EP3645681B1 - Compositions d'huile lubrifiante contenant des composés détergents - Google Patents

Compositions d'huile lubrifiante contenant des composés détergents Download PDF

Info

Publication number
EP3645681B1
EP3645681B1 EP18749527.0A EP18749527A EP3645681B1 EP 3645681 B1 EP3645681 B1 EP 3645681B1 EP 18749527 A EP18749527 A EP 18749527A EP 3645681 B1 EP3645681 B1 EP 3645681B1
Authority
EP
European Patent Office
Prior art keywords
lubricating oil
oil composition
alkylhydroxybenzoate
detergent
lubricating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP18749527.0A
Other languages
German (de)
English (en)
Other versions
EP3645681A1 (fr
Inventor
Alexander Bowman Boffa
Walter Alexander Hartgers
Seyedeh Mahboobeh Hosseini
Curtis Bay Campbell
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron Oronite Technology BV
Chevron Oronite Co LLC
Original Assignee
Chevron Oronite Technology BV
Chevron Oronite Co LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chevron Oronite Technology BV, Chevron Oronite Co LLC filed Critical Chevron Oronite Technology BV
Publication of EP3645681A1 publication Critical patent/EP3645681A1/fr
Application granted granted Critical
Publication of EP3645681B1 publication Critical patent/EP3645681B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
    • C10M129/50—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring monocarboxylic
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10—Sulfonic acids or 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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • 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
    • 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
    • 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
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal 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
    • C10N2010/12—Groups 6 or 16
    • 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
    • C10N2020/071—Branched chain compounds
    • 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
    • C10N2030/06—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
    • C10N2030/12—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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy

Definitions

  • Overbased detergents are well described to provide lubricating properties. Often such detergent additives are proportioned with other lubricating additives to provide lubricating oil compositions that exhibit certain desired lubricating properties.
  • Metal-containing detergents function both as detergents to control deposits, and as acid neutralizers or rust inhibitors, thereby reducing wear, controlling corrosion, and extending engine life.
  • the present disclosure generally relates to lubricating oil compositions which simultaneously achieve wear control and corrosion inhibition, while also achieving improved fuel economy.
  • the lubricating oil compositions are suitable for automotive engines, motorcycle engines, natural gas engines, dual fuel engines, railroad locomotive engines, mobile natural gas engines, and as functional fluids for automotive and industrial applications.
  • the present invention is based on the surprising discovery that a lubricating oil composition containing more highly overbased metal hydroxybenzoate detergent, having a TBN of 600 mgKOH/g or greater on an actives basis, exhibits improved lubricating properties such as superior performance at low temperatures, BN retention, oxidative and thermal stability, corrosion resistance, and oxidative and thermal stability, in addition to providing a more cost effective formulating approach over the use of overbased hydroxybenzoate detergent technology previously described in the art.
  • US2011003726 discloses lubricating oils comprising alkyl salicylates with a TBN about 150 bearing a highly isomerized alkyl substituent.
  • a lubricating oil composition which comprises:
  • Also provided is a method of lubricating an engine comprising lubricating said engine with a lubricating oil composition as defined above.
  • a “major amount” means in excess of 50 weight % of a composition.
  • a “minor amount” means less than 50 weight % of a composition, expressed in respect of the stated additive and in respect of the total mass of all the additives present in the composition, reckoned as active ingredient of the additive or additives.
  • Active ingredients or “actives” or “oil free” refers to additive material that is not diluent or solvent.
  • ppm means parts per million by weight, based on the total weight of the lubricating oil composition.
  • Total base number was determined in accordance with ASTM D2896.
  • Metal refers to alkali metals, alkaline earth metals, or mixtures thereof.
  • High temperature high shear (HTHS) viscosity at 150°C was determined in accordance with ASTM D4863.
  • KVioo Kinematic viscosity at 100°C
  • CCS Cold Cranking Simulator
  • Olefins refers to a class of unsaturated aliphatic hydrocarbons having one or more carbon-carbon double bonds, obtained by a number of processes. Those containing one double bond are called mono-alkenes, and those with two double bonds are called dienes, alkyldienes, or diolefins. Alpha olefins are particularly reactive because the double bond is between the first and second carbons. Examples are 1-octene and 1-octadecene, which are used as the starting point for medium-biodegradable surfactants. Linear and branched olefins are also included in the definition of olefins.
  • Normal Alpha Olefins refers to olefins which are straight chain, non-branched hydrocarbons with carbon-carbon double bond present in beginning and end of the chain.
  • Isomerized Normal Alpha Olefin refers to an alpha olefin that has been subjected to isomerization conditions which results in an alteration of the distribution of the olefin species present and/or the introduction of branching along the alkyl chain.
  • the isomerized olefin product may be obtained by isomerizing a linear alpha olefin containing from 10 to 40 carbon atoms, preferably from about 20 to about 28 carbon atoms, and preferably from about 20 to about 24 carbon atoms.
  • the present disclosure is directed to a lubricating oil composition
  • a lubricating oil composition comprising:
  • a lubricating oil composition comprising:
  • the alkylhydroxybenzoate detergent compound derived from C 10 - C 40 isomerized NAO has a TBN of at least 600, 600 or greater, from 600 - 800, 600 - 750, 600 - 700 mgKOH/gram on an actives basis.
  • the alkylhydroxybenzoate detergent derived from C 10 - C 40 isomerized NAO with a TBN of 600 mgKOH/gram or greater on an oil-free basis can be prepared as described in US Patent 8,993,499 .
  • the alkylhydroxybenzoate detergent derived from C 10 - C 40 isomerized NAO is a Ca alkylhydroxybenzoate detergent.
  • the alkylhydroxybenzoate detergent derived from C 10 - C 40 isomerized NAO can be an alkylated hydroxybenzoate detergent.
  • the detergent can be a salicylate detergent.
  • the detergent can be a carboxylate detergent.
  • the alkylhydroxybenzoate detergent with a TBN of 600 mgKOH/gram or greater on an oil-free basis is made from an alkylphenol having an alkyl group derived from an isomerized alpha olefin having from about 14 to about 28, or from about 20 to about 24 carbon atoms per molecule.
  • the alkylhydroxybenzoate detergent derived from C 10 - C 40 isomerized NAO with a TBN of 600 mgKOH/gram or greater on an actives basis is made from one or more alkylphenols with an alkyl group derived from C 10 - C 40 isomerized NAO and one or more alkylphenols with an alkyl group different from C10 - C40 isomerized NAO.
  • the one or more alkylphenols with an alkyl group different from C 10 - C 40 isomerized NAO has a highly branched alkyl group of at least 9 carbon atoms, from 9 to 24, and from 10-15 carbon atoms.
  • the lubricating oil composition comprises 0.01 to 2 wt.% in terms of Ca content of the alkylhydroxybenzoate detergent derived from C 10 - C 40 isomerized NAO with a TBN of 600 mgKOH/gram or greater on an actives basis, preferably 0.1 to 1 wt. %, more preferably 0.05 to 0.5 wt. %, more preferably 0.1 to 0.5 wt%.
  • the lubricating oil composition comprises the alkylhydroxybenzoate derived from C 10 - C 40 isomerized NAO with TBN 600 or more on an active basis is an automotive engine oil, a gas engine oil, a motorcycle oil, a dual fuel engine oil, a mobile gas engine oil, or a locomotive engine oil.
  • the lubricating oil composition comprises the alkylhydroxybenzoate derived from C 10 - C 40 isomerized NAO with a TBN of 600 mgKOH/gram or more on an oil-free basis is a functional fluid for automotive and industrial applications, such as transmission oil, hydraulic oil, tractor fluid, gear oil, et.
  • the lubricating oil composition comprises the alkylhydroxybenzoate derived from C 10 - C 40 isomerized NAO with a TBN of 600 mgKOH/gram or more on an actives basis is a multi-grade oil.
  • the lubricating oil composition comprises the alkylhydroxybenzoate derived from C 10 - C 40 isomerized NAO with a TBN of 600 mgKOH/gram or more on an actives basis lubricates crankcase, gear as well as clutches. Additional Detergents
  • the lubricating oil composition of the present invention can further contain one or more overbased detergents having a TBN of 10-800, 10-700, 30-690, 100-600, 150-600, 150-500, 200-450 mg KOH/g on an actives basis.
  • Detergents that may be used include oil-soluble overbased sulfonate, non-sulfur containing phenate, sulfurized phenates, salixarate, salicylate, saligenin, complex detergents and naphthenate detergents and other oil-soluble alkylhydroxybenzoates of a metal, particularly the alkali or alkaline earth metals, e.g., barium, 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.
  • Overbased metal detergents are generally produced by carbonating a mixture of hydrocarbons, detergent acid, for example: sulfonic acid, alkylhydroxybenzoate etc., metal oxide or hydroxides (for example calcium oxide or calcium hydroxide) and promoters such as xylene, methanol and water.
  • detergent acid for example: sulfonic acid, alkylhydroxybenzoate etc.
  • metal oxide or hydroxides for example calcium oxide or calcium hydroxide
  • promoters such as xylene, methanol and water.
  • Overbased detergents may be low overbased, e.g., an overbased salt having a TBN below 100 on an actives basis.
  • the TBN of a low overbased salt may be from about 30 to about 100.
  • the TBN of a low overbased salt may be from about 30 to about 80.
  • Overbased detergents may be medium overbased, e.g., an overbased salt having a TBN from about 100 to about 250.
  • the TBN of a medium overbased salt may be from about 100 to about 200.
  • the TBN of a medium overbased salt may be from about 125 to about 175.
  • Overbased detergents may be high overbased, e.g., an overbased salt having a TBN above 250.
  • the TBN of a high overbased salt may be from about 250 to about 800 on an actives basis.
  • the detergent can be one or more alkali or alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid.
  • Suitable hydroxyaromatic compounds include mononuclear monohydroxy and polyhydroxy aromatic hydrocarbons having 1 to 4, and preferably 1 to 3, hydroxyl groups.
  • Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like.
  • the preferred hydroxyaromatic compound is phenol.
  • the alkyl substituted moiety of the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is derived from an alpha olefin having from about 10 to about 80 carbon atoms.
  • the olefins employed may be linear, isomerized linear, branched or partially branched linear.
  • the olefin may be a mixture of linear olefins, a mixture of isomerized linear olefins, a mixture of branched olefins, a mixture of partially branched linear or a mixture of any of the foregoing.
  • the mixture of linear olefins that may be used is a mixture of normal alpha olefins selected from olefins having from about 10 to about 40 carbon atoms per molecule.
  • the normal alpha olefins are isomerized using at least one of a solid or liquid catalyst.
  • At least about 50 mole%, at least about 75 mole%, at least about 80 mole%, at least about 85 mole%, at least about 90 mole%, at least about 95 mole% of the alkyl groups contained within the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid such as the alkyl groups of an alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid detergent are a C 20 or higher.
  • the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is an alkali or alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid that is derived from an alkyl-substituted hydroxybenzoic acid in which the alkyl groups are C 20 to about C 28 normal alpha-olefins.
  • the alkyl group is derived from at least two alkylated phenols.
  • the alkyl group on at least one of the at least two alkyl phenols is derived from an isomerized alpha olefin.
  • the alkyl group on the second alkyl phenol may be derived from branched or partially branched olefins, highly isomerized olefins or mixtures thereof.
  • the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is a salicylate derived from an alkyl group with 20-40 carbon atoms, preferably 20-28 carbon atoms, more preferably, isomerized 20-24 NAO.
  • Sulfonates may be prepared from sulfonic acids which are typically obtained by the sulfonation of alkyl substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum or by the alkylation of aromatic hydrocarbons. Examples included those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives.
  • the alkylation may be carried out in the presence of a catalyst with alkylating agents having from about 3 to more than 70 carbon atoms.
  • the alkaryl sulfonates usually contain from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms, preferably about 16 to 30 carbon atoms, and more preferably 20-24 carbon atoms per alkyl substituted aromatic moiety.
  • Metal salts of phenols and sulfurized phenols which are sulfurized phenate detergents, are prepared by reaction with an appropriate metal compound such as an oxide or hydroxide and neutral or overbased products may be obtained by methods well known in the art.
  • Sulfurized phenols may be prepared by reacting a phenol with sulfur or a sulfur containing compound such as hydrogen sulfide, sulfur monohalide or sulfur dihalide, to form products which are generally mixtures of compounds in which 2 or more phenols are bridged by sulfur containing bridges.
  • the sulfur can be employed either as molten sulfur or as a solid (e.g., powder or particulate) or as a solid suspension in a compatible hydrocarbon liquid.
  • calcium hydroxide As the calcium base because of its handling convenience versus, for example, calcium oxide, and also because it affords excellent results.
  • Other calcium bases can also be used, for example, calcium alkoxides.
  • Suitable alkylphenols which can be used are those wherein the alkyl substituents contain a sufficient number of carbon atoms to render the resulting overbased sulfurized calcium alkylphenate composition oil-soluble. Oil solubility may be provided by a single long chain alkyl substitute or by a combination of alkyl substituents. Typically, the alkylphenol used will be a mixture of different alkylphenols, e.g., C 20 to C 24 alkylphenol.
  • suitable alkyl phenolic compounds will be derived from isomerized alpha olefin alkyl groups having from about 10 to about 40 carbon atoms per molecule, having an isomerized level (1) of the alpha olefin between from about 0.1 to about 0.4.
  • suitable alkyl phenolic compounds will be derived from alkyl groups which are branched olefinic propylene oligomers or mixture thereof having from about 9 to about 80 carbon atoms.
  • the branched olefinic propylene oligomer or mixtures thereof have from about 9 to about 40 carbon atoms.
  • the branched olefinic propylene oligomer or mixtures thereof have from about 9 to about 18 carbon atoms. In one embodiment, the branched olefinic propylene oligomer or mixtures thereof have from about 9 to about 12 carbon atoms.
  • suitable alkyl phenolic compounds comprise distilled cashew nut shell liquid (CNSL) or hydrogenated distilled cashew nut shell liquid.
  • Distilled CNSL is a mixture of biodegradable meta-hydrocarbyl substituted phenols, where the hydrocarbyl group is linear and unsaturated, including cardanol. Catalytic hydrogenation of distilled CNSL gives rise to a mixture of meta-hydrocarbyl substituted phenols predominantly rich in 3-pentadecylphenol.
  • the alkylphenols can be para-alkylphenols, meta-alkylphenols or ortho alkylphenols. Since it is believed that p-alkylphenols facilitate the preparation of highly overbased calcium sulfurized alkylphenate where overbased products are desired, the alkylphenol is preferably predominantly a para alkylphenol with no more than about 45 mole percent of the alkylphenol being ortho alkylphenols; and more preferably no more than about 35 mole percent of the alkylphenol is ortho alkylphenol. Alkyl-hydroxy toluenes or xylenes, and other alkyl phenols having one or more alkyl substituents in addition to at least one long chained alkyl substituent can also be used. In the case of distilled cashew nut shell liquid, the catalytic hydrogenation of distilled CNSL gives rise to a mixture of meta-hydrocarbyl substituted phenols.
  • the one or more overbased detergent can be a complex or hybrid detergent which is known in the art as comprising a surfactant system derived from at least two surfactants described above.
  • the one or more overbased detergent can be a salicylate with an alkyl group having 20-28 carbon atoms, more preferably 20-24Ccarbon atoms.
  • the one or more overbased detergent can be a salicylate with an alkyl group derived from C 14-18 NAO and contribute less than 0.05 wt%, preferably less than 0.025 wt%, more preferably less than 0.01 wt% in terms of Ca content to the lubricating oil.
  • the amount of the detergent can be from about 0.001 wt. % to about 50 wt. %, or from about 0.05 wt. % to about 25 wt. %, or from about 0.1 wt. % to about 20 wt. %, or from about 0.01 to 15 wt. % based on the total weight of the lubricating oil composition.
  • the lubricating oil composition disclosed herein can comprise one or more antiwear agent.
  • Antiwear agents reduce wear of metal parts.
  • ZDDP zinc dihydrocarbyl dithiophosphates
  • R 1 and R 2 groups are alkyl groups having from 2 to 8 carbon atoms (e.g., the alkyl radicals may be ethyl, n -propyl, isopropyl, n- butyl, isobutyl, sec -butyl, n -pentyl, isopentyl, n -hexyl, isohexyl, 2-ethylhexyl).
  • the total number of carbon atoms i.e., R 1 +R 2
  • the zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
  • the zinc dialkyl dithiophosphate is a primary, secondary zinc dialkyl dithiophosphate, or a combination thereof.ZDDP may be present at 3 wt. % or less (e.g., 0.1 to 1.5 wt. %, or 0.5 to 1.0 wt %) of the lubricating oil composition.
  • the lubricating oil composition containing the magnesium salicylate detergent described herein further comprises an antioxidant compound.
  • the antioxidant is a diphenylamine antioxidant.
  • the antioxidant is a hindered phenol antioxidant.
  • the antioxidant is a combination of a diphenylamine antioxidant and a hindered phenol antioxidant.
  • the lubricating oil composition disclosed herein can comprise one or more antioxidant.
  • Antioxidants reduce the tendency of mineral oils during to deteriorate during service. Oxidative deterioration can be evidenced by sludge in the lubricant, varnish-like deposits on the metal surfaces, and by viscosity growth.
  • Suitable antioxidants include hindered phenols, aromatic amines, and sulfurized alkylphenols and alkali and alkaline earth metals salts 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.
  • Suitable hindered phenol antioxidants 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; 4-butyl-2,6-di- tert -butylphenol; and 4-dodecyl-2,6-di- tert butylphenol.
  • antioxidants include 2,6-di-alkyl-phenolic propionic ester derivatives such as IRGANOX ® L-135 from Ciba and bis-phenolic antioxidants such as 4,4'-bis(2,6-di- tert -butylphenol) and 4,4'-methylenebis(2,6-di- tert -butylphenol).
  • Typical aromatic amine antioxidants have at least two aromatic groups attached directly to one amine nitrogen.
  • Typical aromatic amine antioxidants have alkyl substituent groups of at least 6 carbon atoms.
  • aromatic amine antioxidants useful herein include 4,4'-dioctyldiphenylamine, 4,4'-dinonyldiphenylamine, N -phenyl-1-naphthylamine, N- (4 -tert- octyphenyl)-1-naphthylamine, and N -(4-octylphenyl)-1-naphthylamine.
  • Antioxidants may be present at 0.01 to 5 wt. % (e.g., 0.1 to 2 wt. %) of the lubricating oil composition.
  • the lubricating oil composition disclosed herein can comprise one or more dispersant.
  • Dispersants maintain in suspension materials resulting from oxidation during engine operation that are insoluble in oil, thus preventing sludge flocculation and precipitation or deposition on metal parts.
  • Dispersants useful herein include nitrogen-containing, ashless (metal-free) dispersants known to effective to reduce formation of deposits upon use in gasoline and diesel engines.
  • Suitable dispersants include hydrocarbyl succinimides, hydrocarbyl succinamides, mixed ester/amides of hydrocarbyl-substituted succinic acid, hydroxyesters of hydrocarbyl-substituted succinic acid, and Mannich condensation products of hydrocarbyl-substituted phenols, formaldehyde and polyamines. Also suitable are condensation products of polyamines and hydrocarbyl-substituted phenyl acids. Mixtures of these dispersants can also be used.
  • Baseic nitrogen-containing ashless dispersants are well-known lubricating oil additives and methods for their preparation are extensively described in the patent literature.
  • Preferred dispersants are the alkenyl succinimides and succinamides where the alkenyl-substituent is a long-chain of preferably greater than 40 carbon atoms. These materials are readily made by reacting a hydrocarbyl-substituted dicarboxylic acid material with a molecule containing amine functionality. Examples of suitable amines are polyamines such as polyalkylene polyamines, hydroxy-substituted polyamines and polyoxyalkylene polyamines.
  • Particularly preferred ashless dispersants are the polyisobutenyl succinimides formed from polyisobutenyl succinic anhydride and a polyalkylene polyamine such as a polyethylene polyamine of formula 2: NH 2 (CH 2 CH 2 NH) z H Formula 2, wherein z is 1 to 11.
  • the polyisobutenyl group is derived from polyisobutene and preferably has a number average molecular weight (M n ) in a range of 700 to 3000 Daltons (e.g., 900 to 2500 Daltons).
  • the polyisobutenyl succinimide may be a bis-succinimide derived from a polyisobutenyl group having a M n of 900 to 2500 Daltons.
  • the dispersants may be post-treated (e.g., with a boronating agent or a cyclic carbonate, ethylene carbonate etc).
  • Nitrogen-containing ashless (metal-free) dispersants are basic, and contribute to the TBN of a lubricating oil composition to which they are added, without introducing additional sulfated ash.
  • Dispersants may be present at 0.1 to 10 wt. % (e.g., 2 to 5 wt. %) of the lubricating oil composition.
  • the lubricating oil composition disclosed herein can comprise one or more foam inhibitor that can break up foams in oils.
  • suitable foam inhibitors or anti-foam inhibitors include silicone oils or polydimethylsiloxanes, fluorosilicones, alkoxylated aliphatic acids, polyethers (e.g., polyethylene glycols), branched polyvinyl ethers, alkyl acrylate polymers, alkyl methacrylate polymers, polyalkoxyamines and combinations thereof.
  • the lubricating oil compositions of the present disclosure may also contain other conventional additives that can impart or improve any desirable property of the lubricating oil composition in which these additives are dispersed or dissolved.
  • Any additive known to a person of ordinary skill in the art may be used in the lubricating oil compositions disclosed herein.
  • Some suitable additives have been described in Mortier et al., “Chemistry and Technology of Lubricants", 2nd Edition, London, Springer, (1996 ); and Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications", New York, Marcel Dekker (2003 ), both of which are incorporated herein by reference.
  • the lubricating oil compositions can be blended with antioxidants, anti-wear agents, detergents such as metal detergents, rust inhibitors, dehazing agents, demulsifying agents, metal deactivating agents, friction modifiers, pour point depressants, antifoaming agents, co-solvents, corrosion-inhibitors, ashless dispersants, multifunctional agents, dyes, extreme pressure agents and the like and mixtures thereof.
  • detergents such as metal detergents, rust inhibitors, dehazing agents, demulsifying agents, metal deactivating agents, friction modifiers, pour point depressants, antifoaming agents, co-solvents, corrosion-inhibitors, ashless dispersants, multifunctional agents, dyes, extreme pressure agents and the like and mixtures thereof.
  • detergents such as metal detergents, rust inhibitors, dehazing agents, demulsifying agents, metal deactivating agents, friction modifiers, pour point depressants, antifoaming agents, co-solvents, corrosion-inhibitors, ashless
  • additives in the form of 10 to 100 wt. % active ingredient concentrates in hydrocarbon oil, e.g. mineral lubricating oil, or other suitable solvent.
  • concentrates may be diluted with 3 to 100, e.g., 5 to 40, parts by weight of lubricating oil per part by weight of the additive package in forming finished lubricants, e.g. crankcase motor oils.
  • the purpose of concentrates is to make the handling of the various materials less difficult and awkward as well as to facilitate solution or dispersion in the final blend.
  • each of the foregoing additives when used, is used at a functionally effective amount to impart the desired properties to the lubricant.
  • a functionally effective amount of this friction modifier would be an amount sufficient to impart the desired friction modifying characteristics to the lubricant.
  • the concentration of each of the additives in the lubricating oil composition when used, may range from about 0.001 wt. % to about 20 wt. %, from about 0.01 wt. % to about 15 wt. %, or from about 0.1 wt. % to about 10 wt. %, from about 0.005 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 2.5 wt.%, based on the total weight of the lubricating oil composition.
  • the total amount of the additives in the lubricating oil composition may range from about 0.001 wt.% to about 20 wt.%, from about 0.01 wt.% to about 10 wt.%, or from about 0.1 wt.% to about 5 wt.%, based on the total weight of the lubricating oil composition.
  • Oil of lubricating viscosity Oil of lubricating viscosity
  • 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).
  • a base oil is useful for making concentrates as well as for making lubricating oil compositions therefrom, and may be selected from natural and synthetic lubricating oils and combinations thereof.
  • Natural oils include animal and vegetable oils, 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.
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., malonic acid, alkyl malonic acids, alkenyl malonic acids, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, fumaric acid, azelaic acid, suberic acid, sebacic acid, adipic acid, linoleic acid dimer, phthalic acid) 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., malonic acid, alkyl malonic acids, alkenyl malonic acids, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, fumaric acid, azelaic acid, suberic acid, sebac
  • 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.
  • the base oil may be derived from Fischer-Tropsch synthesized hydrocarbons.
  • Fischer-Tropsch synthesized hydrocarbons are made from synthesis gas containing H 2 and CO using a Fischer-Tropsch catalyst.
  • Such hydrocarbons typically require further processing in order to be useful as the base oil.
  • the hydrocarbons may be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed; using processes known to those skilled in the art.
  • Unrefined, refined and re-refined oils can be used in the present lubricating oil composition.
  • 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.
  • the base oil which may be used to make the present lubricating oil composition may be selected from any of the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (API Publication 1509).
  • Such base oil groups are summarized in Table 1 below: Table 1 Base Oil Properties Group (a) Saturates (b) , wt. % Sulfur (c) , wt.
  • Group I % Viscosity Index
  • Group II % Viscosity Index
  • Group III % Viscosity Index
  • Group IV Polyalphaolefins (PAOs) Group V All other base stocks not included in Groups I, II, III or IV
  • Groups I-III are mineral oil base stocks.
  • (b) Determined in accordance with ASTM D2007.
  • (c) Determined in accordance with ASTM D2622, ASTM D3120, ASTM D4294 or ASTM D4927.
  • (d) Determined in accordance with ASTM D2270.
  • Base oils suitable for use herein are any of the variety corresponding to API Group II, Group III, Group IV, and Group V oils and combinations thereof, preferably the Group III to Group V oils due to their exceptional volatility, stability, viscometric and cleanliness features.
  • the oil of lubricating viscosity for use in the lubricating oil compositions of this disclosure is typically present in a major amount, e.g., an amount of greater than 50 wt. %, preferably greater than about 70 wt. %, more preferably from about 80 to about 99.5 wt. % and most preferably from about 85 to about 98 wt. %, based on the total weight of the composition.
  • base oil as used herein shall be understood to mean a base stock or blend of base stocks which is a lubricant component that is produced by a single manufacturer to the same specifications (independent of feed source or manufacturer's location); that meets the same manufacturer's specification; and that is identified by a unique formula, product identification number, or both.
  • the base oil for use herein can be any presently known or later-discovered oil of lubricating viscosity used in formulating lubricating oil compositions for any and all such applications, e.g., engine oils, marine cylinder oils, functional fluids such as hydraulic oils, gear oils, transmission fluids, etc.
  • the base oils for use herein can optionally contain viscosity index improvers, e.g., polymeric alkylmethacrylates; olefinic copolymers, e.g., an ethylene-propylene copolymer or a styrenebutadiene copolymer; and the like and mixtures thereof.
  • viscosity index improvers e.g., polymeric alkylmethacrylates
  • olefinic copolymers e.g., an ethylene-propylene copolymer or a styrenebutadiene copolymer; and the like and mixtures thereof.
  • the viscosity of the base oil is dependent upon the application. Accordingly, the viscosity of a base oil for use herein will ordinarily range from about 2 to about 2000 centistokes (cSt) at 100° Centigrade (C.). Generally, individually the base oils used as engine oils will have a kinematic viscosity range at 100° C.
  • a lubricating oil composition having an SAE Viscosity Grade of 0W, 0W-8, 0W-12, 0W-16, 0W-20, 0W-26, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, 15W-40, 30, 40 and the like.
  • the level of sulfur in the lubricating oil compositions of the present invention is less than or equal to about 0.7 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of sulfur of about 0.01 wt. % to about 0.70 wt. %, 0.01 to 0.6 wt.%, 0.01 to 0.5 wt.%, 0.01 to 0.4 wt.%, 0.01 to 0.3 wt.%, 0.01 to 0.2 wt.%, 0.01 wt. % to 0.10 wt. %. In one embodiment, the level of sulfur in the lubricating oil compositions of the present invention is less than or equal to about 0.60 wt.
  • % less than or equal to about 0.50 wt. %, less than or equal to about 0.40 wt. %, less than or equal to about 0.30 wt. %, less than or equal to about 0.20 wt. %, less than or equal to about 0.10 wt. % based on the total weight of the lubricating oil composition.
  • the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.12 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.12 wt. %. In one embodiment, the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.11 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.11 wt. %.
  • the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.10 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.10 wt. %. In one embodiment, the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.09 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.09 wt. %.
  • the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.08 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.08 wt. %. In one embodiment, the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.07 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.07 wt. %.
  • the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.05 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.05 wt. %.
  • the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 1.60 wt. % as determined by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to about 1.60 wt. % as determined by ASTM D 874. In one embodiment, the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 1.00 wt. % as determined by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to about 1.00 wt. % as determined by ASTM D 874.
  • the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 0.80 wt. % as determined by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to about 0.80 wt. % as determined by ASTM D 874. In one embodiment, the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 0.60 wt. % as determined by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to about 0.60 wt. % as determined by ASTM D 874.
  • the isomerization level (I) of the olefin was determined by hydrogen-1 (1H) NMR.
  • the NMR spectra were obtained on a Bruker Ultrashield Plus 400 in chloroform-dl at 400 MHz using TopSpin 3.2 spectral processing software.
  • the isomerized level (I) of the alpha olefin is between from about 0.1 to about 0.4, preferably from about 0.1 to about 0.3, more preferably from about 0.12 to about 0.3.
  • the isomerization level of the NAO is about 0.16, and having from about 20 to about 24 carbon atoms.
  • the isomerization level of the NAO is about 0.26, and having from about 20 to about 24 carbon atoms.
  • a 5W-40 lubricating oil composition was prepared that contained a major amount of a base oil of lubricating viscosity and the following additives:
  • alkylated phenol and a Ca alkylhydroxybenzoate were prepared in substantially the same manner as in U.S. Patent No. 8,993,499 using a C 20-24 isomerized normal alpha olefin.
  • the isomerization level of the alpha olefin is about 0.16.
  • the resulting alkylhydroxybenzoate composition has a TBN of about 630 and Ca content of about 22.4 wt.% on an oil-free basis.
  • alkylated phenol and Ca alkylhydroxybenzoate were prepared in substantially the same manner as in U.S. Patent No. 8,993,499 using a C 20-24 isomerized normal alpha olefin.
  • the isomerization level of the alpha olefin is about 0.16.
  • the resulting alkylhydroxybenzoate composition has a TBN of about 225 and Ca content of about 8 wt.% on an oil-free basis.
  • An alkylhydroxybenzoate was prepared from an alkylphenol with an alkyl group derived from C 14-18 NAO and a TBN about 300 and Ca content about 1 0.6 wt. % on an oil-free basis.
  • alkylated phenol and alkylhydroxybenzoate were prepared in substantially the same manner as in U.S. Patent No. 8,030,258 using a C 20-28 NAO available from CP Chem.
  • the resulting alkylhydroxybenzoate composition has a TBN of about 520 and Ca content of about 18.7 wt.% on an oil-free basis.
  • the ASTM D6594 HTCBT test is used to test diesel engine lubricants to determine their tendency to corrode various metals, specifically alloys of lead and copper commonly used in cam followers and bearings.
  • Four metal specimens of copper, lead, tin and phosphor bronze are immersed in a measured amount of engine oil.
  • the oil, at an elevated temperature (170 °C), is blown with air (5 l/h) for a period of time (168 h).
  • the copper specimen and the stressed oil are examined to detect corrosion and corrosion products, respectively.
  • the concentrations of copper, lead, and tin in the new oil and stressed oil and the respective changes in metal concentrations are reported. To be a pass the concentration of lead should not exceed 120 ppm and the copper 20 ppm.
  • a heavy duty automotive lubricating oil composition was prepared that contained a major amount of a base oil of lubricating viscosity and the following additives, to provide an SAE 15W-40 finished oil:
  • alkylated phenol and a Ca alkylhydroxybenzoate were prepared in substantially the same manner as in U.S. Patent No. 8,993,499 using a C 20-24 isomerized normal alpha olefin.
  • the isomerization level of the alpha olefin is about 0.16.
  • the resulting alkylhydroxybenzoate composition has a TBN of about 120 and Ca content of about 4.2 wt.% on an oil-free basis.
  • a passenger car automotive lubricating oil composition was prepared that contained a major amount of a base oil of lubricating viscosity and the following additives, to provide an SAE 5W-30 finished oil:
  • Example 3 To formulation baseline 3 was added a mixture of both a calcium alkylhydroxybenzoate of Example A (32.3 mMol) and Example C (23.3 mMol) in a total amount of 0.2230 wt.%.
  • a passenger car automotive lubricating oil composition was prepared that contained a major amount of a base oil of lubricating viscosity and the following additives, to provide an SAE 5W-40 finished oil:
  • test oil is first heated, and then cooled to test temperature, in this case -40° C., in a mini-rotary viscometer cell.
  • test temperature in this case -40° C.
  • Each cell contains a calibrated rotor-stator set, in which the rotor is rotated by means of a string wound around the rotor shaft and attached to a weight.
  • a series of increasing weights are applied to the string starting with a 10 g weight until rotation occurs to determine the yield stress. Results are reported as Yield Stress as the applied force in Pascals.
  • a 150 g weight is then applied to determine the apparent viscosity of the oil. The larger the apparent viscosity, the more likely it is that the oil will not be continuously and adequately supplied to the oil pump inlet. Results are reported as Viscosity in centipoise.
  • lubricating oils formulated with an alkylhydroxybenzoate detergent of the invention perform as well as or better than formulations containing alkyhydroxybenzoates which are not derived from isomerized NAO having from about 10 to about 40 carbon atoms.

Landscapes

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

Claims (13)

  1. Composition d'huile lubrifiante comprenant :
    (a) une quantité majeure d'une huile à viscosité lubrifiante, où « quantité majeure » signifie en excès de 50 pour cent en poids de la composition d'huile lubrifiante, et
    (b) un ou plusieurs détergents comprenant au moins un composé alkylhydroxybenzoate dérivé d'une alpha-oléfine normale isomérisée (NAO) ayant de 10 à 40 atomes de carbone,
    où l'indice de basicité du composé alkylhydroxybenzoate déterminé selon ASTM D2896 est au moins 600 mgKOH/gm à la base d'actifs ;
    où
    le composé alkylhydroxybenzoate est und composé Ca alkylhydroxybenzoate ;
    et
    la composition d'huile lubrifiante comprend 0,01 à 2 pour cent en poids du composé alkylhydroxybenzoate en termes de contenu Ca.
  2. Composition d'huile lubrifiante selon la revendication 1 où l'indice de basicité du composé alkylhydroxybenzoate est de 600 à 800 mgKOH/gm à la base d'actifs.
  3. Composition d'huile lubrifiante selon la revendication 1 comprenant en plus un ou plusieurs détergents sélectionnés parmi un sulfonate, un phénate ou un salixarate de métal alcalin ou alcalino-terreux, un alcool salicylique, ou un détergent complexe, carboxylate ou salicylate, qui est dérivé d'un groupe alkyle avec 20 à 40 atomes de carbone et différent du composé détergent alkylhydroxybenzoate dans la revendication 1.
  4. Composition d'huile lubrifiante selon la revendication 3, dans lequel l'un ou les plusieurs détergents est un sulfonate de métal alcalin ou alcalino-terreux avec un indice de basicité de 10 à 700 mgKOH/gm.
  5. Composition d'huile lubrifiante selon la revendication 3, dans lequel l'un ou les plusieurs détergents est un phénate de métal alcalin ou alcalino-terreux avec un indice de basicité de 100 à 600 mgKOH/gm.
  6. Composition d'huile lubrifiante selon la revendication 3, dans lequel l'un ou les plusieurs détergents est un alkylhydroxybenzoate de métal alcalin ou alcalino-terreux et dérivé d'un groupe alkyle avec 20 à 28 atomes de carbone et ayant un indice de basicité de 10 à 590 mgKOH/gm.
  7. Composition d'huile lubrifiante selon la revendication 1, dans lequel l'alpha-oléfine normale isomérisée a un indice d'isomérisation (I) de l'alpha-oléfine normale de 0,1 à 0,4 où l'indice d'isomérisation (I) de l'oléfine est déterminé par RMN hydrogène-1 (1H) obtenu sur un Bruker Ultrashield Plus 400 dans le chloroforme-d1 à 400 MHz en utilisant le logiciel de traitement spectral TopSpin 3.2, et l'indice d'isomérisation (I) est : I = m / m + n
    Figure imgb0004
     où m est l'intégrale RMN pour groupes méthyle avec des déplacements chimiques entre 0,3 ± 0,03 ppm et 1,01 ± 0,03 ppm, et n est l'intégrale RMN pour groupes méthylène avec des déplacements chimiques entre 1,01 ± 0,03 ppm und 1,38 ± 0,10 ppm.
  8. Composition d'huile lubrifiante selon la revendication 1 comprenant en plus un détergent supplémentaire.
  9. Composition d'huile lubrifiante selon la revendication 8, dans lequel le détergent supplémentaire est un alkylhydroxybenzoate, un phénate, un sulfonate, ou une de leurs combinaisons.
  10. Composition d'huile lubrifiante selon la revendication 9, dans lequel le détergent est dérivé d'une NAO, d'une NAO isomérisée ou d'une de leurs combinaisons.
  11. Composition d'huile lubrifiante selon la revendication 10, dans lequel le détergent est un alkylhydroxybenzoate de magnésium dérivé d'une NAO isomérisée.
  12. Composition d'huile lubrifiante selon la revendication 9, dans lequel le sulfonate est un sulfonate de calcium ou un sulfonate de magnésium.
  13. Procédé pour lubrifier un moteur comprenant lubrifier ledit moteur avec une composition d'huile lubrifiante selon une quelconque des revendications 1 à 12.
EP18749527.0A 2017-06-30 2018-06-28 Compositions d'huile lubrifiante contenant des composés détergents Active EP3645681B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762527089P 2017-06-30 2017-06-30
PCT/IB2018/054806 WO2019003178A1 (fr) 2017-06-30 2018-06-28 Compositions d'huile lubrifiante contenant des composés détergents

Publications (2)

Publication Number Publication Date
EP3645681A1 EP3645681A1 (fr) 2020-05-06
EP3645681B1 true EP3645681B1 (fr) 2021-09-22

Family

ID=63080224

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18749527.0A Active EP3645681B1 (fr) 2017-06-30 2018-06-28 Compositions d'huile lubrifiante contenant des composés détergents

Country Status (6)

Country Link
US (1) US20190002791A1 (fr)
EP (1) EP3645681B1 (fr)
JP (1) JP7348079B2 (fr)
CN (1) CN110785477A (fr)
CA (1) CA3068667C (fr)
WO (1) WO2019003178A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020003071A1 (fr) * 2018-06-27 2020-01-02 Chevron Oronite Technology B.V. Composition d'huile lubrifiante
KR20220027237A (ko) * 2019-07-05 2022-03-07 셰브런 재팬 리미티드 윤활유 조성물
KR20220057555A (ko) * 2019-09-05 2022-05-09 셰브런 오로나이트 컴퍼니 엘엘씨 윤활유 조성물
CN113249157B (zh) * 2020-02-13 2023-03-10 中国石油化工股份有限公司 黏度指数改进剂及其制备方法、用途
JP2023520938A (ja) * 2020-04-10 2023-05-22 シェブロン・オロナイト・カンパニー・エルエルシー バイオベース基油を含む潤滑油組成物
WO2022018623A1 (fr) * 2020-07-21 2022-01-27 Chevron Japan Ltd. Composition d'huile lubrifiante contenant du salicylate pour véhicules hybrides
WO2024030899A1 (fr) * 2022-08-01 2024-02-08 Chevron Oronite Company Llc Composition d'huile lubrifiante pour lutter contre la corrosion

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2680096A (en) 1951-02-12 1954-06-01 California Research Corp Process for preparing sulfurized polyvalent metal phenates
US3178368A (en) 1962-05-15 1965-04-13 California Research Corp Process for basic sulfurized metal phenates
US3801507A (en) 1972-08-18 1974-04-02 Chevron Res Sulfurized metal phenates
CA2528380C (fr) * 2004-11-30 2013-05-14 Infineum International Limited Compositions d'huile lubrifiante a faible teneur en cendres sulfatees contenant un detergent surbasique
US8030258B2 (en) 2005-07-29 2011-10-04 Chevron Oronite Company Llc Overbased alkaline earth metal alkylhydroxybenzoates having low crude sediment
US8993499B2 (en) * 2007-12-28 2015-03-31 Chevron Oronite Company Llc Low temperature performance lubricating oil detergents and method of making the same
US20100029525A1 (en) * 2008-07-31 2010-02-04 Chevron Oronite Company Llc Antiwear hydraulic fluid composition with useful emulsifying and rust prevention properties
US8399388B2 (en) * 2009-07-01 2013-03-19 Chevron Oronite Company Llc Low temperature performance lubricating oil detergents and method of making the same
US8580717B2 (en) 2009-11-24 2013-11-12 Chevron Oronite Company Llc Process for making an overbased, sulfurized salt of an alkylated hydroxyaromatic compound
US9206374B2 (en) * 2011-12-16 2015-12-08 Chevron Oronite Sas Trunk piston engine lubricating oil compositions
SG11201405647XA (en) * 2012-03-26 2014-10-30 Lubrizol Corp Manual transmission lubricants with improved synchromesh performance
CN105814180B (zh) * 2013-11-06 2019-12-10 雪佛龙奥伦耐技术有限责任公司 船用柴油机汽缸润滑剂油组合物
SG10201710483WA (en) * 2013-11-06 2018-02-27 Chevron Oronite Tech Bv Marine diesel cylinder lubricant oil compositions
EP3215592A1 (fr) * 2014-11-06 2017-09-13 Chevron Oronite Technology B.V. Compositions d'huiles lubrifiantes pour cylindres de moteurs diesel marins
CN104531269B (zh) * 2014-12-05 2017-06-13 中国石油天然气股份有限公司 一种船用柱塞式发动机润滑油组合物
US11168280B2 (en) * 2015-10-05 2021-11-09 Infineum International Limited Additive concentrates for the formulation of lubricating oil compositions
JP6235549B2 (ja) * 2015-12-07 2017-11-22 Ｅｍｇルブリカンツ合同会社 潤滑油組成物
JP6334503B2 (ja) * 2015-12-07 2018-05-30 出光興産株式会社 潤滑油組成物及びその製造方法

Also Published As

Publication number Publication date
US20190002791A1 (en) 2019-01-03
CN110785477A (zh) 2020-02-11
CA3068667A1 (fr) 2019-01-03
JP7348079B2 (ja) 2023-09-20
WO2019003178A1 (fr) 2019-01-03
JP2020525585A (ja) 2020-08-27
CA3068667C (fr) 2024-04-16
EP3645681A1 (fr) 2020-05-06

Similar Documents

Publication Publication Date Title
EP3645681B1 (fr) Compositions d'huile lubrifiante contenant des composés détergents
US20210002578A1 (en) Lubricating oil composition
EP3645679B1 (fr) Détergents à base de magnésium pour huile lubrifiante et procédé de fabrication et d'utilisation de ces détergents
EP3645680B1 (fr) Compositions d'huile lubrifiante pour moteur contenant des composés détergents
EP3814461B1 (fr) Compositions d'huile lubrifiante
US20230002698A1 (en) Lubricating oil compositions comprising a polyalphaolefin
EP4025674A1 (fr) Compositions d'huile lubrifiante
US20190264128A1 (en) Functional fluids lubricating oil compositions

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20191121

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20201126

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

INTC Intention to grant announced (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20210517

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018023950

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1432343

Country of ref document: AT

Kind code of ref document: T

Effective date: 20211015

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20210922

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211222

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211222

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1432343

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210922

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211223

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220122

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220124

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602018023950

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20220623

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20220630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220628

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220630

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220628

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220630

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230530

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230510

Year of fee payment: 6

Ref country code: DE

Payment date: 20230502

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20230504

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210922

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20180628