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
  • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
  • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
  • C10M129/04—Hydroxy compounds
  • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
  • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
  • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
  • C10M133/56—Amides; Imides
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
  • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
  • C10M137/04—Phosphate esters
  • C10M137/10—Thio derivatives
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
  • C10M159/12—Reaction products
  • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
  • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
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  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/027—Neutral salts thereof
• • C—CHEMISTRY; METALLURGY
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/086—Imides
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/26—Amines
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/28—Amides; Imides
• • 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
  • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2217/042—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone
• • 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
  • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2217/043—Mannich bases
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
• • 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
  • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/046—Overbasedsulfonic acid salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
  • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
  • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
  • C10M2219/088—Neutral salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
  • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
  • C10M2219/089—Overbased salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/045—Metal containing thio derivatives
• • 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
  • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
  • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
  • C10M2227/061—Esters derived from boron
• • C—CHEMISTRY; METALLURGY
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  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
• • C—CHEMISTRY; METALLURGY
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  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines
• • 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
  • C10N2040/253—Small diesel engines

Definitions

• the present invention relates to a crankcase lubricant which exhibits superior performance properties in heavy duty (HD) diesel (compression ignited) internal combustion engines whilst being a low phosphorus formulation.
• Such lubricants may be referred to variously as lubricating oils, lubricating oil compositions, and lubricating oil formulations.
• the present invention is directed, in a first aspect, towards a heavy duty diesel engine lubricating oil composition comprising a major amount of an oil of lubricating viscosity to which has been added:
• composition is preferably free of aminic, such as aromatic amine, antioxidants.
• a major amount means in excess of 50 mass % of the composition and a minor amount means less than 50 mass % of the composition, both in respect of the stated additive, and in respect of the total mass % of all of the additives present in the composition.
• the additives of the composition may react under the conditions of formulation, storage, or use and that the invention also provides the product obtainable or obtained as a result of any such reaction.
• the invention is directed towards a concentrate for blending with an oil of lubricating viscosity to provide a heavy duty diesel engine lubricating oil composition, said concentrate comprising:
• the invention is directed towards a method of lubricating a heavy duty diesel engine which comprises supplying to the crankcase thereof a lubricating oil composition according to the first aspect of the invention.
• the invention is directed towards the use in a crankcase lubricating oil composition of a combination of additives (a) to (e) according to the first aspect of the invention to achieve adequate performance in one or more of the following tests for crankcase lubricating oils:
• the invention is directed towards a combination comprising
• the oil of lubricating viscosity may be selected from any of the synthetic or natural oils used as crankcase lubricating oils for heavy duty diesel (compression-ignited) engines.
• the oil of lubricating viscosity conveniently has a viscosity of 2.5 to 12, preferably 2.5 to 9, mm 2 /s at 100°C. Mixtures of synthetic and natural base oils may be used if desired.
• the ashless dispersant comprises an oil-soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
• Dispersants may be present in amounts of from 2 to 10, preferably 3 to 5, mass %.
• the dispersants comprise amine, alcohol, amide, or ester polar moieties attached to the polymer backbone often via a bridging group.
• the dispersant may be, for example, selected from oil-soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of long chain hydrocarbons; long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine, and Koch reaction products.
• the oil-soluble polymeric hydrocarbon backbone is typically an olefin polymer, especially polymers comprising a major molar amount (i.e. greater than 50 mole %) of a C 2 to C 18 olefin (e.g., ethylene, propylene, butylene, isobutylene, pentene, octene-1, styrene), and typically a C 2 to C 5 olefin.
• a C 2 to C 18 olefin e.g., ethylene, propylene, butylene, isobutylene, pentene, octene-1, styrene
• the oil-soluble polymeric hydrocarbon backbone may be a homopolymer (e.g., polypropylene or polyisobutylene) or a copolymer of two or more of such olefins (e.g., copolymers of ethylene and an alpha-olefin such as propylene and butylene or copolymers of two different alpha-olefins).
• a homopolymer e.g., polypropylene or polyisobutylene
• a copolymer of two or more of such olefins e.g., copolymers of ethylene and an alpha-olefin such as propylene and butylene or copolymers of two different alpha-olefins.
• olefin polymers polybutenes and specifically polyisobutenes (PIB) or poly-n-butenes, such as may be prepared by polymerization of a C 4 refinery stream.
• PIB polyisobutenes
• poly-n-butenes such as may be prepared by polymerization of a C 4 refinery stream.
• Another preferred class of olefin polymers is ethylene alpha-olefin (EAO) copolymers or alpha-olefin homo- and copolymers such as may be prepared using metallocene chemistry having in each case a high degree (e.g. >30%) of terminal vinylidene unsaturation.
• EAO ethylene alpha-olefin
• the oil-soluble polymeric hydrocarbon backbone will usually have number average molecular weight ( M n) within the range of from 300 to 20,000.
• M n of the backbone is preferably within the range of 500 to 10,000, more preferably 700 to 5,000 where the use of the backbone is to prepare a component having the primary function of dispersancy.
• Hetero polymers such as polyepoxides are also usable to prepare components.
• Both relatively low molecular weight ( M n 500 to 1500) and relatively high molecular weight ( M n 1500 to 5,000 or greater) polymers are useful to make dispersants.
• Particularly useful olefin polymers for use in dispersants have M n within the range of from 900 to 3000.
• the component is also intended to have a viscosity modification effect it is desirable to use higher molecular weight, typically with M n of from 2,000 to 20,000, and if the component is intended to function primarily as a viscosity modifier then the molecular weight may be even higher with an M n of from 20,000 up to 500,000 or greater.
• the functionalized olefin polymers used to prepare dispersants preferably have approximately one terminal double bond per polymer chain.
• the M n for such polymers can be determined by several known techniques.
• a convenient method for such determination is by gel permeation chromatography (GPC) which additionally provides molecular weight distribution information.
• the oil-soluble polymeric hydrocarbon backbone may be functionalized to incorporate a functional group into the backbone of the polymer, or as one or more groups pendant from the polymer backbone.
• the functional group typically will be polar and contain one or more hetero atoms such as P, O, S, N, halogen, or boron. It can be attached to a saturated hydrocarbon part of the oil soluble polymeric hydrocarbon backbone via substitution reactions or to an olefinic portion via addition or cycloaddition reactions. Alternatively, the functional group can be incorporated into the polymer in conjunction with oxidation or cleavage of the polymer chain end (e.g., as in ozonolysis).
• Useful functionalization reactions include: halogenation of the polymer allylic to the olefinic bond and subsequent reaction of the halogenated polymer with an ethylenically unsaturated functional compound (e.g., maleation where the polymer is reacted with maleic acid or anhydride); reaction of the polymer with an unsaturated functional compound by the "ene" reaction absent halogenation; reaction of the polymer with at least one phenol group (this permits derivatization in a Mannich base-type condensation); reaction of the polymer at a point of unsaturation with carbon monoxide using a hydroformylation catalyst or a Koch-type reaction to introduce a carbonyl group attached to a -CH 2 - or in an iso or neo position; reaction of the polymer with the functionalizing compound by free radical addition using a free radical catalyst; reaction with a thiocarboxylic acid derivative; and reaction of the polymer by air oxidation methods, epoxidation, chloroamination, or
• the functionalized oil-soluble polymeric hydrocarbon backbone is then further derivatized with a nucleophilic reactant such as an amine, amino-alcohol, alcohol, metal compound or mixture thereof to form a corresponding derivative.
• a nucleophilic reactant such as an amine, amino-alcohol, alcohol, metal compound or mixture thereof.
• Useful amine compounds for derivatizing functionalized polymers comprise at least one amine and can comprise one or more additional amine or other reactive or polar groups. These amines may be hydrocarbyl amines or may be predominantly hydrocarbyl amines in which the hydrocarbyl group includes other groups, e.g., hydroxy groups, alkoxy groups, amide groups, nitriles, imidazoline groups, and the like.
• Particularly useful amine compounds include mono- and polyamines, e.g.
• polyalkylene and polyoxyalkylene polyamines of about 2 to 60, conveniently 2 to 40 (e.g., 3 to 20) total carbon atoms and about 1 to 12, conveniently 3 to 12, and preferably 3 to 9 nitrogen atoms in the molecule.
• Mixtures of amine compounds may advantageously be used such as those prepared by reaction of alkylene dihalide with ammonia.
• Preferred amines are aliphatic saturated amines, including, e.g., 1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane; 1,6-diaminohexane; polyethylene amines such as diethylene triamine; triethylene tetramine; tetraethylene pentamine; and polypropyleneamines such as 1,2-propylene diamine; and di-(1,3-propylene) triamine.
• 1,2-diaminoethane 1,3-diaminopropane
• 1,4-diaminobutane 1,6-diaminohexane
• polyethylene amines such as diethylene triamine; triethylene tetramine; tetraethylene pentamine
• polypropyleneamines such as 1,2-propylene diamine; and di-(1,3-propylene) triamine.
• a preferred group of dispersants includes those substituted with succinic anhydride groups and reacted with polyethylene amines (e.g., tetraethylene pentamine), aminoalcohols such as trismethylolaminomethane, polymer products of metallocene catalyzed polymerisations, and optionally additional reactants such as alcohols and reactive metals e.g., pentaerythritol, and combinations thereof).
• polyethylene amines e.g., tetraethylene pentamine
• aminoalcohols such as trismethylolaminomethane
• polymer products of metallocene catalyzed polymerisations and optionally additional reactants such as alcohols and reactive metals e.g., pentaerythritol, and combinations thereof.
• additional reactants such as alcohols and reactive metals e.g., pentaerythritol, and combinations thereof.
• dispersants wherein a polyamine is attached directly to the
• Mannich base condensation products are prepared by condensing about one mole of an alkyl-substituted mono- or polyhydroxy benzene with about 1 to 2.5 moles of carbonyl compounds (e.g., formaldehyde and paraformaldehyde) and about 0.5 to 2 moles polyalkylene polyamine as disclosed, for example, in US 3,442,808.
• carbonyl compounds e.g., formaldehyde and paraformaldehyde
• the dispersant can be further post-treated by a variety of conventional post treatments such as boration, as generally taught in US 3,087,936 and 3,254,025. This is readily accomplished by treating an acyl nitrogen-containing dispersant with a boron compound selected from the group consisting of boron oxide, boron halides, boron acids and esters of boron acids or highly borated low M w dispersant, in an amount to provide a boron to nitrogen mole ratio of 0.01 to 3.0.
• a boron compound selected from the group consisting of boron oxide, boron halides, boron acids and esters of boron acids or highly borated low M w dispersant
• Preferred for use in the invention is a polyisobutenyl succinimide dispersant wherein the Mn of the polyisobutenyl groups is from 1500 to 3000, such as 2000 to 2300, or a borated derivative thereof which contains not more than 0.3, for example not more than 0.2, such as not more than 0.1, for example 0.01 to 0.1, mass % boron, as elemental boron.
• the lubricant oil of the present invention includes a neutral calcium phenate.
• "Neutral" means the phenate contains a substantially stoichiometric amount of metal.
• the phenate will be used in amounts from 0.3 to 1.5, preferably from 0.3 to 0.8, more preferably from 0.45 to 0.65, mass %.
• alkylated calcium phenates and preferably sulfurized alkylated calcium phenates are included in the present invention. Such salts are readily obtainable in the art. Methods for preparing phenates are disclosed in, for example U.S. Patent 3,966,621.
• Calcium salts of phenols and sulfurized phenols may be prepared by reaction with an appropriate metal compound such as an oxide or hydroxide and neutral.
• Sulfurised phenols may be prepared by reacting a phenol with sulfur or sulfur-containing compounds such as hydrogen sulfide, sulfur monohalide or sulfur dihalide, to form products which are generally mixtures of compounds in which two or more phenols are bridged by sulfur-containing bridges.
• the neutral calcium phenate used in the oils of the invention is, as stated above, the sole neutral metal detergent in the composition of the present invention which is free of other neutral metal detergent additives.
• compositions of the instant invention also include, as stated, oil-soluble overbased calcium or magnesium sulfonate or both; an amount of 0.2 to 2 mass % is preferred. Also as stated, the compositions of the present invention do not contain more than 0.05 mass % magnesium; 0.03 to 0.05 mass % magnesium is preferred or not more than 0.025 mass % magnesium.
• Metal-containing or ash-forming sulfonate detergents function both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life.
• Detergents generally comprise a polar head with a long hydrophobic tail, with the polar head comprising a metal salt of an acidic organic compound. It is possible to include large amounts of a metal base by reacting an excess of a metal compound such as an oxide or hydroxide with an acidic gas such as carbon dioxide.
• the resulting overbased detergent sulfonate comprises neutralised detergent as the outer layer of a metal base (e.g. carbonate) micelle.
• Such overbased sulfonate detergents may have a TBN of 150 or greater, and typically of from 250 to 450 or more.
• Sulfonates may be prepared from sulfonic acids which are typically obtained by the sulfonation of alkyl-substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum or by the alkylation of aromatic hydrocarbons. Examples included those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene.
• the alkylation may be carried out in the presence of a catalyst with alkylating agents having from 3 to more than 70 carbon atoms.
• the alkaryl sulfonates usually contain from 9 to 80 or more, preferably from 16 to 60, carbon atoms per alkyl-substituted aromatic moiety.
• the oil-soluble sulfonates or alkyl aryl sulfonic acids may be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylate, sulfides, hydrosulfides, nitrates, borates and ethers of the metal.
• the amount of metal compound is chosen having regard to the desired TBN of the final product but typically ranges from 125 to 220 mass % of that stoichiometrically required.
• Dihydrocarbyl dithiophosphate metal salts are frequently used as anti-wear and antioxidant agents.
• the compositions of this invention preferably contain a metal dihydrocarbyl dithiophosphate in an amount such that from 0.05 to 0.10, such as 0.05 to 0.07 or to 0.08, mass % phosphorus is present in the finished lubricating oil.
• the metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper, but zinc salts are preferred and may be present in amounts of 0.1 to 1.5, preferably 0.5 to 1.0, mass %, based upon the total weight of the lubricating oil composition.
• DDPA dihydrocarbyl dithiophosphoric acid
• a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols.
• multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character.
• any basic or neutral zinc compound could be used, but the oxides, hydroxides and carbonates are most generally employed. Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralization reaction.
• the preferred zinc dihydrocarbyl dithiophosphates are oil-soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula: wherein R and R' may be the same or different hydrocarbyl radicals containing from 1 to 18, preferably 2 to 12, carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R and R' groups are alkyl groups of 2 to 8 carbon atoms.
• the radicals may, for example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl.
• the total number of carbon atoms i.e.
• the zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
• at least 50 mole % of the alcohols used to introduce hydrocarbyl groups into the dithiophosphoric acids are secondary alcohols.
• the alcohols used to introduce the hydrocarbyl groups may be 60 or 75 mole % secondary. Most preferably, the hydrocarbyl groups are more than 90 mole % secondary.
• Metal dithiophosphates that are secondary in character give better wear control in tests such as the Sequence VE (ASTM D5302) and the GM 6.2L tests.
• the lubricant of this invention includes 0.1 to 1.5, preferably about 0.2 to 1.0, mass %, of an antioxidant (e).
• Hindered phenols are preferred and are generally oil-soluble phenols substituted at one or both ortho positions.
• Suitable compounds include monohydric and mononuclear phenols such as 2,6-di-tertiary alkylphenols (e.g. 2,6-di-t-butylphenol, 2,4,6-tri-t-butyl phenol, 2-t-butyl phenol, 4-alkyl, 2,6-t-butyl phenol, 2,6-di-isopropylphenol, and 2,6-dimethyl, 4-t-butyl phenol).
• 2,6-di-tertiary alkylphenols e.g. 2,6-di-t-butylphenol, 2,4,6-tri-t-butyl phenol, 2-t-butyl phenol, 4-alkyl, 2,6-t-butyl
• hindered phenols include polyhydric and polynuclear phenols such as alkylene-bridged hindered phenols (4,4-methylenebis(6-tert-butyl-o-cresol), 4,4'-methylenebis(2-tert-amyl-o-cresol), and 2,2'-methylenebis(2,6-di-t-butylphenol).
• the hindered phenol may be borated or sulfurized.
• Preferred hindered phenols have good oil-solubility and relatively low volatility.
• aromatic amine antioxidants having at least two aromatic groups attached directly to the nitrogen. Although these materials may be used in small amounts, preferred embodiments of the present invention are free of these compounds. These aromatic amines have been found to impact soot-induced viscosity increases. They are preferably used in only small amounts, or more preferably avoided altogether other than such amounts as may result as an impurity from another component of the composition.
• Typical oil-soluble aromatic amines having at least two aromatic groups attached directly to one amine nitrogen contain from 6 to 16 carbon atoms.
• the amines may contain more than two aromatic groups.
• Compounds having a total of at least three aromatic groups in which two aromatic groups are linked by a covalent bond or by an atom or group (e.g., an oxygen or sulfur atom, or a -CO-, -SO 2 - or alkylene group) and two aromatic groups are directly attached to one amine nitrogen are also considered aromatic amines having at least two aromatic groups attached directly to the nitrogen.
• the aromatic rings are typically substituted by one or more substituents selected from alkyl, cycloalkyl, alkoxy, aryloxy, acyl, acylamino, hydroxy, and nitro groups. These compounds should be minimized or avoided altogether.
• the amount of any such oil soluble aromatic amines having at least two aromatic groups attached directly to one amine nitrogen should preferably not exceed 0.2 mass %.
• additives may be present as optional ingredients in the composition of this invention and these are listed below.
• Rust inhibitors selected from the group consisting of nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, and anionic alkyl sulfonic acids may be used.
• Copper- and lead- bearing corrosion inhibitors may be used, but are typically not required with the formulation of the present invention.
• such compounds are the thiadiazole polysulfides containing from 5 to 50 carbon atoms, their derivatives and polymers thereof.
• Derivatives of 1,3,4 thiadiazoles such as those described in U.S. Pat. Nos. 2,719,125; 2,719,126; and 3,087,932 are typical.
• Other similar materials are described in U.S. Pat. Nos. 3,821,236; 3,904,537; 4,097,387; 4,107,059; 4,136,043; 4,188,299; and 4,193,882.
• additives are the thio and polythio sulfenamides of thiadiazoles such as those described in UK. Patent Specification No. 1,560,830. Benzotriazoles derivatives also fall within this class of additives. When these compounds are included in the lubricating composition, they are preferably present in an amount not exceeding 0.2 mass %.
• a small amount of a demulsifying component may be used.
• a preferred demulsifying component is described in EP 330,522. It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide with a polyhydric alcohol.
• the demulsifier should be used at a level not exceeding 0.1, conveniently 0.001 to 0.05, mass %.
• pour point depressants otherwise known as lube oil flow improvers, lower the minimum temperature at which the fluid will flow or can be poured.
• Such additives are well-known. Typical of those additives which improve the low temperature fluidity of the fluid are C 8 to C 18 dialkyl fumarate/vinyl acetate copolymers and polyalkylmethacrylates. Likewise, the dialkyl fumarate and vinyl acetate may be used as compatibilizing agents.
• Foam control can be provided by many compounds including an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
• Viscosity modifiers function to impart high and low temperature operability to a lubricating oil.
• the VM used may have that sole function, or may be multifunctional.
• Multifunctional viscosity modifiers that also function as dispersants are also known.
• Suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene and higher alpha-olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, inter polymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene, and isoprene/butadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene and isoprene/divinylbenzene.
• additives can provide a multiplicity of effects; thus for example, a single additive may act as a dispersant-oxidation inhibitor.
• each additive is typically blended into the oil of lubricating viscosity, or base oil, in an amount which enables the additive to provide its desired function. Effective amounts of additives (a) to (e) have been described above.
• each additive may be incorporated into a base oil in any convenient way.
• each additive can be added directly to the oil by dispersing or dissolving it in the oil at the desired level of concentration. Such blending may occur at ambient temperature or at an elevated temperature.
• all of the additives except for the viscosity modifier and the pour point depressant are blended into a concentrate that is subsequently blended into the base oil to make a finished lubricant.
• Use of such concentrates , or additives packages, is conventional.
• the concentrate will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration in the final formulation when the concentrate is combined with a predetermined amount of base lubricant.
• the concentrate is made in accordance with the method described in US-A-4,938,880. That patent describes making a premix of dispersant and metal detergents that is pre-blended at a temperature of at least about 100°C. Thereafter the pre-mix is cooled to at least 85°C and the additional additives are added.
• the final compositions may employ from 2 to 15, preferably 5 to 10, typically 7 to 8, mass % of the additive package(s), the remainder being base oil.
• Oil 1-1 Dispersant (Borated) 3.240 4.860 Neutral Ca Phenate 0.391 0.598 Neutral Ca Sulfonate 0.484 - Phenol Antioxidant 0.600 0.600 ZDDP* 0.915 0.914 Overbased Mg Sulfonate** 0.256 0.256 Overbased Ca Sulfonate 0.797 0.797
• Oil 1-A Oil 1-1 Hours to 375% KV Increase 68.8 76.1 KV Increase at 64 hours 237% 98% (API CH-4 fail) (API CH-4 pass)
• Oil 1-1 is an oil of the invention. Oil 1-A is for comparison. The data show the beneficial effect of employing neutral calcium phenate as the sole neutral detergent. The additional dispersant in Oil 1-1 has no effect on viscosity increase due to oxidation.
• Oil 2-1 is an oil of the invention and shows the advantages attributable to a formulation which has calcium phenate as the sole neutral detergent.
• the additional dispersant in Oil 2-1 does not affect bore polish performance in the OM364LA test.
• Oil 3-1 contains less Mg than Oil 2-1.
• the OM364LA data for Oil 3-1 are below tabulated in comparison with the same data for Oil 2-1 of Example 2.
• Oil 3-1 shows the improvement resulting from the lowering of the Mg content in the bore polish value.
• Oil 3-1 Oil 2-1 Bore Polish, % 0.2 0.6 Piston Cleanliness, Merits 43.0 47.0 Cylinder Wear, Average, Microns 2.0 1.7 Engine Sludge Average, Merits 9.7 9.7 Oil Consumption, kg. 11.9 11.9
• Oil 4-1 Oil 3-1 Oil Filter Delta Pressure, kPa 54 63 Crosshead Wear, mg. 5.0 6.0 Sludge, Merits 8.9 9.2

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• 2001
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