the additive component (B) in the lubricating oil composition to any metal detergents is preferably in the range of 0.1 to 4, preferably 0.1 to 3, preferably 0.1 to 2, or most preferably 0.2 to 1.6.
  • metal detergents are calcium salicylate, magnesium salicylate, calcium sulfonate, magnesium sulfonate, calcium phenate and mixtures thereof.
  • Friction modifiers include glyceryl monoesters of higher fatty acids, for example, glyceryl mono-oleate; esters of long chain polycarboxylic acids with diols, for example, the butane diol ester of a dimerized unsaturated fatty acid; oxazoline compounds; and alkoxylated alkylsubstituted mono-amines, diamines and alkyl ether amines, for example, ethoxylated tallow amine and ethoxylated tallow ether amine.
  • Other known friction modifiers comprise oil-soluble organo-molybdenum compounds. Such organo-molybdenum friction modifiers also provide antioxidant and antiwear credits to a lubricating oil composition. Suitable oil-soluble organo-molybdenum compounds have a molybdenum-sulfur core. As examples there may be mentioned dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and mixtures thereof Particularly preferred are molybdenum dithiocarbamates, dialkyldithiophosphates, alkyl xanthates and alkylthioxanthates. The molybdenum compound is dinuclear or trinuclear.
  • One class of preferred organo-molybdenum compounds useful in all aspects of the present invention is tri-nuclear molybdenum compounds of the formula Mo 3 S k L n Q z and mixtures thereof wherein L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compounds soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 through to 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. At least 21 total carbon atoms should be present among all the ligands' organo groups, such as at least 25, at least 30, or at least 35 carbon atoms.
  • the molybdenum compounds may be present in a lubricating oil composition at a concentration in the range 0.1 to 2 mass %, or providing at least 10 such as 50 to 2,000 ppm by mass of molybdenum atoms.
  • the molybdenum from the molybdenum compound is present in an amount of from 10 to 1500, such as 20 to 1000, more preferably 30 to 750, ppm based on the total weight of the lubricant.
  • the molybdenum is present in an amount of greater than 500 ppm.
  • Anti-oxidants are sometimes referred to as oxidation inhibitors; they increase the resistance of the lubricant to oxidation and may work by combining with and modifying peroxides to render them harmless, by decomposing peroxides, or by rendering an oxidation catalyst inert. Oxidative deterioration can be evidenced by sludge in the lubricant, varnish-like deposits on the metal surfaces, and by viscosity growth.
  • radical scavengers e.g. sterically-hindered phenols, secondary aromatic amines, and organo-copper salts
  • hydroperoxide decomposers e.g., organosulfur and organophosphorus additives
  • multifunctionals e.g. zinc dihydrocarbyl dithiophosphates, which may also function as anti-wear additives, and organo-molybdenum compounds, which may also function as friction modifiers and anti-wear additives).
  • antioxidants are selected from copper-containing antioxidants, sulfur-containing antioxidants, aromatic amine-containing antioxidants, hindered phenolic antioxidants, dithiophosphates derivatives, metal thiocarbamates, and molybdenum-containing compounds.
  • Dihydrocarbyl dithiophosphate metals salts are frequently used as antiwear and antioxidant agents.
  • the metal may be an alkali or alkaline earth metal, or aluminium, lead, tin, zinc molybdenum, manganese, nickel or copper.
  • Zinc salts are most commonly used in lubricants such as in amounts of 0.1 to 10, preferably 0.2 to 2, mass %, based upon the total mass of the lubricant. They may be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohols or a phenol with P 2 S 5 , and then neutralising the formed DDPA with a zinc compound.
  • DDPA dihydrocarbyl dithiophosphoric acid
  • a dithiophosphoric acid may be made by reaction with mixtures of primary and secondary alcohols.
  • multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one acid are entirely secondary in character and the hydrocarbyl groups on the other acids are entirely primary in character.
  • any basic or neutral zinc compound could be used but the oxides, hydroxides and carbonates are most generally employed. Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralisation reaction.
  • Anti-wear agents reduce friction and excessive wear and are usually based on compounds containing sulfur or phosphorous or both, for example that are capable of depositing polysulfide films on the surfaces involved.
  • dihydrocarbyl dithiophosphates such as the zinc dialkyl dithiophosphates (ZDDPs) discussed herein.
  • ashless anti-wear agents examples include 1,2,3-triazoles, benzotriazoles, thiadiazoles, sulfurised fatty acid esters, and dithiocarbamate derivatives.
  • Rust and corrosion inhibitors serve to protect surfaces against rust and/or corrosion.
  • rust inhibitors there may be mentioned non-ionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, and anionic alkyl sulfonic acids.
  • Pour point depressants otherwise known as lube oil flow improvers, lower the minimum temperature at which the oil will flow or can be poured.
  • Such additives are well known. Typical of these additive are C 8 to C 18 dialkyl fumarate/vinyl acetate copolymers and polyalkylmethacrylates.
  • Additives of the polysiloxane type for example silicone oil or polydimethyl siloxane, can provide foam control.
  • a small amount of a demulsifying component may be used.
  • a preferred demulsifying component is described in EP-A-330,522 . It is obtained by reacting an alkylene oxide with an adduct obtained by reaction of a bis-epoxide with a polyhydric alcohol.
  • the demulsifier should be used at a level not exceeding 0.1 mass % active ingredient. A treat rate of 0.001 to 0.05 mass % active ingredient is convenient.
  • Viscosity modifiers impart high and low temperature operability to a lubricant.
  • Viscosity modifiers that also function as dispersants are also known and may be prepared as described above for ashless dispersants.
  • these dispersant viscosity modifiers are functionalised polymers (e.g. interpolymers of ethylene-propylene post grafted with an active monomer such as maleic anhydride) which are then derivatised with, for example, an alcohol or amine.
  • the lubricant may be formulated with or without a conventional viscosity modifier and with or without a dispersant viscosity modifier.
  • Suitable compounds for use as viscosity modifiers are generally high molecular weight hydrocarbon polymers, including polyesters.
  • Oil-soluble viscosity modifying polymers generally have weight average molecular weights of from 10,000 to 1,000,000, preferably 20,000 to 500,000, which may be determined by gel permeation chromatography or by light scattering.
  • a mixture of 95% para-substituted, branched dodecylphenol (1910g), alkyl benzene sulfonic acid catalyst (l9.1g) and toluene (574g) was heated to 110°C over 60 minutes in a 5L reactor under a blanket of nitrogen gas which remained throughout the reaction process.
  • An aqueous formaldehyde solution (37%, 497g) was added stepwise over 2 hours and 30 minutes. The temperature was increased to 120°C and the contents of the reactor maintained at this temperature for 1 hour and 30 minutes. The contents were cooled to 90°C and an aqueous NaOH solution (50%, 42g) added over 35 minutes.
  • the contents of the reactor were heated to 130°C over 25 minutes, kept at this temperature for 2 hours and toluene stripped therefrom by vacuum distillation.
  • the temperature was lowered to 110°C and group I 150 neutral oil added (2278g) and mixed for 1 hour to make an ethoxylated methylene-bridged alkylphenol mixture at 50% active ingredient (4556g).
  • Heavy duty diesel lube oil formulation A was prepared containing ashless dispersant, metal containing detergent, zinc dialkyl dithiophosphate anti-wear agent, supplementary antioxidant, viscosity modifier and flow improver in a base oil.
  • the weight ratio of the ashless detergent of Example 2 relative to the metal containing detergents in Heavy duty diesel lube oil formulation B was 1.2 on an active ingredient basis.
  • Heavy duty diesel formulation B containing the ashless detergent of Example 2 exhibited significantly enhanced deposit control capability relative to Heavy duty diesel formulation A which contained only ash-containing detergents.
  • Passenger car diesel lube oil formulation C was prepared containing ashless dispersant, metal containing detergent, zinc dialkyl dithiophosphate anti-wear agent, supplementary antioxidant, viscosity modifier and flow improver in a base oil.
  • the weight ratio of the ashless detergent of Example 2 relative to the metal containing detergents in Passenger car diesel lube oil formulation D was 0.6 on an active ingredient basis.
  • Example 2 The procedure of Example 2 was repeated with different amounts of the ethylene carbonate reagent to produce ethoxylated methylene-bridged alkylphenol mixtures of formula (I) with varying amounts of oxyalkyl moieties as shown in Table III.
  • Heavy duty diesel lube oil formulation E was prepared containing ashless dispersant, metal containing detergent, zinc dialkyl dithiophosphate anti-wear agent, supplementary antioxidant, viscosity modifier and flow improver in a base oil.
  • the weight ratio of the ashless detergent in relation to the metal containing detergents in Heavy duty diesel lube oil formulation D was 1.3 on an active ingredient basis.
  • Example 1 The procedure of Example 1 was repeated, on a smaller scale (branched dodecyl phenol - 400g; alkylbenzene sulfonic acid catalyst - 4g; aqueous formaldehyde solution (37%) - 104g), except that the 50% aqueous NaOH was replaced by an equal mass percentage of 50% aqueous KOH (l0g).
  • Xylene (120g) was added to the intermediate that was produced (418g), and then ethylene carbonate (2 equivalents per hydroxyl group, 270g) at 90°C over 30 minutes. The contents of the reactor were heated to reflux (150-160°C). Reaction continued for 4 hours, when it was determined that the reaction was not completed and temperature was decreased.
  • Group I 150 neutral oil was added (475g) and mixed for 1 hour to make an ethoxylated methylene-bridged alkylphenol mixture at 50% active ingredient (950g).
  • Heavy duty diesel lube oil formulation G was prepared containing ashless dispersant, metal containing detergent, zinc dialkyl dithiophosphate anti-wear agent, supplementary antioxidant, viscosity modifier and flow improver in a base oil.
  • Heavy duty diesel formulation H was prepared with the same amount of all additives except that 1.6 wt% active ingredient of Example 2 was added in place of 1.6 wt% base oil.
  • Heavy duty diesel lube oil formulation I was prepared with the same amount of all the additives except that 1.6 wt% active ingredient of Example 8 was substituted for the 1.6 wt% active ingredient of Example 2.
  • the weight ratio of the ashless detergent relative to the metal containing detergents in all Heavy duty diesel lube oil formulations was 1.3.
  • the region between 60 - 76 ppm is the chemical shift range for all of the carbons of the (poly-)ethoxylated groups.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP11155213A 2010-04-06 2011-02-21 A lubricating oil composition comprising alkoxylated phenol-formaldehyde condensate Active EP2374866B1 (en)

Applications Claiming Priority (1)

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US12/754,640 US20110239978A1 (en) 2010-04-06 2010-04-06 Lubricating Oil Composition

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EP2374866B1 true EP2374866B1 (en) 2012-09-19

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WO2016138227A1 (en) 2015-02-26 2016-09-01 The Lubrizol Corporation Aromatic detergents and lubricating compositions thereof
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JP5743658B2 (ja) 2015-07-01
JP2011219755A (ja) 2011-11-04
CA2736308C (en) 2017-09-26
CN102212409A (zh) 2011-10-12
EP2374866A1 (en) 2011-10-12
CN102212409B (zh) 2015-04-08
CA2736308A1 (en) 2011-10-06

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