EP0008193B1 - Schmiermittelzusammensetzung und Verfahren zum Schmieren eines Schiffsdieselmotors - Google Patents

Schmiermittelzusammensetzung und Verfahren zum Schmieren eines Schiffsdieselmotors Download PDF

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Publication number
EP0008193B1
EP0008193B1 EP79301536A EP79301536A EP0008193B1 EP 0008193 B1 EP0008193 B1 EP 0008193B1 EP 79301536 A EP79301536 A EP 79301536A EP 79301536 A EP79301536 A EP 79301536A EP 0008193 B1 EP0008193 B1 EP 0008193B1
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EP
European Patent Office
Prior art keywords
lubricating
composition
lubricating composition
dispersant
base oil
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EP79301536A
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English (en)
French (fr)
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EP0008193A1 (de
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Ernst Ludwig Neustadter
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BP PLC
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BP PLC
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M141/06—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 nitrogen-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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/027—Neutral salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/18—Tall oil acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/044—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms having cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086—Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26—Amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen 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
    • 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
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • 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
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • This invention relates to lubricating compositions suitable for use in marine diesel engines.
  • a cylinder lubricant having a highly basic nature, i.e. having a high total base number.
  • These lubricants usually contain an overbased metal salt such as an over-based calcium or barium phenate or sulphonate.
  • metal-containing salts are ash forming, i.e. when they are burnt there is a metal containing residue. It would be desirable to reduce or eliminate the use of ash-forming additives for such applications by replacing at least a proportion of such additives with ashless additives.
  • a lubricant containing an ashless basic additive viz a lubricating composition
  • a lubricating composition comprising a branched chain alkyl or alkenyl polyamine in which the alkyl or alkenyl group has a number average molecular weight of 350 to 500 and which has a total base number of at least 200.
  • the polyamine component of the additive e.g. a polyalkylene polyamine
  • the branched chain alkyl or alkenyl group e.g. a polyisobutenyl group
  • solubilising branched chain alkyl or alkenyl group in the additive is relatively bulky, and there would be advantages in being able to use a simple polyamine without the added solubilising group.
  • microemulsions in which the continuous phase is a liquid hydrocarbon medium are known from US Patent No. 3346494.
  • the microemulsified phase may be a volatile medium such as water (which is preferred), methanol, or aqueous or methanolic solutions of inorganic salts and bases (oxides and hydroxides) or it may be a non-volatile medium such as ethylene glycol or glycerol.
  • organic bases such as amines can also form the microemulsified phase in lubricating oils in the absence of water or methanol or other solvent. Since the amine is present to react with acidic products of combustion, e.g. sulphur oxides, it has also been found that the lubricating composition should contain a dispersant.
  • a lubricating composition comprising a lubricating base oil as a continuous phase and a hydrocarbon insoluble compound as a microemulsified phase is characterised in that the microemulsified phase is a hydrocarbyl amine and the lubricating composition also contains a dispersant for hydrocarbyl amine salts which may be formed during use of the lubricating composition.
  • the hydrocarbyl amine may be an aryl, cycloalkyl or alkylamine.
  • Alkylene polyamines are preferred, particularly polyalkylene polyamines and more particularly polyethylene polyamines. Since it is not necessary to have a large hydrocarbyl group to solubilise the amine, the hydrocarbyl amine may have a total of from 1 to 20 carbon atoms. Such a low content of hydrocarbyl groups means that the amine has a high total base number, e.g. a TBN of the order of 1000mgKOH/g.
  • suitable amines are ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine.
  • the lubricating base oil may be any known lubricating oil and may be synthetic or natural.
  • synthetic oils may be the diesters or complex esters known as synthetic lubricants, or liquid polymers formed from low molecular weight olefins.
  • the oils are mineral oils derived from petroleum, e.g. petroleum fractions boiling above 300°C. These fractions may be distillate fractions boiling in the range 300 to 600°C or de- ashphalted residual fractions.
  • the choice of base oil will be determined by the proposed use and, for the preferred lubricating compositions for use as cylinder lubricants for diesel engines, the oils may have a viscosity of from 8 to 23 x 10- e m z /s at 100°C.
  • Microemulsions of a hydrocarbon insoluble component in a liquid hydrocarbon medium, particularly a mineral oil, can be formed by simple mixing provided the type and quantity of emulsifiers are correctly chosen.
  • the disperse phase droplets are small, e.g. in the range 60-1000A, and the microemulsions are stable at ambient temperature almost indefinitely.
  • the emulsifiers noramlly required for forming microemulsions are a fatty acid and an alkyl phenol with an amino alcohol as co-surfactant.
  • the ratio in parts by weight of the three components may be:-
  • the amino alcohol co-surfactant can be an optional component in the present invention where the microemulsified phase is a hydrocarbyl amine.
  • the fatty acid may have from 12 to 25 carbon atoms and may be saturated or unsaturated.
  • suitable acids are stearic, oleic, linoleic, lauric and palmitic acids. Mixtures of acids, e.g. tall oil fatty acids may also be used.
  • the alkyl phenol may be mono or polyhydroxy and the alkyl group is preferably a straight chain alkyl group and has preferably, from 6 to 15 carbon atoms. There may be additional C l -C l5 alkyl groups on the aromatic ring, although this is not necessary.
  • Preferred alkyl phenols are octyl and nonyl phenols and octyl and nonyl cresols.
  • the amino alcohol if present, is preferably an alkanolarnine, which may be a primary, secondary or tertiary amine and the alkyl group or groups of which may have from 2 to 6 carbon atoms.
  • alkanolarnine which may be a primary, secondary or tertiary amine and the alkyl group or groups of which may have from 2 to 6 carbon atoms.
  • suitable alkanolamines are mono-, di- and tri-isopropanolamines.
  • microemuisions As compared with macroemulsions, microemuisions have a relatively high proportion of emulsifiers in relation to the microemulsified phase and the continuous phase.
  • the microemulsified phase is a hydrocarbyl amine the total quantity of emulsifiers is preferably from 2 to 25% wt. by weight of the total composition.
  • the proportion of hydrocarbyl amine to lubricating base oil will depend on the total base number of the amine and that required in the finished oil.
  • the TBN of the finished oil may be from 5 to 500 mgKOH/g preferably 20 to 100, and the proportion of hydrocarbyl amine may be from 1 to 20% by weight of total composition.
  • the microemulsions may be prepared by simple mixing at room temperature.
  • the emulsifiers are added to the base oil and then the hydrocarbyl amine.
  • the primary function of the hydrocarbyl amine is to react with acidic products of combustion of the engine being lubricated. With high sulphur content fuels these combustion products will be sulphur oxides or acids giving amine sulphates as the reaction products. Amine sulphates tend to be crystalline solids with a tendency to settle out on cooler parts of the engine. It is necessary, therefore, for the lubricating composition to have a dispersant capable of holding the amine salts in suspension so that they are removed from the cylinder with the lubricant and other exhaust products.
  • Dispersant additives capable of holding particulate solids, e.g. carbon, in suspension are well known in the lubricating oil art and suitable dispersants for use in the present invention may be selected from the known dispersant additives by suitable experiments and/or engine tests.
  • Preferred dispersants are the polyisobutenyl succinimides. They may be of the mono- or bis- type, preferably the latter.
  • the polyisobutenyl group may have from 8 to 200 carbon atoms and the amine used to form the compound may be a hydrocarbyl amine of the same type as that in the microemulsified phase, preferably an alkylene polyamine having a total of from 1 to 20 carbon atoms.
  • the dispersant may be a known detergent additive, e.g. a barium, calcium or sodium phenate, sulphonate or carboxylate.
  • a known detergent additive e.g. a barium, calcium or sodium phenate, sulphonate or carboxylate.
  • Such additives are known ash-forming detergent additives, so in this embodiment the lubricant will be a low-ash rather than a wholly ashless composition.
  • the amount of ash-forming material can be significantly reduced and may be from 0.1 to 5% wt. of the total composition.
  • the hydrocarbyl amine is likely to have a relatively high TBN per unit of weight (particularly the preferred hydrocarbyl amines with from 1 to 20 C atoms) and could make a significant contribution to the TBN of the composition even if present in relatively small amounts by weight.
  • Preferred compositions may contain from 1 to 10% wt. of hydrocarbyl amine and from 1 to 15% wt. of ash-forming detergent
  • the contribution of the ash-forming detergent additive to the overall dispersancy may, however, not be sufficient in itself and may be supplemented by another dispersant additive, e.g. a polyisobutenyl succinimide as described above or one or more of the dispersants described below.
  • another dispersant additive e.g. a polyisobutenyl succinimide as described above or one or more of the dispersants described below.
  • Other dispersants for the hydrocarbyl amine sulphate reaction products may be alcohols and phenols having surfactant properties. These can be, for example, the type of organic compounds used to form the salts and overbased salts referred to above.
  • Preferred compounds are alkyl and alkeny! alcohols or pheno!s having from 6 to 100 carbon atoms in the alkyl or alkenyl group. The group preferably has from 9 to 20 carbon atoms and is preferably a straight chain group.
  • Exampes of suitable compounds are nonyl phenol, dodecanol, lauryl alcohol and stearyl alcohol.
  • VI improvers are not normally required in marine diesel lubricants
  • another type of dispersant may be a dispersant polymer used as a VI improver, e.g. a polyalkylmethacrylate.
  • compositions of the present invention may contain other known additives suitable for use in diesel cylinder lubricants, e.g. corrosion inhibitors such as metal sulphonates.
  • the total amount of dispersant may be from 1 to 30% wt., preferably from 5 to 20% wt. by weight of the total composition.
  • some of the compounds contributing to the dispersancy may be present partly for other reasons and for other functions.
  • a conventional ash-forming detergent may be present as indicated above and may contribute to the dispersancy.
  • some of the dispersants listed above may be the same as the emulsifiers used to form the microemulsion (e.g. alkyl phenols). In such circumstances the quantity quoted above is the total quantity of dispersant in the composition irrespective of whether the dispersant has additional functions or not, it being impractical to apportion the total amount in respect of differing functions.
  • a microemulsion of tetraethylene pentamine in a lubricating base oil was prepared using the following amounts of components by weight:-
  • the polyisobutenyl mono-succinimide was an ashless dispersant sold by Orobis Limited under the Trade Name Oloa 1200.
  • the lubricating base oil was a petroleum lubricating oil having a viscosity of 10.09 1 x 10-emz/s at 100°C and a viscosity index of 73.
  • the microemulsion was prepared as follows.
  • the oleic acid and nonyl phenol were added to half the weight of the base oil and stirred at room temperature.
  • the tetraethylenepentamine was then added and stirred until homogeneous and clear.
  • the polyisobutylene mono-succinimide was next added followed by the isopropanolamine and the rest of the base oil.
  • microemulsion was found to be stable for a period of at least 2 years. It had a total base number of 59.
  • composition was tested for suitability as a cylinder lubricant for a marine diesel engine using a 24 hour test in a Ruston engine.
  • the Ruston engine test is carried out in a Ruston 7XHR diesel engine.
  • the engine has a single piped oil supply which is the sole source of lubricant for the piston and rings.
  • the piston and its rings Prior to the test, the piston and its rings are cleaned and the rings are weighed.
  • the cylinder bore is measured in two diametrical positions at 30 stations along its length, covering the extent of ring travel.
  • the engine is run for the test period with the lubricant under test being supplied to the cylinder and using a fuel having a nominal viscosity of 1500 seconds Redwood No 1 (3.7x10 -4 m 2 /S) at 38°C (100°F) and a sulphur content of approximately 2.75% by weight.
  • the condition of the engine is rated on a demerit system, low numbers indicating good condition.
  • the piston rings are re-weighed and the cylinder bore is remeasured in order to determine the wear rates on a 1000 hour basis.
  • the wear rate obtained for the microemulsion composition was comparable to that of a conventional non-ashless diesel cylinder lubricant.
  • a microemulsion of tetraethylene pentamine in a lubricating base oil was prepared using the following components:-
  • the base oil was a petroleum lubricating oil having a viscosity of 17.6x 10-emz/s at 100°C.
  • microemulsion was prepared as follows:-
  • the oleic acid and nonyl phenol were added to half the weight of the base oil and stirred.
  • the tetraethylenepentamine was then added together with the rest of the base oil and stirred. The whole operation was carried out at room temperature and the finished microemulsion had a TBN of 71.
  • the overbased calcium phenate was an ash-forming alkaline marine cylinder lubricant additive sold by Orobis Limited under the Trade Name Oloa 219.
  • the lubricating base oil was the same as that used for the microemulsion.
  • the finished oil had a TBN of 70.
  • the neutralisations were carried out by adding sulphuric acid dropwise to the stirred oils which were then stirred at 90°C for 10 minutes.
  • Equal weights of the two neutralised oils were mixed with stirring giving, as the final product, a 90% neutralised half-ash microemulsion.
  • a half-ash microemulsion of tetraethylenepentamine in a lubricating base oil was prepared using the following components:-
  • overbased calcium phenate was the same as in Example 2.
  • the polyisobutenyl succinimides were also supplied by Orobis Limited under the Trade Names indicated above.
  • the lubricating base oil was a blend of distillate and bright stock oil chosen so that the finished composition was of SAE 50 grade viscosity (16.7 to 17.2x 1 0 -6 m 2 /S at 100°C).
  • the microemulsion was prepared as follows.
  • the oleic acid and nonyl phenol were added to half the weight of the base oil and stirred.
  • the tetraethylene pentamine was then added and stirred until homogeneous and clear.
  • the overbased calcium phenate, the polyisobutenyl succinimides and the rest of the base oil were then added and stirred at 50°C for 15 minutes.
  • the finished microemulsion had a TBN of 69.5.
  • a low-ash microemulsion of tetraethylenepentamine in a lubricating base oil was prepared using the following components:-
  • the polyisobutenyl mono-succinimide was the same as in Example 3.
  • the dispersant/detergent package was also supplied by Orobis Limited under the Trade Name indicated above.
  • the package was a blend of overbased calcium phenate, polyisobutenyl bis- succinimide and metal sulphonate.
  • the lubricating base oil was a blend of distillate and bright stock oil chosen so that the finished composition was of SAE 50 grade viscosity (16.7 to 17.2 x 10- B m 2 /s at 100° C).
  • the microemulsion was prepared as follows.
  • the oleic acid and nonyl phenol were added to half the weight of the base oil and stirred.
  • the tetraethylenepentamine was then added and stirred until homogeneous and clear.
  • the dispersant/detergent package (Oloa 853), polyisobutenyl mono-succinimide (Oloa 1200) and the rest of the base oil were added and stirred at 50°C for 15 minutes.
  • the finished microemulsion had a TBN of 70.
  • This composition (which had an ash content of 1.85%wt.) was tested for suitability as a cylinder lubricant for marine diesel engines using a 125 hour test in a Ruston engine.

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

Claims (8)

1. Schmiermittel, enthaltend ein Schmierölgrundöl als geschlossene Phase und eine in Kohlenwasserstoffen unlösliche Verbindung als mikroemulgierte Phase, dadurch gekennzeichnet, daß die mikroemulgierte Phase ein Kohlenwasserstoffamin ist und das Schmiermittel außerdem ein Dispergiermittel für Kohlenwasserstoffaminsalze enthält, die während des Gebrauchs des Schmiermittels gebildet werden können.
2. Schmiermittel nach Anspruch 1, dadurch gekennzeichnet, daß das Kohlenwasserstoffamin ein Polyalkylenpolyamin mit 1 bis 20 Kohlenstoffatomen ist.
3. Schmiermittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Mikroemulsion unter Verwendung von Emulgatoren in den in Gew.-Teilen ausgedrückten Verhältnissen von
Figure imgb0011
hergestellt ist.
4. Schmiermittel nach Ansprüchen 1, 2 oder 3, dadurch gekennzeichnet, daß es 1 bis 20 Gew.-% Kohlenwasserstoffamin und 2 bis 25 Gew.-% Emulgatoren, bezogen auf das Gewicht des gesamten Schmiermittels, enthält.
5. Schmiermittel nach einem beliebigen der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Dispergermittel ein Polyisobutenylsuccinimid ist.
6. Schmiermittel nach einem beliebigen der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Dispergiermittel ein Barium-, Calcium-oder Natriumphenolat, -sulfonat oder - carboxylat ist.
7. Schmiermittel nach einem beliebigen der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es 1 bis 30 Gew.-% Dispergiermittel, bezogen auf das Gewicht des gesamten Schmiermittels, enthält.
8. Verfahren zum Schmieren eines Schiffsdieselmotors mit einem Zylinderschmiersystem, dadurch gekennzeichnet, daß das verwendete Schmiermittel ein in den Ansprüchen 1 bis 8 beanspruchtes Schmiermittel ist.
EP79301536A 1978-08-01 1979-08-01 Schmiermittelzusammensetzung und Verfahren zum Schmieren eines Schiffsdieselmotors Expired EP0008193B1 (de)

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GB3188478 1978-08-01
GB7831884 1978-08-01

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EP0008193B1 true EP0008193B1 (de) 1982-06-30

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JP (1) JPS5521490A (de)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0839840B2 (de) † 1996-10-29 2016-01-20 Idemitsu Kosan Company Limited Schmierölzusatz enthaltend Bernsteinsäureimid-Verbindung und dessen Verwendung für Dieselmotoren
RU2598848C2 (ru) * 2011-04-14 2016-09-27 Тоталь Маркетин Сервис Смазка цилиндра двухтактного судового двигателя

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1265506A (en) * 1984-11-21 1990-02-06 Kirk Emerson Davis Alkyl phenol and amino compound compositions and two- cycle engine oils and fuels containing same
US4808325A (en) * 1987-03-30 1989-02-28 Amoco Corporation Mannich dispersant VI-improver blended with phenolic compound for improved storage stability
GB8804171D0 (en) * 1988-02-23 1988-03-23 Exxon Chemical Patents Inc Dispersant for marine diesel cylinder lubricant
DE68911129D1 (de) * 1988-09-16 1994-01-13 Idemitsu Kosan Co Schmierölzusammensetzung.
SG55446A1 (en) * 1996-10-29 1998-12-21 Idemitsu Kosan Co Lube oil compositions for diesel engines
PT1914295E (pt) * 2006-10-11 2014-03-05 Total Marketing Services Lubrificante marítimo para óleo combustível com alto ou baixo teor de enxofre
FR2932813B1 (fr) * 2008-06-18 2010-09-03 Total France Lubrifiant cylindre pour moteur marin deux temps

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1068547A (en) * 1963-12-26 1967-05-10 Exxon Research Engineering Co Metal carbonate overbased lubricant detergent-dispersants
US3346494A (en) * 1964-04-29 1967-10-10 Exxon Research Engineering Co Microemulsions in liquid hydrocarbons
GB1386620A (en) * 1972-06-01 1975-03-12 British Petroleum Co Lubricating composition
DE2622066A1 (de) * 1975-05-23 1976-11-25 Cooper Ltd Ethyl Korrosionsinhibitoren fuer schmieroele

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0839840B2 (de) † 1996-10-29 2016-01-20 Idemitsu Kosan Company Limited Schmierölzusatz enthaltend Bernsteinsäureimid-Verbindung und dessen Verwendung für Dieselmotoren
RU2598848C2 (ru) * 2011-04-14 2016-09-27 Тоталь Маркетин Сервис Смазка цилиндра двухтактного судового двигателя

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CA1118750A (en) 1982-02-23
DE2963239D1 (en) 1982-08-19
JPS5521490A (en) 1980-02-15
EP0008193A1 (de) 1980-02-20

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