EP2607461B1 - Schmierung für einen schiffsmotor - Google Patents
Schmierung für einen schiffsmotor Download PDFInfo
- Publication number
- EP2607461B1 EP2607461B1 EP12196825.9A EP12196825A EP2607461B1 EP 2607461 B1 EP2607461 B1 EP 2607461B1 EP 12196825 A EP12196825 A EP 12196825A EP 2607461 B1 EP2607461 B1 EP 2607461B1
- Authority
- EP
- European Patent Office
- Prior art keywords
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- composition
- brightstock
- oil
- polymer
- 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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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- 239000003377 acid catalyst Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
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- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- WLLCYXDFVBWGBU-UHFFFAOYSA-N bis(8-methylnonyl) nonanedioate Chemical compound CC(C)CCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC(C)C WLLCYXDFVBWGBU-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
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- DZQISOJKASMITI-UHFFFAOYSA-N decyl-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound CCCCCCCCCCP(O)(O)=O DZQISOJKASMITI-UHFFFAOYSA-N 0.000 description 1
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- 150000005195 diethylbenzenes Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000010699 lard oil Substances 0.000 description 1
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- LQXXINHQWGDYNZ-UHFFFAOYSA-N lithium;2-methanidylprop-1-ene Chemical compound [Li+].CC([CH2-])=C LQXXINHQWGDYNZ-UHFFFAOYSA-N 0.000 description 1
- WDDLHZXDSVMNRK-UHFFFAOYSA-N lithium;3-methanidylheptane Chemical compound [Li+].CCCCC([CH2-])CC WDDLHZXDSVMNRK-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- VCPPTNDHEILJHD-UHFFFAOYSA-N lithium;prop-1-ene Chemical compound [Li+].[CH2-]C=C VCPPTNDHEILJHD-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920006216 polyvinyl aromatic Polymers 0.000 description 1
- 229920001447 polyvinyl benzene Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical class CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 150000003336 secondary aromatic amines Chemical class 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010729 system oil Substances 0.000 description 1
- 150000001911 terphenyls Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JZALLXAUNPOCEU-UHFFFAOYSA-N tetradecylbenzene Chemical class CCCCCCCCCCCCCCC1=CC=CC=C1 JZALLXAUNPOCEU-UHFFFAOYSA-N 0.000 description 1
- MQHSFMJHURNQIE-UHFFFAOYSA-N tetrakis(2-ethylhexyl) silicate Chemical compound CCCCC(CC)CO[Si](OCC(CC)CCCC)(OCC(CC)CCCC)OCC(CC)CCCC MQHSFMJHURNQIE-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ZAGXLQIHXTXRFW-UHFFFAOYSA-N tris(2-ethyl-4-methylhexyl)-tris(2-ethyl-4-methylhexyl)silyloxysilane Chemical compound CCC(C)CC(CC)C[Si](CC(CC)CC(C)CC)(CC(CC)CC(C)CC)O[Si](CC(CC)CC(C)CC)(CC(CC)CC(C)CC)CC(CC)CC(C)CC ZAGXLQIHXTXRFW-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
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
- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
- C10M143/12—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing conjugated diene
-
- 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
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01M—LUBRICATING OF MACHINES OR ENGINES IN GENERAL; LUBRICATING INTERNAL COMBUSTION ENGINES; CRANKCASE VENTILATING
- F01M9/00—Lubrication means having pertinent characteristics not provided for in, or of interest apart from, groups F01M1/00 - F01M7/00
- F01M9/02—Lubrication means having pertinent characteristics not provided for in, or of interest apart from, groups F01M1/00 - F01M7/00 having means for introducing additives to lubricant
-
- 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
- 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
- C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
-
- 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
- C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
-
- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
-
- 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
- C10N2020/073—Star shaped polymers
-
- 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
- C10N2020/075—Dendrimers
-
- 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.
- a further 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.
- star polymers such as amorphous styrene-diene copolymer in an MDCL or a TPEO enables the above problem to be overcome.
- the present invention provides a two-stroke or four-stroke marine engine lubricating oil composition comprising 50 mass % or more an oil of lubricating viscosity and
- the present invention comprises:-
- 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 of tetraethylene 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.
- 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 25-60, 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.
- This invention employs polymers comprising a core and a plurality of polymeric arms extending from the core.
- Such polymers are known as star-shaped polymers (or star or radial polymers).
- Examples of ranges of (B) in the composition include 0.1 - 6, 0.1 - 5, 0.1 - 4, 0.1 - 3, mass % and a lower limit of 1 mass %.
- the viscosity modifier may comprise at least one star-shaped, at least partially hydrogenated, polymer derivable, at least in part, from the polymerisation of one or more conjugated diene monomers as defined hereinbefore.
- the star-shaped polymer includes multiple arms extending from a central core; the arms being derived from the polymerisation of one or more conjugated diene monomers as defined hereinbefore, and optionally a vinyl aromatic hydrocarbon monomer as defined hereinbefore.
- the arms of the star polymer may be a homopolymer derived essentially from the polymerisation of a single conjugated diene monomer as defined herein, such as isoprene or 1,3-butadiene, particularly isoprene.
- the arms of the star polymer may be a copolymer derived essentially from the polymerisation of two or more conjugated diene monomers as defined herein, such as an isoprene and 1,3-butadiene copolymer, or a copolymer derived essentially from the polymerisation of one or more conjugated diene monomers as defined herein and a vinyl aromatic hydrocarbon monomer as defined herein, such as an isoprene-styrene copolymer, a butadiene-styrene copolymer or an isoprene-butadiene-styrene copolymer.
- derived essentially permits the inclusion of other substances not materially affecting the characteristics of the polymer to which it applies.
- derived essentially means the specified monomer and comonomers, in the case of a copolymer, are present in an amount of at least 90 %, more preferably 95 %, even more preferably greater than 99 % by mass of the polymer.
- the arms of the star polymer may also be a block copolymer, preferably a linear block copolymer, more preferably a linear diblock copolymer, such as one represented by the following general formula: A z -(B-A) y -B x wherein:
- the arms of the star polymer may also be a tapered linear block copolymer such as one represented by the following general formula: A-A/B-B wherein:
- the arms of the star polymer comprise a hydrogenated isoprene-butadiene copolymer, a hydrogenated styrene-isoprene-butadiene copolymer, a hydrogenated isoprene-styrene copolymer or a hydrogenated butadiene-styrene copolymer.
- the arms of the star polymer comprise a linear diblock copolymer as defined herein.
- the linear diblock copolymer comprises at least one block derivable predominantly from a vinyl aromatic hydrocarbon monomer as defined herein and at least one block derivable predominantly from one or more conjugated diene monomers as defined herein.
- the vinyl aromatic hydrocarbon monomer comprises styrene.
- the one or more conjugated diene monomers comprise isoprene, butadiene or a mixture thereof.
- the linear diblock copolymer is at least partially hydrogenated.
- the at least one block derivable predominantly from a vinyl aromatic hydrocarbon monomer (e.g. styrene) in the linear diblock copolymer is present in an amount of up to 35 %, even more preferably up to 25 %, most preferably 5 to 25 %, by mass based on the total mass of the linear diblock copolymer.
- a vinyl aromatic hydrocarbon monomer e.g. styrene
- the at least one block derivable from predominantly from one or more conjugated diene monomers is present in an amount of greater than 65 %, even more preferably greater than or equal to 75 %, most preferably 75 to 95 %, by mass based on the total mass of the linear diblock copolymer.
- the linear diblock copolymer comprises at least one polystyrene block and a block derived from isoprene, butadiene, or a mixture thereof.
- Highly preferred linear diblock copolymers comprise linear diblock copolymers including at least one linear diblock copolymer selected from hydrogenated styrene/isoprene diblock copolymers, hydrogenated styrene/butadiene diblock copolymers and hydrogenated styrene/isoprene-butadiene diblock copolymers.
- the linear diblock copolymer comprises at least one isoprene-butadiene block
- the block is derived predominantly from 70 to 90 mass % isoprene monomers and 30 to 10 mass % 1,3-butadiene monomers.
- the arms of the star polymer typically comprise a copolymer derived from 70 to 90 mass % isoprene monomers and 30 to 10 mass % 1,3-butadiene monomers. More preferably, the arms of the star polymer further include a vinyl aromatic hydrocarbon monomer as defined herein, particularly styrene.
- a highly preferred copolymer is derived from isoprene monomers, 1,3-butadiene monomers and a vinyl aromatic hydrocarbon monomer, especially styrene.
- the vinyl aromatic hydrocarbon monomer may be present in an amount of up to 35 mass %, preferably up to 25 mass %, based on the total mass of the copolymer.
- the arms of the star polymer are formed via anionic polymerization to form a living polymer.
- Anionic polymerization has been found to provide copolymers having a narrow molecular weight distribution (Mw/Mn), such as a molecular weight distribution of less than about 1.2
- living polymers may be prepared by anionic solution polymerization of a mixture of the conjugated diene monomers in the presence of an alkali metal or an alkali metal hydrocarbon, e.g., sodium naphthalene, as anionic initiator.
- an alkali metal or an alkali metal hydrocarbon e.g., sodium naphthalene
- the preferred initiator is lithium or a mono lithium hydrocarbon.
- Suitable lithium hydrocarbons include unsaturated compounds such as allyl lithium, methallyl lithium; aromatic compounds such as phenyl lithium, the tolyl lithiums, the xylyl lithiums and the naphthyl lithiums, and in particular, the alkyl lithiums such as methyl lithium, ethyl lithium, propyl lithium, butyl lithium, amyl lithium, hexyl lithium, 2-ethylhexyl lithium and n-hexadecyl lithium.
- Secondary-butyl lithium is the preferred initiator.
- the initiator(s) may be added to the polymerization mixture in two or more stages, optionally together with additional monomer.
- the living polymers are olefinically unsaturated.
- the solvents in which the living polymers are formed are inert liquid solvents, such as hydrocarbons e.g., aliphatic hydrocarbons such as pentane, hexane, heptane, octane, 2-ethylhexane, nonane, decane, cyclohexane, methylcyclohexane, or aromatic hydrocarbons e.g., benzene, toluene, ethylbenzene, the xylenes, diethylbenzenes, propylbenzenes. Cyclohexane is preferred. Mixtures of hydrocarbons e.g., lubricating oils, may also be used.
- hydrocarbons e.g., aliphatic hydrocarbons such as pentane, hexane, heptane, octane, 2-ethylhexane, nonane, decane, cyclohexane
- the temperature at which the polymerization is conducted may be varied within a wide range, such as from about -50°C to about 150°C, preferably from about 20°C to about 80°C.
- the reaction is suitably carried out in an inert atmosphere, such as nitrogen, and may optionally be carried out under pressure e.g., a pressure of from about 0.5 to about 10 bars.
- the concentration of the initiator used to prepare the living polymer may also vary within a wide range and is determined by the desired molecular weight of the living polymer.
- the living polymers formed via the foregoing process are reacted in an additional reaction step, with a polyalkenyl coupling agent.
- Polyalkenyl coupling agents capable of forming star polymers have been known for a number of years and are described, for example, in U.S. Patent No. 3,985,830 .
- Polyalkenyl coupling agents are conventionally compounds having at least two non-conjugated alkenyl groups. Such groups are usually attached to the same or different electron-withdrawing moiety e.g. an aromatic nucleus.
- Such compounds have the property that at least of the alkenyl groups are capable of independent reaction with different living polymers and in this respect are different from conventional conjugated diene polymerizable monomers such as butadiene, isoprene, etc.
- Pure or technical grade polyalkenyl coupling agents may be used.
- Such compounds may be aliphatic, aromatic or heterocyclic. Examples of aliphatic compounds include the polyvinyl and polyallyl acetylene, diacetylenes, phosphates and phosphates as well as dimethacrylates, e.g. ethylene dimethylacrylate. Examples of suitable heterocyclic compounds include divinyl pyridine and divinyl thiophene.
- the preferred coupling agents are polyalkenyl aromatic compounds and most preferred are the polyvinyl aromatic compounds.
- examples of such compounds include those aromatic compounds, e.g. benzene, toluene, xylene, anthracene, naphthalene and durene, which are substituted with at least two alkenyl groups, preferably attached directly thereto.
- Specific examples include the polyvinyl benzenes e.g.
- divinyl, trivinyl and tetravinyl benzenes divinyl, trivinyl and tetravinyl ortho-, meta- and para-xylenes, divinyl naphthalene, divinyl ethyl benzene, divinyl biphenyl, diisobutenyl benzene, diisopropenyl benzene, and diisopropenyl biphenyl.
- divinyl benzene containing other monomers e.g. styrene and ethyl styrene
- the coupling agents may be used in admixture with small amounts of added monomers which increase the size of the nucleus, e.g. styrene or alkyl styrene.
- the nucleus can be described as a poly(dialkenyl coupling agent/monoalkenyl aromatic compound) nucleus, e.g. a poly(divinylbenzene/monoalkenyl aromatic compound) nucleus.
- the polyalkenyl coupling agent should be added to the living polymer after the polymerization of the monomers is substantially complete, i.e. the agent should be added only after substantially all the monomer has been converted to the living polymers.
- the amount of polyalkenyl coupling agent added may vary within a wide range, but preferably, at least 0.5 mole of the coupling agent is used per mole of unsaturated living polymer. Amounts of from about 1 to about 15 moles, preferably from about 1.5 to about 5 moles per mole of living polymer are preferred. The amount, which can be added in two or more stages, is usually an amount sufficient to convert at least about 80 mass % to 85 mass % of the living polymer into star-shaped polymer.
- the coupling reaction can be carried out in the same solvent as the living polymerization reaction.
- the coupling reaction can be carried out at temperatures within a broad range, such as from 0°C to 150°C, preferably from about 20°C to about 120°C.
- the reaction may be conducted in an inert atmosphere, e.g. nitrogen, and under pressure of from about 0.5 bar to about 10 bars.
- the star polymers thus formed are characterized by a dense centre or nucleus of crosslinked poly(polyalkenyl coupling agent) and a number of arms of substantially linear unsaturated polymers extending outwardly from the nucleus.
- the number of arms may vary considerably, but is typically between about 4 and 25.
- the resulting star polymers can then be hydrogenated using any suitable means.
- a hydrogenation catalyst may be used e.g. a copper or molybdenum compound. Catalysts containing noble metals, or noble metal-containing compounds, can also be used.
- Preferred hydrogenation catalysts contain a non-noble metal or a non-noble metal-containing compound of Group VIII of the periodic Table i.e., iron, cobalt, and particularly, nickel. Specific examples of preferred hydrogenation catalysts include Raney nickel and nickel on kieselguhr.
- Particularly suitable hydrogenation catalysts are those obtained by causing metal hydrocarbyl compounds to react with organic compounds of any one of the group VIII metals iron, cobalt or nickel, the latter compounds containing at least one organic compound that is attached to the metal atom via an oxygen atom as described, for example, in U.K. Patent No. 1,030,306 .
- nickel diisopropyl salicylate nickel naphthenate, nickel 2-ethyl hexanoate, nickel di-tert-butyl benzoate, nickel salts of saturated monocarboxylic acids obtained by reaction of olefins having from 4 to 20 carbon atoms in the molecule with carbon monoxide and water in the presence of acid catalysts) or with nickel enolates or phenolates (e.g., nickel acetonylacetonate, the nickel salt of butylacetophenone).
- Suitable hydrogenation catalysts will be well known to those skilled in the art and the foregoing list is by no means intended to be exhaustive.
- the hydrogenation of the star polymer is suitably conducted in solution, in a solvent which is inert during the hydrogenation reaction.
- a solvent which is inert during the hydrogenation reaction.
- Saturated hydrocarbons and mixtures of saturated hydrocarbons are suitable.
- the hydrogenation solvent is the same as the solvent in which polymerization is conducted.
- at least 50%, preferably at least 70%, more preferably at least 90%, most preferably at least 95% by mass of the original olefinic unsaturation is hydrogenated.
- the hydrogenated star polymer may then be recovered in solid form from the solvent in which it is hydrogenated by any convenient means, such as by evaporating the solvent.
- oil e.g. lubricating oil may be added to the solution, and the solvent stripped off from the mixture so formed to provide a concentrate.
- Suitable concentrates contain from about 3 mass % to about 25 mass %, preferably from about 5 mass % to about 15 mass % of the hydrogenated star polymer VI improver.
- the star polymers useful in the practice of the present invention can have a number average molecular weight of from about 10,000 to 700,000, preferably from about 30,000 to 500,000.
- number average molecular weight refers to the number average weight as measured by Gel Permeation Chromatography ("GPC") with a polystyrene standard, subsequent to hydrogenation. It is important to note that, when determining the number average molecular weight of a star polymer using this method, the calculated number average molecular weight will be less than the actual molecular weight due to the three dimensional structure of the star polymer.
- the star polymer of the present invention is derived from about 75 % to about 90 % by mass isoprene and about 10 % to about 25 % by mass butadiene, and greater than 80 % by mass of the butadiene units are incorporated 1,4-addition product.
- the star polymer of the present invention comprises amorphous butadiene units derived from about 30 to about 80 % by mass 1,2-, and from about 20 to about 70 % by mass 1,4-incorporation of butadiene.
- the star polymer is derived from isoprene, butadiene, or a mixture thereof, and further contains from about 5 to about 35 % by mass styrene units.
- the star polymer has a Shear Stability Index (SSI) of from about 1 % to 35 % (30 cycle).
- SSI Shear Stability Index
- An example of a commercially available star polymer VI improver having an SSI equal to or less than 35 is Infineum SV200TM, available from Infineum USA L.P. and Infineum UK Ltd.
- Other examples of commercially available star polymer VI improver having an SSI equal to or less than 35 include Infineum SV250TM, Infineum SV261TM and Infineum SV270TM, also available from Infineum USA L.P. and Infineum UK Ltd.
- the viscosity modifier may be provided in an amount of from 0.01 to 20, preferably 1 to 15, mass % based on the mass of the lubricating oil composition.
- one or both types of viscosity modifiers used in the practice of the invention can be provided with nitrogen-containing functional groups that impart dispersant capabilities to the VI improver.
- nitrogen-containing functional groups can be added to a polymeric VI improver by grafting a nitrogen- or hydroxyl- containing moiety, preferably a nitrogen-containing moiety, onto the polymeric backbone of the VI improver (functionalizing).
- Processes for the grafting of a nitrogen-containing moiety onto a polymer include, for example, contacting the polymer and nitrogen-containing moiety in the presence of a free radical initiator, either neat, or in the presence of a solvent.
- the free radical initiator may be generated by shearing (as in an extruder) or heating a free radical initiator precursor, such as hydrogen peroxide.
- the amount of nitrogen-containing grafting monomer will depend, to some extent, on the nature of the substrate polymer and the level of dispersancy required of the grafted polymer. To impart dispersancy characteristics to both star and linear copolymers, the amount of grafted nitrogen-containing monomer is suitably between about 0.4 and about 2.2 mass %, preferably from about 0.5 to about 1.8 mass %, most preferably from about 0.6 to about 1.2 mass %, based on the total weight of grafted polymer.
- 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 star polymer in the form of amorphous styrene-diene copolymer.
- 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 as used in the MDCL's.
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Claims (12)
- Schmierölzusammensetzung für Zweitakt- oder Viertakt-Schiffsmotoren, die 50 Massen-% oder mehr Öl mit Schmierviskosität und(A) weniger als 50 Massen-% Additive, und(B) Viskositätsmodifizierungsmittel in Form von Polymer, das einen Kern und eine Vielzahl sich davon erstreckender polymerer Arme umfasst, in einer Menge im Bereich von 0,05 bis 6 Massen-% umfasst,wobei die Zusammensetzung weniger als 0,5 Massen-%, vorzugsweise weniger als 0,1 Massen-% Brightstock einschließt, wobei in der Zusammensetzung vorzugsweise Brightstock vollkommen fehlt, und wobei die Schmierölzusammensetzung für Zweitakt-Schiffsmotoren eine TBN von 40 bis 100 gemäß ASTM D2896 oder die Schmierölzusammensetzung für Viertakt-Schiffsmotoren eine TBN von 25 bis 60 gemäß ASTM D2896 aufweist.
- Zusammensetzung nach Anspruch 1, bei der die Arme des Polymers hydriertes Isopren-Butadien-Copolymer, hydriertes Styrol-Isopren-Butadien-Copolymer, hydriertes Isopren-Styrol-Copolymer oder hydriertes Butadien-Styrol-Copolymer umfassen.
- Zusammensetzung nach Anspruch 1 oder Anspruch 2, bei der die polymeren Arme lineares Diblockcopolymer umfassen.
- Zusammensetzung nach einem der Ansprüche 1 bis 3, bei der das Polymer ein durchschnittliches Molekulargewicht (Zahlenmittel) von 10 000 bis 700 000 aufweist, wie 30 000 bis 500 000.
- Zusammensetzung nach einem der Ansprüche 1 bis 4 in Form eines Schiffsdieselzylinderschmierstoffs.
- Zusammensetzung nach einem der Ansprüche 1 bis 4 in Form eines Tauchkolbenmotoröls.
- Verwendung eines Viskositätsmodifizierungsmittels (B) gemäß einem der Ansprüche 1 bis 4 als teilweiser oder vollständiger Ersatz für Brightstock in einem Schiffsdieselzylinderschmierstoff oder Tauchkolbenmotoröl, so dass der Schiffsdieselzylinderschmierstoff oder das Tauchkolbenmotoröl weniger als 0,5 Massen-%, vorzugsweise weniger als 0,1 Massen-% Brightstock einschließt.
- Verfahren zum Schmieren eines Kreuzkopf-Schiffsdieselmotors, bei dem der Kolben/Zylinder-Anordnung des Motors eine Zusammensetzung gemäß einem der Ansprüche 1 bis 5 zugeführt wird.
- Verfahren zum Schmieren eines Tauchkolbenschiffsdieselmotors, bei dem dem Motor eine Zusammensetzung gemäß einem der Ansprüche 1 bis 4 oder 6 zugeführt wird.
- Verfahren zum Reduzieren der Menge an Brightstock in einer Schmierölzusammensetzung für Zweitakt- oder Viertakt-Schiffsmotoren, welche 50 Massen-% oder mehr Öl mit Schmierviskosität und (A) weniger als 50 Massen-% Additive umfasst; wobei das Verfahren den Schritt umfasst, in dem teilweise oder vollständig das Brightstock durch (B) Viskositätsmodifizierungsmittel in Form von Polymer, das einen Kern und eine Vielzahl sich davon erstreckender polymerer Arme umfasst, in einer Menge im Bereich von 0,05 bis 6 Massen-% ersetzt wird; wobei die Schmierölzusammensetzung für Zweitakt- oder Viertakt-Schiffsmotoren weniger als 0,5 Massen-% Brightstock umfasst.
- Verfahren nach Anspruch 10, bei dem die Zusammensetzung weniger als 0,1 Massen-% Brightstock einschließt; wobei die Zusammensetzung vorzugsweise vollkommen frei von Brightstock ist.
- Verfahren nach einem der Ansprüche 10 oder 11, bei dem die Schmierölzusammensetzung für Zweitakt-Schiffsmotoren eine TBN von 40 bis 100 gemäß ASTM D2896 oder die Schmierölzusammensetzung für Viertakt-Schiffsmotoren eine TBN von 25 bis 60 gemäß ASTM D2896 aufweist.
Priority Applications (1)
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EP12196825.9A EP2607461B1 (de) | 2011-12-21 | 2012-12-12 | Schmierung für einen schiffsmotor |
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EP11195002 | 2011-12-21 | ||
EP12196825.9A EP2607461B1 (de) | 2011-12-21 | 2012-12-12 | Schmierung für einen schiffsmotor |
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EP2607461A1 EP2607461A1 (de) | 2013-06-26 |
EP2607461B1 true EP2607461B1 (de) | 2018-01-17 |
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US (1) | US20140005088A1 (de) |
EP (1) | EP2607461B1 (de) |
JP (2) | JP6649655B2 (de) |
KR (1) | KR102052208B1 (de) |
CN (1) | CN103173264A (de) |
AU (1) | AU2012268822B2 (de) |
CA (1) | CA2799597C (de) |
ES (1) | ES2657913T3 (de) |
SG (1) | SG191543A1 (de) |
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US9879201B2 (en) * | 2014-02-28 | 2018-01-30 | Cosmo Oil Lubricants Co., Ltd. | Engine oil composition |
BR112016024170B1 (pt) * | 2014-04-17 | 2021-11-30 | Versalis S.P.A. | Polímeros hidrogenados com uma estrutura radial tendo um núcleo à base de calixarenos, método para sua síntese e composições lubrificantes que contêm os mesmos |
US11078437B2 (en) | 2014-04-17 | 2021-08-03 | Eni S.P.A. | Hydrogenated polymers with a radial structure having a core based on calixarenes and use thereof in lubricant compositions |
EP3492569B1 (de) * | 2017-12-01 | 2022-06-08 | Infineum International Limited | Schiffsmotorschmierung |
FR3108620B1 (fr) * | 2020-03-25 | 2022-09-09 | Total Marketing Services | Utilisation de polymère styrène diène hydrogéné pour réduire les émissions de particules |
CA3176642A1 (en) * | 2020-05-13 | 2021-11-18 | Regents Of The University Of Michigan | Cysteamine for the treatment of sars-cov-2 infection |
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US5070131A (en) * | 1990-09-28 | 1991-12-03 | Shell Oil Company | Gear oil viscosity index improvers |
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US5674819A (en) * | 1995-11-09 | 1997-10-07 | The Lubrizol Corporation | Carboxylic compositions, derivatives,lubricants, fuels and concentrates |
DE69709668T2 (de) | 1996-09-24 | 2004-02-05 | Shell Internationale Research Maatschappij B.V. | Viskositätsindexverbesserungsdispergiermittel |
GB9709006D0 (en) * | 1997-05-02 | 1997-06-25 | Exxon Chemical Patents Inc | Lubricating oil compositions |
CN1147515C (zh) | 1997-10-28 | 2004-04-28 | 卡斯特罗尔有限公司 | 制备接枝共聚物的方法 |
US6339051B1 (en) | 1998-06-11 | 2002-01-15 | Mobil Oil Corporation | Diesel engine cylinder oils |
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EP2021442B1 (de) * | 2006-04-24 | 2016-08-17 | The Lubrizol Corporation | Schmiermittelzusammensetzung enthaltend sternpolymere |
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WO2009026201A1 (en) * | 2007-08-20 | 2009-02-26 | The Lubrizol Corporation | Polymers with pendant heterocyclic-containing groups and lubricating oil compositions containing same |
DE102009034983A1 (de) * | 2008-09-11 | 2010-04-29 | Infineum International Ltd., Abingdon | Verfahren zum Vermindern von Asphaltenablagerung in einem Motor |
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JP5802664B2 (ja) * | 2009-07-08 | 2015-10-28 | ザ ルブリゾル コーポレイションThe Lubrizol Corporation | 粘度調整剤として有用なポリマーブレンド |
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WO2011077811A1 (ja) * | 2009-12-24 | 2011-06-30 | Jx日鉱日石エネルギー株式会社 | クロスヘッド型ディーゼル機関用システム潤滑油組成物 |
EP2363454B1 (de) * | 2010-02-23 | 2018-09-26 | Infineum International Limited | Verwendung einer schmierölzusammensetzung |
KR20140035357A (ko) * | 2011-04-05 | 2014-03-21 | 셰브런 오로나이트 컴퍼니 엘엘씨 | 저점도 선박 실린더 윤활유 조성물 |
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- 2012-12-12 ES ES12196825.9T patent/ES2657913T3/es active Active
- 2012-12-12 EP EP12196825.9A patent/EP2607461B1/de active Active
- 2012-12-18 KR KR1020120148133A patent/KR102052208B1/ko active IP Right Grant
- 2012-12-20 SG SG2012094470A patent/SG191543A1/en unknown
- 2012-12-20 US US13/721,117 patent/US20140005088A1/en not_active Abandoned
- 2012-12-21 JP JP2012280157A patent/JP6649655B2/ja active Active
- 2012-12-21 CN CN2012105606095A patent/CN103173264A/zh active Pending
- 2012-12-21 AU AU2012268822A patent/AU2012268822B2/en active Active
- 2012-12-21 CA CA2799597A patent/CA2799597C/en active Active
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Also Published As
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KR20130072149A (ko) | 2013-07-01 |
CN103173264A (zh) | 2013-06-26 |
AU2012268822B2 (en) | 2014-02-20 |
US20140005088A1 (en) | 2014-01-02 |
KR102052208B1 (ko) | 2019-12-04 |
CA2799597C (en) | 2020-01-07 |
SG191543A1 (en) | 2013-07-31 |
JP2013129833A (ja) | 2013-07-04 |
EP2607461A1 (de) | 2013-06-26 |
CA2799597A1 (en) | 2013-06-21 |
AU2012268822A1 (en) | 2013-07-11 |
JP2018087353A (ja) | 2018-06-07 |
JP6649655B2 (ja) | 2020-02-19 |
ES2657913T3 (es) | 2018-03-07 |
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