EP1798278B1 - Use of a rust inhibitor in a lubricating oil composition - Google Patents

Use of a rust inhibitor in a lubricating oil composition Download PDF

Info

Publication number
EP1798278B1
EP1798278B1 EP20060122378 EP06122378A EP1798278B1 EP 1798278 B1 EP1798278 B1 EP 1798278B1 EP 20060122378 EP20060122378 EP 20060122378 EP 06122378 A EP06122378 A EP 06122378A EP 1798278 B1 EP1798278 B1 EP 1798278B1
Authority
EP
Grant status
Grant
Patent type
Prior art keywords
oil
use according
preferably
oils
group
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
EP20060122378
Other languages
German (de)
French (fr)
Other versions
EP1798278A1 (en )
Inventor
Raymond c/o INFINEUM UK LTD Fellows
Robert William c/o INFINEUM UK LTD Shaw
Simon Siu Ming c/o INFINEUM UK LTD Chung
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.)
Infineum International Ltd
Original Assignee
Infineum International Ltd
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
Grant date

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04Hydroxy compounds
    • C10M129/10Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/86Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
    • C10M129/88Hydroxy compounds
    • C10M129/91Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/20Condensation polymers of aldehydes or ketones
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M167/00Lubricating 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/024Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028Overbased salts thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26Overbased carboxylic acid salts
    • C10M2207/262Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/101Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046Overbasedsulfonic acid salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/045Metal containing thio derivatives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2210/00Nature of the metal present as such or in compounds, i.e. in salts
    • C10N2210/02Group II, e.g. Mg, Ca, Ba, Zn, Cd, Hg
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2220/00Specified physical or chemical properties or characteristics, i.e. function, of single compounds in lubricating compositions
    • C10N2220/02Physico-chemical properties
    • C10N2220/021Molecular weight
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2230/00Specified physical or chemical properties of lubricating compositions
    • C10N2230/02Viscosity or viscosity index
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2230/00Specified physical or chemical properties of lubricating compositions
    • C10N2230/04Detergent properties, e.g. for cleaning, inhibition or removing varnish; Dispersion properties, e.g. for dispersing solids, carbon residues, sludge
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2230/00Specified physical or chemical properties of lubricating compositions
    • C10N2230/06Resistance to extreme pressure; Oiliness; Abrasion resistance; Friction; Anti-wear
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2230/00Specified physical or chemical properties of lubricating compositions
    • C10N2230/12Resistance to rust or corrosion
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2230/00Specified physical or chemical properties of lubricating compositions
    • C10N2230/40Low content or no content compositions
    • C10N2230/42Phosphor free or low phosphor content compositions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2230/00Specified physical or chemical properties of lubricating compositions
    • C10N2230/40Low content or no content compositions
    • C10N2230/43Sulfur free or low sulfur content compositions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2230/00Specified physical or chemical properties of lubricating compositions
    • C10N2230/40Low content or no content compositions
    • C10N2230/45Ashless or low ash content

Description

  • The invention is directed to the use of an ashless oil soluble hydrocarbyl phenol aldehyde condensate as a rust inhibitor in a lubricating oil composition.
  • Lubricating oil compositions for use in crankcase engine oils comprise a major amount of base stock oil and minor amounts of additives that improve the performance of the engine. There are many different types of additives used in lubricating oil compositions, each performing one or more different functions in the oil.
  • As the permitted levels of sulfated ash, phosphorus and sulfur (SAPS) emissions from passenger car motor vehicles decrease the levels of conventional additives such as metal-based detergents that can be used are decreased. This leads to an imbalance in the additive combinations conventionally used in passenger car motor vehicles and leads the formulator to consider new additive combinations in order to meet the requirements of vehicle manufacturers.
  • European patent application number 0 575 154 discloses a lubricating oil comprising a carboxylic dispersant, a rust inhibitor combination comprising a mixture of a hydrocarbyl-substituted carboxylic acid and a non-ionic surfactant, an antioxidant combination comprising at least a reaction product of a hydrocarbyl-substituted phenol and an aldehyde and optionally a hindered phenol, and at least one material having an acidic or phenolic functionality which has been reacted with a basic metal species, such that the total sulfated ash content of the composition is between 0.25 and 1 wt%.
  • The present invention provides use of an ashless oil-soluble hydrocarbyl phenol aldehyde condensate as a rust inhibitor in a lubricating oil composition having a sulfated ash content of less than 1.0 % by weight of the composition, the ashless, oil-soluble hydrocarbyl phenol aldehyde condensate having the following structure,
    Figure imgb0001
    wherein n is 0 to 10, 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 carbon atoms.
  • Other and further objects, advantages and features of the present invention will be understood by reference to the following specification.
  • The hydrocarbyl phenol aldehyde condensate is preferably a hydrocarbyl phenol formaldehyde condensate. The term "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. Advantageously, 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.
  • Preferred embodiments of the present invention comprise a hydrocarbyl phenol aldehyde condensate according to Formula (I) above, wherein n is preferably 1 to 8, more preferably 2 to 7, and most preferably 3 to 6 and/or R preferably comprises 8 to 18, and most preferably 9 to 15 carbon atoms.
  • The hydrocarbyl phenol aldehyde condensate preferably has a weight average molecular weight (Mw) in the range of 600 to 4000, preferably 800 to 3500, more preferably 1000 to 2000, even more preferably 1200 to 1900, and most preferably 1250 to 1680, as measured by MALDI-TOF (Matrix Assisted Laser Desorption Ionization- Time of Flight) Mass Spectrometry.
  • The hydrocarbyl phenol aldehyde condensate is preferably one obtained by a 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 mass %, more preferably to less than 3 mass %, even more preferably to less than 1 mass %, of unreacted hydrocarbyl phenol. Most preferably, the product includes less than 0.5 mass %, such as, for example, less than 0.1 mass % of unreacted hydrocarbyl phenol.
  • Although a basic catalyst can be used, an acid catalyst is preferred. 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 acid treated clay. The amount of catalyst used may vary from 0.05 to 10 mass % or more, such as for example 0.1 to 1 mass % of the total reaction mixture.
  • In particular, the hydrocarbyl phenol aldehyde condensate is preferably branched dodecyl phenol formaldehyde condensate, such as, for example, a tetrapropenyl tetramer phenol formaldehyde condensate.
  • The ashless hydrocarbyl phenol aldehyde condensate has a Total Base Number (TBN) of 0, because of the absence of metal ions in the compound.
  • The lubricating oil composition used in performance of the present invention may further comprise one or more detergent additives. Suitable detergent additives include overbased metal salts of organic acids.
  • Overbased metal salts of an organic acid generally comprise a polar head with a long hydrophobic tail. The polar head comprises a metal salt of an acidic organic compound. In a neutral or normal salt the salt may contain a substantially stoichiometric amount of the metal and would typically have a total base number or TBN (as can be measured by ASTM D2896) of from 0 to 80. In an overbased metal salt a large amount of a metal base may be incorporated by reacting excess metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide). The resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base (e.g. carbonate) micelle. Such overbased detergents may have a TBN of 150 or greater, and typically will have a TBN of from 250 to 450 or more.
  • Overbased metal salts of organic acids that may be used in the detergent composition include oil-soluble, overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, including hydroxybenzoates, naphthenates and other oil-soluble carboxylates 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, magnesium and sodium, and mixtures of thereof calcium and/or magnesium.
  • Particularly convenient overbased metal salts of organic acids are overbased metal salts of sulfonates, phenates, sulfurized phenates and salicylates.
  • The metal of the metal salt is preferably, sodium, magnesium or calcium, and more preferably calcium or magnesium. The one of more overbased metal salts of organic acids useful as a detergent may comprise a plurality of different metal salts derived from different organic acids and comprising different metals. In one embodiment, the plurality of overbased metal salts comprise metal salts derived from the same or different organic acids and each comprising the same metal. For example, the detergent may comprise a plurality of overbased calcium salts of organic acids. Alternatively, the detergent may comprise a plurality of overbased magnesium salts of organic acids. As a further alternative, the detergent may comprise a mixture of one or more overbased magnesium salt of an organic acid and one or more calcium salt of an organic acid.
  • 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 include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene. 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 per alkyl substituted aromatic moiety.
  • The oil soluble sulfonates or alkaryl sulfonic acids may be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylate, sulfides, hydrosulfides, nitrates, borates and ethers of the metal. The amount of metal compound is chosen having regard to the desired TBN of the final product but typically ranges from about 100 to 220 mass % (preferably at least 125 mass %) of that stoichiometrically required.
  • Metal salts of phenols and sulfurized phenols 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.
  • Carboxylate detergents, e.g., salicylates, can be prepared by reacting an aromatic carboxylic acid 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. The aromatic moiety of the aromatic carboxylic acid can contain heteroatoms, such as nitrogen and oxygen. Preferably, the moiety contains only carbon atoms; more preferably the moiety contains six or more carbon atoms; for example benzene is a preferred moiety. The aromatic carboxylic acid may contain one or more aromatic moieties, such as one or more benzene rings, either fused or connected via alkylene bridges. The carboxylic moiety may be attached directly or indirectly to the aromatic moiety. Preferably the carboxylic acid group is attached directly to a carbon atom on the aromatic moiety, such as a carbon atom on the benzene ring. More preferably, the aromatic moiety also contains a second functional group, such as a hydroxy group or a sulfonate group, which can be attached directly or indirectly to a carbon atom on the aromatic moiety.
  • Preferred examples of aromatic carboxylic acids are salicylic acids and sulfurized derivatives thereof, including hydroxybenzoates such as those described in US 5,808,145 or EP 933 417 , such as hydrocarbyl substituted salicylic acid and derivatives thereof. Processes for sulfurizing, for example a hydrocarbyl - substituted salicylic acid, are known to those skilled in the art. Salicylic acids are typically prepared by carboxylation, for example, by the Kolbe - Schmitt process, of phenoxides, and in that case, will generally be obtained, normally in a diluent, in admixture with uncarboxylated phenol.
  • Preferred substituents in oil - soluble salicylic acids are alkyl substituents. In alkyl - substituted salicylic acids, the alkyl groups advantageously contain 5 to 100, preferably 9 to 30, especially 14 to 20, carbon atoms. Where there is more than one alkyl group, the average number of carbon atoms in all of the alkyl groups is preferably at least 9 to ensure adequate oil solubility.
  • Overbased metal salts of organic acids generally useful in the formulation of lubricating oil compositions also include "hybrid" detergents formed with mixed surfactant systems, e.g., phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, and sulfonate/phenate/salicylates, as described, for example, in pending U.S. Patent Nos. 6,429,178 , 6,429,179 , 6,153,565 and 6,281,179 .
  • Overbased metal salts of organic acids suitably have a total base number (TBN) of at least 250, and preferably at least 300. The one or more overbased metal salts of organic acids providing component (A) of the detergent composition may comprise a combination of additives with different TBN values. In this case, the average TBN of the overbased metal salts of organic acids is suitably at least 250 and preferably at least 300.
  • Overbased metal salts of organic acids can be defined by their metal ratio, which is the ratio of the total equivalents of metal to the equivalents of acidic organic compound reacted with the metal Overbased metal salts of organic acids suitable for use in the present invention suitably have a metal ratio of greater than 1, preferably at least 5, more preferably at least 10 and possibly of up to 25.
  • The total amount of the one or more overbased metal salts of organic acids suitably provides the lubricating oil composition with a sulfated ash content of less than 1.0 mass % based on the mass of the lubricating oil composition, preferably less than 0.5 mass % and more preferably less than 0.3 mass %.
  • The oil of lubricating viscosity, useful for making lubricating oil compositions, may be selected from natural (vegetable, animal or mineral) and synthetic lubricating oils and mixtures thereof. It may range in viscosity from light distillate mineral oils to heavy lubricating oils such as gas engine oil, mineral lubricating oil, motor vehicle oil, and heavy duty diesel oil. Generally, the viscosity of the oil ranges from 2 centistokes to 30 centistokes, especially 5 centistokes to 20 centistokes, at 100°C.
  • Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil); liquid petroleum oils and hydro-refined, solvent-treated or acid-treated mineral oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale also serve as useful base oils.
  • Synthetic lubricating oils include hydrocarbon oils and halo-substituted 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); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and derivative, analogs and homologs thereof.
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc., constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyiso-propylene glycol ether having a molecular weight of 1000 or diphenyl ether of poly-ethylene glycol having a molecular weight of 1000 to 1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters and C13 Oxo acid diester of tetraethylene glycol.
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Examples of such 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 C5 to C12 monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
  • Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils comprise another useful class of synthetic lubricants; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes. Other synthetic lubricating oils include liquid esters of phosphorous-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
  • The oil of lubricating viscosity may comprise a Group I, Group II, Group III, Group IV or Group V oil or blends of the aforementioned oils. The oil of lubricating viscosity may also comprise a blend of a Group I oil and one or more of Group II, Group III, Group IV or Group V oil.
  • Definitions for the oils as used herein are the same as those found in the American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System", Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998. Said publication categorizes oils as follows:
  1. a) Group I oils contain less than 90 percent saturates and/or greater than 0.03 percent sulfur and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table 1.
  2. b) Group II oils contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table 1. Although not a separate Group recognized by the API, Group II oils having a viscosity index greater than about 110 are often referred to as "Group II+" oils.
  3. c) Group III oils contain greater than or equal to 90 percent saturates and less than or equal to 0.03 percent sulfur and have a viscosity index greater than or equal to 120 using the test methods specified in Table 1.
  4. d) Group IV oils are polyalphaolefins (PAO).
  5. e) Group V oils are all other base stocks not included in Group I, II, III, or IV.
Table 1
Property Test Method
Saturates ASTM D2007
Viscosity Index ASTM D2270
Sulfur ASTM D4294
  • The oil of lubricating viscosity preferably has a saturate content of at least 65%, more preferably at least 75%, such as at least 85%. Most preferably, the oil of lubricating viscosity has a saturate content of greater than 90%. Preferably, the oil of lubricating viscosity has a sulfur content of less than 1%, preferably less than 0.6%, more preferably less than 0.3%, by mass, such as 0 to 0.3% by mass.
  • Preferably the volatility of the oil of lubricating viscosity, as measured by the Noack test (ASTM D5880), is less than or equal to about 40 mass %, such as less than or equal to about 35 mass %, preferably less than or equal to about 32 mass %, such as less than or equal to about 28 mass %, more preferably less than or equal to about 16 mass %. Preferably, the viscosity index (VI) of the oil of lubricating viscosity is at least 85, preferably at least 100, most preferably from about 105 to 140.
  • The TBN of a lubricating oil composition will depend to some extent on the application of the composition. For lubricating the crankcase of an internal combustion engine, the TBN of the composition is suitably less than 20, preferably less than 15, and more preferably less than 10.
  • The sulfated ash content of the lubricating oil composition useful in the present invention will also depend to some extent upon the application of the composition and the current market requirements. The total sulfated ash content of a lubricating oil composition suitable for use in the present invention may have a sulfated ash content of less than 0.8 mass %, more preferably less than 0.5 mass % and potentially less than 0.1 mass %.
  • A lubricating oil composition suitably has a sulfur content of less than 1.0 mass%, preferably less than 0.5 mass % and more preferably less than 0.3 mass %, based on the mass of the lubricating oil composition.
  • A lubricating oil composition suitably has a phosphorus content of less than 0.5 mass %, preferably less than 0.3 mass % and suitably 0.1 wt% or less.
  • A lubricating oil composition suitable for use in the present invention, may further comprise one or more other performance improving additives selected from ashless dispersants, antiwear agents, oxidation inhibitors or antioxidants, ashless and metal-containing friction modifiers and fuel economy agents, antifoamants, corrosion inhibitors, and polyalkenyl acylating agent. Conventionally, when formulating a lubricant, the additives will be provided to the formulator in one or more, preferably a single concentrated additive package, oftentimes referred to as a DI (dispersant-inhibitor) package and a VI improver and/or VI improver and LOFI, will be provided in a second package.
  • Ashless dispersants maintain in suspension oil insolubles resulting from oxidation of the oil during wear or combustion. They are particularly advantageous for preventing the precipitation of sludge and the formation of varnish, particularly in gasoline engines.
  • Dihydrocarbyl dithiophosphate metal salts are frequently used as antiwear and antioxidant agents. The metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. The zinc salts are most commonly used in lubricating oil and may be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohol or a phenol with P2S5 and then neutralizing the formed DDPA with a zinc compound. For example, a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols. Alternatively, multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character. To make the zinc salt, any basic or neutral zinc compound could be used but the oxides, hydroxides and carbonates are most generally employed. Commercial additives frequently contain an excess of zinc due to the use of an excess of the basic zinc compound in the neutralization reaction.
  • Oxidation inhibitors or antioxidants reduce the tendency of mineral oils to deteriorate in service. Oxidative deterioration can be evidenced by sludge in the lubricant, varnish-like deposits on the metal surfaces, and by viscosity growth. Such oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkylphenolthioesters having preferably C5 to C12 alkyl side chains, calcium nonylphenol sulfide, oil soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons, phosphorous esters, metal thiocarbamates, oil soluble copper compounds as described in U.S. Patent No. 4,867,890 , and molybdenum-containing compounds and aromatic amines.
  • Known metal-containing friction modifiers include oil-soluble organo-molybdenum compounds. Such organo-molybdenum friction modifiers also provide antioxidant and antiwear credits to a lubricating oil composition. As an example of such oil soluble organo-molybdenum compounds, there may be mentioned the dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof. Particularly preferred are molybdenum dithiocarbamates, dialkyldithiophosphates, alkyl xanthates and alkylthioxanthates.
  • Metal free friction modifiers are commonly known as organic friction modifiers, and include oil-soluble compounds containing at least one polar group selected from hydroxyl and amine groups, which compounds are capable of reducing friction under hydrodynamic and mixed hydrodynamic/boundary layer conditions. Examples of such materials include glycerol esters of higher fatty acids, for example, glycerol mono-oleate; esters of long chain polycarboxylic acids with diols, for example, the butane diol ester of a dimerized unsaturated fatty acid; oxazoline compounds; and alkoxylated alkyl-substituted mono-amines, diamines and alkyl ether amines, for example, ethoxylated tallow amine and ethoxylated tallow ether amine. Particularly preferred surface active agents include glycerol oleates, particularly glycerol monooleate, and ethoxylated amines, particularly ethoxylated tallow amine.
  • Foam control can be provided by an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
  • Suitably, a lubricating oil composition comprises no rust inhibitor apart from the ashless, oil-soluble hydrocarbyl phenol aldehyde condensate of formula (I). In particular the lubricating oil composition preferably does not comprise a non-ionic surfactant rust inhibitor or a hydrocarbyl-substituted carboxylic acid or derivative thereof rust inhibitor as described on page 4, lines 16-48 of EP 0 575 154 .
  • Some of the above-mentioned additives can provide a multiplicity of effects; thus for example, a single additive may act as a dispersant-oxidation inhibitor. This approach is well known and need not be further elaborated herein.
  • Representative effective amounts of such additional additives, when used in fully formulated crankcase lubricants, are listed below in Table 2: Table 2
    ADDITIVE Mass % (Broad) Mass % (Preferred)
    Ashless Dispersant 0.1 - 20 1 - 8
    Corrosion Inhibitor 0 - 5 0 - 1.5
    Metal Dihydrocarbyl Dithiophosphate 0.1 - 6 0.1 - 4
    Antioxidant 0 - 5 0.01 - 2
    Pour Point Depressant 0.01 - 5 0.01 - 1.5
    Antifoaming Agent 0 - 5 0.001 - 0.15
    Supplemental Antiwear Agents 0 - 1.0 0 - 0.5
    Friction Modifier 0 - 5 0 - 1.5
    Basestock Balance Balance
  • This invention will be further understood by reference to the following examples, which are illustrative of the invention.
  • EXAMPLES Example 1
  • Oils having the compositions set out in Table 3 below, were blended and subjected to the ASTM D6557 Ball Rust Test, which measures iron corrosion. In performance of the Ball Rust Test, multiple test tubes each containing the test oil and a specimen are placed in a rack which is attached to a mechanical shaker. The shaker speed and temperature are controlled. Air and an acidic solution are continuously fed into each tube over a period of 18 hours to create a corrosive environment. The specimens are then removed, rinsed and analysed by an optical imaging system designed to quantify the antirust capability of each oil. The ASTM D6557 Ball Rust Test is a merit test that measures average grey value, with a higher numerical value indicating less rust formation.
  • The quantities given in Table 3 are in mass % of the total mass of the fully formulated oil composition. Table 3
    Component Oil 1 Oil 2 Oil 3 Oil 4
    Detergent 1 - - 1.00 -
    Detergent 2 - - 0.61 1.10
    Detergent 3 1.51 - - -
    Detergent 4 0.95 1.33 - -
    Hydrocarbyl phenol aldehyde condensate - 0.54 - 0.50
    Additive Package 1 10.20 10.20 10.20 10.20
    Base Oil + Viscosity Modifier 87.34 87.93 88.19 88.2
    % Sulfated Ash 0.56 0.56 0.56 0.56
    Mass soap 0.77 0.76 0.58 0.62
    % Ca 0.035 0.000 0.054 0.000
    % Mg 0.072 0.100 0.056 0.100
    % P 0.05 0.05 0.05 0.05
    % S 0.18 0.18 0.21 0.18
  • Detergent 1 is a calcium phenate detergent having a TBN of 145. Detergent 2 is a magnesium sulfonate detergent having a TBN of 400. Detergent 3 is a Calcium salicylate detergent having a TBN of 64 and Detergent 4 is a Magnesium salicylate detergent having a TBN of 342.
  • The hydrocarbyl phenol aldehyde condensate is in accordance with Formula (1) set out above, and has a number average molecular weight of 1500.
  • Each of Oils 1, 2, 3, and 4 comprised additional additives in the same quantities, referred to above as Additive Package 1. Additive package 1 comprised dispersant, zinc dialkyldithiophosphate, friction modifier, antioxidant and antifoamant. The base stock and viscosity modifier used for each of Oils 1, 2, 3, and 4 were the same, although the quantity of diluent oil in the additive package varied slightly due to the variation in detergent quantities. The quantity of detergent and hydrocarbyl phenol aldehyde condensate in each oil was balanced such that each of Oils 1 & 2 and 3 & 4 have equivalent sulfated ash, soap, phosphorus and sulfur content.
  • It can be seen from Table 3, that Oils 1 and 3 are comparative examples and Oils 2 and 4 are in accordance with the present invention.
  • The results of the Ball Rust Test are set out below in Table 4. Table 4
    Oil Oil 1 Oil 2 Oil 3 Oil 4
    Result 80 106 67 110
  • Table 4 clearly illustrates that at constant sulfated ash, use of an ashless hydrocarbyl phenol aldehyde condensate effects an improved performance in the ASTM D6557 Ball Rust Test.
  • Example 2
  • The Oils set out in Table 5 below, were blended and subjected to the ASTM D6557 Ball Rust Test, described above. The quantities given in Table 5 are in mass % of the total mass of the fully formulated oil composition. Table 5
    Component Oil 5 Oil 6 Oil 7 Oil 8
    Detergent 5 - - 0.77 0.98
    Detergent 6 0.92 0.70 - -
    Calcium salt of hydrocarbyl phenol aldehyde condensate - 0.95 0.90 -
    Hydrocarbyl phenol aldehyde condensate 0.80 - - 0.75
    Additive Package 2 14.13 14.13 14.13 14.13
    Additive Package Diluent 1.05 1.12 1.10 1.04
    Base Oil + Viscosity Modifier 83.1 83.1 83.1 83.1
    % Sulfated Ash 0.54 0.54 0.54 0.54
    Mass soap 0.66 0.66 0.66 0.66
    % Ca 0.115 0.114 0.114 0.114
    % P 0.05 0.05 0.05 0.05
    % S 0.125 0.124 0.133 0.137
  • Detergent 5 is a calcium sulfonate detergent having a TBN of 300. Detergent 6 is a calcium salicylate detergent having a TBN of 344.
  • The hydrocarbyl phenol aldehyde condensate of Oils 5 and 8 is in accordance with Formula (1) set out above, and has a number average molecular weight of 1500. The calcium salt of hydrocarbyl phenol aldehyde condensate of Oils 6 and 7 is the calcium salt of the hydrocarbyl phenol aldehdye condensate used in Oils 5 and 8.
  • Each of oils 5, 6, 7, and 8 comprised additional additives in the same quantities, referred to above as Additive Package 2. Additive package 2 comprised dispersant, zinc dialkyldithiophosphate, friction modifier, antioxidant and antifoamant. The diluent oil, base stock and viscosity modifier used for each of Oils 5, 6, 7, and 8 were the same, although the quantity of diluent oil in the additive package varied slightly due to the variation in detergent quantities. The quantity of detergent and hydrocarbyl phenol aldehyde condensate or its calcium salt in each oil was balanced such that each of Oils 5 & 6 and Oils 7 & 8 have equivalent sulfated ash, soap, calcium, phosphorus and sulfur content.
  • It can be seen from Table 5 that Oils 6 and 7 are comparative examples and Oils 5 and 8 are in accordance with the present invention
  • The results of the Ball Rust Test are set out below in Table 6. Table 6
    Test Oil 5 Oil 6 Oil 7 Oil 8
    88 68 61 69
    % improvement of hydrocarbyl phenol aldehyde condensate compared to calcium salt. 29 12
  • Table 6 clearly illustrates that at constant sulfated ash and soap content, use of an ashless hydrocarbyl phenol aldehyde condensate effects an improved performance in the ASTM D6557 Ball Rust Test compared to a calcium salt of hydrocarbyl phenol aldehyde condensate.
  • A description of a composition comprising, consisting of, or consisting essentially of multiple specified components, as presented herein and in the appended claims, should be construed to also encompass compositions made by admixing said multiple specified components.
  • Claims (10)

    1. Use of an ashless oil-soluble hydrocarbyl phenol aldehyde condensate as a rust inhibitor in a lubricating oil composition having a sulfated ash content of less than 1.0 % by weight of the composition, the ashless oil-soluble hydrocarbyl phenol aldehyde condensate having the following structure,
      Figure imgb0002
      wherein n is 0 to 10, Y is a divalent bridging group, and R is a hydrocarbyl group having from 4 to 30 carbon atoms.
    2. A use according to claim 1, wherein the divalent bridging group is a hydrocarbyl group having from 1 to 4 carbon atoms.
    3. A use according to claim 1 or 2, wherein the oil-soluble hydrocarbyl phenol aldehyde condensate has a weight average molecular weight (Mw) of 600 to 4000, as measured by MALDI-TOF (Matrix Assisted Laser Desorption Ionization- Time of Flight) mass spectrometry.
    4. A use according to claim 3, wherein the oil-soluble hydrocarbyl phenol aldehyde condensate has a weight average molecular weight (Mw) of 800 to 3500.
    5. A use according to claim 4, wherein the oil-soluble hydrocarbyl phenol aldehyde condensate has a weight average molecular weight (Mw) of 1250 to 1680.
    6. A use according to any one of claims 1 to 5, wherein n is 1 to 8,
    7. A use according to claim 6, wherein n is 3 to 5.
    8. A use according to any one of claims 1 to 7, wherein R is a hydrocarbyl group having from 8 to 18 carbon atoms.
    9. A use according to claim 8, wherein R has from 9 to 15 carbon atoms.
    10. A use according to any one of claims 1 to 9, wherein the lubricating oil further comprises one or more overbased metal salts of an organic acids, preferably, one or more alkali metal salt or an alkaline earth metal salt of a phenate, sulfonate, salicylate or a complex detergent comprising a combination of any two of an alkali metal salt or an alkaline earth metal salt of a phenate, sulfonate or salicylate.
    EP20060122378 2005-12-15 2006-10-16 Use of a rust inhibitor in a lubricating oil composition Active EP1798278B1 (en)

    Priority Applications (2)

    Application Number Priority Date Filing Date Title
    EP05270092 2005-12-15
    EP20060122378 EP1798278B1 (en) 2005-12-15 2006-10-16 Use of a rust inhibitor in a lubricating oil composition

    Applications Claiming Priority (1)

    Application Number Priority Date Filing Date Title
    EP20060122378 EP1798278B1 (en) 2005-12-15 2006-10-16 Use of a rust inhibitor in a lubricating oil composition

    Publications (2)

    Publication Number Publication Date
    EP1798278A1 true EP1798278A1 (en) 2007-06-20
    EP1798278B1 true EP1798278B1 (en) 2015-07-29

    Family

    ID=38039061

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP20060122378 Active EP1798278B1 (en) 2005-12-15 2006-10-16 Use of a rust inhibitor in a lubricating oil composition

    Country Status (1)

    Country Link
    EP (1) EP1798278B1 (en)

    Families Citing this family (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    WO2009086140A3 (en) * 2007-12-28 2009-09-03 Chevron Oronite Company Llc Low temperature performance lubricating oil detergents and method of making the same
    CN105695045A (en) 2009-06-04 2016-06-22 吉坤日矿日石能源株式会社 Lubricant oil composition
    CN102459543A (en) 2009-06-04 2012-05-16 吉坤日矿日石能源株式会社 A lubricating oil composition and a method for making the same
    DE102012223638A1 (en) * 2011-12-21 2013-06-27 Infineum International Ltd. A method for reducing the rate of decrease of the basicity of a lubricating oil composition which is used in a motor

    Family Cites Families (6)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE1067955B (en) * 1956-07-11
    NL245484A (en) * 1958-11-20
    GB2056482A (en) 1979-08-13 1981-03-18 Exxon Research Engineering Co Lubricating oil compositions
    US5259967A (en) * 1992-06-17 1993-11-09 The Lubrizol Corporation Low ash lubricant composition
    EP1304368A1 (en) * 2001-09-28 2003-04-23 Infineum International Limited A gas engine lubricating oil composition
    EP1642956A1 (en) * 2004-06-11 2006-04-05 Infineum International Limited Detergent additive combination for lubricating compositions

    Also Published As

    Publication number Publication date Type
    EP1798278A1 (en) 2007-06-20 application

    Similar Documents

    Publication Publication Date Title
    US6331510B1 (en) Synthetic diesel engine lubricants containing dispersant-viscosity modifier and functionalized phenol detergent
    US6333298B1 (en) Molybdenum-free low volatility lubricating oil composition
    US20040102335A1 (en) Additive formulation for lubricating oils
    US20040235686A1 (en) Carboxylated detergent-dispersant additive for lubricating oils
    US6143701A (en) Lubricating oil having improved fuel economy retention properties
    WO2008128656A2 (en) An overbased metal hydrocarbyl substituted hydroxybenzoate for reduction of asphaltene precipitation
    US20040127371A1 (en) Combination of a low ash lubricating oil composition and low sulfur fuel
    US20040235688A1 (en) Lubricating oil composition
    US20050137100A1 (en) Lubricating oil composition containing an alkali metal detergent
    US5919740A (en) Alkylthiophosphate salts for lubricating oils
    US20070006855A1 (en) EGR equipped diesel engines and lubricating oil compositions
    EP1018539A2 (en) Overbased metal detergents
    US20020151445A1 (en) Synthetic diesel engine lubricants containing dispersant-viscosity modifier and functionalized phenol detergent
    EP2071009A1 (en) Trunk piston engine lubricating oil compositions
    WO1999060080A1 (en) Lubricant compositions for and their use in internal combustion engines
    EP2319904A1 (en) Lubrication and lubricating oil compositions comprising phenylene diamines
    US20040235682A1 (en) Low emission diesel lubricant with improved corrosion protection
    US20090281009A1 (en) Lubricating oil composition and method for use with low sulfur marine residual fuel
    US20100062957A1 (en) Method of Reducing Asphaltene Precipitation in an Engine
    CA2812480A1 (en) Lubricating oil compositions
    US6645923B2 (en) Lubricating oil composition
    US20080039349A1 (en) Lubricating oil composition
    US6649575B2 (en) Lubricating oil compositions
    EP1889896A2 (en) Lubricating oil composition containing detergent additives
    US20050153847A1 (en) Lubricant composition

    Legal Events

    Date Code Title Description
    AK Designated contracting states:

    Kind code of ref document: A1

    Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

    17P Request for examination filed

    Effective date: 20061016

    AX Request for extension of the european patent to

    Extension state: AL BA HR MK YU

    17Q First examination report

    Effective date: 20070827

    AKX Payment of designation fees

    Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

    RIN1 Inventor (correction)

    Inventor name: CHUNG, SIMON SIU MING, C/O INFINEUM UK LTD

    Inventor name: FELLOWS, RAYMOND, C/O INFINEUM UK LTD

    Inventor name: SHAW, ROBERT WILLIAM, C/O INFINEUM UK LTD

    INTG Announcement of intention to grant

    Effective date: 20150310

    AK Designated contracting states:

    Kind code of ref document: B1

    Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK 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: CH

    Ref legal event code: EP

    REG Reference to a national code

    Ref country code: AT

    Ref legal event code: REF

    Ref document number: 739303

    Country of ref document: AT

    Kind code of ref document: T

    Effective date: 20150815

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FG4D

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FG2A

    Ref document number: 2544239

    Country of ref document: ES

    Kind code of ref document: T3

    Effective date: 20150828

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R096

    Ref document number: 602006046088

    Country of ref document: DE

    REG Reference to a national code

    Ref country code: AT

    Ref legal event code: MK05

    Ref document number: 739303

    Country of ref document: AT

    Kind code of ref document: T

    Effective date: 20150729

    REG Reference to a national code

    Ref country code: LT

    Ref legal event code: MG4D

    REG Reference to a national code

    Ref country code: NL

    Ref legal event code: FP

    PG25 Lapsed in a contracting state announced via postgrant inform. from nat. 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: 20150729

    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: 20150729

    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: 20150729

    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: 20151030

    PG25 Lapsed in a contracting state announced via postgrant inform. from nat. office to epo

    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: 20150729

    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: 20150729

    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: 20151129

    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: 20150729

    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: 20151130

    PG25 Lapsed in a contracting state announced via postgrant inform. from nat. 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: 20150729

    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: 20150729

    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: 20150729

    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: 20150729

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R097

    Ref document number: 602006046088

    Country of ref document: DE

    PG25 Lapsed in a contracting state announced via postgrant inform. from nat. office to epo

    Ref country code: LU

    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: 20151016

    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: 20150729

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    PG25 Lapsed in a contracting state announced via postgrant inform. from nat. 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: 20150729

    26N No opposition filed

    Effective date: 20160502

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: MM4A

    PG25 Lapsed in a contracting state announced via postgrant inform. from nat. office to epo

    Ref country code: CH

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

    Effective date: 20151031

    Ref country code: LI

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

    Effective date: 20151031

    PG25 Lapsed in a contracting state announced via postgrant inform. from nat. 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: 20150729

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 11

    PG25 Lapsed in a contracting state announced via postgrant inform. from nat. office to epo

    Ref country code: IE

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

    Effective date: 20151016

    PGFP Postgrant: annual fees paid to national office

    Ref country code: GB

    Payment date: 20160926

    Year of fee payment: 11

    PGFP Postgrant: annual fees paid to national office

    Ref country code: FR

    Payment date: 20160926

    Year of fee payment: 11

    PG25 Lapsed in a contracting state announced via postgrant inform. from nat. office to epo

    Ref country code: BE

    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: 20150729

    PGFP Postgrant: annual fees paid to national office

    Ref country code: NL

    Payment date: 20161007

    Year of fee payment: 11

    Ref country code: DE

    Payment date: 20161031

    Year of fee payment: 11

    PGFP Postgrant: annual fees paid to national office

    Ref country code: ES

    Payment date: 20161010

    Year of fee payment: 11

    Ref country code: IT

    Payment date: 20161020

    Year of fee payment: 11

    PG25 Lapsed in a contracting state announced via postgrant inform. from nat. office to epo

    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: 20150729

    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: 20061016

    PG25 Lapsed in a contracting state announced via postgrant inform. from nat. office to epo

    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: 20150729

    PG25 Lapsed in a contracting state announced via postgrant inform. from nat. office to epo

    Ref country code: TR

    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: 20150729

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R119

    Ref document number: 602006046088

    Country of ref document: DE

    REG Reference to a national code

    Ref country code: NL

    Ref legal event code: MM

    Effective date: 20171101

    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 20171016

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: ST

    Effective date: 20180629

    PG25 Lapsed in a contracting state announced via postgrant inform. from nat. office to epo

    Ref country code: DE

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

    Effective date: 20180501

    Ref country code: GB

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

    Effective date: 20171016

    Ref country code: NL

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

    Effective date: 20171101

    PG25 Lapsed in a contracting state announced via postgrant inform. from nat. office to epo

    Ref country code: FR

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

    Effective date: 20171031