WO2010053890A1 - Composition containing a block copolymer and a method of lubricating an internal combustion engine - Google Patents
Composition containing a block copolymer and a method of lubricating an internal combustion engine Download PDFInfo
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- WO2010053890A1 WO2010053890A1 PCT/US2009/063046 US2009063046W WO2010053890A1 WO 2010053890 A1 WO2010053890 A1 WO 2010053890A1 US 2009063046 W US2009063046 W US 2009063046W WO 2010053890 A1 WO2010053890 A1 WO 2010053890A1
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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
- C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
- C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M149/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
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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
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/04—Fatty oil fractions
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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
- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
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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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/02—Well-defined hydrocarbons
- C10M105/04—Well-defined hydrocarbons aliphatic
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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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/02—Well-defined hydrocarbons
- C10M105/06—Well-defined hydrocarbons aromatic
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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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/10—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
- C10M105/14—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms polyhydroxy
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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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/22—Carboxylic acids or their salts
- C10M105/24—Carboxylic acids or their salts having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
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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
- 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
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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
- C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
- C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
- C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M149/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
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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
- C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
- C10M151/02—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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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
- C10M153/00—Lubricating compositions characterised by the additive being a macromolecular compound containing phosphorus
- C10M153/02—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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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
- 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
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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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
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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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
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- 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
- C10N2030/26—Waterproofing or water resistance
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- 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
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- 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
- C10N2040/251—Alcohol fueled engines
Definitions
- Lubricants are often exposed to contaminant amounts of water.
- the contaminant amounts of water are believed to be caused by ingress of water through equipment seals during operation, or from combustion by-products that pass into the crankcase via blow-by.
- the water may form a second layer in the lubricant.
- emulsifiers and/or dispersants are employed. If the water concentration becomes high enough, an emulsion results. If the emulsion is unstable, the contaminant water may then cause additional difficulties such as corrosion. The corrosion may be from copper or lead bearings, or iron.
- lubricant base oils may also contain waxy components. Waxes may agglomerate and cause accumulation of crystals in a lubricant. When this occurs, problems arising include reduced low temperature oil pumpability, poorer cold temperature properties or reduced fuel economy. Accordingly, in one embodiment it may also be desirable to employ a pour point depressant that reduces wax agglomeration.
- the RAFT polymers may have a variety of architectures including diblock copolymers. All of polymers are derived from C 12-15 alkyl (meth)acrylates. There is no disclosure or teaching of linear or star polymers having emulsifier and/or pour point depressant properties.
- a hydrophobic first block having Ci_3o alkyl (meth)acrylic units wherein at least 50 wt % of the Ci_3o alkyl (meth)acrylic units are C 12-15 alkyl (meth)acrylic units, and up to 50 wt % of the Ci_3o alkyl (meth)acrylic units are C16-20 alkyl (meth)acrylic units, with the proviso that alkyl groups of the Ci_3o alkyl (meth)acrylic units have an average total number of carbon atoms of at least 8; and (b) a second block having (meth)acrylic units which further have a non- carbonyl heteroatom-containing group providing a polar group to such units, whereby said second block exhibits greater hydrophilicity than does the hydrophobic first block.
- the second block having (meth)acrylic units which further have a non- carbonyl heteroatom-containing group providing a polar group to such units, whereby said second block exhibits greater hydrophilicity than does the hydrophobic first block, may also be described as a second block having (meth)acrylic units further having a heteroatom group providing a polar group.
- the invention provides a lubricating composition comprising an oil of lubricating viscosity and a diblock copolymer, wherein the diblock copolymer comprises:
- a hydrophobic first block having Ci_3o alkyl (meth)acrylic units wherein at least 50 wt % of the Ci_3o alkyl (meth)acrylic units are C 12-15 alkyl (meth)acrylic units, and up to 50 wt % of the Ci_3o alkyl (meth)acrylic units are C 16 - 20 alkyl (meth)acrylic units, with the proviso that alkyl groups of the Ci_ 3 o alkyl (meth)acrylic units have an average total number of carbon atoms of at least 8; and
- the invention provides a diblock copolymer product (and optionally a lubricating composition) obtained/obtainable by a process comprising: (1) contacting:
- step (1) one or more Ci_3o alkyl (meth)acrylic monomer units, wherein at least 50 wt % of the Ci_3o alkyl (meth)acrylic monomer units contain C 12-15 alkyl (meth)acrylic units, and up to 50 wt % of the Ci_3o alkyl (meth)acrylic units are C16-20 alkyl (meth)acrylic units, with the proviso that alkyl groups of the Ci_3o alkyl (meth)acrylic units have an average total number of carbon atoms of at least 8, to form a polymer; wherein the process of step (1) is typically a controlled radical or other living polymerisation process with living characteristics (for instance a controlled radical polymerisation process); and at least about 50 wt % of the polymer chains from step (1) contain a reactive end group capable of reacting with a polyvalent coupling agent;
- step (2) optionally contacting the polymer of step (1) with a polymerisation inhibitor
- the C16-20 alkyl (meth)acrylic units may be C 16-18 alkyl (meth)acrylic units, or C18-20 alkyl (meth)acrylic units.
- the C16-20 alkyl (meth)acrylic units may also contain up to 10 wt % (or typically up to 5 wt %) of C 14 alkyl (meth)acrylic units.
- the C16-20 alkyl (meth)acrylic units may be in the form of a mixture of (meth)acrylic compounds having alkyl groups containing 16 to 20, or 16 to 18 carbon atoms.
- the first step of the process may be performed in the presence of a mineral oil, synthetic oil, hexane, toluene, tetrahydrofuran, or other known polymerisation solvents.
- the invention provides a diblock copolymer product (and optionally a lubricating composition) obtained/obtainable by a process comprising: (1) contacting:
- a chain transfer agent typically containing a thiocarbonyl thio group useful in RAFT polymerisation processes
- step (1) with one or more (meth)acrylic units typically at least 50 wt % or at least 75 wt % of the said units further having a heteroatom- containing group, wherein the process of step (1) is typically a controlled radical or other living polymerisation process with living characteristics; and at least about 50 wt % of the polymer chains from step (1) contain a reactive end group capable of reacting with a polyvalent coupling agent;
- step (3) optionally mixing the polymer of step (3) with an oil of lubricating viscosity to form a lubricating composition.
- the invention provides a method of lubricating a flexible fuel vehicle (flex fuel vehicle or FFV) internal combustion engine comprising supplying to the engine a lubricating composition comprising an oil of lubricating viscosity and a block copolymer, wherein the block copolymer comprises:
- the flexible fuel vehicle may be fuelled with gasoline typically containing 5 wt % to 85 wt %, or 10 wt % up to 85 wt %, or 15 wt % to up to 85 wt % alcohol.
- the alcohol may for instance be ethanol.
- the invention provides a method of lubricating an internal combustion engine comprising supplying to the engine a lubricating composition comprising an oil of lubricating viscosity and a block copolymer, wherein the block copolymer comprises:
- Ci_3o alkyl (meth)acrylic units (a) a hydrophobic first block having Ci_3o alkyl (meth)acrylic units, wherein at least 50 wt % of the Ci_3o alkyl (meth)acrylic units are C 12-15 alkyl (meth)acrylic units, and up to 50 wt % of the Ci_3o alkyl (meth)acrylic units are C16-20 alkyl (meth)acrylic units, with the proviso that alkyl groups of the Ci_3o alkyl (meth)acrylic units have an average total number of carbon atoms of at least 8; and
- the invention provides for the use of a block copolymer comprising:
- Ci_3o alkyl (meth)acrylic units (a) a hydrophobic first block having Ci_3o alkyl (meth)acrylic units, wherein at least 50 wt % of the Ci_3o alkyl (meth)acrylic units are C 12-15 alkyl (meth)acrylic units, and up to 50 wt % of the Ci_3o alkyl (meth)acrylic units are C16-20 alkyl (meth)acrylic units, with the proviso that alkyl groups of the Ci_3o alkyl (meth)acrylic units have an average total number of carbon atoms of at least 8; and
- the block copolymer may be an emulsifier and/or pour point depressant in an internal combustion engine.
- Emulsifier properties may occur for any block copolymer composition of the present invention.
- Emulsifier and pour point depressant properties typically occur when the diblock block copolymer contains C16-20 alkyl (meth)acrylic units, and C 12-
- the lubricating composition may be further characterised as having at least one of (i) a sulphur content of 0.8 wt % or less,
- the lubricating composition further includes at least one of a friction modifier, a viscosity modifier, an antioxidant, an overbased detergent, a succinimide dispersant, a pour point depressant, or mixtures thereof.
- the lubricating composition further includes a viscosity modifier and an overbased detergent.
- the present invention provides a lubricating composition and a method for lubricating a mechanical device as disclosed above.
- the mechanical device may be an internal combustion engine.
- the molecular weight of the block copolymer has been determined using known methods, such as GPC analysis using polystyrene standards. Methods for determining molecular weights of polymers are well known. The methods are described for instance: (i) P.J. Flory, “Principles of Polymer Chemistry", Cornell University Press 91953), Chapter VII, pp 266-315; or (ii) "Macromolecules, an Introduction to Polymer Science", F. A. Bovey and F. H. Winslow, Editors, Academic Press (1979), pp 296-312. [0041]
- the block copolymer may be a diblock, a triblock, or a higher block copolymer.
- the diblock copolymer may have a AB composition, where A is a hydrophobic unit, and B is a hydrophilic unit.
- the weight average molecular weight of the block copolymer may be in the range of 1000 to 400,000, or 1000 to 150,000, or 15,000 to 100,000.
- the weight ratio of the second block to the first block may be in the range of 1 :2 to 1 : 100, or 1 :4 to 1 :30, or 1 :6 to 1 : 18.
- the length of the first block to the second block may have a ratio of 10: 1 to 1 : 10, or 6: 1 to 1 :2.
- Ci_3o alkyl (meth)acrylic units may be derived from an alkyl (meth)acrylate.
- the alkyl (meth)acrylate includes for example compounds derived from saturated alcohols, such as methyl methacrylate, butyl methacrylate, 2-methylpentyl (meth)acrylate, 2-propylheptyl (meth)acrylate, 2-butyloctyl (meth)acrylate, 2-ethylhexyl (meth) aery late, octyl (meth)acrylate, nonyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, 2-tert-butyl- heptyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (methacrylate, 2-methyldodecyl (meth)acrylate, tridecyl
- the alkyl (meth)acrylates with long-chain alcohol-derived groups may be obtained, for example, by reaction of a (meth)acrylic acid (by direct esterification) or methyl methacrylate (by transesterification) with long-chain fatty alcohols, in which reaction a mixture of esters such as (meth)acrylate with alcohol groups of various chain lengths is generally obtained.
- These fatty alcohols include Oxo Alcohol® 7911, Oxo Alcohol® 7900 and Oxo Alcohol®
- the block copolymer may be a methacrylate polymer.
- the hydrophobic first block may contain 70 wt % or more, or 80 wt
- the hydrophobic first block may contain up to 30 wt %, or up to 20 wt % of the Ci_3o alkyl (meth)acrylic units containing C16-20 alkyl (meth)acrylic units.
- the hydrophobic first block contains Ci_ 3 o alkyl
- the hydrophobic first block contains Ci_ 3 o alkyl
- Ci_3o alkyl (meth)acrylic units wherein at least 80 wt % of the Ci_3o alkyl (meth)acrylic units may be C 12-15 alkyl (meth)acrylic units, and up to 20 wt % of the Ci_3o alkyl (meth)acrylic units are C16-20 alkyl (meth)acrylic units, with the proviso that alkyl groups of the Ci_3o alkyl (meth)acrylic units have an average total number of carbon atoms of at least 8 (or at least 10 carbon atoms).
- the hydrophobic first block contains Ci_3o alkyl (meth)acrylic units, wherein at least 50 wt % to 99 wt % of the Ci_3o alkyl (meth)acrylic units are C 12-15 alkyl (meth)acrylic units, and 1 up to 50 wt % of the Ci_3o alkyl (meth)acrylic units are C16-20 alkyl (meth)acrylic units, with the proviso that alkyl groups of the Ci_3o alkyl (meth)acrylic units have an average total number of carbon atoms of at least 8 (or at least 10 carbon atoms).
- the hydrophobic first block contains Ci_3o alkyl (meth)acrylic units, wherein at least 75 wt % to 95 wt % of the Ci_3o alkyl (meth)acrylic units are C 12-15 alkyl (meth)acrylic units, and 5 up to 25 wt % of the Ci_3o alkyl (meth)acrylic units are C16-20 alkyl (meth)acrylic units, with the proviso that alkyl groups of the Ci_3o alkyl (meth)acrylic units have an average total number of carbon atoms of at least 8 (or at least 10 carbon atoms).
- the hydrophobic first block contains Ci_3o alkyl (meth)acrylic units, wherein at least 80 wt % to 95 wt % of the Ci_3o alkyl (meth)acrylic units are C 12-15 alkyl (meth)acrylic units, and 1 up to 20 wt % of the Ci_3o alkyl (meth)acrylic units are C16-20 alkyl (meth)acrylic units, with the proviso that alkyl groups of the Ci_3o alkyl (meth)acrylic units have an average total number of carbon atoms of at least 8 (or at least 10 carbon atoms).
- the second block having (meth)acrylic units have a heteroatom- containing group providing the polar group, with the heteroatom including sulphur, nitrogen, non-carbonyl oxygen, phosphorus, or mixtures thereof.
- the heteroatom may be nitrogen.
- non-carbonyl oxygen is not meant to exclude the presence of a carbonyl oxygen, but rather to indicate that if such is present , there will also be a heteroatom that is not a carbonyl oxygen (that is, neither an oxygen atom of an aldehyde, ketone or either oxygen atoms of a carboxylic acid or ester).
- the copolymer of the invention further includes a heteratom group derived from a nitrogen or oxygen containing group.
- the group may be derived from a nitrogen or oxygen containing compound capable of being incorporated during copolymerisation.
- the nitrogen or oxygen containing group may be derived from an aminoalkyl (meth)acrylamide or a nitrogen containing (meth)acrylate monomer that may be represented by the formula: wherein
- Q is hydrogen or methyl and, in one embodiment, Q is methyl
- Z is an N-H group or an NR 2 group or O (oxygen); each R 2 is independently hydrogen or a hydrocarbyl group containing 1 to 8, or 1 to 4 carbon atoms; each R 1 is independently hydrogen or a hydrocarbyl group containing 1 to 2 carbon atoms and, in one embodiment, each R 1 is hydrogen; and g is an integer in ranges including 1 to 6, or 1 to 3.
- suitable nitrogen-containing compounds capable of being incorporated into the copolymer include N,N-dimethylacrylamide, N-vinyl carbonamides (such as, N-vinyl-formamide, N-vinylacetoamide, N-vinyl propionamides, N-vinyl hydroxyacetoamide, vinyl pyridine, N-vinyl imidazole, N-vinyl pyrrolidinone, N-vinyl caprolactam, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminobutylacrylamide, dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate, dimethyl- aminopropylacrylamide, dimethylaminopropylmethacrylamide, dimethylamino- ethylacrylamide or mixtures thereof.
- N-vinyl carbonamides such as, N-vinyl-formamide, N-vinylacetoamide, N-vinyl pro
- the heteratom group derived from a nitrogen containing group may include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropylacrylamide, dimethylaminopropyl- methacrylamide, nitriles of (meth)acrylic acid and other nitrogen-containing (meth)acrylates, such as N-(methacryloyloxyethyl)diisobutyl ketimine, N- (methacryloyloxyethyl)dihexadecyl ketimine, methacryloylamidoacetonitrile, 2-methacryloyloxyethylmethylcyanamide, cyanomethyl methacrylate, or mixtures thereof.
- suitable non-carbonyl oxygen containing compounds capable of being incorporated into the copolymer include methacrylates of ether alcohols, such as tetrahydro fur fury 1 methacrylate, vinyloxyethoxy ethyl methacrylate, methoxyethoxyethyl methacrylate, 1- butoxypropyl methacrylate, l-methyl-(2-vinyloxy)ethyl methacrylate, cyclo- hexyloxymethyl methacrylate, methoxymethoxyethyl methacrylate, benzyloxy- methyl methacrylate, furfuryl methacrylate, 2-butoxyethyl methacrylate, 2- ethoxyethoxymethyl methacrylate, 2-ethoxyethyl methacrylate, allyloxymethyl methacrylate, 1-ethoxybutyl methacrylate, methoxymethyl methacrylate, 1- ethoxyethyl methacrylate,
- the block copolymer may be obtained/obtainable from controlled radical or other living polymerisation techniques such as RAFT (Reversible Addition Fragmentation Transfer), ATRP (Atom Transfer Radical Polymerisation), nitroxide-mediated and anionic. These polymerisation techniques are known to a person skilled in the art.
- the controlled radical polymerisation process employed to prepare the block copolymer may be a RAFT process.
- the controlled radical polymerisation process employed to prepare the block copolymer may be an ATRP process.
- groups that may be transferred by a radical mechanism include halogens (from a halogen-containing compound) or various ligands.
- groups that may be transferred is described in US Patent 6,391 ,996, or paragraphs 61 to 65 of US Patent Application 2005/038146.
- the controlled radical polymerisation process may be a RAFT process.
- chain transfer agents are important. A more detailed review of suitable chain transfer agents is found in paragraphs 66 to 71 of US Patent Application US 2005/038146.
- a suitable RAFT chain transfer agent includes 2-Dodecylsulphanylthiocarbonylsulphanyl-2-methyl-propionic acid butyl ester, cumyl dithiobenzoate or mixtures thereof. Oils of Lubricating Viscosity
- the lubricating composition comprises an oil of lubricating viscosity.
- oils include natural and synthetic oils, oil derived from hydrocracking, hydro gen ation, and hydrofinishing, unrefined, refined and re- refined oils and mixtures thereof.
- Unrefined oils are those obtained directly from a natural or synthetic source generally without (or with little) further purification treatment.
- Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Purification techniques are known in the art and include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation and the like.
- Natural oils useful in making the inventive lubricants include animal oils, vegetable oils (e.g., castor oil), mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
- animal oils e.g., castor oil
- mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types and oils derived from coal or shale or mixtures thereof.
- dodecylbenzenes dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2- ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); diphenyl alkanes, alkylated diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulphides and the derivatives, analogs and homo logs thereof or mixtures thereof.
- polyphenyls e.g., biphenyls, terphenyls, alkylated polyphenyls
- diphenyl alkanes alkylated diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulphides and the derivatives, analogs and homo logs thereof or mixtures
- Other synthetic lubricating oils include polyol esters (such as Prolube®3970), diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans.
- Synthetic oils may be produced by Fischer-Tropsch reactions and typically may be hydroisomerised Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
- Oils of lubricating viscosity may also be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines.
- the five base oil groups are as follows: Group I (sulphur content >0.03 wt %, and/or ⁇ 90 wt % saturates, viscosity index 80-120); Group II (sulphur content ⁇ 0.03 wt %, and >90 wt % saturates, viscosity index 80-120); Group III (sulphur content ⁇ 0.03 wt %, and >90 wt % saturates, viscosity index >120); Group IV (all polyalphaolefins (PAOs)); and Group V (all others not included in Groups I, II, III, or IV).
- PAOs polyalphaolefins
- the oil of lubricating viscosity includes an API Group I, Group II, Group III, Group IV, Group V oil or mixtures thereof. Often the oil of lubricating viscosity is an API Group I, Group II, Group III, Group IV oil or mixtures thereof.
- the amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 wt % the sum of the amount of the compound of the invention and the other performance additives.
- the lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant.
- the composition optionally includes other performance additives.
- the other performance additives comprise at least one of metal deactivators, viscosity modifiers, detergents, friction modifiers, antiwear agents, corrosion inhibitors, dispersants, dispersant viscosity modifiers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers (other than the block copolymer of the invention), pour point depressants (other than the block copolymer of the invention), seal swelling agents and mixtures thereof.
- fully-formulated lubricating oil will contain one or more of these performance additives.
- the lubricating composition further includes known neutral or overbased detergents.
- Suitable detergent substrates include phenates, sulphur containing phenates, sulphonates, salixarates, salicylates, carboxylic acid, phosphorus acid, mono- and/or di- thiophosphoric acids, alkyl phenols, sulphur coupled alkyl phenol compounds, or saligenins.
- Various overbased detergents and their methods of preparation are described in greater detail in numerous patent publications, including WO2004/096957 and references cited therein.
- the detergent substrate may be salted with a metal such as calcium, magnesium, potassium, sodium, or mixtures thereof.
- the overbased detergent is selected from the group consisting of phenates, sulphur containing phenates, sulphonates, salixarates, salicylates, and mixtures thereof.
- the selected overbased detergent include calcium or magnesium phenates, sulphur containing phenates, sulphonates, salixarates, saliginens, salicylates, or mixtures thereof.
- the detergent may be a calcium salicylate.
- the detergent may be a calcium sulphonate.
- the detergent may be a mixture of a calcium sulphonate and a calcium salicylate.
- the detergent may be a calcium phenate. In one embodiment the detergent may be a calcium sulphonate. In one embodiment the invention the detergent may be a mixture of a calcium sulphonate and a calcium phenate.
- the detergent may be present (on an oil free basis i.e., an actives basis) at 0 wt % to 10 wt %, or 0.1 wt % to 8 wt %, or 1 wt % to 4 wt % of the lubricating composition.
- the amount of detergent (on an oil free basis i.e., an actives basis)may be 0 wt % to 40 wt %, or 2 wt % to 35 wt %, or 5 wt % to 30 wt % of the lubricating composition.
- Dispersants are often known as ashless-type dispersants because, prior to mixing in a lubricating oil composition, they do not contain ash- forming metals and they do not normally contribute any ash forming metals when added to a lubricant and polymeric dispersants.
- Ashless type dispersants are characterised by a polar group attached to a relatively high molecular weight hydrocarbon chain.
- Typical ashless dispersants include N-substituted long chain alkenyl succinimides. Examples of N-substituted long chain alkenyl succinimides include polyisobutylene succinimide with number average molecular weight of the polyisobutylene substituent in the range 350 to 5000, or 500 to 3000.
- Succinimide dispersants and their preparation are disclosed, for instance in US Patent 3,172,892 or US Patent 4,234,435.
- Succinimide dispersants are typically the imide formed from a polyamine, typically a po Iy (ethy leneamine) .
- the invention further includes at least one dispersant which is a polyisobutylene succinimide derived from a polyisobutylene with number average molecular weight in the range 350 to 5000, or 500 to 3000.
- the polyisobutylene succinimide may be used alone or in combination with other dispersants.
- the invention further includes at least one dispersant derived from polyisobutylene succinic anhydride, an amine and zinc oxide to form a polyisobutylene succinimide complex with zinc.
- the polyisobutylene succinimide complex with zinc may be used alone or in combination.
- Mannich bases are the reaction products of alkyl phenols with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines).
- aldehydes especially formaldehyde
- amines especially polyalkylene polyamines
- the alkyl group typically contains at least 30 carbon atoms.
- the dispersants may also be post-treated by conventional methods by a reaction with any of a variety of agents.
- the dispersant typically a polyisobutylene succinimide
- the dispersant may have a high total base number or the dispersant may have a high total acid number.
- dispersants with a high TAN number have a carbonyl to nitrogen ratio of 1 or higher, in one aspect 1.2 or higher, in another aspect 1.4 or higher and in yet another aspect 1.45 or higher, for example 1.5.
- dispersants with a high TBN number have a carbonyl to nitrogen ratio of less than 1, in one aspect 0.94 or lower, in another aspect 0.88 or lower and in another aspect 0.8 or lower, for instance 0.77.
- the carbonyl to nitrogen ratio is to be calculated on a molar basis, that is, the ratio of moles of carbonyl functionality (e.g., -C(O)O- ) to the moles of nitrogen functionality (e.g., amine nitrogens).
- the dispersant may be in a mixture of (i) a dispersant with a carbonyl to nitrogen ratio of 1 or higher; and (ii) a dispersant with a carbonyl to nitrogen ratio of less than 1.
- Antioxidant compounds include for example, sulphurised olefins, alkylated diphenylamines (typically di-nonyl diphenylamine, octyl diphenylamine, di-octyl diphenylamine), hindered phenols, molybdenum compounds (such as molybdenum dithio carbamates), or mixtures thereof. Antioxidant compounds may be used alone or in combination.
- the antioxidant may be present in ranges (on an oil free basis i.e., an actives basis) of 0 wt % to 20 wt %, or 0.1 wt % to 10 wt %, or 1 wt % to 5 wt %, of the lubricating composition.
- the hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
- the phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and/or a bridging group linking to a second aromatic group.
- hindered phenol antioxidants examples include 2,6-di-tert- butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4- dodecyl-2,6-di-tert-butylphenol.
- the hindered phenol antioxidant may be an ester and may include, e.g., IrganoxTM L-135 from Ciba. A more detailed description of suitable ester-containing hindered phenol antioxidant chemistry is found in US Patent 6,559,105.
- the lubricating composition further includes a molybdenum compound.
- Suitable examples of molybdenum dithiocarbamates which may be used as an antioxidant include commercial materials sold under the trade names such as Molyvan 822TM, MolyvanTM A and Molyvan 855TM from R. T.
- the molybdenum compound may provide 5 ppm to
- Viscosity modifiers include hydrogenated copolymers of maleic anhydride-(alpha olefin) copolymers, styrene -butadiene, ethylene-propylene copolymers, polyisobutenes, hydrogenated styrene-isoprene polymers, hydrogenated isoprene polymers, polymethacrylates, polyacrylates, polyalkyl styrenes, hydrogenated alkenyl arene conjugated diene copolymers, polyolefins, esters of maleic anhydride-styrene copolymers.
- Dispersant viscosity modifiers include functionalised polyolefins, for example, ethylene-propylene copolymers that have been functionalized with an acylating agent such as maleic anhydride and an amine; polymethacrylates functionalised with an amine, or esterified styrene-maleic anhydride copolymers reacted with an amine.
- an acylating agent such as maleic anhydride and an amine
- polymethacrylates functionalised with an amine or esterified styrene-maleic anhydride copolymers reacted with an amine.
- the lubricating composition further includes an antiwear agent.
- the additional antiwear agent may be either ashless or ash-forming.
- the antiwear agent may be present (on an oil free basis i.e., an actives basis) in ranges including 0 wt % to 15 wt %, or 0 wt % to 10 wt %, or 0.05 wt % to 5 wt %, or 0.1 wt % to 3 wt % of the lubricating composition.
- the lubricating composition further includes a phosphorus-containing antiwear agent.
- the phosphorus-containing antiwear agent may be present in an amount to deliver the ranges of phosphorus described below in the subject matter under the sub-heading "Industrial Application".
- the zinc dialkyldithiophosphates or zinc dialkylphosphates may in one embodiment be defined as a zinc salt of a mixture of phosphorus-containing compounds represented by the formula: wherein in formula, J 1 and J 2 are independently S or O, and R 3 and R 4 may be independently hydrocarbyl groups, the average total number of carbon atoms in R 3 plus R 4 for the mixture of phosphorus-containing compounds being at least 9.5; wherein R 3 and R 4 are characterised in that (i) 4 to 70 mole percent of such groups contain 2 to 4 carbon atoms and (ii) 30 to 96 mole percent such groups contain 5 to 12 carbon atoms; and wherein, in less than 8 mole percent of the molecules of the formula in the mixture of phosphorus-containing compounds, each of R 3 and R 4 contain 2 to 4 carbon atoms and in greater than 11 mole percent of the molecules of the formula in said mixture R has 2 to 4 carbon atoms and R 4 has 5 to 12 carbon atoms; and wherein, within the formula, the
- Suitable olefins that may be sulphurised to form an sulphurised olefin include propylene, butylene, isobutylene, pentene, hexane, heptene, octane, nonene, decene, undecene, dodecene, undecyl, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, octadecenene, nonodecene, eicosene or mixtures thereof.
- EP agents that are soluble in the oil include sulphur- and chlorosulphur-containing EP agents, chlorinated hydrocarbon EP agents and phosphorus EP agents.
- EP agents include chlorinated wax; organic sulphides and polysulphides such as dibenzyldisulphide, bis-(chlorobenzyl) disulphide, dibutyl tetrasulphide, sulphurised methyl ester of oleic acid, sulphurised alkylphenol, sulphurised dipentene, sulphurised terpene, and sulphurised Diels-Alder adducts; phosphosulphurised hydrocarbons such as the reaction product of phosphorus sulphide with turpentine or methyl oleate; phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphites, e.g., dibutyl phosphite, diheptyl phos
- the lubricating composition further includes a friction modifier, or mixtures thereof.
- the friction modifier may be present (on an oil free basis i.e., an actives basis) in ranges including 0 wt % to 10 wt %, or 0.05 wt % to 8 wt %, or 0.1 wt % to 4 wt %.
- Suitable friction modifiers include long chain fatty acid derivatives of amines, esters, or epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; or fatty alkyl tartramides.
- Friction modifiers may also encompass materials such as fatty alkyl tartrates; fatty alkyl tartrimides, sulphurised fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil or monoester of a polyol and an aliphatic carboxylic acid (all these friction modifiers may also be described as antioxidants or antiwear agents).
- the friction modifier friction modifier is selected from the group consisting of long chain fatty acid derivatives of amines, esters, or epoxides; fatty alkyl tartrates; fatty alkyl tartrimides; and fatty alkyl tartramides.
- the friction modifier may be a long chain fatty acid ester (previously described above as an ashless antiwear agent).
- the long chain fatty acid ester may be a mono-ester, e.g., a monoglyceride, and in one embodiment the long chain fatty acid ester may be a (tri)glyceride.
- corrosion inhibitors include those described in paragraphs 5 to 8 of US Application US05/038319 (filed on October 25, 2004 McAtee and Boyer as named inventors), octylamine octanoate, condensation products of dodecenyl succinic acid or anhydride and a fatty acid such as oleic acid with a poly amine.
- the corrosion inhibitors include the Synalox® corrosion inhibitor.
- the Synalox® corrosion inhibitor is typically a homopolymer or copolymer of propylene oxide.
- the Synalox® corrosion inhibitor is described in more detail in a product brochure with Form No. 118-01453-0702 AMS, published by The Dow Chemical Company.
- Metal deactivators including derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles, benzimid- azoles, 2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides may be useful.
- Foam inhibitors that may be useful in the compositions of the invention include copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers.
- Pour point depressants that may be useful in the compositions of the invention include polyalphaolefins, esters of maleic anhydride-styrene copolymers, fumarate ester-vinyl acetate copolymers, polyalkyl(meth)acrylates, polyalkylacrylates or polyalkylacrylamides.
- the mechanical device is an internal combustion engine.
- the internal combustion engine may be a diesel fueled engine, a gasoline fueled engine, a natural gas fueled engine or a mixed gasoline/alcohol fueled engine. In one embodiment the internal combustion engine may be a diesel fueled engine and in one embodiment a gasoline fueled engine.
- the internal combustion engine may be a 2-stroke or 4-stroke engine.
- Suitable internal combustion engines include marine diesel engines, aviation piston engines, low-load diesel engines, and automobile and truck engines.
- the components of the internal combustion engine include all of the parts of the engine derived from metal lubricated by an engine lubricant. This includes for example, cylinder liners, camshafts, pistons, bearings, oil coolers etc.
- the internal combustion engine contains components ferric (i.e., ferrous) components.
- ferric components include
- Fe, FeO, Fe 3 O 4 or other materials containing iron are examples of materials containing iron.
- the internal combustion engine contains components of an aluminium-alloy.
- the aluminium- alloy includes aluminium silicates, aluminium oxides, or other ceramic materials.
- the aluminium-alloy is an aluminium-silicate surface.
- the lubricating composition for an internal combustion engine may be suitable for any engine lubricant irrespective of the sulphur, phosphorus or sulphated ash (ASTM D-874) content.
- the sulphur content of the engine oil lubricant may be 1 wt % or less, or 0.8 wt % or less, or 0.5 wt % or less, or 0.3 wt % or less. In one embodiment the sulphur content may be in the range of
- the phosphorus content may be 0.2 wt % or less, or 0.1 wt % or less, or 0.085 wt % or less, or even
- the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm.
- the total sulphated ash content may be 2 wt % or less, or 1.5 wt % or less, or
- the sulphated ash content may be 0.05 wt % to 0.9 wt %, or
- the lubricating composition may be an engine oil, wherein the lubricating composition may be characterised as having (i) a sulphur content of 0.5 wt % or less, (ii) a phosphorus content of 0.08 wt % or less, and (iii) a sulphated ash content of 1.5 wt % or less.
- the lubricating composition may be suitable for a 2-stroke or a 4-stroke marine diesel internal combustion engine.
- the marine diesel combustion engine is a 2-stroke engine.
- the block copolymer of the invention may also be used in a variety of lubricants requiring emulsifiers and/or pour point depressants.
- the block copolymer of the invention may be an emulsifier and/or pour point depressant in driveline devices, industrial gears, hydraulic devices, off-highway mobile equipment such as farm tractors, greases, metalworking fluids and fuels.
- lubricant formulation may, as a person skilled in the art will appreciate, change due to the different additives and treat rates commonly employed in each lubricant type. None the less, the block copolymer is believed to function as an emulsifier and/or pour point depressant.
- Driveline devices include gearboxes, axle gears, traction drive transmissions, automatic transmissions or manual transmissions.
- Automatic transmissions include continuously variable transmissions (CVT), infinitely variable transmissions (IVT), Torroidal transmissions, continuously slipping torque converted clutches (CSTCC), stepped automatic transmissions or dual clutch transmissions (DCT).
- Preparative Example 1 is a diblock copolymer of (Ci 2 -i 5 -alkyl methacrylate and 2-ethylhexylmethacrylate)-b-dimethylaminoethyl meth- acrylate.
- the diblock copolymer is prepared by charging reagents into a 4- necked flask equipped with a nitrogen inlet, thermocouple and a heating mantle.
- the reagents added include 99.2 g of C 12-15 -alkyl methacrylate, 48 g of 2-ethylhexylmethacrylate, 5.04 g of a chain transfer agent (dodecyl- trithiocarbonate butyl ester), 0.87 g of Trigonox®21 initiator and 41.48 g of PAO-4 diluent oil.
- the flask is stirred and purged with nitrogen for 30 minutes.
- the nitrogen flow rate is 0.028 m 3 /hr (or 1 SCFH).
- the flask is then heated to 90 0 C and the nitrogen flow is reduced to 0.014 m 3 /hr (or 0.5 SCFH) and held for 150 minutes.
- the flask is then charged with 12.8 g of dimethyl amino ethyl methacrylate.
- the flask is held for a further 3 hours at 90 0 C, before cooling.
- the product is a viscous liquid.
- Preparative Example 2 is a diblock copolymer of (Ci 2 -i 5 -alkyl methacrylate and 2-ethylhexylmethacrylate)-b-dimethylaminoethyl methacrylate.
- 1 11.6 g of Ci2-i5-alkyl methacrylate, 54 g of 2-ethylhexyl- methacrylate, and 0.97 g of Trigonox®21 initiator are blended to form a blend. About one third of the blend is charged into a 4-necked flask equipped with a nitrogen inlet, thermocouple and a heating mantle.
- a chain transfer agent (dodecyl-trithiocarbonate butyl ester) is then added to the flask.
- the flask is stirred and purged with nitrogen for 30 minutes. The nitrogen flow rate is 0.028 m 3 /hr (or 1 SCFH).
- the flask is then heated to 80 0 C and the nitrogen flow is reduced to 0.014 m 3 /hr (or 0.5 SCFH) and the remaining two thirds of the blend is added over a period of 90 minutes.
- the flask is maintained at 80 0 C and held for 150 minutes.
- the flask is then charged with 14.4 g of dimethylaminoethyl methacrylate.
- Preparative Example 3 is a diblock copolymer of (Ci 2 -i 5 -alkyl methacrylate and Ci 6 -i 8 -alkyl methacrylate)-b-dimethylaminoethyl methacrylate.
- the flask is stirred and purged with nitrogen for 30 minutes.
- the nitrogen flow rate is 0.056 m 3 /hr (or 2 SCFH).
- the flask is then heated to 80 0 C and the nitrogen flow is reduced to 0.014 m 3 /hr (or 0.5 SCFH) and the remaining two thirds of the blend is added over a period of 90 minutes.
- the flask is maintained at 80 0 C and held for 15 hours.
- the flask is then charged with 240 g of dimethylaminoethyl methacrylate.
- the flask is held for at 90 0 C for 2 hours.
- Three separate charges (each 1 g) of Trigonox®21 initiator are added over a period of 5 hours.
- the product is a viscous liquid before dilution with diluent oil to form a 40 % polymer mixture in oil.
- Preparative Example 4 is a diblock copolymer prepared by a process similar to EX3, except the final polymer is a block copolymer of (C 12- i 5 -alkyl methacrylate and Ci 6 -i 8 -alkyl methacrylate)-b-(dimethylaminoethyl methacrylate and methylmethacrylate). The methyl methacrylate is added concurrently with dimethylaminoethyl methacrylate.
- the ratio of the weight percent of Ci2-i5-alkyl methacrylate to Ci6-i8-alkyl methacrylate is 85: 15 (the Ci6-i8-alkyl methacrylate also contains up to 5 wt % C ⁇ -alkyl methacrylate and up to 2 wt % C 2 o-alkyl methacrylate).
- the ratio of the weight percent of dimethylaminoethyl methacrylate to methylmethacrylate is 91 :9.
- the ratio weight percent of hydrophobic block to the second block containing a polar group is 87: 13.
- the product is a viscous liquid before dilution with diluent oil to form a 50 % polymer mixture in oil.
- Comparative Preparative Example 1 is a random polymer of Ci 2 -i 5 -alkyl methacrylate, 2-ethylhexylmethacrylate, and dimethylaminoethyl methacrylate.
- the random polymer is prepared by charging reagents into a 4- necked flask equipped with a nitrogen inlet, thermocouple and a heating mantle.
- the reagents added include 99.2 g of C 12-15 -alkyl methacrylate, 48 g of 2-ethylhexylmethacrylate, 12.8 g of dimethylaminoethyl methacrylate, 5.04 g of a chain transfer agent (dodecyl-trithiocarbonate butyl ester), 0.87 g of Trigonox®21 initiator and 41.48 g of PAO-4 diluent oil. The flask is then heated to 90 0 C as is described in EXl .
- Comparative Lubricant Example 1 is a SAE 5W-30 engine lubricant.
- Comparative Lubricant Example 2 is a 5W-30 engine lubricant similar to CLCl, except it further contains 0.05 wt % of the product of CPl .
- Comparative Lubricant Example 3 is a 5W-30 engine lubricant similar to CLCl, except it further contains 0.12 wt % of the product of CPl .
- Comparative Lubricant Example 4 is a oil mixture of 80 wt
- Lubricant Example 1 (LCD is a 5W-30 engine lubricant similar to
- CLCl except it further contains 0.05 wt % of the product of EXl .
- Lubricant Example 2 is a 5W-30 engine lubricant similar to
- CLCl except it further contains 0.12 wt % of the product of EXl .
- Lubricant Example 3 is a 5W-30 engine lubricant similar to
- Lubricant Example 4 is a 5W-30 engine lubricant similar to
- Lubricant Example 5 is a 5W-30 engine lubricant similar to
- Lubricant Example 6 is a 5W-30 engine lubricant similar to
- Lubricant Example 7 is a 5W-30 engine lubricant similar to
- Lubricant Example 8 is a 5W-30 engine lubricant similar to
- Lubricant Example 9 is similar to CLC4, except it contains
- Lubricant Example 10 (LClO) is similar to CLC4, except it contains
- Lubricant Example 11 (LCI l) is similar to CLC4, except it contains
- Lubricant examples LCl to LC8 and comparative Lubricant examples CLCl to CLC3 are evaluated in the following ASTM tests D445,
- ASTM D445 relates to measurement of kinematic viscosity (units mm 2 /s) at 100 0 C.
- ASTM D4684-07 Mini-Rotary Viscometer or MRV
- MRV MRV
- Yield stress and low-shear- rate viscosity are measured after cooling at controlled rates over a period exceeding 45 hour to a final test temperature between -10 0 C and -40 0 C.
- the units are Centipoise (cP) or mPa-s.
- D5985-02 covers the determination of pour point of petroleum products by an automatic instrument that continuously rotates the test specimen against a suspended detection device during cooling of the test specimen.
- the Chrysler FFV emulsion stability test involves the steps of combining 10 volume % E85 fuel, 10% water, and 80% fully formulated engine oil and mixing them in a Waring blender. The resultant emulsion is stored in graduated cylinders at 0 0 C and room temperature (25 0 C) for 24 hours. At the end of the test, the volume percent oil (% oil), percent emulsion (% emul), and percent water (% H 2 O) are recorded. Typically, a formulated oil is considered to pass the FFV test if %H 2 O at both 0 0 C and room temperature is zero. [0167] The results obtained for the tests described above are as follows:
- n/m indicates a data point not measured
- Ci_3o alkyl (meth)acrylic units relate to product formed by the polymerisation of Ci_3o alkyl (meth)acrylic monomer.
- the Ci_3o alkyl (meth)acrylic units may then be used to form the block(s) as described herein above. Reference to the percentage of Ci_3o alkyl (meth)acrylic units is considered as a mole percent.
- hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
- hydrocarbyl groups include:
- hydrocarbon substituents that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
- aliphatic e.g., alkyl or alkenyl
- alicyclic e.g., cycloalkyl, cycloalkenyl
- aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
- substituted hydrocarbon substituents that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulphoxy);
- hetero substituents that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl;
- heteroatoms including sulphur, oxygen, and nitrogen.
- no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group.
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/127,114 US20110263470A1 (en) | 2008-11-05 | 2009-11-03 | Composition Containing a Block Copolymer and a Method of Lubricating an Internal Combustion Engine |
CN2009801534821A CN102272278A (en) | 2008-11-05 | 2009-11-03 | Composition containing a block copolymer and a method of lubricating an internal combustion engine |
BRPI0921231A BRPI0921231A2 (en) | 2008-11-05 | 2009-11-03 | composition containing a block copolymer and a method for lubricating an internal combustion engine |
CA2742516A CA2742516C (en) | 2008-11-05 | 2009-11-03 | Composition containing a block copolymer and a method of lubricating an internal combustion engine |
EP09748200A EP2358849A1 (en) | 2008-11-05 | 2009-11-03 | Composition containing a block copolymer and a method of lubricating an internal combustion engine |
AU2009311294A AU2009311294A1 (en) | 2008-11-05 | 2009-11-03 | Composition containing a block copolymer and a method of lubricating an internal combustion engine |
JP2011534870A JP5559803B2 (en) | 2008-11-05 | 2009-11-03 | Compositions containing block copolymers and methods for lubricating internal combustion engines |
KR1020117012684A KR101679090B1 (en) | 2008-11-05 | 2009-11-03 | Composition containing a block copolymer and a method of lubricating an internal combustion engine |
US15/249,873 US20160362628A1 (en) | 2008-11-05 | 2016-08-29 | Composition Containing A Block Copolymer And A Method Of Lubricating An Internal Combustion Engine |
US15/730,879 US20180030366A1 (en) | 2008-11-05 | 2017-10-12 | Composition Containing a Block Copolymer and a Method of Lubricating an Internal Combustion Engine |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US11140808P | 2008-11-05 | 2008-11-05 | |
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US15/249,873 Continuation US20160362628A1 (en) | 2008-11-05 | 2016-08-29 | Composition Containing A Block Copolymer And A Method Of Lubricating An Internal Combustion Engine |
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EP (1) | EP2358849A1 (en) |
JP (1) | JP5559803B2 (en) |
KR (1) | KR101679090B1 (en) |
CN (2) | CN102272278A (en) |
AU (2) | AU2009311294A1 (en) |
BR (1) | BRPI0921231A2 (en) |
CA (1) | CA2742516C (en) |
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WO2011031659A1 (en) * | 2009-09-14 | 2011-03-17 | The Lubrizol Corporation | Farm tractor lubricating composition with good water tolerance |
WO2012048931A1 (en) * | 2010-10-14 | 2012-04-19 | Evonik Rohmax Additives Gmbh | A motor having improved properties |
US20130340325A1 (en) * | 2012-06-22 | 2013-12-26 | Baker Hughes Incorporated | Charged Block Co-polymers as Pour Point Depressants |
WO2014049363A1 (en) * | 2012-09-27 | 2014-04-03 | The University Of Sheffield | Block copolymer synthesis |
WO2020126494A1 (en) | 2018-12-19 | 2020-06-25 | Evonik Operations Gmbh | Use of associative triblockcopolymers as viscosity index improvers |
US11034909B2 (en) | 2016-06-17 | 2021-06-15 | Total Marketing Services | Lubricant polymers |
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US9051529B2 (en) * | 2009-06-04 | 2015-06-09 | The Lubrizol Corporation | Lubricating composition containing friction modifier and viscosity modifier |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3816314A (en) * | 1972-05-31 | 1974-06-11 | Exxon Research Engineering Co | Block copolymers of unsaturated ester and a nitrogen containing monomer as v.i.improving and dispersant additives for oils |
EP0265254A2 (en) * | 1986-10-23 | 1988-04-27 | E.I. Du Pont De Nemours And Company | Oil additives |
US4985160A (en) * | 1989-02-08 | 1991-01-15 | E. I. Du Pont De Nemours And Company | Branched polymers as fuel oil additives |
US6080794A (en) * | 1996-02-02 | 2000-06-27 | Roehm Gmbh | Demulsifiers |
WO2005056739A1 (en) * | 2003-11-26 | 2005-06-23 | Arkema Inc. | Controlled radical acrylic copolymer thickeners |
US20060189490A1 (en) * | 2003-03-31 | 2006-08-24 | Alexander Dardin | Lubricating oil composition with good frictional properties |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4941984A (en) * | 1989-07-31 | 1990-07-17 | The Lubrizol Corporation | Lubricating oil compositions and methods for lubricating gasoline-fueled and/or alcohol-fueled, spark-ignited engines |
FR2833186B1 (en) * | 2001-12-12 | 2004-01-23 | Rhodia Chimie Sa | USE OF CATIONIC BLOCK COPOLYMERS AS AID FOR DEPOSITION OF SINGLE OR MULTIPLE EMULSIONS |
CN1658823B (en) * | 2002-05-03 | 2011-05-11 | 巴斯福股份公司 | Cosmetic product comprising at least one water-soluble copolymer which contains (meth)acrylamide units |
JP2007238663A (en) * | 2006-03-06 | 2007-09-20 | Sanyo Chem Ind Ltd | Lubricating oil additive and lubricating oil composition |
DE102005015931A1 (en) * | 2005-04-06 | 2006-10-12 | Rohmax Additives Gmbh | Polyalkyl (meth) acrylate copolymers with excellent properties |
JP5106778B2 (en) * | 2006-01-24 | 2012-12-26 | 三洋化成工業株式会社 | Lubricant sludge dispersant |
WO2007105769A1 (en) * | 2006-03-15 | 2007-09-20 | Nippon Oil Corporation | Lube base oil, lubricating oil composition for internal combustion engine, and lubricating oil composition for drive transmission device |
-
2009
- 2009-11-03 BR BRPI0921231A patent/BRPI0921231A2/en not_active Application Discontinuation
- 2009-11-03 CN CN2009801534821A patent/CN102272278A/en active Pending
- 2009-11-03 JP JP2011534870A patent/JP5559803B2/en active Active
- 2009-11-03 EP EP09748200A patent/EP2358849A1/en not_active Withdrawn
- 2009-11-03 CN CN201510634360.1A patent/CN105296063A/en active Pending
- 2009-11-03 KR KR1020117012684A patent/KR101679090B1/en active IP Right Grant
- 2009-11-03 AU AU2009311294A patent/AU2009311294A1/en not_active Abandoned
- 2009-11-03 CA CA2742516A patent/CA2742516C/en active Active
- 2009-11-03 WO PCT/US2009/063046 patent/WO2010053890A1/en active Application Filing
- 2009-11-03 US US13/127,114 patent/US20110263470A1/en not_active Abandoned
-
2016
- 2016-08-24 AU AU2016219628A patent/AU2016219628A1/en not_active Abandoned
- 2016-08-29 US US15/249,873 patent/US20160362628A1/en not_active Abandoned
-
2017
- 2017-10-12 US US15/730,879 patent/US20180030366A1/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3816314A (en) * | 1972-05-31 | 1974-06-11 | Exxon Research Engineering Co | Block copolymers of unsaturated ester and a nitrogen containing monomer as v.i.improving and dispersant additives for oils |
EP0265254A2 (en) * | 1986-10-23 | 1988-04-27 | E.I. Du Pont De Nemours And Company | Oil additives |
US4985160A (en) * | 1989-02-08 | 1991-01-15 | E. I. Du Pont De Nemours And Company | Branched polymers as fuel oil additives |
US6080794A (en) * | 1996-02-02 | 2000-06-27 | Roehm Gmbh | Demulsifiers |
US20060189490A1 (en) * | 2003-03-31 | 2006-08-24 | Alexander Dardin | Lubricating oil composition with good frictional properties |
WO2005056739A1 (en) * | 2003-11-26 | 2005-06-23 | Arkema Inc. | Controlled radical acrylic copolymer thickeners |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011031659A1 (en) * | 2009-09-14 | 2011-03-17 | The Lubrizol Corporation | Farm tractor lubricating composition with good water tolerance |
AU2010292401B2 (en) * | 2009-09-14 | 2016-10-06 | The Lubrizol Corporation | Farm tractor lubricating composition with good water tolerance |
US9528072B2 (en) | 2009-09-14 | 2016-12-27 | The Lubrizol Corporation | Farm tractor lubricating composition with good water tolerance |
WO2012048931A1 (en) * | 2010-10-14 | 2012-04-19 | Evonik Rohmax Additives Gmbh | A motor having improved properties |
US20130199482A1 (en) * | 2010-10-14 | 2013-08-08 | Evonik Oil Additives Gmbh | Motor having improved properties |
CN103249820A (en) * | 2010-10-14 | 2013-08-14 | 赢创油品添加剂有限公司 | A motor having improved properties |
US20130340325A1 (en) * | 2012-06-22 | 2013-12-26 | Baker Hughes Incorporated | Charged Block Co-polymers as Pour Point Depressants |
WO2014049363A1 (en) * | 2012-09-27 | 2014-04-03 | The University Of Sheffield | Block copolymer synthesis |
US11034909B2 (en) | 2016-06-17 | 2021-06-15 | Total Marketing Services | Lubricant polymers |
WO2020126494A1 (en) | 2018-12-19 | 2020-06-25 | Evonik Operations Gmbh | Use of associative triblockcopolymers as viscosity index improvers |
Also Published As
Publication number | Publication date |
---|---|
CN102272278A (en) | 2011-12-07 |
BRPI0921231A2 (en) | 2018-06-26 |
EP2358849A1 (en) | 2011-08-24 |
US20180030366A1 (en) | 2018-02-01 |
AU2016219628A1 (en) | 2016-09-08 |
KR20110095286A (en) | 2011-08-24 |
CA2742516A1 (en) | 2010-05-14 |
CA2742516C (en) | 2019-06-04 |
US20160362628A1 (en) | 2016-12-15 |
US20110263470A1 (en) | 2011-10-27 |
JP5559803B2 (en) | 2014-07-23 |
KR101679090B1 (en) | 2016-11-23 |
AU2009311294A1 (en) | 2010-05-14 |
JP2012507613A (en) | 2012-03-29 |
CN105296063A (en) | 2016-02-03 |
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