EP1046698A1 - Compositions lubrifiantes pour la lubrification d'un moteur diesel marin - Google Patents

Compositions lubrifiantes pour la lubrification d'un moteur diesel marin Download PDF

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Publication number
EP1046698A1
EP1046698A1 EP20000201236 EP00201236A EP1046698A1 EP 1046698 A1 EP1046698 A1 EP 1046698A1 EP 20000201236 EP20000201236 EP 20000201236 EP 00201236 A EP00201236 A EP 00201236A EP 1046698 A1 EP1046698 A1 EP 1046698A1
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EP
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Prior art keywords
oil
composition
detergent
soluble
surfactants
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.)
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EP20000201236
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German (de)
English (en)
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EP1046698B1 (fr
Inventor
Adrian Dr. Dunn
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Infineum International Ltd
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Infineum International Ltd
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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
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/005—Macromolecular compounds, e.g. macromolecular compounds composed of alternatively specified monomers not covered by the same main group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/16—Ethers
    • C10M129/18—Epoxides
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/02—Sulfurised compounds
    • C10M135/04—Hydrocarbons
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/02—Sulfurised compounds
    • C10M135/06—Esters, e.g. fats
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/22—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
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    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
    • C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
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    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C—CHEMISTRY; METALLURGY
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    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C—CHEMISTRY; METALLURGY
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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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    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • C—CHEMISTRY; METALLURGY
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    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • 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
    • C10M2207/028—Overbased salts thereof
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    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
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    • C10M2207/26—Overbased carboxylic acid salts
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    • C10M2215/064—Di- and triaryl amines
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    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
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    • C10M2215/066—Arylene diamines
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    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—Neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives

Definitions

  • This invention relates to a lubricating oil composition for marine applications, particularly for use as a marine diesel lubricant for both cross-head engines and trunk piston engines for improving resistance to viscosity increase in use.
  • marine does not restrict the engines to those used in water-borne vessels; as is understood in the art, it includes land-based engines of the above types, such as used for power-generation.
  • Lubricating oils for cross-head engines and trunk piston engines are known and are known to include, as additives to improve their performance, ashless dispersants and overbased detergents.
  • International Patent Application PCT/EP97/0269 describe detergents, the surfactant of which includes a salicylate, for such applications.
  • a problem when using a lubricant that contain such detergents is the tendency of its viscosity to rise with time for reasons that include oxidative degradation.
  • the viscosity can rise to levels such as to render the lubricant unacceptable to engine manufacturers and therefore unsuitable for its intended purpose.
  • This invention solves the problem by using defined anti-oxidants in the lubricants; it has surprisingly been found that their use can ensure stable lubricant viscosities over a period of time that are acceptable for the intended application-lifetime of the lubricant, during which, steady viscosity growth would normally be expected to occur.
  • a first aspect of the present invention is a lubricating oil composition for a marine diesel engine comprising a major amount of an oil of lubricating viscosity and, comprising or provided by admixing therewith or added thereto, minor amounts of the following additives:
  • a second aspect of the present invention is the use of additives (a), (b) and one or both of (c1) and (c2), as defined in the first aspect of the invention, to enhance the resistance to viscosity increase of a lubricating oil composition for a marine diesel engine comprising the additives.
  • a third aspect of the present invention is a method of lubricating a marine diesel engine, such as a trunk piston engine, which comprises supplying to the engine a lubricating oil composition according to the first aspect of the invention.
  • Major amount means in excess of 50 mass % of the composition.
  • Minor amount means less than 50 mass % of the composition, both in respect of stated additive and in respect of the total mass % of all of the additives present in composition, reckoned as active ingredient of the additive or additives.
  • TBN Total Base Number
  • Viscosity index is as defined by ASTM D2270.
  • the lubricating oil composition of the present invention may be suitable for use in a 4-stroke trunk piston engine having an engine speed of 100-1,500 rpm, e.g. 300-1,000 rpm, and a brake horse-power (BHP) per cylinder of 50-3,000 preferably 100-2,000.
  • the engine can also be a 2-stroke cross-head engine having a speed of 40-200 rpm, preferably 60-120 rpm and a BHP per cylinder of 500-10,000.
  • the engine is a trunk piston engine.
  • the TBN of the lubricant composition is at least 20, for example in the range of from 20 to 100, such as from 30 to 70.
  • the viscosity index of the lubricant composition is at least 90, such as at least 95, especially at least 110.
  • the lubricant composition may, for example, have a kinematic viscosity at 100°C (as measured by ASTM D445) of at least 10, preferably at least 12, more preferably in the range of from 13 to 30, for example from 13 to 25, mm 2 s -1 .
  • the oil of lubricating viscosity may be any oil suitable for the lubrication of a cross-head engine or a trunk piston engine.
  • the lubricating oil may suitably be an animal, a vegetable or a mineral oil.
  • the lubricating oil is a petroleum-derived lubricating oil, such as a naphthenic base, paraffinic base or mixed base oil.
  • the lubricating oil may be a synthetic lubricating oil.
  • Suitable synthetic lubricating oils include synthetic ester lubricating oils, which oils include diesters such as di-octyl adipate, di-octyl sebacate and tri-decyl adipate, or polymeric hydrocarbon lubricating oils, for example liquid polyisobutene and poly-alpha olefins. Commonly, a mineral oil is employed.
  • the lubricating oil may generally comprise greater than 60, typically greater than 70, mass % of the composition, and typically have a kinematic viscosity at 100°C of from 2 to 40, for example from 3 to 15, mm 2 s -1 and a viscosity index of from 80 to 100, for example from 90 to 95.
  • hydrocracked oils Another class of lubricating oils is hydrocracked oils, where the refining process further breaks down the middle and heavy distillate fractions in the presence of hydrogen at high temperatures and moderate pressures.
  • Hydrocracked oils typically have kinematic viscosity at 100°C of from 2 to 40, for example from 3 to 15, mm 2 s -1 and a viscosity index typically in the range of from 100 to 110, for example from 105 to 108.
  • 'brightstock' refers to base oils which are solvent-extracted, de-asphalted products from vacuum residuum generally having a kinematic viscosity at 100°C of from 28 to 36 mm 2 s -1 and are typically used in a proportion of less than 30, preferably less than 20, more preferably less than 15, most preferably less than 10, such as less than 5, mass %, based on the mass of the composition.
  • a dispersant is an additive for a lubricating composition whose primary function is to hold solid and liquid contaminants in suspension, thereby passivating them and reducing engine deposits at the same time as reducing sludge depositions.
  • a dispersant maintains in suspension oil-insoluble substances that result from oxidation during use of the lubricant, thus preventing sludge flocculation and precipitation or deposition on metal parts of the engine.
  • Ashless means that the dispersant is a non-metallic organic material that forms substantially no ash on combustion, in contrast to metal-containing, hence ash-forming, materials.
  • Ashless dispersants comprise a long chain hydrocarbon with a polar head, the polarity being derived from inclusion of, e.g. an O, P or N atom.
  • the hydrocarbon is an oleophilic group that confers oil-solubility, having, for example 40 to 500 carbon atoms.
  • ashless dispersants may comprise an oil-soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
  • the dispersants comprise amine, alcohol, amide, or ester polar moieties attached to the polymer backbone often via a bridging group.
  • the ashless dispersant may be, for example, selected from oil-soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon-substituted mono- and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of long chain hydrocarbons; long chain aliphatic hydrocarbons having a polyamine attached directly thereto, and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine, such as described in US-A-3,442,808.
  • the oil-soluble polymeric hydrocarbon backbone is typically an olefin polymer or polyene, especially polymers comprising a major molar amount (i.e., greater than 50 mole %) of a C 2 to C 18 olefin (e.g., ethylene, propylene, butylene, isobutylene, pentene, octene-1, styrene), and typically a C 2 to C 5 olefin.
  • a C 2 to C 18 olefin e.g., ethylene, propylene, butylene, isobutylene, pentene, octene-1, styrene
  • the oil-soluble polymeric hydrocarbon backbone may be a homopolymer (e.g., polypropylene or polyisobutylene) or a copolymer of two or more of such olefins (e.g., copolymers of ethylene and an alpha-olefin such as propylene or butylene, or copolymers of two different alpha-olefins).
  • a homopolymer e.g., polypropylene or polyisobutylene
  • a copolymer of two or more of such olefins e.g., copolymers of ethylene and an alpha-olefin such as propylene or butylene, or copolymers of two different alpha-olefins.
  • copolymers include those in which a minor molar amount of the copolymer monomers, e.g., 1 to 10 mole %, is an ⁇ , ⁇ -diene, such as a C 3 to C 22 non-conjugated diolefin (e.g., a copolymer of isobutylene and butadiene, or a copolymer of ethylene, propylene and 1,4-hexadiene or 5-ethylidene-2-norbornene).
  • Atactic propylene oligomers typically having an M n of from 700 to 5000 may also be used, as described in EP-A-490454, as well as heteropolymers such as polyepoxides.
  • a preferred class of olefin polymers is polybutenes, specifically polyisobutenes (PIB) or poly-n-butenes, such as may be prepared by polymerization of a C 4 refinery stream.
  • Other preferred classes of olefin polymers are ethylene alpha-olefin (EAO) copolymers and alpha-olefin homo- and copolymers having in each case a high degree (e.g., >30%) of terminal vinylidene unsaturation, such as described in WO-94/13709, which may be functionalised and aminated to give dispersants.
  • EAO ethylene alpha-olefin
  • Dispersants include, for example, derivatives of long chain hydrocarbon-substituted carboxylic acids, examples being derivatives of high molecular weight hydrocarbyl-substituted succinic acid.
  • a noteworthy group of dispersants are hydrocarbon-substituted succinimides, made, for example, by reacting the above acids (or derivatives) with a nitrogen-containing compound, advantageously a polyalkylene polyamine, such as a polyethylene polyamine.
  • reaction products of polyalkylene polyamines with alkenyl succinic anhydrides such as described in US-A-3,202,678; -3,154,560; -3,172,892; - 3,024,195, -3,024,237; -3,219,666; and -3,216,936; and BE-A-66,875 that may be post-treated to improve their properties, such as borated (as described in US-A-3,087,936 and -3,254,025), fluorinated and oxylated.
  • boration may be accomplished by treating an acyl nitrogen-containing dispersant with a boron compound selected from boron oxide, boron halides, boron acids and esters of boron acids.
  • a detergent is an additive that reduces formation of piston deposits, for example high-temperature varnish and lacquer deposits, in engines; it normally has acid-neutralising properties and is capable of keeping finely divided solids in suspension.
  • Most detergents are based on metal "soaps", that is metal salts of acidic organic compounds, sometimes referred to as surfactants.
  • Detergents generally comprise a polar head with a long hydrophobic tail, the polar head comprising a metal salt of an acidic organic compound.
  • Large amounts of a metal base are included by reacting an excess of a metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide to give an overbased detergent which comprises neutralised detergent as the outer layer of a metal base (e.g. carbonate) micelle.
  • the overbased detergents of this invention may have a TBN of at least 200, preferably at least 250, especially at least 300, such as up to 600.
  • Surfactants that may be used, in addition to salicylate, include sulfonates, phenates, sulfurized phenates, thiophosphonates, and naphthenates and other oil-soluble carboxylates. Sulfurized phenates are preferred.
  • the metal may be an alkali or alkaline earth metal, e.g., sodium, potassium, lithium, calcium, and magnesium. Calcium is preferred.
  • Surfactants for the surfactant system of the overbased metal compounds preferably contain at least one hydrocarbyl group, for example, as a substituent on an aromatic ring.
  • hydrocarbyl as used herein means that the group concerned is primarily composed of hydrogen and carbon atoms and is bonded to the remainder of the molecule via a carbon atom, but does not exclude the presence of other atoms or groups in a proportion insufficient to detract from the substantially hydrocarbon characteristics of the group.
  • hydrocarbyl groups in surfactants for use in accordance with the invention are aliphatic groups, preferably alkyl or alkylene groups, especially alkyl groups, which may be linear or branched. The total number of carbon atoms in the surfactants should be at least sufficient to impart the desired oil-solubility.
  • Salicylate surfactants used in accordance with the invention may be non-sulfurized or sulfurized, and may be chemically modified and/or contain additional substituents, for example, as discussed below for phenates. Processes similar to those described below may also be used for sulfurizing a hydrocarbyl-substituted salicylic acid, and are well known to those skilled in the art. Salicylic acids are typically prepared by the carboxylation, by the Kolbe-Schmitt process, of phenoxides, and in that case, will generally be obtained (normally in a diluent) in admixture with uncarboxylated phenol.
  • Preferred substituents in oil-soluble salicylic acids from which salicylates in accordance with the invention may be derived are the substituents represented by R in the discussion below of phenols.
  • the alkyl groups advantageously contain 5 to 100, preferably 9 to 30, especially 14 to 20, carbon atoms.
  • Phenate surfactants for use in this invention may be non-sulfurized or, preferably, sulfurized.
  • phenate includes those containing more than one hydroxyl group (for example, from alkyl catechols) or fused aromatic rings (for example, alkyl naphthols) and those which have been modified by chemical reaction, for example, alkylene-bridged and Mannich base-condensed and saligenin-type (produced by the reaction of a phenol and an aldehyde under basic conditions).
  • Preferred phenols on which the phenate surfactants are based may be derived from the formula I below: where R represents a hydrocarbyl group and y represents 1 to 4. Where y is greater than 1, the hydrocarbyl groups may be the same or different.
  • Sulfurized hydrocarbyl phenols may typically be represented by the formula II below: where x is generally from 1 to 4. In some cases, more than two phenol molecules may be linked by S x , bridges.
  • hydrocarbyl groups represented by R are advantageously alkyl groups, which advantageously contain 5 to 100, preferably 5 to 40, especially 9 to 12, carbon atoms, the average number of carbon atoms in all of the R groups being at least about 9 in order to ensure adequate solubility in oil.
  • Preferred alkyl groups are nonyl (tripropylene) groups.
  • hydrocarbyl-substituted phenols will for convenience be referred to as alkyl phenols.
  • a sulfurizing agent for use in preparing a sulfurized phenol or phenate may be any compound or element which introduces -(S) x - bridging groups between the alkyl phenol monomer groups, wherein x is generally from 1 to about 4.
  • the reaction may be conducted with elemental sulfur or a halide thereof, for example, sulfur dichloride or, more preferably, sulfur monochloride. If elemental sulfur is used, the sulfurization reaction may be effected by heating the alkyl phenol compound at from 50 to 250, preferably at least 100, °C. The use of elemental sulfur will typically yield a mixture of bridging groups -(S) X - as described above.
  • the sulfurization reaction may be effected by treating the alkyl phenol at from -10 to 120, preferably at least 60, °C.
  • the reaction may be conducted in the presence of a suitable diluent.
  • the diluent advantageously comprises a substantially inert organic diluent, for example mineral oil or an alkane.
  • the reaction is conducted for a period of time sufficient to effect substantial reaction. It is generally preferred to employ from 0.1 to 5 moles of the alkyl phenol material per equivalent of sulphurizing agent.
  • sulfurizing agent it may be desirable to use a basic catalyst, for example, sodium hydroxide or an organic amine, preferably a heterocyclic amine (e.g., morpholine).
  • a basic catalyst for example, sodium hydroxide or an organic amine, preferably a heterocyclic amine (e.g., morpholine).
  • sulfurized alkyl phenols useful in preparing overbased metal compounds generally comprise diluent and unreacted alkyl phenols and generally contain from 2 to 20, preferably 4 to 14, most preferably 6 to 12, mass % of sulfur, based on the mass of the sulfurized alkyl phenol.
  • phenol as used herein includes phenols which have been modified by chemical reaction with, for example, an aldehyde, and Mannich base-condensed phenols.
  • Aldehydes with which phenols may be modified include, for example, formaldehyde, propionaldehyde and butyraldehyde.
  • the preferred aldehyde is formaldehyde.
  • Aldehyde-modified phenols suitable for use are described in, for example, US-A-5 259 967.
  • Mannich base-condensed phenols are prepared by the reaction of a phenol, an aldehyde and an amine. Examples of suitable Mannich base-condensed phenols are described in GB-A-2 121 432.
  • the phenols may include substituents other than those mentioned above provided that such substituents do not detract significantly from the surfactant properties of the phenols.
  • substituents are methoxy groups and halogen atoms.
  • the detergent may, for example, be a complex comprising an overbased mixture of a sulfurised calcium alkyl phenate and a calcium alkyl salicylate, e.g. a hybrid material in which the phenate and salicylate surfactant groups are incorporated during the overbasing process.
  • hybrid materials include:
  • the TBN of the hybrid material is at least 330, such as at least 350, more preferably at least 400, most preferably in the range of from 400 to 600, such as up to 500.
  • the amount of overbased metal compound in a lubricant composition is at least 0.5 mass %, based on the active ingredient, particularly in the range of from 0.5 to 20 mass %, based on the mass of the composition, such as from 2 to 12, e.g. 2 to 7, mass %.
  • the percentage of surfactant in the overbased calcium detergent, and the percentages of the individual surfactants, for example, phenol, in the surfactant system, are the percentages measured by the method set out below.
  • a known amount (A g, approximately 20 g) of the liquid overbased calcium detergent compound (substantially free from other lubricating oil additives) is dialysed through a membrane in a Soxhlet extractor (150 mm height x 75 mm internal diameter) using n-hexane siphoning at a rate of 3 to 4 times per hour for 20 hours.
  • the membrane should be one which retains substantially all the metal-containing material, and passes substantially all the remainder of the sample.
  • An example of a suitable membrane is a gum rubber membrane supplied by Carters Products, Division of Carter Wallace Inc., New York, NY 10105 under the trade name Trojans.
  • the dialysate and residue obtained on completion of the dialysis step are evaporated to dryness, any remaining volatile material then being removed in a vacuum oven (100°C at less than 1 torr or less than about 130 Pa).
  • the mass of the dried residue, in grams, is designated B.
  • a known amount (D g, approximately 10 g) of the dried residue is hydrolyzed as specified in sections 8.1 to 8.1.2 of ASTM D3712, except that at least 200 ml of 25 % by volume hydrochloric acid (sp. gr. 1.18) is used in section 8.1.1.
  • the amount of hydrochloric acid used should be sufficient to effect acidification/hydrolysis of the overbased detergent residue into organic materials (surfactants) and inorganic materials (calcium-containing materials, for example, calcium chloride).
  • the combined ether extracts are dried by passing them through anhydrous sodium sulphate. The sodium sulphate is rinsed with clean ether, and the combined ether solutions are evaporated to dryness (at approximately 110°C) to yield a hydrolyzed residue.
  • the mass of the dried hydrolyzed residue, in grams, is designated E.
  • the techniques described below isolate the individual surfactants, in hydrolyzed form, from the hydrolyzed surfactant mixture derived from the overbased detergent.
  • the proportion of each individual surfactant is the proportion by mass of the individual surfactant, in hydrolyzed form, in the hydrolyzed surfactant mixture.
  • the overbased detergent contains a calcium phenate/sulphonate/salicylate surfactant system
  • the proportions of the individual surfactants in the surfactant system are expressed as the proportions of phenol, sulphonic acid and salicylic acid respectively
  • the proportions of individual surfactants may be determined by the following method.
  • a known amount (F g, approximately 1 g) of the dried hydrolyzed residue obtained as described above is placed at the top of a 450 x 25 mm (internal diameter) fritted glass column filled with 60-100 US mesh Florisil.
  • Florisil is magnesium silicate with a CAS number of 8014-97-9.
  • the column is eluted with a 250 ml portion of each of seven solvents of increasing polarity, namely, heptane, cyclohexane, toluene, ethyl ether, acetone, methanol, and, lastly, a mixture of 50 volume % chloroform, 44 volume % isopropanol, and 6 volume % ammonia solution (sp. gr. 0.88).
  • Each fraction is collected, evaporated to dryness, and the resulting residue is weighed and then analyzed to determine the amount (G 1 , G 2 , G 3 ... g) and nature of the surfactant(s) contained in
  • Analysis of the fractions can be carried out by, for example, chromatographic, spectroscopic, and/or titration (colour indicator or potentiometric) techniques known to those skilled in the art.
  • the overbased detergent contains a sulphonate surfactant and a salicylate surfactant
  • the sulphonic acid and salicylic acid obtained by hydrolysis of these surfactants will usually be eluted from the column together.
  • the proportion of sulphonic acid in the mixture can be determined by the method described by Epton in Trans.Far.Soc. April 1948, 226.
  • the mass (in grams, designated H 1 ) of a given surfactant, in hydrolyzed form is determined from the fraction(s) containing it, and thus the proportion of that surfactant in the surfactant system of the original overbased detergent is H 1 F x 100%
  • the percentages (by mass) of the individual surfactants (in their free form, that is, not in the form of a salt or other derivative) based on the surfactant system can be predicted from the proportions of the surfactants used as starting materials, provided that the percentage of 'reactive ingredient' (r.i.) is known for each of the surfactant starting materials.
  • the percentage of the total surfactants (in their free form) in the liquid overbased product can then be predicted, and the TBN : % surfactant ratio can be determined.
  • the term 'reactive ingredient' is the percentage by mass of surfactant that will be associated with the metal calcium.
  • the detergent may, for example, comprise a sulphurized and then overbased mixture of a calcium alkyl phenate and a calcium alkyl salicylate: an example is described in EP-A-750,659, namely a detergent-dispersant additive for lubricating oil of the sulfurised and superalkalinised, alkaline earth alkylsalicylate-alkylphenate type, characterised in that:
  • sulfur-containing antioxidants examples include 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, phosphosulfurized or sulfurized hydrocarbons, phosphorus esters and other sulfur-containing molybdenum-containing compounds.
  • sulfur-containing antioxidants are metal salts of dihydrocarbyl dithiophosphate or dihydrocarbyl dithiocarbamate compounds, wherein the metal is selected from Zn, Mn, Ni, Al, Group 1 metals and Group 2 metals.
  • sulfur-containing compounds include those described in EP-A-699 759, for example, sulfides of oils, fats or polyolefins, in which a sulfur group having two or more sulfur atoms is ajoined and bonded together in a molecular structure.
  • sulfurized sperm oil sulfurized pinene oil, sulfurized soybean oil, sulfurixed polyolefin, sulfurized esters, dialkyl disulfide, dialkyl polysulfide, dibenzyl disulfide, ditertiary butyl disulfide, polyolefine polysulfide, thiadiazole type compound such as bis-alkyl polysulfide thiadiazole, and sulfurized phenol.
  • sulfurized alkyl phenols described above in connection with the preparation of phenate surfactants such as represented by formula II.
  • Phenolic anti-oxidants include those known in the art.
  • aromatic amine-containing antioxidants are aromatic amines which have at least one aromatic group directly attached to at least one amine nitrogen atom. Secondary aromatic amines, especially those having two aromatic groups attached to the same amine nitrogen atom, are preferred, but the use of other aromatic amines is not excluded.
  • the amines may contain one or more aromatic groups, for example at least two aromatic groups. Where two aromatic groups are present, both are preferably bonded directly to the same amine nitrogen.
  • Compounds in which two aromatic groups are linked by a covalent bond or by an atom or group e.g., an oxygen or sulfur atom, or a -CO-, -SO 2 - or alkylene group
  • an atom or group e.g., an oxygen or sulfur atom, or a -CO-, -SO 2 - or alkylene group
  • Aromatic rings which are preferably hydrocarbon, may be unsubstituted or substituted by one or more substituents selected from alkyl, cycloalkyl, alkoxy, aryloxy, acyl, acylamino, hydroxy, and nitro groups.
  • Amines containing alkyl-substituted aromatic hydrocarbon rings are preferred, especially those containing two alkyl- substituted phenyl groups.
  • Preferred N-aryl amines are naphthylamines and, especially, diphenylamines, including alkyl substituted diphenylamines, wherein the alkyl group may be the same or different and have 1 to 28 carbon atoms.
  • Other nitrogen- containing antioxidants for example, phenothiazine type compounds, may also be used.
  • additives may be incorporated into the lubricating oil compositions of the invention provided they are different from the additives defined in the invention. They may, for example, include dispersants; detergents, e.g. single or mixed detergent systems; rust inhibitors; anti-wear agents; anti-oxidants; corrosion inhibitors; friction modifiers or friction reducing agents; pour point depressants; anti-foaming agents; viscosity modifiers; and surfactants.
  • Typical proportions for additives for a TPEO are as follows: Additive Mass % a.i. (Broad) Mass % a.i. (Preferred) Detergent(s) 0.5-15 2-7 Dispersant(s) 0.5-5 1-3 Anti-wear agent(s) 0.1-1.5 0.5-1.3 Anti-oxidant 0.1-3 0.5-1.5 Rust inhibitor 0.03-0.15 0.05-0.1 Pour point depressant 0.03-0.15 0.05-0.1 Mineral or synthetic base oil Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance
  • Typical proportions for additives for a MDCL are as follows: Additive Mass % a.i. (Broad) Mass % a.i. (Preferred) Detergent(s) 1-25 3-12 Dispersant(s) 0.5-5 1-3 Anti-wear agent(s) 0.1-1.5 0.5-1.3 Anti-oxidant 0.1-5 0.5-3 Pour point depressant 0.03-0.15 0.05-0.1 Mineral or synthetic base oil Balance Balance
  • additive package(s) When a plurality of additives are employed it may be desirable, although not essential, to prepare one or more additive packages or concentrates comprising the additives, whereby several additives can be added simultaneously to the base oil to form the lubricating oil composition. Dissolution of the additive package(s) into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential.
  • the additive package(s) will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration, and/or to carry out the intended function, in the final formulation when the additive package(s) is/are combined with a predetermined amount of base lubricant.
  • components a) and b) in accordance with the present invention may be admixed with small amounts of base oil or other compatible solvents together with other desirable additives to form additive packages containing active ingredients in an amount, based on the additive package, of, for example, from 2.5 to 90, preferably from 5 to 75, most preferably from 8 to 60, mass % by weight, additives in the appropriate proportions, the remainder being base oil.
  • the final formulations may typically contain about 5 to 40 mass % of the additive package(s) with the remainder being base oil.
  • 'active ingredient' refers to the additive material that is not diluent.
  • 'oil-soluble' or 'oil-dispersible' do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
  • the lubricant compositions of this invention comprise defined individual (i.e. separate) components that may or may not remain the same chemically before and after mixing.
  • Toluene (490 g), methanol (330 g), water (30 g) and 150N diluent oil (22 g) were introduced into a reactor and mixed while maintaining the temperature at approximately 20°C.
  • Calcium hydroxide (Ca(OH) 2 ) 150 g was added, and the mixture was heated to 40°C, with stirring.
  • To the slurry obtained in this way was added a mixture, maintained at 40°C, of phenol surfactant (127 g), sulphonic acid surfactants (98 g), as specified below, and toluene (100 g) followed by a further quantity (50 g) of toluene.
  • a salicylic acid surfactant (172g) was introduced into the mixture.
  • the temperature of the mixture was reduced to approximately 28°C and was maintained at approximately 28°C while carbon dioxide (62 g) was injected into the mixture at a rate such that substantially all the carbon dioxide was absorbed in the reaction mixture to form the basic material.
  • the temperature was then raised to 60°C over 60 minutes, following which the mixture was cooled to a temperature of approximately 28°C over 30 minutes.
  • a further quantity of calcium hydroxide (122 g) was added and carbon dioxide (62 g) was charged. After this second carbonation step, the temperature was raised to 60°C over 90 minutes.
  • Lubricant compositions as marine diesel lubricating oils were prepared by admixing with a basestock the component X and components P to U, as identified above. The admixing was carried out by blending at elevated temperature. The composition contained the following proportions by mass %: X 11.4; Q 7.5; R 7.5; P 2.22.
  • the lubricating composition was tested by periodically sampling and measuring its kinematic viscosity at 100°C according to the method ASTM D445 during use of the composition to lubricate marine diesel engine. Tests were carried out on two different medium speed trunk piston marine diesel engines.
  • the detergent there may be used one where the surfactant system is derived from a 2-hydroxybenzene sulfonic acid or from an alkaryl ethanoic acid, e.g. in the form of their calcium salts, and/or as an anti-oxidant, there may be used a zinc dihydrocarbyl dithiophosphate (ZDDP).
  • ZDDP zinc dihydrocarbyl dithiophosphate

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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)
EP00201236A 1999-04-17 2000-04-04 Compositions lubrifiantes pour la lubrification d'un moteur diesel marin Expired - Lifetime EP1046698B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9908771.0A GB9908771D0 (en) 1999-04-17 1999-04-17 Lubricity oil composition
GB9908771 1999-04-17

Publications (2)

Publication Number Publication Date
EP1046698A1 true EP1046698A1 (fr) 2000-10-25
EP1046698B1 EP1046698B1 (fr) 2002-06-19

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EP (1) EP1046698B1 (fr)
JP (1) JP4384784B2 (fr)
KR (1) KR100648792B1 (fr)
CN (1) CN1177915C (fr)
AT (1) ATE219510T1 (fr)
CA (1) CA2303660C (fr)
DE (1) DE60000219T2 (fr)
ES (1) ES2174795T3 (fr)
GB (1) GB9908771D0 (fr)
SG (1) SG77283A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1191088A1 (fr) * 2000-09-22 2002-03-27 Infineum International Limited Lubrification d'un moteur à piston plongeur
EP1209218A1 (fr) * 2000-11-27 2002-05-29 Infineum International Limited Compositions d'huiles lubrifiantes
EP1209219A1 (fr) * 2000-11-27 2002-05-29 Infineum International Limited Compositions d'huile lubrifiante
EP1229101A1 (fr) * 2001-02-06 2002-08-07 Infineum International Limited Lubrifiant pour un moteur diesel marin
EP1229102A1 (fr) * 2001-02-06 2002-08-07 Infineum International LTD Composition d'huile lubrifiante
EP1236792A1 (fr) * 2001-02-16 2002-09-04 Infineum International LTD Additifs détergents superbasiques
WO2003048281A1 (fr) * 2001-11-29 2003-06-12 Crompton Corporation Inhibition de la croissance de la viscosite dans des concentres d'additifs d'huile
EP1486556A1 (fr) * 2003-06-13 2004-12-15 Infineum International Limited Composition d'huile lubrifiante
SG126767A1 (en) * 2003-06-13 2006-11-29 Infineum Int Ltd Lubricant composition
EP1728849A1 (fr) * 2005-05-27 2006-12-06 Infineum International Limited Procédé de lubrification des chemises de cylindre et des carters dans des moteurs marins Diesel de type à crosse

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Publication number Priority date Publication date Assignee Title
ATE320476T1 (de) * 2000-09-22 2006-04-15 Infineum Int Ltd Tauchkolbenmotorschmierung
EP1233052A1 (fr) * 2001-02-16 2002-08-21 Infineum International Limited Des additifs détergents surbasiques
EP1236791A1 (fr) * 2001-02-16 2002-09-04 Infineum International Limited Additifs surbasiques en tant que détergents
US20050119140A1 (en) * 2003-10-30 2005-06-02 Laurent Chambard Method of reducing deposit formation in a centrifuge system in a trunk piston diesel engine
US8680030B2 (en) 2005-11-18 2014-03-25 Exxonmobil Research And Engineering Company Enhanced deposit control for lubricating oils used under sustained high load conditions employing glycerine derivative with a grafted hindered phenolic and/or a hindered phenolic containing a thioether group
AU2010243817B2 (en) * 2009-05-01 2014-06-05 Infineum International Limited Marine engine lubrication
ES2620681T3 (es) * 2014-12-04 2017-06-29 Infineum International Limited Lubricación de motores marinos
CN105238524B (zh) * 2015-10-19 2018-04-13 中国石油化工股份有限公司 柴油机油组合物及用途
CN109642175B (zh) * 2016-08-29 2023-07-18 雪佛龙奥伦耐技术有限责任公司 船用柴油机汽缸润滑油组合物
CN106675701B (zh) * 2016-12-21 2019-09-20 李旺达 一种抗摩、减磨的生物质机油净化滤芯的化学添加剂及其制备方法
CN111019740A (zh) * 2018-10-10 2020-04-17 中国石油天然气股份有限公司 一种船用润滑油
EP3778841B1 (fr) * 2019-08-15 2021-11-24 Infineum International Limited Procédé de réduction de dépôts de piston dans un moteur diesel marin

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US4681694A (en) * 1985-12-23 1987-07-21 Texaco Inc. Marine crankcase lubricant
EP0662508A2 (fr) * 1994-01-11 1995-07-12 Bp Chemicals (Additives) Limited Compositions d'huile lubrifiante comprenant un détergent à base de phenate surbasique
EP0686689A2 (fr) * 1994-06-06 1995-12-13 NIPPON OIL Co. Ltd. Composition lubrifiante pour moteurs à combustion interne
EP0725129A2 (fr) * 1995-02-01 1996-08-07 The Lubrizol Corporation Composition lubrificante à faible teneur en cendre
WO1997046643A1 (fr) * 1996-05-31 1997-12-11 Exxon Chemical Patents Inc. Detergents surbasiques contenant des metaux
US5744430A (en) * 1995-04-28 1998-04-28 Nippon Oil Co., Ltd. Engine oil composition

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US4681694A (en) * 1985-12-23 1987-07-21 Texaco Inc. Marine crankcase lubricant
EP0662508A2 (fr) * 1994-01-11 1995-07-12 Bp Chemicals (Additives) Limited Compositions d'huile lubrifiante comprenant un détergent à base de phenate surbasique
EP0686689A2 (fr) * 1994-06-06 1995-12-13 NIPPON OIL Co. Ltd. Composition lubrifiante pour moteurs à combustion interne
EP0725129A2 (fr) * 1995-02-01 1996-08-07 The Lubrizol Corporation Composition lubrificante à faible teneur en cendre
US5744430A (en) * 1995-04-28 1998-04-28 Nippon Oil Co., Ltd. Engine oil composition
WO1997046643A1 (fr) * 1996-05-31 1997-12-11 Exxon Chemical Patents Inc. Detergents surbasiques contenant des metaux

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1191088A1 (fr) * 2000-09-22 2002-03-27 Infineum International Limited Lubrification d'un moteur à piston plongeur
EP1209218A1 (fr) * 2000-11-27 2002-05-29 Infineum International Limited Compositions d'huiles lubrifiantes
EP1209219A1 (fr) * 2000-11-27 2002-05-29 Infineum International Limited Compositions d'huile lubrifiante
EP1229101A1 (fr) * 2001-02-06 2002-08-07 Infineum International Limited Lubrifiant pour un moteur diesel marin
EP1229102A1 (fr) * 2001-02-06 2002-08-07 Infineum International LTD Composition d'huile lubrifiante
SG105535A1 (en) * 2001-02-06 2004-08-27 Infineum Int Ltd Lubrication
EP1236792A1 (fr) * 2001-02-16 2002-09-04 Infineum International LTD Additifs détergents superbasiques
WO2003048281A1 (fr) * 2001-11-29 2003-06-12 Crompton Corporation Inhibition de la croissance de la viscosite dans des concentres d'additifs d'huile
EP1486556A1 (fr) * 2003-06-13 2004-12-15 Infineum International Limited Composition d'huile lubrifiante
SG126767A1 (en) * 2003-06-13 2006-11-29 Infineum Int Ltd Lubricant composition
AU2004202588B2 (en) * 2003-06-13 2009-05-21 Infineum International Ltd Lubricant Composition
EP1728849A1 (fr) * 2005-05-27 2006-12-06 Infineum International Limited Procédé de lubrification des chemises de cylindre et des carters dans des moteurs marins Diesel de type à crosse
AU2006202228B2 (en) * 2005-05-27 2011-06-09 Infineum International Limited A method of lubricating a crosshead engine
AU2006202228A8 (en) * 2005-05-27 2011-06-30 Infineum International Limited A method of lubricating a crosshead engine
AU2006202228B8 (en) * 2005-05-27 2011-06-30 Infineum International Limited A method of lubricating a crosshead engine
US8377857B2 (en) 2005-05-27 2013-02-19 Infineum International Limited Method of lubricating a crosshead engine

Also Published As

Publication number Publication date
ATE219510T1 (de) 2002-07-15
CN1270997A (zh) 2000-10-25
ES2174795T3 (es) 2002-11-16
JP2000319683A (ja) 2000-11-21
CA2303660C (fr) 2008-01-15
GB9908771D0 (en) 1999-06-09
DE60000219D1 (de) 2002-07-25
JP4384784B2 (ja) 2009-12-16
KR100648792B1 (ko) 2006-11-23
CN1177915C (zh) 2004-12-01
DE60000219T2 (de) 2003-01-23
CA2303660A1 (fr) 2000-10-17
EP1046698B1 (fr) 2002-06-19
SG77283A1 (en) 2000-12-19
KR20000071686A (ko) 2000-11-25

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