Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
  • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
  • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
  • C10M145/14—Acrylate; Methacrylate
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • C10M2203/108—Residual fractions, e.g. bright stocks
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
  • C10M2209/084—Acrylate; Methacrylate
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • 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
  • C10N2020/02—Viscosity; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/52—Base number [TBN]
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines

Definitions

• This invention relates to the lubrication of 2-stroke and 4-stroke marine diesel internal combustion engines, the former usually being referred to as cross-head engines and the latter as trunk piston engines.
• Respective lubricants therefor are usually known as marine diesel cylinder lubricants (“MDCL's”) and trunk piston engine oils (“TPEO's").
• Cross-head engines are slow engines with a high to very high power range. They include two separately-lubricated parts: the piston/cylinder assembly lubricated with total-loss lubrication by a highly viscous oil (an MDCL); and the crankshaft lubricated by a less viscous lubricant, usually referred to as a system oil.
• MDCL highly viscous oil
• system oil a less viscous lubricant
• Trunk piston engines may be used in marine, power-generation and rail traction applications and have a higher speed than cross-head engines.
• a single lubricant (TPEO) is used for crankcase and cylinder lubrication. All major moving parts of the engine, i.e. the main and big end bearings, camshaft and valve gear, are lubricated by means of a pumped circulation system.
• the cylinder liners are lubricated partially by splash lubrication and partially by oil from the circulation systems that finds its way to the cylinder wall through holes in the piston skirt via the connecting rod and gudgeon pin.
• brightstock in MDCL's and TPEO's, brightstock being a high viscosity oil that is highly refined and dewaxed and that is produced from residual stocks or bottoms. It may, for example, have a kinematic viscosity at 100°C of greater than 25, usually greater than 30, mm 2 s -1 , such as a solvent-extracted, de-asphalted product from vacuum residuum generally having a kinematic viscosity at 100°C of 28-36 mm 2 s -1 .
• a problem in the art is to formulate brightstock-free MDCL's and TPEO's at reduced cost and at the same time provide improved antiwear properties.
• the present invention provides a two-stroke or four-stroke marine engine lubricating oil composition comprising an oil of lubricating viscosity in a major amount and
• the present invention comprises:-
• a viscosity modifier (B) to improve the anti-wear properties of a marine diesel cylinder lubricant of a trunk piston engine oil which includes less than 0.5 mass%, preferably less than 0.1 mass%, of brightstock; preferably brightstock is absent or is substantially absent from the marine diesel cylinder lubricant or the trunk piston engine oil;
• a method of lubricating a cross-head marine diesel engine comprising supplying the composition to the piston/cylinder assembly of the engine;
• a method of lubricating a trunk piston marine diesel engine comprising supplying the composition to the engine.
• the lubricant composition contains a major proportion of an oil of lubricating viscosity.
• Such lubricating oils may range in viscosity from light distillate mineral oils to heavy lubricating oils. Generally, the viscosity of the oil ranges from 2 to 40, such as 3 to 15, mm 2 /sec, as measured at 100°C, and a viscosity index of 80 to 100, such as 90 to 95.
• the lubricating oil may comprise greater than 60, typically greater than 70. mass % of the composition.
• Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil); liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale also serve as useful base oils.
• Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes)); alkybenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulphides and derivative, analogues and homologues thereof.
• Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyiso-propylene glycol ether having a molecular weight of 1000 or diphenyl ether of poly-ethylene glycol having a molecular weight of 1000 to 1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3 -C 8 fatty acid esters and C 13 oxo acid diester of tetraethylene glycol.
• polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide
• alkyl and aryl ethers of polyoxyalkylene polymers e.
• Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
• dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linole
• esters includes dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles oftetraethylene glycol and two moles of 2-ethylhexanoic acid.
• Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
• Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils comprise another useful class of synthetic lubricants; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes.
• oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexy
• Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
• Unrefined, refined and re-refined oils can be used in lubricants of the present invention.
• Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations; petroleum oil obtained directly from distillation; or ester oil obtained directly from esterification and used without further treatment are unrefined oils.
• MDCL Marine Diesel Cylinder Lubricant
• An MDCL may employ 10-35, preferably 13-30, most preferably 16-24, mass % of a concentrate or additive package, the remainder being base stock. It preferably includes at least 50, more preferably at least 60, even more preferably at least 70, mass % of oil of lubricating viscosity based on the total mass of MDCL. Preferably, the MDCL has a compositional TBN (using ASTM D2896) of 40-100, such as 50-60.
• Additive Mass% a.i. Broad
• Mass % a.i. Preferred detergent(s) 1-20 3-15 dispersant(s) 0.5-5 1-3 anti-wear agent(s) 0.1-1.5 0.5-1.3
• Trunk Piston Engine Oil (“TPEO)
• a TPEO may employ 7-35, preferably 10-28, more preferably 12-24, mass % of a concentrate or additives package, the remainder being base stock.
• the TPEO has a compositional TBN (using D2896) of 20-60, such as 25-55.
• Additive Mass% a.i. Broad
• Mass % a.i. Preferred detergent(s) 0.5-12 2-8 dispersant(s) 0.5-5 1-3 anti-wear agent(s) 0.1-1.5 0.5-1.3 oxidation inhibitor 0.2-2 0.5-1.5 rust inhibitor 0.03-0.15 0.05-0.1 pour point dispersant 0.03-1.15 0.05-0.1 base stock balance balance
• additive package(s) When a plurality of additives is employed it may be desirable, although not essential, to prepare one or more additive packages 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.
• compounds 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.
• a detergent is an additive that reduces formation of deposits, for example, high-temperature varnish and lacquer deposits, in engines; it has acid-neutralising properties and is capable of keeping finely divided solids in suspension. It is based on metal "soaps", that is metal salts of acidic organic compounds, sometimes referred to as surfactants.
• a detergent comprises a polar head with a long hydrophobic tail.
• 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.
• a metal compound such as an oxide or hydroxide
• an acidic gas such as carbon dioxide
• the detergent is preferably an alkali metal or alkaline earth metal additive such as an overbased oil-soluble or oil-dispersible calcium, magnesium, sodium or barium salt of a surfactant selected from phenol, sulphonic acid, carboxylic acid, salicylic acid and naphthenic acid, wherein the overbasing is provided by an oil-insoluble salt of the metal, e.g. carbonate, basic carbonate, acetate, formate, hydroxide or oxalate, which is stabilised by the oil-soluble salt of the surfactant.
• the metal of the oil-soluble surfactant salt may be the same or different from that of the metal of the oil-insoluble salt.
• the metal, whether the metal of the oil-soluble or oil-insoluble salt is calcium.
• the TBN of the detergent may be low, i.e. less than 50 mg KOH/g, medium, i.e. 50-150 mg KOH/g, or high, i.e. over 150 mg KOH/g, as determined by ASTM D2896.
• the TBN is medium or high, i.e. more than 50 TBN.
• the TBN is at least 60, more preferably at least 100, more preferably at least 150, and up to 500, such as up to 350 mg KOH/g, as determined by ASTM D2896.
• the trunk piston diesel engine lubricant composition may include at least one anti-oxidant.
• the anti-oxidant may be aminic or phenolic.
• secondary aromatic amines such as diarylamines, for example diphenylamines wherein each phenyl group is alkyl-substituted with an alkyl group having 4 to 9 carbon atoms.
• anti-oxidants there may be mentioned hindered phenols, including mono-phenols and bis-phenols.
• the anti-oxidant if present, is provided in the composition in an amount of up to 3 mass %, based on the total amount of the lubricant composition.
• pour point depressants such as pour point depressants, anti-foamants, metal rust inhibitors, pour point depressants and/or demulsifiers may be provided, if necessary.
• 'oil-soluble' or 'oil-dispersable' 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.
• additive package(s) may be prepared, although not essential, to prepare one or more additive packages or concentrates comprising the additives, whereby the additives can be added simultaneously to the oil of lubricating viscosity 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.
• the additives 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 % of additives in the appropriate proportions, the remainder being base oil.
• the final formulations may typically contain about 5 to 40 mass % of the additive packages(s), the remainder being base oil.
• a viscosity modifier (B) is additionally provided.
• ranges in the composition include 0.1 - 6, 0.1 - 5, 0.1 - 4, 0.1 - 2.5, and lower limits of 0.5 and 1 mass %.
• the polymethacrylate-based viscosity index improvers which may be used in the present invention are any type of non-dispersion type or dispersion type polymethacrylate compounds which are used as viscosity modifiers for a lubricating oil.
• R 1 is a straight chain or branched alkyl group such as methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups.
• R 2 and R 4 are each independently hydrogen or methyl.
• R 3 is a straight chain or branched alkylene group having 1 to 18 carbon atoms, such as ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, and octadecylene groups; a is 0 or 1; X 1 and X 2 are each independently an amino-or heterocyclic- residue having 1 or 2 nitrogen atoms and 0 to 2 oxygen atoms.
• X 1 and X 2 are dimethylamino, diethylamino, dipropylamino, dibutylamino, anilino, toluidino, xylidino, acetylamino, benzoilamino, morpholino, pryrolyl, pyridyl, methylpyridyl, pyrolidinyl, piperidinyl, quinonyl, pyrrolidonyl, pyrrolidono, imidazolino, and pyrazino groups.
• nitrogen-containing monomers represented by formula (2) and (3) are dimethylaminomethylmethacrylate, diethylaminomethylmethacrylate, dimethylaminoethylmethacrylate, diethylaminoethylmethacrylate, 2-methyl-5-vinylpyridine, morpholinomethylmethacrylate, morpho linoethylmethacrylate, N-vinylpyrrolidone, and mixtures thereof.
• the lower limit of the weight-average molecular weight of the polymethacrylate-based viscosity modifier, which is effective in improving the performance of an engine oil, is preferably 180,000, more preferably 190,000.
• the upper limit is preferably 500,000, more preferably 400,000.
• An engine oil composition according to the present invention may contain the polymethacrylate-based viscosity modifier in such an amount that the composition has a kinematic viscosity at 100°C of 4.0 to 9.3 mm 2 /s.
• a set of MDCL's was formulated, each containing 20.89 mass % of the same additives in the proportions and having a TBN of about 70.
• the set comprised a control consisting of additive and base oil; a reference consisting of additives, base oil and brightstock; and an inventive MDCL consisting of additives, base oil and viscosity modifier.
• the additives were additives known in the art and used in proportions known in the art for conferring MDCL properties.
• the viscosity modifier was a polymethcylate (PMA) supplied by Rohmax.
• the brightstock was a Group I bright stock with a kinematic viscosity of >20cSt at 100°C.
• the base oil was a Group 1 base oil.
• a set of TPEO's was formulated, each containing 16 mass % of the same additives in the same proportions and having a TBN of about 40.
• the set comprised a control consisting of additives and base oil; a reference consisting of additives, base oil and bright stock; and an inventive MDCL consisting of additives, base oil and viscosity modifier.
• the additives were additives known in the art and used in proportions known in the art for conferring TPEO properties.
• the viscosity modifier, brightstock and base oil were used in the MDCL's.

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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)

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Citations (7)

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• 2012
  • 2012-12-14 EP EP12197188.1A patent/EP2607465A1/fr not_active Withdrawn
  • 2012-12-20 US US13/721,153 patent/US20140005087A1/en not_active Abandoned

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