EP1605034B1 - L'utilisation d'un additif détergent pour compositions lubrifiante - Google Patents

L'utilisation d'un additif détergent pour compositions lubrifiante Download PDF

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Publication number
EP1605034B1
EP1605034B1 EP05104350A EP05104350A EP1605034B1 EP 1605034 B1 EP1605034 B1 EP 1605034B1 EP 05104350 A EP05104350 A EP 05104350A EP 05104350 A EP05104350 A EP 05104350A EP 1605034 B1 EP1605034 B1 EP 1605034B1
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EP
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Prior art keywords
hydrocarbyl
lubricating oil
hydrocarbyl phenol
mass
condensate
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EP05104350A
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German (de)
English (en)
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EP1605034A1 (fr
Inventor
Robert Shaw
Simon Chung
James Dodd
Raymond Fellows
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Infineum International Ltd
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Infineum International Ltd
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Priority to EP05111664A priority Critical patent/EP1642956A1/fr
Priority to EP05104350A priority patent/EP1605034B1/fr
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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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/86—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
    • C10M129/88—Hydroxy compounds
    • C10M129/91—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M165/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • 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
    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06—Well-defined aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/22—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts
    • 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
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2030/40—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

Definitions

  • the present invention relates to detergent additives for lubricating oil compositions.
  • Detergent additives are used in a wide variety of automotive, marine, railroad and industrial lubricants to minimize high temperature engine varnish and lacquer deposits. They are usually metal salts of sulphonates, phenates and salicylates, such as, for examples, calcium sulphurized phenates. However, the use of sulphur-containing detergents will soon be restricted due to imposed chemical limits on sulphur.
  • the aim of the present invention is to provide a detergent that is free of sulphur and metal (i.e. ash).
  • n is 0 to 10, preferably 1 to 8, more preferably 2 to 6, and most preferably 3 to 5;
  • Y is a divalent bridging group, and is preferably a hydrocarbyl group, preferably having from 1 to 4 carbon atoms; and
  • R is a hydrocarbyl group having from 4 to 30, preferably 8 to 18, and most preferably 9 to 15 carbon atoms;
  • the oil-soluble hydrocarbyl phenol aldehyde condensate having a weight average molecular weight (Mw) of 1250 to 1680, as measured by MALDI-TOF (Matrix Assisted Laser Desorption lonization- Time of Flight) mass spectrometry.
  • Mw weight average molecular weight
  • the hydrocarbyl phenol aldehyde condensate has the advantage of being free of metals (such as, for example, calcium and magnesium) and sulphur. Furthermore, unlike salicylate detergents, the hydrocarbyl phenol aldehyde condensate does not exhibit negative interactions with dispersants.
  • the hydrocarbyl phenol aldehyde condensate is preferably a hydrocarbyl phenol formaldehyde condensate.
  • hydrocarbyl as used herein means that the group concerned is primarily composed of hydrogen and carbon atoms and is bonded to the remainder of the molecule via a carbon atom, but does not exclude the presence of other atoms or groups in a proportion insufficient to detract from the substantially hydrocarbon characteristics of the group.
  • the hydrocarbyl group is preferably composed of only hydrogen and carbon atoms.
  • the hydrocarbyl group is an aliphatic group, preferably alkyl or alkylene group, especially alkyl groups, which may be linear or branched.
  • R is preferably an alkyl or alkylene group.
  • R is preferably branched.
  • a method of improving the detergency of a lubricating oil composition including the step of adding the hydrocarbyl phenol aldehyde condensate defined above to the lubricating oil composition.
  • the hydrocarbyl phenol aldehyde condensate preferably has a weight average molecular weight (Mw) in the range of 1280 to 1650, preferably 1300 to 1650, more preferably 1350 to 1600, as measured by MALDI-TOF (Matrix Assisted Laser Desorption lonization- Time of Flight) Mass Spectrometry.
  • Mw weight average molecular weight
  • the hydrocarbyl phenol aldehyde condensate is preferably obtainable by the condensation reaction between at least one aldehyde or ketone or reactive equivalent thereof and at least one hydrocarbyl phenol, in the presence of an acid catalyst such as, for example, an alkyl benzene sulphonic acid.
  • the product is preferably subjected to stripping to remove any unreacted hydrocarbyl phenol, preferably to less than 5.0% mass, more preferably to less than 3.0% mass, even more preferably to less than 1.0% mass, of unreacted hydrocarbyl phenol.
  • the product includes less than 0.5%, such as, for example, less than 0.1 %, mass of unreacted hydrocarbyl phenol.
  • the acid catalyst may be selected from a wide variety of acidic compounds such as, for example, phosphoric acid, sulphuric acid, sulphonic acid, oxalic acid and hydrochloric acid.
  • the acid may also be present as a component of a solid material such as an acid treated clay.
  • the amount of catalyst used may vary from 0.05 to 10% or more, such as for example 0.1 to 1%, by mass of the total reaction mixture.
  • the hydrocarbyl phenol aldehyde condensate is preferably branched dodecyl phenol formaldehyde condensate, such as, for example, a tetrapropenyl tetramer phenol formaldehyde condensate.
  • the hydrocarbyl phenol aldehyde condensate is preferably used in the lubricating oil composition in an amount ranging from 0.1 to 20 mass%, more preferably from 0.2 to 15 mass%, and most preferably from 0.3 to 10 mass%, based on the mass of the lubricating oil composition.
  • the lubricating oil composition will include an oil of lubricating viscosity.
  • the oil of lubricating viscosity (also referred to as lubricating oil) may be any oil suitable for the lubrication of automotive, marine, railroad and industrial engines.
  • the lubricating oil may suitably be an animal, a vegetable or a mineral oil.
  • the lubricating oil is a petroleum-derived lubricating oil, such as a naphthenic base, paraffinic base or mixed base oil.
  • the lubricating oil may be a synthetic lubricating oil.
  • Suitable synthetic lubricating oils include synthetic ester lubricating oils, which oils include diesters such as di-octyl adipate, di-octyl sebacate and tridecyl adipate, or polymeric hydrocarbon lubricating oils such as, for example, liquid polyisobutene and poly-alpha olefins. Commonly, a mineral oil is employed.
  • the lubricating oil generally comprises greater than 60, typically greater than 70, mass% of the lubricant.
  • the lubricating oil typically has a kinematic viscosity at 100°C of from 2 to 40, for example from 3 to 15, mm 2 s -1 and a viscosity index of from 80 to 100, for example, from 90 to 95.
  • hydrocracked oils Another class of lubricating oils is hydrocracked oils, where the refining process further breaks down the middle and heavy distillate fractions in the presence of hydrogen at high temperatures and moderate pressures.
  • Hydrocracked oils typically have a kinematic viscosity at 100°C of from 2 to 40, for example from 3 to 15, mm 2 s -1 and a viscosity index typically in the range of from 100 to 110, for example from 105 to 108.
  • the oil may include 'brightstock' which refers to base oils that are solvent-extracted, de-asphalted products from vacuum residuum generally having a kinematic viscosity at 100°C of from 28 to 36 mm 2 s -1 and are typically used in a proportion of less than 30, preferably less than 20, more preferably less than 15, most preferably less than 10, such as less than 5, mass%, based on the mass of the composition.
  • 'brightstock' refers to base oils that are solvent-extracted, de-asphalted products from vacuum residuum generally having a kinematic viscosity at 100°C of from 28 to 36 mm 2 s -1 and are typically used in a proportion of less than 30, preferably less than 20, more preferably less than 15, most preferably less than 10, such as less than 5, mass%, based on the mass of the composition.
  • the oil of lubricating viscosity is present in the lubricating oil composition in an amount greater than 50 mass%, more preferably greater than 60 mass%, and most preferably greater than 65 mass%, based on the mass of the lubricating oil composition.
  • the lubricating oil composition may also include one or more detergent additives based on metal "soaps", that is metal salts of acidic organic compounds, sometimes referred to as surfactants.
  • the metal may be an alkali or alkaline earth metal such as, for example, sodium, potassium, lithium, calcium, barium and magnesium. Calcium is preferred.
  • the surfactant may be a salicylate, a sulphonate, a carboxylate, a phenate, a thiophosphate or a naphthenate.
  • the detergent may also be a complex/hybrid detergent prepared from a mixture of more than one metal surfactant, such as a calcium alkyl phenate and a calcium alkyl salicylate.
  • a complex detergent is a hybrid material in which the surfactant groups, for example phenate and salicylate, are incorporated during the overbasing process. Examples of complex detergents are described in the art, such as, for example, in EP 902 827B.
  • Surfactants for the surfactant system of the metal detergents contain at least one hydrocarbyl group, for example, as a substituent on an aromatic ring.
  • the detergents may be non-sulphurized or sulphurized, and may be chemically modified and/or contain additional substituents. Suitable sulphurizing processes are well known to those skilled in the art.
  • the detergent may have a low TBN of from 10 to 50, a medium TBN of 50 to 150, or a high TBN of greater than 150, such as, for example, 150 to 400.
  • the detergents may be used in a proportion in the range of 0.5 to 30, preferably 2 to 20, or more preferably 2 to 15, mass% based on the mass of the lubricating oil composition.
  • the lubricant composition may include at least one dispersant.
  • a dispersant is an additive for a lubricating composition whose primary function in lubricants is to accelerate neutralization of acids by the detergent system.
  • Ashless dispersants comprise a long chain hydrocarbon 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 hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
  • ashless dispersants are succinimides, e.g. polyisobutene succinic anhydride; and polyamine condensation products that may be borated or unborated.
  • the dispersants may be used in a proportion in the range of 0 to 10.0, preferably 0.5 to 6.0, or more preferably 1.0 to 4.0, mass% based on the mass of the lubricating oil composition.
  • Antiwear additives may be present in the lubricating oil composition.
  • the antiwear additives may be metallic or non-metallic, preferably the former.
  • Dihydrocarbyl dithiophosphate metal salts are examples of anti-wear additives that may be used in the present invention.
  • the metal in the dihydrocarbyl dithiophosphate metal salts may be an alkali or alkaline earth metal, or aluminium, lead, tin, molybdenum, manganese, nickel or copper.
  • Zinc salts are preferred, preferably in the range of 0.1 to 1.5, preferably 0.5 to 1.3, mass%, based upon the total mass of the lubricating oil composition.
  • DDPA dihydrocarbyl dithiophosphoric acid
  • a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols.
  • multiple dithiophosphoric acids can be prepared comprising both hydrocarbyl groups that are entirely secondary and hydrocarbyl groups that are entirely primary.
  • any basic or neutral zinc compound may 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 neutralization reaction.
  • the preferred zinc dihydrocarbyl dithiophosphates are oil-soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula: [(RO) (R 1 O) P(S)S] 2 Zn where R and R 1 may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R and R 1 groups are alkyl groups of 2 to 8 carbon atoms.
  • the radicals may, for example, be ethyl, n-propyl, I-propyl, n-butyl, I-butyl, sec-butyl, amyl, n-hexyl, I-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.
  • the total number of carbon atoms (i.e. in R and R 1 ) in the dithiophoshoric acid will generally be 5 or greater.
  • the zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
  • the antiwear additive may be used in a proportion in the range of 0.1 to 1.5, preferably 0.2 to 1.3, or more preferably 0.5 to 0.9, mass% based on the mass of the lubricating oil composition.
  • Antioxidants may also be added to the lubricating oil composition. These may be aminic or phenolic. Examples of aminic include secondary aromatic amines such as diarylamines, for example diphenylamines wherein each phenyl group is alkylsubstituted with an alkyl group having 4 to 15 carbon atoms. Examples of phenolics include hindered phenols, including mono-phenols and bis-phenols. The anti-oxidant may be present in an amount of up to 3 mass%.
  • One or more of the following additives may also be present in the lubricating oil composition: pour point depressants such as poly(meth)acrylates or alkyl aromatic polymers; anti-foaming agents such as silicone anti-foaming agents; viscosity index improvers such as olefin copolymers; dyes; metal deactivators such as aryl thiazines, triazoles or alkyl substituted dimercapto thiadiazoles; and demulsifiers.
  • pour point depressants such as poly(meth)acrylates or alkyl aromatic polymers
  • anti-foaming agents such as silicone anti-foaming agents
  • viscosity index improvers such as olefin copolymers
  • dyes such as olefin copolymers
  • metal deactivators such as aryl thiazines, triazoles or alkyl substituted dimercapto thiadiazoles
  • demulsifiers demulsifiers.
  • the additive package may be added simultaneously to the base oil to form the lubricating oil composition. Dissolution of the additive package into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating.
  • the additive package will typically be formulated to contain the detergent in proper amounts to provide the desired concentration, and/or to carry out the intended function in the final formulation when the additive package is combined with a predetermined amount of base lubricant.
  • the additive package may contain active ingredients in an amount, based on the additive package, of, for example, from 2.5 to 90, preferably from 5 to 75, most preferably from 8 to 60, mass% of additives in the appropriate proportions, the remainder being base oil.
  • the final formulations may typically contain about 5 to 40 mass% of the additive package, the remainder being base oil.
  • 'oil-soluble' or 'oil-dispersable' do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
  • the dodecylphenol, sulphonic acid catalyst, paraformaldehyde, water and heptane were added to a 5L baffled reactor with stirrer (200 rpm), nitrogen blanket (600ml/min), condenser, Dean and Stark trap, a temperature controlling system, and Cardice/Acetone trap vacuum system.
  • the reaction components were heated from ambient to 80°C over 30 minutes, then heated further from 80 to 100°C over 2 hours, during which time water was removed by azeotropic distillation.
  • the residual heptane and dodecyl phenol were removed from the reaction mixture under reduced pressure at 200°C. Finally, the temperature was decreased to 120°C at which point ESN 150 was added to produce the desired level of active ingredient (A.I.).
  • Lubricating oil compositions were prepared and tested in the Caterpillar 1N engine test. Both compositions have the same ash and soap levels (i.e. 1% ash and 0.9% soap).
  • Example 1 Comparative Example 1 300 TBN Calcium sulphonate 1.81 1.26 400 TBN Magnesium Sulphonate 0.26 0.26 147 TBN Calcium Sulphurized Phenate 1.13 Dodecylphenol Formaldehyde Condensate- 1585 mw 0.45 0 Succinimide Dispersant 6.10 6.10 ZDDP Antioxidant 1.31 1.31 Antioxidant 0.26 0.26 Seals Moderator 0.17 0.17 SN150 Diluent 1.84 1.70 Group I Base Oil,600N 18.5 19.8 Group I Base Oil, 150N 61.3 60 Viscosity Modifier 7.8 7.8 Pour Point Depressant 0.2 0.2 Ash (%mass) 1.00 1.00 TBN (D2896) 8.61 8.65 Soap (%mass) 0.91 0.91 Sulphur (%mass) 0.257 0.2
  • the Caterpillar 1N engine test is designed to measure detergency.
  • the test is made up of three detergency measurements: the amount of carbon in the top piston groove (top groove fill); the amount of heavy carbon on the top land of the piston (top land heavy carbon); and the overall piston cleanliness, measured as weighted demerits (weighted demerits, or WDN).
  • WDN weighted demerits
  • Lubricating oil compositions were also prepared and tested in the Komatsu Hot Tube Test.
  • Example 2 Comparative Example 2 300 TBN Calcium Sulphonate 1.45 1.45 400 TBN Magnesium Sulphonate 0.30 0.30 147 TBN Calcium Sulphurized Phenate - 1.30 Succinimide Dispersant 7.00 7.00 ZDDP Antiwear 1.60 1.60 Antioxidant 0.40 0.40 Antifoam 0.003 0.003 PIBSA 0.20 0.20 Dodecylphenol Formaldehyde Condensate (stripped to ⁇ 1% alkyl phenol) Mw 1500 1.08 - SN 150 Diluent 2.37 2.15 Gp I Base Oil Balance Balance
  • hydrocarbyl phenol aldehyde condensates having weight average molecular weights of 1300, 1500 and 1585 show surprisingly better performance in the Caterpillar 1N test than the hydrocarbyl phenol aldehyde condensates having weight average molecular weights of 1100 and 1700.

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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)

Claims (9)

  1. Utilisation comme détergent dans une composition d'huile lubrifiante d'un produit de condensation hydrocarbylphénol-aldéhyde ayant la structure suivante :
    Figure imgb0004
     dans laquelle n a une valeur de 0 à 10, avantageusement de 1 à 8, plus avantageusement de 2 à 6 et de préférence de 3 à 5 ; Y représente un groupe de pontage divalent, et représente de préférence un groupe hydrocarbyle, ayant de préférence 1 à 4 atomes de carbone ; et R représente un groupe hydrocarbyle ayant 4 à 30, avantageusement 8 à 18 et de préférence 9 à 15 atomes de carbone ; le produit de condensation hydrocarbylphénol-aldéhyde soluble dans l'huile ayant une moyenne en poids du poids moléculaire (Mw) de 1250 à 1680, de la manière mesurée par spectrométrie de masse MALDI-TOF (ionisation par désorption laser assistée par matrice - temps de vol).
  2. Utilisation suivant la revendication 1, dans laquelle le produit de condensation hydrocarbylphénol-aldéhyde a une moyenne en poids du poids moléculaire (Mw) comprise dans l'intervalle de 1280 à 1650, avantageusement de 1300 à 1650, plus avantageusement de 1350 à 1600, de la manière mesurée par spectrométrie de masse MALDI-TOF (ionisation par désorption laser assistée par matrice - temps de vol).
  3. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle le produit de condensation comprend moins de 5,0 % en masse, plus avantageusement moins de 3,0 % en masse, encore plus avantageusement moins de 1,0 % en masse d'hydrocarbylphénol n'ayant pas réagi.
  4. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle le produit de condensation hydrocarbylphénol-aldéhyde peut être obtenu par la réaction de condensation entre au moins un aldéhyde ou une cétone ou un de ses équivalents réactifs et un hydrocarbylphénol, en présence d'un catalyseur acide.
  5. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle le groupe hydrocarbyle dans le produit de condensation hydrocarbylphénol-aldéhyde est ramifié.
  6. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle le produit de condensation hydrocarbylphénol-aldéhyde est un produit de condensation hydrocarbylphénol-formaldéhyde.
  7. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle le produit de condensation hydrocarbylphénol-aldéhyde est un produit de condensation tétrapropénylphénol-formaldéhyde.
  8. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle la composition d'huile lubrifiante comprend au moins un des additifs suivants : un détergent métallique surbasique, un dispersant, un antioxydant, un auditif anti-usure, un agent abaissant le point d'écoulement, un agent antimousse, un agent améliorant l'indice de viscosité, un colorant, un désactivateur de métaux, un désémulsionnant ou un de leurs mélanges.
  9. Procédé pour améliorer le pouvoir détergent d'une composition d'huile lubrifiante, le procédé comprenant l'étape d'addition du produit de condensation hydrocarbylphénol-aldéhyde suivant l'une quelconque des revendications précédentes à la composition d'huile lubrifiante.
EP05104350A 2004-06-11 2005-05-23 L'utilisation d'un additif détergent pour compositions lubrifiante Not-in-force EP1605034B1 (fr)

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EP1798278B1 (fr) * 2005-12-15 2015-07-29 Infineum International Limited Utilisation d'un agent antirouille dans une composition d'huile lubrifiante
ES2731475T3 (es) * 2006-08-08 2019-11-15 Infineum Int Ltd Composición de aceite lubricante que contiene aditivos detergentes
US7781385B2 (en) 2006-08-08 2010-08-24 Infineum International Limited Lubricating oil composition
WO2009064827A1 (fr) * 2007-11-16 2009-05-22 The Lubrizol Corporation Nouveaux matériaux couplés à base de phénol substitué par un groupe hydrocarbyle en tant qu'inhibiteurs de cires de champ pétrolifère
US20100256030A1 (en) * 2009-04-06 2010-10-07 Hartley Rolfe J Lubricating Oil Composition
CA2827438A1 (fr) 2011-02-17 2012-08-23 The Lubrizol Corporation Lubrifiants possedant une bonne retention du tbn
DE102012223638A1 (de) * 2011-12-21 2013-06-27 Infineum International Ltd. Verfahren zur Herabsetzung der Abnahmerate der Basizität einer Schmierölzusammensetzung, die in einem Motor verwendet wird
CA2936276A1 (fr) * 2014-01-10 2015-07-16 The Lubrizol Corporation Procede de lubrification d'un moteur a combustion interne
US20160326453A1 (en) * 2014-01-10 2016-11-10 The Lubrizol Corporation Method of lubricating an internal combustion engine
CN112760142A (zh) * 2020-12-18 2021-05-07 圣保路石油化工（天津）股份有限公司 一种超长换油里程的节能柴油及其制备方法
CN114806683A (zh) * 2022-03-28 2022-07-29 龙蟠润滑新材料（天津）有限公司 船舶上中速筒状活塞柴油机用润滑油组合物及其制备方法
CN115678651A (zh) * 2022-10-24 2023-02-03 统一石油化工有限公司 一种减排低碳ch-4柴油机油组合物

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US3256183A (en) * 1963-07-10 1966-06-14 Lubrizol Corp Lubricant having improved oxidation resistance
US5259967A (en) * 1992-06-17 1993-11-09 The Lubrizol Corporation Low ash lubricant composition
JP3454593B2 (ja) * 1994-12-27 2003-10-06 旭電化工業株式会社 潤滑油組成物
EP0725129B1 (fr) * 1995-02-01 2001-12-12 The Lubrizol Corporation Composition lubrificante à faible teneur en cendre
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