EP1512737B1 - Schmiermittelzusammensetzung für Schiffsmotoren - Google Patents

Schmiermittelzusammensetzung für Schiffsmotoren Download PDF

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Publication number
EP1512737B1
EP1512737B1 EP04254680A EP04254680A EP1512737B1 EP 1512737 B1 EP1512737 B1 EP 1512737B1 EP 04254680 A EP04254680 A EP 04254680A EP 04254680 A EP04254680 A EP 04254680A EP 1512737 B1 EP1512737 B1 EP 1512737B1
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EP
European Patent Office
Prior art keywords
composition
oil
molybdenum
rust inhibitor
alkyl
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.)
Not-in-force
Application number
EP04254680A
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English (en)
French (fr)
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EP1512737A1 (de
Inventor
Ricardo Alfredo Bloch
Rolfe John Hartley
Michael Dennis Hoey
George C. L'heureax
Salvatore Rea
Malcolm Waddoups
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Infineum International Ltd
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Infineum International Ltd
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Publication of EP1512737A1 publication Critical patent/EP1512737A1/de
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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
    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
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    • 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
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
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    • 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
    • C10M2207/127—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 polycarboxylic
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/288—Partial esters containing free carboxyl 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
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
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    • 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
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/047—Thioderivatives not containing metallic elements
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/09—Complexes with metals
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    • C10M2229/02—Unspecified siloxanes; Silicones
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    • 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
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/085—Non-volatile compounds
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/74—Noack Volatility
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    • 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
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    • 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

Definitions

  • the present invention relates to lubricating oil compositions. More particularly, the present invention relates to lubricating oil compositions, which are designed for use with four cycle marine engines.
  • the invention embodies new oil blends specifically formulated for use in four cycle marine engines, especially outboard engines. These oils have a high phosphorus level. These oils also contain a molybdenum antioxidant/antiwear additive and a rust inhibitor additive.
  • oils embodied in this invention provide specific performance improvements desirable in four cycle outboard engines: improved antioxidancy, antiwear, rust inhibition, shear stability, good water tolerance, air entrainment and high temperature foam properties.
  • a lubricating oil composition for use in four cycle marine engines, which composition comprises at least one oil of lubricating viscosity, an ashless dispersant, a metal detergent, at least one molybdenum compound in an amount sufficient to provide the composition with 15 to 1,000 ppm by mass of molybdenum, an amount of ZDDP (zinc dialkyldithiophosphate) that contributes at least 1,200 ppm of phosphorus to the lubricating oil composition, an effective amount of a rust inhibitor system comprising certain combinations of rust inhibitors and, optionally, a viscosity modifier, the lubricating oil composition having a NOACK volatility of 15 wt.% or less.
  • ZDDP zinc dialkyldithiophosphate
  • a further embodiment of this invention comprises a method of operating and lubricating a four cycle marine engine which comprises supplying to said engine the lubricating oil composition of this invention.
  • the lubricating compositions of the present invention contain an oil of lubricating viscosity, an ashless dispersant, a metal detergent, a rust inhibitor, a relatively high amount of ZDDP, and an amount of a molybdenum compound sufficient to provide the composition with 15-1,000 ppm by mass of molybdenum.
  • An amount of about 15 ppm to 1,000 ppm by mass of molybdenum from a molybdenum compound has been found to be effective as an antiwear agent in combination with the high levels of ZDDP.
  • the volatility of the lubricating oil composition be about 15 wt.% or less, such as in the range of 4 to 15 wt.%, preferably in the range of 8 to 15 wt.%.
  • the NOACK Volatility Test is used to measure the evaporative loss of an oil after 1 hour at 250°C according to the procedure of ASTM D5800. The evaporative loss is reported in mass percent.
  • the oil of lubricating viscosity useful in the context of the present invention is selected from the group consisting of Group I, Group II, or Group III, Group IV or Group V base stocks or base oil blends of the aforementioned base stocks.
  • the viscosity of such oils ranges from about 2 mm 2 /sec (centistokes) to about 40 mm 2 /sec at 100°C.
  • Preferred are base stocks or base stock mixtures having an intrinsic viscosity of from about 4.0 to about 5.5 mm2/sec at 100°C.
  • base stocks and base stock mixtures having a volatility, as measured by the NOACK test (measured by determining the evaporative loss in mass percent of an oil after 1 hour at 250°C according to the procedure of ASTM D5800), of less than 15%, more preferably less than 12%, most preferably less than 10%.
  • the most preferred oils are:
  • base stocks and base oils in this invention 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 base stocks as follows:
  • Lubricating compositions of this invention which exhibit a biodegradability of at least 50% in the ASTM D5864-95 modified Sturm test may be prepared using synthetic ester base stocks prepared from polyhydric or monohydric alcohols and carboxylic acids.
  • Table E-1 - Analytical Methods for Base Stock Property Test Method Saturates ASTM D 2007 Viscosity Index ASTM D 2270 Sulfur ASTM D 2622 ASTM D 4294 ASTM D 4927 ASTM D 3120
  • Suitable ashless dispersants for use in this invention include hydrocarbyl succinimides, hydrocarbyl succinamides, mixed ester/amides of hydrocarbyl-substituted succinic acid, hydroxyesters of hydrocarbyl-substituted succinic acid, and Mannich condensation products of hydrocarbyl-substituted phenols, formaldehyde and polyamines. Also useful are condensation products of polyamines and hydrocarbyl substituted phenyl acids. Mixtures of these dispersants can also be used.
  • Mannich dispersants which are condensation products of hydrocarbyl-substituted phenols, formaldehyde and polyamines are described, for example, in U.S. patents numbers: 3,368,972 ; 3,413,347 ; 3,539,633 ; 3,697,574 ; 3,725,277 ; 3,725,480 ; 3,726,882 ; 3,798,247 ; 3,803,039 ; 3,985,802 ; 4,231,759 and 4,142,980 .
  • Amine dispersants and methods for their production from high molecular weight aliphatic or alicyclic halides and amines are described, for example, in U.S. patent numbers: 3,275,554 ; 3,438,757 ; 3,454,55 and 3,565,804 .
  • the preferred dispersants are the alkenyl succinimides and succinamides.
  • the succinimide or succinamide dispersants can be formed from amines containing basic nitrogen and additionally one or more hydroxy groups.
  • the amines are polyamines such as polyalkylene polyamines, hydroxy-substituted polyamines and polyoxyalkylene polyamines.
  • Examples of polyalkylene polyamines include diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine.
  • Low cost poly(ethyleneamines) averaging about 5 to 7 nitrogen atoms per molecule are available commercially under trade names such as "Polyamine H", "Polyamine 400", “Dow Polyamine E-100", etc.
  • Hydroxy-substituted amines include N-hydroxyalkyl-alkylene polyamines such as N-(2-hydroxyethyl)ethylene diamine, N-(2-hydroxyethyl)piperazine, and N-hydroxyalkylated alkylene diamines of the type described in U.S. 4,873,009 .
  • Polyoxyalkylene polyamines typically include polyoxyethylene and polyoxypropylene diamines and triamines having average molecular weights in the range of 200 to 2500. Products of this type are available under the Jeffamine trademark.
  • the amine is readily reacted with the selected hydrocarbyl-substituted dicarboxylic acid material, e.g., alkylene succinic anhydride, by heating an oil solution containing 5 to 95 wt. % of said hydrocarbyl-substituted dicarboxylic acid material at about 100° to 250°C, preferably 125° to 175° C, generally for 1 to 10, e.g., 2 to 6 hours until the desired amount of water is removed.
  • the heating is preferably carried out to favor formation of imides or mixtures of imides and amides, rather than amides and salts.
  • Reaction ratios of hydrocarbyl-substituted dicarboxylic acid material to equivalents of amine as well as the other nucleophilic reactants described herein can vary considerably, depending on the reactants and type of bonds formed. Generally from 0.1 to 1.0, preferably from about 0.2 to 0.6, e.g., 0.4 to 0.6, equivalents of dicarboxylic acid unit content (e.g., substituted succinic anhydride content) is used per reactive equivalent of nucleophilic reactant, e.g., amine.
  • dicarboxylic acid unit content e.g., substituted succinic anhydride content
  • a pentamine having two primary amino groups and five reactive equivalents of nitrogen per molecule
  • alkenyl succinimides which have been treated with a boronating agent are also suitable for use in the compositions of this invention as they are much more compatible with elastomeric seals made from such substances as fluoro-elastomers and silicon-containing elastomers.
  • Dispersants may be post-treated with many reagents known to those skilled in the art. (see, e.g., U.S. Pat. Nos. 3,254,025 , 3,502,677 and 4,857,214 ).
  • the preferred ashless dispersants are polyisobutenyl succinimides formed from polyisobutenyl succinic anhydride and an alkylene polyamine such as triethylene tetramine or tetraethylene pentamine wherein the polyisobutenyl substituent is derived from polyisobutene having a number average molecular weight (Mn) in the range of 300 to 2500 (preferably 1600 to 2500).
  • Mn number average molecular weight
  • the polyisobutenyl succinic anhydride used to prepare the dispersant may be chlorine-free such as one made from a highly reactive, terminally unsaturated polyisobutylene or it may be a mixture of chlorine-containing and chlorine-free polyisobutenyl succinic anhydride such that the finished oil has less than 50 ppm chlorine.
  • the ashless dispersants of the invention should be present, on an active ingredient basis, in an amount of from 1.0 to 3.75 wt.%.
  • Heavy duty diesel lubricants commonly used as four cycle marine engine (e.g. outboard engine) lubricants will typically have 4-8 wt.% of dispersant.
  • Metal-containing or ash-forming detergents function both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life.
  • Detergents generally comprise a polar head with long hydrophobic tail, with the polar head comprising a metal salt of an acid organic compound.
  • the salts may contain a substantially stoichiometric amount of the metal in which they are usually described as normal or neutral salts, and would typically have a total base number (TBN), as may be measured by ASTM D-2896 of from 0 to 80. It is possible to include large amounts of a metal base by reacting an excess of a metal compound such as an oxide or hydroxide with an acid gas such as 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 from 250 to 450 or more.
  • Known detergents include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g., sodium, potassium, lithium, calcium, and magnesium.
  • a metal particularly the alkali or alkaline earth metals, e.g., sodium, potassium, lithium, calcium, and magnesium.
  • the most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium.
  • Particularly convenient metal detergents are neutral and overbased calcium sulfonates having TBN of from 20 to 450 TBN, and neutral and overbased calcium phenates and sulfurized phenates having TBN of from 50 to 450 and mixtures of calcium phenates and sulfonates.
  • the detergents of the present invention may be salts of one type of organic acid or salts of more than one type of organic acids, for example hybrid complex detergents. Preferably, they are salts of one type of organic acid.
  • the hybrid complex detergent is where the basic material within the detergent is stabilised by more than one type of organic acid.
  • organic acid may contain a mixture of organic acids of the same type.
  • a sulfonic acid may contain a mixture of sulfonic acids of varying molecular weights.
  • Such an organic acid composition is considered as one type.
  • complex detergents are distinguished from mixtures of two or more separate overbased detergents, an example of such a mixture being one of an overbased calcium salicylate detergent with an overbased calcium phenate detergent.
  • overbased complex detergents examples include calcium phenate-salicylate-sulfonate detergent, calcium phenate-sulfonate detergent and calcium phenate-salicylate detergent.
  • EP-A-0 750 659 describes a calcium salicylate phenate complex made by carboxylating a calcium phenate and then sulfurising and overbasing the mixture of calcium salicylate and calcium phenate. Such complexes may be referred to as "phenalates”.
  • Preferred complex detergents are salicylate-based detergents, for example, a calcium phenate-salicylate-sulfonate detergent and "phenalates".
  • Metal detergents are present typically in amounts of 0.25 to 3.0 wt.% on an active ingredient basis.
  • any suitable soluble organo-molybdenum compound having anti-wear properties in lubricating oil compositions may be employed.
  • soluble organo-molybdenum compounds there may be mentioned the dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof.
  • the molybdenum compound may be mono-, di-, tri- or tetra-nuclear. Dinuclear and trinuclear molybdenum compounds are preferred.
  • the molybdenum compound is preferably an organo-molybdenum compound. More preferably, the molybdenum compound is selected from the group consisting of a molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate, molybdenum dithiophosphinate, molybdenum xanthate, molybdenum thioxanthate, molybdenum sulfide and mixtures thereof. Most preferably, the molybdenum compound is present as molybdenum dithiocarbamate or a trinuclear organo-molybdenum compound.
  • MoDTC molybdenum dithiocarbamate
  • the molybdenum compound is present as molybdenum dithiocarbamate or
  • the molybdenum compound may be an acidic molybdenum compound. These compounds will react with a basic nitrogen compound as measured by ASTM test D-664 or D-2896 titration procedure and are typically hexavalent. Included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkaline metal molybdates and other molybdenum salts, e.g., hydrogen sodium molybdate, MoOCl 4 , MoO 2 Br 2 , Mo 2 O 3 Cl 6 , molybdenum trioxide or similar acidic molybdenum compounds.
  • molybdenum compounds useful in the compositions of this invention are organo-molybdenum compounds of the formula Mo(ROCS 2 ) 4 and Mo(RSCS 2 ) 4 wherein R is an organo group selected from the group consisting of alkyl, aryl, aralkyl and alkoxyalkyl, generally of from 1 to 30 carbon atoms, and preferably 2 to 12 carbon atoms and most preferably alkyl of 2 to 12 carbon atoms.
  • R is an organo group selected from the group consisting of alkyl, aryl, aralkyl and alkoxyalkyl, generally of from 1 to 30 carbon atoms, and preferably 2 to 12 carbon atoms and most preferably alkyl of 2 to 12 carbon atoms.
  • dialkyldithiocarbamates of molybdenum are especially preferred.
  • One class of preferred organo-molybdenum compounds useful in the lubricating compositions of this invention are trinuclear molybdenum compounds, especially those of the formula Mo 3 S k L n Q z and mixtures thereof wherein the L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 through 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. At least 21 total carbon atoms should be present among all the ligands' organo groups, such as at least 25, at least 30, or at least 35 carbon atoms.
  • the ligands are independently selected from the group of -X- R 1, and and mixtures thereof, wherein X, X 1 , X 2 , and Y are independently selected from the group of oxygen and sulfur, and wherein R 1 , R 2 , and R are independently selected from hydrogen and organo groups that may be the same or different.
  • the organo groups are hydrocarbyl groups such as alkyl (e.g., in which the carbon atom attached to the remainder of the ligand is primary or secondary), aryl, substituted aryl and ether groups. More preferably, each ligand has the same hydrocarbyl group.
  • hydrocarbyl denotes a substituent having carbon atoms directly attached to the remainder of the ligand and is predominantly hydrocarbyl in character within the context of this invention.
  • substituents include the following:
  • the organo groups of the ligands have a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil.
  • the number of carbon atoms in each group will generally range between about 1 to about 100, preferably from about 1 to about 30, and more preferably between about 4 to about 20.
  • Preferred ligands include dialkyldithiophosphate, alkylxanthate, and dialkyldithiocarbamate, and of these dialkyldithiocarbamate is more preferred.
  • Organic ligands containing two or more of the above functionalities are also capable of serving as ligands and binding to one or more of the cores. Those skilled in the art will realize that formation of the compounds of the present invention requires selection of ligands having the appropriate charge to balance the core's charge.
  • Oil-soluble or dispersible trinuclear molybdenum compounds can be prepared by reacting in the appropriate liquid(s)/solvent(s) a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 ⁇ n(H 2 O), where n varies between 0 and 2 and includes non-stoichiometric values, with a suitable ligand source such as a tetralkylthiuram disulfide.
  • a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 ⁇ n(H 2 O), where n varies between 0 and 2 and includes non-stoichiometric values
  • oil-soluble or dispersible trinuclear molybdenum compounds can be formed during a reaction in the appropriate solvent(s) of a molybdenum source such as (NH 4 ) 2 Mo 3 S) 3 ⁇ n(H 2 O), a ligand source such as tetralkylthiuram disulfide, dialkyldithiocarbamate, or dialkyldithiophosphate, and a sulfur abstracting agent such cyanide ions, sulfite ions, or substituted phosphines.
  • a molybdenum source such as (NH 4 ) 2 Mo 3 S) 3 ⁇ n(H 2 O)
  • a ligand source such as tetralkylthiuram disulfide, dialkyldithiocarbamate, or dialkyldithiophosphate
  • a sulfur abstracting agent such cyanide ions, sulfite ions, or substituted phosphines.
  • a trinuclear molybdenum-sulfur halide salt such as [M'] 2[ Mo 3 S 7 A 6] , where M' is a counter ion, and A is a halogen such as Cl, Br, or I, may be reacted with a ligand source such as a dialkyldithiocarbamate or dialkyldithiophosphate in the appropriate liquid(s)/solvent(s) to form an oil-soluble or dispersible trinuclear molybdenum compound.
  • the appropriate liquid/solvent may be, for example, aqueous or organic.
  • a compound's oil solubility or dispersibility may be influenced by the number of carbon atoms in the ligand's organo groups. In the compounds of the present invention, at least 21 total carbon atoms should be present among all the ligand's organo groups.
  • the ligand source chosen has a sufficient number of carbon atoms in its organo groups to render the compound soluble or dispersible in the lubricating composition.
  • composition of this invention will contain about 25-300 ppm molybdenum.
  • oil-soluble or “dispersible” used herein do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible, or capable of being suspended in the oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
  • Zinc dihydrocarbyl dithiophosphate (ZDDP) metal salts 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 P 2 S 5 and then neutralizing the formed DDPA with a zinc compound.
  • DDPA dihydrocarbyl dithiophosphoric acid
  • a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols.
  • 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.
  • 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.
  • composition of this invention will contain ZDDP in such amounts so as to provide at least 1,200 ppm P in the finished outboard engine oil, up to about 2,000 ppm P.
  • the preferred zinc dihydrocarbyl dithiophosphates are oil soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula: wherein R and R' may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R and R' groups are alkyl groups of 2 to 8 carbon atoms or mixtures thereof.
  • the radicals may, for example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.
  • the total number of carbon atoms (i.e. R and R') in the dithiophosphoric acid will generally be about 5 or greater.
  • the zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
  • the zinc dialkylthiophosphate compound can be primary zinc, secondary zinc, or mixtures thereof, that is, the ZDDP contains primary and/or secondary alkyl groups derived from primary or secondary alcohols, but secondary alkyl groups are preferred, or ZDDP which has about 85% secondary alkyl groups and about 15% primary alkyl groups, such as 85% sec-butyl and 15% isooctyl.
  • the marine engine oil compositions of the present invention contain an effective amount of an oil soluble rust inhibitor system which comprises an ethoxylated C 4 -C 18 alkyl, preferably nonyl, phenol rust inhibitor containing about 2 to 10, preferably 3 to 5, such as 4 moles of ethylene oxide per mol in combination with a second, or a second and a third, rust inhibitor, with each rust inhibitor being present in an amount of from about 0.05 to 1.5 wt.%.
  • the second rust inhibitor may be a glycerol ester of a C 8 -C 22 fatty acid, with oleic acid being preferred.
  • glycerol oleates comprising a major amount of a mixture of glycerol monooleate and dioleate and very minor amounts of trioleate, such as a mixture comprising about 55 wt.% glycerol monooleate, 40 wt.% glycerol dioleate and the balance glycerol trioleate.
  • Other useful second rust inhibitors are (i) the C 2 -C 4 alkylene glycol, preferably propylene glycol, half esters of a C 8 -C 22 alkyl or alkenyl succinic acid and (ii) C 8 -C 22 alkyl or alkenyl succinic acids or anhydrides, where the alkyl or alkenyl is preferably dodecyl or isomerized octadecenyl.
  • second rust inhibitor is the glycerol ester and third rust inhibitor is present which is either the aforesaid glycol half ester or the aforesaid alkyl or alkenyl succinic acid or anhydride, preferably the propylene glycol half ester of dodecyl succinic anhydride or dodecyl or isomerized octadecenyl succinic acid or anhydride.
  • each rust inhibitor in all the combinations described herein is present in an amount of 0.10 to 0.40, preferably 0.20 to 0.35 wt.%.
  • compositions of the present invention will contain effective amounts of a viscosity modifier as an optional ingredient depending on the viscosity grade of the oil which is desired. These are typically present in amounts ranging from 0.5 to 5.0 wt.% on an active ingredient basis. Shear stable viscosity modifiers are preferred.
  • Suitable compounds for use as viscosity modifiers are generally high molecular weight hydrocarbon polymers, including polyesters.
  • Oil soluble viscosity modifying polymers generally have weight average molecular weights from about 10,000 to 1,000,000, preferably from about 20,000 to 500,000, as determined by gel permeation chromatography or light scattering methods.
  • suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene and higher alpha-olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of unsaturated dicarboxylic acid and vinyl compound, inter polymers of styrene and acrylic ester, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene and isoprene/butadiene, as well as partially hydrogenated homopolymers of butadiene and isoprene and isoprene/divinylbenzene.
  • Additional additives may be present in the composition of the present invention include stabilizers and seal compatibility additives such as polyisobutenyl succinic anhydride, prepared from chlorinated polyisobutylene or chlorine-free polyisobutylene, including highly reactive polyisobutylene having terminal unsaturation, oxidation inhibitors, demulsifiers, antifoam additives and pour depressants.
  • stabilizers and seal compatibility additives such as polyisobutenyl succinic anhydride, prepared from chlorinated polyisobutylene or chlorine-free polyisobutylene, including highly reactive polyisobutylene having terminal unsaturation, oxidation inhibitors, demulsifiers, antifoam additives and pour depressants.
  • compositions of this invention may also contain 0.05 to 1.5 wt.% each of one or more phosphorus-free oxidation inhibitors or antioxidants, and these include hindered phenols, alkaline earth metal salts of alkylphenolthioesters having preferably C 5 to C 12 alkyl side chains, calcium nonylphenol sulfide, ashless oil soluble phenates and sulfurized phenates, sulfurized hydrocarbons, metal thiocarbamates and oil soluble copper compounds as described in U.S. 4,867,890 .
  • phosphorus-free oxidation inhibitors or antioxidants include hindered phenols, alkaline earth metal salts of alkylphenolthioesters having preferably C 5 to C 12 alkyl side chains, calcium nonylphenol sulfide, ashless oil soluble phenates and sulfurized phenates, sulfurized hydrocarbons, metal thiocarbamates and oil soluble copper compounds as described in U.S. 4,867,890 .
  • Aromatic amines having at least two aromatic groups attached directly to the nitrogen constitute another class of compounds that is frequently used for antioxidancy.
  • Typical oil soluble aromatic amines having at least two aromatic groups attached directly to one amine nitrogen contain from 6 to 16 carbon atoms. The amines may contain more than two aromatic groups.
  • the aromatic rings are typically substituted by one or more substituents selected from alkyl, cycloalkyl, alkoxy, aryloxy, acyl, acylamino, hydroxy, and nitro groups. Dinonyl-diphenyl amine is a preferred antioxidant.
  • the amount of any such oil soluble aromatic amines having at least two aromatic groups attached directly to one amine nitrogen is in the range of 0.05 to 1.5 wt. % active ingredient.
  • Hindered phenols are preferably used in the range of 0.05 to 0.5 wt.%.
  • Hindered phenols will generally be of the type in which there is a sterically hindered phenolic group, especially one containing a t-butyl group in the ortho position to the phenolic OH group. Examples of such compounds are many. These include both monocyclic and bisphenols.
  • Preferred examples are tetrakis(methylene-3-(-3',5'-di-tert-butyl-4'hydroxyphenyl)-propionate) methane; octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate; 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) benzene; 4,4'-(2,2-diphenylpropyl)-diphenylamine; esters of ethoxylated aryl phenols; 2,2'-thiodiethylbis(3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate; octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate and mixtures of any of the foregoing. Most preferred is isooctyl-3,
  • a small amount of a demulsifying component may be used.
  • a preferred demulsifying component is described in EP 330,522 . It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide with a polyhydric alcohol.
  • the demulsifier should be used at a level not exceeding 0.1 mass % active ingredient. A treat rate of 0.001 to 0.05 mass % active ingredient is convenient.
  • Pour point depressants otherwise known as lube oil flow improvers, lower the minimum temperature at which the fluid will flow or can be poured.
  • Such additives are well known. Typical of those additives which improve the low temperature fluidity of the fluid are C 8 to C 18 dialkyl fumarate/vinyl acetate copolymers, polyalkylmethacrylates and the like.
  • Foam control can be provided by many antifoam compounds including a fluorosilicone or an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane usually used in amounts of from 0.0001 to 0.01 wt.% active ingredient.
  • a fluorosilicone or an antifoamant of the polysiloxane type for example, silicone oil or polydimethyl siloxane usually used in amounts of from 0.0001 to 0.01 wt.% active ingredient.
  • each of the components can be added directly to the base stock or base oil blend by dispersing or dissolving it in the base stock or base oil blend at the desired level of concentration. Such blending may occur at ambient temperature or at an elevated temperature.
  • all the additives except for the viscosity modifier and the pour point depressant are blended into a concentrate or additive package described herein as the additive package, that is subsequently blended into base stock to make the finished lubricant.
  • the concentrate will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration in the final formulation when the concentrate is combined with a predetermined amount of a base lubricant.
  • the concentrate is preferably made in accordance with the method described in US 4,938,880 . That patent describes making a pre-mix of ashless dispersant and metal detergents that is pre-blended at a temperature of at least about 100°C. Thereafter, the pre-mix is cooled to at least 85°C and the additional components are added.
  • the final lubricating oil formulation may employ from 2 to 20 mass %, preferably 4 to 18 mass %, and most preferably about 5 to 17 mass % of the concentrate or additive package with the remainder being base stock.
  • the following 10W30 viscosity grade oil was prepared and subjected to rust testing for suitability as a four stroke outboard marine engine oil in the "FC-W" Rust Test. Percentages are by weight of active ingredient, except as otherwise indicated.
  • the oil has 42 ppm molybdenum, 1210 ppm phosphorus and a NOACK volatility less than 15%.
  • Six versions differing in the amount of rust inhibitor were tested.
  • FC-W Fluor Cycle-Water Rust Test
  • NMMA National Marine Manufacturers Association
  • FC-W rust test will be one of the test requirements for FC-W oil quality certification. While the test is still under development by the testing laboratories, it is based on an in-house test by Mercury Marine.
  • Weight % (a) Calcium sulfonate (TBN 300) 1.017 (b) Molybdenum trimer dithiocarbamate 0.045 (c) Calcium phenate (neutral) 0.230 (d) Polyisobutenyl succinimide dispersant 3.540 (e) Amine antioxidant 0.600 (f) Viscosity modifier (as 15% solution of polymer) 6.000 (g) ZDDP 1.200 (h) Rust inhibitors Table 2 (i) Lube oil flow improver 0.300 (j) Silicone antifoam agent 0.001 (k) Polyalphaolefin Base Oil 8.000 (l) Polyol ester 2.000 (m) Mn 950 polyisobutenyl succinic anhydride 0.320 (n) Mineral oil basestocks Balance
  • FC-W Rust Test was carried out on a commercially available Pennzoil-Quaker State 10W30 oil which is known to contain no rust inhibitor.
  • the rust results were 60% and 70% for the replicate panels, the average being 65%.

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Claims (19)

  1. Schmierölzusammensetzung, die zur Verwendung in einem Viertakt-Schiffsmotor geeignet ist, die Öl mit Schmierviskosität enthält, das ein Gemisch von
    a) 1 bis 3,75 Gew.-% aschefreiem Dispergiermittel,
    b) Metalldetergens,
    c) öllöslicher Molybdänverbindung in einer Menge, die ausreichend ist, um 15 bis 1000 ppm Molybdän in der Zusammensetzung bereitzustellen,
    d) Zinkdialkyldithiophosphat in einer Menge, die ausreichend ist, um mindestens 1200 ppm Phosphor in der Zusammensetzung bereitzustellen,
    e) einem Rostschutzsystem, das (i) als erstes Rostschutzmittel ethoxyliertes C4- bis C18-Alkylphenol mit 2 bis 10 mol Ethylenoxid pro mol in Kombination mit einem zweiten Rostschutzmittel enthält, das aus der Gruppe bestehend aus (ii) einem Glycerinester einer C8- bis C22-Fettsäure, (iii) einem Halbester einer C8- bis C22-Alkyl- oder Alkenylbernsteinsäure und eines C2- bis C4-Alkylenglykols und (iv) einer bzw. eines C8- bis C22-Alkyl- oder Alkenylbernsteinsäure oder -anhydrids ausgewählt ist, und
    f) gegebenenfalls Viskositätsverbesserer enthält,
    wobei die Zusammensetzung eine NOACK-Flüchtigkeit von weniger als 15 % aufweiset.
  2. Zusammensetzung nach Anspruch 1, bei der das zweite Rostschutzmittel der Glycerinester ist und die Zusammensetzung ferner ein drittes Rostschutzmittel enthält, das aus der Gruppe bestehend aus (i) einem Halbester einer C8- bis C22-Alkyl- oder Alkenylbernsteinsäure und eines C2- bis C4-Alkylenglykols und (ii) einer bzw. eines C8- bis C22-Alkyl- oder Alkenylbernsteinsäure und -anhydrids ausgewählt ist.
  3. Zusammensetzung nach Anspruch 1 oder 2, bei der der Glycerinester eine Mischung rist, die etwa 55 Ges.-% Glycerinmonooleat, 40 Gew.-% Glycerindioleat und etwa 5 Gew.-% Glycerintrioleat enthält.
  4. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei der das ethoxylierte Alkylphenol das 4 mol-Ethoxylat von Nonylphenol ist.
  5. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei der der Halbester Propylenglykoldodecylbernsteinsäure ist.
  6. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei der die bzw. das Alkyl- oder Alkenylbernsteinsäure oder -anhydrid Dodecyl- oder isomerisiertes Octadecenylbernsteinsäureanhydrid ist.
  7. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei der jedes Rostschutzmittel in einem Bereich von 0,05 bis 1,5 Gew.-% der Zusammensetzung vorliegt.
  8. Zusammensetzung nach Anspruch 4, bei der das zweite Rostschutzmittel Dodecylbernsteinsäure ist und jedes Rostschutzmittel in dem Bereich von 0,1 bis 0,4 Gew.-% vorliegt.
  9. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei der das Metalldetergens ein Calciumsulfonat oder Calciumphenolat oder eine Mischung davon ist.
  10. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei der das Dispergiermittel ein Polyisobutenylbernsteinsäureimid ist, wobei das Polyisobutenyl ein Mn von 1600 bis 2500 aufweist.
  11. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei der die Molybdänverbindung ein Molybdändithiocarbamat ist.
  12. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei der die Molybdänverbindung eine dreikernige Verbindung der Formel Mo3SkLnQ, ist, in der L öllösliche organische Gruppen darstellt, n 1 bis 4 ist, k 4 bis 7 ist und Q eine neutrale, elektronendonierende Verbindung ist und z 0,5 ist.
  13. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei der das Zinkdialkyldithiophosphat in einer Menge vorliegt, die ausreichend ist, um bis zu 2000 ppm P in der Zusammensetzung bereitzustellen.
  14. Zusammensetzung nach Anspruch 13, bei der Zinkdialkyldithiophosphat sekundäre Alkylgruppen mit 2 bis 8 Kohlenstoffatomen umfasst.
  15. Zusammensetzung nach einem der vorhergehenden Ansprüche, bei der der Viskositätsverbesserer scherstabil ist und in einer Menge von 0,5 bis 5 Gew.-% vorliegt.
  16. Zusammensetzung nach einem der vorhergehenden Ansprüche, die ferner ein oder mehrere phosphorfreie Antioxidantien enthält.
  17. Zusammensetzung nach einem der vorhergehenden Ansprüche, die ferner Entschäumer enthält.
  18. Zusammensetzung nach einem der vorhergehenden Ansprüche, die ferner Schmierölfließverbesserer enthält.
  19. Verfahren zum Betreiben und Schmieren eines Viertakt-Schiffsmotors, bei dem dem Motor die Schmierölzusammensetzung gemäß einem der Ansprüche 1 bis 18 zugeführt wird.
EP04254680A 2003-09-08 2004-08-04 Schmiermittelzusammensetzung für Schiffsmotoren Not-in-force EP1512737B1 (de)

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US10/657,687 US20040121918A1 (en) 2002-07-08 2003-09-08 Lubricating oil composition for marine engines
US657687 2003-09-08

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US20040121918A1 (en) 2004-06-24
ATE506427T1 (de) 2011-05-15
DE602004032297D1 (de) 2011-06-01
CA2480935A1 (en) 2005-03-08
CA2480935C (en) 2012-12-18

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