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
  • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
  • C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic 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
  • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
  • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-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
  • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
• • 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
• • 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
  • C10M2207/046—Hydroxy ethers
• • 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/26—Overbased carboxylic acid salts
  • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
• • 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
• • 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/287—Partial esters
  • C10M2207/288—Partial esters containing free carboxyl groups
• • 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
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
• • 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
  • 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
  • C10M2219/086—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing sulfur atoms bound to carbon atoms of six-membered aromatic rings
• • 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
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/04—Molecular weight; Molecular weight distribution
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/04—Detergent property or dispersant property
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/52—Base number [TBN]
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines

Definitions

• This invention concerns diesel engine lubrication, more specifically trunk piston diesel engine lubrication using trunk piston engine oil (‘TPEO’) and system lubrication of crosshead (also referred to as two-stroke or slow speed) diesel engines.
• TPEO trunk piston engine oil
• crosshead also referred to as two-stroke or slow speed diesel engines.
• Trunk piston diesel engines are used in marine, power generation and rail traction applications and typically have a rated speed of between 300 and 1000 rpm.
• trunk piston diesel engines a single lubricant composition is used for crankcase and cylinder lubrication. All major moving parts of the engine, i.e. the main and big end bearings, camshaft and valve gear, are lubricated by a pumped circulation system.
• the cylinder liners are lubricated partially by splash lubrication and partially by oil from the circulation system which finds its way to the cylinder wall through holes in the piston skirt via the connecting rod and gudgeon pin.
• Crosshead diesel engines are lubricated using two separate lubricants; the engine cylinders are lubricated using a marine diesel cylinder lubricant (or ‘MDCL’), and the engine crankcase is lubricated using a separate lubricant referred to as a system oil.
• MDCL marine diesel cylinder lubricant
• Trunk piston diesel engines use a centrifuge system to remove contaminants, such as for example, soot or water, from the lubricating oil composition. Similar centrifuge systems are used to treat the system oil of some crosshead marine diesel engines.
• the centrifuge system relies on the use of a sealing medium that is heavier than the lubricating oil composition.
• the sealing medium is generally water.
• the lubricating oil composition passes through the centrifuge system, it comes into contact with the water.
• the lubricating oil composition therefore needs to be capable of shedding the water and remaining stable in the presence of water. If the lubricating oil composition is unable to shed the water, the water builds up in the lubricating oil composition forming an emulsion, which leads to deposits building up in the centrifuge system and prevents the centrifuge system from working properly.
• the present invention provides lubrication that improves soot handling and that is capable of shedding media used in centrifuge systems.
• the invention employs the above-mentioned linked aromatic compounds in combination with nitrogen-containing ashless dispersant in defined ratios.
• the invention comprises a method of lubricating a trunk piston diesel engine, or cross-head diesel engine, having a centrifuge system including a sealing medium, the method comprising operation of the engine and lubrication of the trunk piston engine or system lubrication of the cross-head engine with a lubricating oil composition comprising:
• the invention comprises a method of enhancing the water-shedding properties, as measured by a centrifuge water shedding test, of a lubricating oil composition in the lubrication of a trunk piston engine, or the system lubrication of cross-head diesel engine, having a centrifuge system including a sealing medium, by employing a lubricating oil composition as defined in the first aspect of the invention when compared with a corresponding lubricating oil composition where (B) contains only (B2).
• the invention comprises a trunk piston or cross-head diesel engine lubricating oil composition having a total base number of at least 15, such as at least 20, mg KOH/g, as determined by ASTM D2896, comprising:
• each Ar independently represents an aromatic moiety having 0 to 3 substituents selected from the group consisting of alkyl, alkoxy, alkoxyalkyl, hydroxy, hydroxyalkyl, halo and combinations thereof; each L is independently a linking moiety comprising a carbon-carbon single bond or a linking group; each Y is independently a moiety of the formula H(O(CR 2 ) n ) y X—, wherein X is selected from the group consisting of (CR′ 2 ) z , O and S; R and R′ are each independently selected from H, C 1 to C 6 alkyl and aryl; z is 1 to 10; n is 0 to 10 when X is (CR′ 2 ) z , and 2 to 10 when X is O or S; and y is 1 to 30; each a is independently 0 to 3, with the proviso that at least one Ar moiety bears at least one group Y; and m is 1 to 100.
• Aromatic moieties Ar of Formula (I) can be a mononuclear carbocyclic moiety (phenyl) or a polynuclear carbocyclic moiety.
• Polynuclear carbocyclic moieties may comprise two or more fused rings, each ring having 4 to 10 carbon atoms (e.g., naphthalene) or may be linked mononuclear aromatic moieties, such as biphenyl, or may comprise linked, fused rings (e.g., binaphthyl).
• suitable polynuclear carbocyclic aromatic moieties include naphthalene, anthracene, phenanthrene, cycopentenophenanthrene, benzanthracene, dibenzanthracene, chrysene, pyrene, benzpyrene and coronene and dimer, trimer and higher polymers thereof.
• Ar can also represent a mono- or polynuclear heterocyclic moiety.
• Heterocyclic moieties Ar include those comprising one or more rings each containing 4 to 10 atoms, including one or more hetero atoms selected from N, O and S.
• Suitable monocylic heterocyclic aromatic moieties include pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrimidine and purine.
• Suitable polynuclear heterocyclic moieties Ar include, for example, quinoline, isoquinoline, carbazole, dipyridyl, cinnoline, phthalazine, quinazoline, quinoxaline and phenanthroline. Each aromatic moiety (Ar) may be independently selected such that all moieties Ar are the same or different. Polycyclic carbocyclic aromatic moieties are preferred. Most preferred are compounds of Formula I wherein each Ar is naphthalene.
• Each aromatic moiety Ar may independently be unsubstituted or substituted with 1 to 3 substituents selected from alkyl, alkoxy alkoxyalkyl, hydroxyl, hydroxyalkyl, halo, and combinations thereof.
• each Ar is unsubstituted (except for group(s) Y and terminal groups).
• Each linking group (L) may be the same or different, and can be a carbon to carbon single bond between the carbon atoms of adjacent moieties Ar, or a linking group.
• Suitable linking groups include alkylene linkages, ether linkages, diacyl linkages, ether-acyl linkages, amino linkages, amido linkages, carbamido linkages, urethane linkages, and sulfur linkage.
• Preferred linking groups are alkylene linkages such as —CH 3 CHC(CH 3 ) 2 —, or C(CH 3 ) 2 —; diacyl linkages such as —COCO— or —CO(CH 2 ) 4 CO—; and sulfur linkages, such as —S 1 — or —S x —. More preferred linking groups are alkylene linkages, most preferably —CH 2 —.
• Ar of Formula (I) represents naphthalene, and more preferably, Ar is derived from 2-(2-naphthyloxy)-ethanol.
• each Ar is derived from 2-(2-naphthyloxy)-ethanol, and m is 2 to 25.
• Y of Formula (I) is the group H(O(CR 2 ) 2 ) y O—, wherein y is 1 to 6. More preferably, Ar is naphthalene, Y is HOCH 2 C 2 O— and L is —CH 2 —.
• a hydroxyl aromatic compound, such as naphthol can be reacted with an alkylene carbonate (e.g., ethylene carbonate) to provide a compound of the formula AR—(Y) a .
• an alkylene carbonate e.g., ethylene carbonate
• the hydroxyl aromatic compound and alkylene carbonate are reacted in the presence of a base catalyst, such as aqueous sodium hydroxide, and at a temperature of from 25 to 300, preferably from 50 to 200° C.
• a base catalyst such as aqueous sodium hydroxide
• reaction product can be collected, and cooled to solidify.
• a hydroxyl aromatic compound such as naphthol
• an epoxide such as ethylene oxide, propylene oxide, butylenes oxide or styrene oxide, under similar conditions to incorporate one or more oxy-alkylene groups.
• the resulting intermediate compound Ar—(Y) a may be further reacted with a polyhalogenated (preferably dihalogenated) hydrocarbon (e.g., 1-4-dichlorobutane, 2,2-dichloropropane, etc.), or a di- or poly-olefin (e.g., butadiene, isoprene, divinylbenzene, 1,4-hexadiene, 1,5-hexadiene, etc.) to yield a compound of Formula (I) having an alkylene linking groups.
• a polyhalogenated hydrocarbon e.g., 1-4-dichlorobutane, 2,2-dichloropropane, etc.
• a di- or poly-olefin e.g., butadiene, isoprene, divinylbenzene, 1,4-hexadiene, 1,5-hexadiene, etc.
• Reaction of moieties Ar—(Y) a and a ketone or aldehyde provides an alkylene-linked compound.
• An acyl-linked compound can be formed by reacting moieties Ar—(Y) a with a diacid or anhydride (e.g., oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, succinic anhydride, etc.).
• Sulfide, polysulfide, sulfinyl and sulfonyl linkages may be provided by reaction of the moieties Ar—(Y) a with a suitable difunctional sulfurizing agent (e.g., sulfur monochloride, sulfur dichloride, thionyl chloride (SOCl 2 ), sulfuryl chloride (SO 2 Cl 2 ), etc.).
• a suitable difunctional sulfurizing agent e.g., sulfur monochloride, sulfur dichloride, thionyl chloride (SOCl 2 ), sulfuryl chloride (SO 2 Cl 2 ), etc.
• moieties Ar—(Y) a can be reacted with a divinylether.
• Compounds of Formula (I), wherein L is a direct carbon to carbon link may be formed via oxidative coupling polymerization using a mixture of aluminum chloride and cuprous chloride, as described, for example, by P. Kovacic, et al., J. Polymer Science: Polymer Chem. Ed., 21, 457 (1983).
• such compounds may be formed by reacting moieties Ar—(Y) a and an alkali metal as described, for example, in “Catalytic Benzene Coupling on Caesium/Nanoporous Carbon Catalysts”, M. G. Stevens, K. M. Sellers, S. Subramoney and H. C. Foley, Chemical Communications, 2679-2680 (1988).
• a reaction mixture can be neutralized with acid, preferably with an excess of acid (e.g., a sulfonic acid) and reacted with an aldehyde, preferably formaldehyde, and preferably in the presence of residual acid, to provide an alkylene, preferably methylene bridged compound of Formula (I).
• acid e.g., a sulfonic acid
• aldehyde preferably formaldehyde
• residual acid e.g., a sulfonic acid
• the degree of polymerization of the compounds of Formula I range from 2 to 101 (corresponding to a value of m of from 1 to 100), preferably from 2 to 50, most preferably from 2 to 25.
• the compounds of formula (II) can be formed by reacting a compound of formula (I) with at least one of an acylating agent, an alkylating agent and an arylating agent, and are represented by the formula:
• each Y′ is independently a moiety of the formula Z(O(CR 2 ) n ) y X—;
• Z is an acyl group, an alkyl group or an aryl group or H, and
• Ar, L, X, R, z, n and y are the same as defined in Formula (I), with the proviso that, at least one Ar moiety bears at least one substituent group Y′ in which Z is not H; and m is 1 to 100.
• Suitable acylating agents include hydrocarbyl carbonic acid, hydrocarbyl carbonic acid halides, hydrocarbyl sulfonic acid and hydrocarbyl sulfonic acid halides, hydrocarbyl phosphoric acid and hydrocarbyl phosphoric halides, hydrocarbyl isocyanates and hydrocarbyl succinic acylating agents.
• Preferred acylating agents are C 8 and higher hydrocarbyl isocyanates, such as dodecyl isocyanate and hexadodecyl isocyanate and C 8 or higher hydrocarbyl acylating agents, more preferably polybutenyl succinic acylating agents such as polybutenyl, or polyisobutenyl succinic anhydride (PIBSA).
• the hydrocarbyl succinic acylating agent will have a number average molecular weight ( M n ) of from 100 to 5000, preferably from 200 to 3000, more preferably from 450 to 2500.
• Preferred hydrocarbyl isocyanate acylating agent will have a number average molecular weight ( M n ) of from 100 to 5000, preferably from 200 to 3000, more preferably from 200 to 2000.
• Acylating agents can be prepared by conventional methods known to those skilled in the art, such as chlorine-assisted, thermal and radical grafting methods.
• the acylating agents can be mono- or polyfunctional.
• the acylating agents have a functionality of less than 1.3.
• Acylating agents are used in the manufacture of dispersants, and a more detailed description of methods for forming acylating agents is described in the description of suitable dispersants, presented infra.
• Suitable alkylating agents include C 8 to C 30 alkane alcohols, preferably C 8 to C 18 alkane alcohols.
• Suitable arylating agents include C 8 to C 30 , preferably C 8 to C 18 alkane-substituted aryl mono- or polyhydroxide.
• Molar amounts of the compound of Formula (I) and the acylating, alkylating and/or arylating agent can be adjusted such that all, or only a portion, such as 25% or more, 50% or more or 75% or more of groups Y are converted to groups Y′.
• the compound of Formula (I) has hydroxy and/or alkyl hydroxy substituents, and such compounds are reacted with an acylating group, it is possible that all or a portion of such hydroxy and/or alkylhydroxy substituents will be converted to acyloxy or acyloxy alkyl groups.
• a salt form of compounds of Formula (II) in which Z is an acylating group, which salts result from neutralization with base (as may occur, for example, due to interaction with a metal detergent, either in an additive package or a formulated lubricant), is also considered to be within the scope of the invention.
• Compounds of Formula (II) can be derived from the precursors of Formula (I) by reacting the precursors of Formula (I) with the acylating agent, preferably in the presence of a liquid acid catalyst, such as sulfonic acid, e.g., dodecyl benzene sulfonic acid, paratoluene sulfonic acid or polyphosphoric acid or a solid acid catalyst such as Amberlyst-15, Amberlyst-36, zeolites, mineral acid clay or tungsten polyphosphoric acid; at a temperature of from about 0 to 300, preferably from 50 to 250° C.
• the preferred polybutenyl succinic acylating agents can form diesters, acid esters or lactone esters with the compound of Formula (I).
• Compounds of Formula (II) can be derived from the precursors of Formula (I) by reacting the precursors of Formula (I) with the alkylating agent or arylating agent, preferably in the presence of triphenylphosphine and diethyl azodicarboxylate (DEAD), a liquid acid catalyst, such as sulfonic acid, e.g., dodecyl benzene sulfonic acid, paratoluene sulfonic acid or polyphosphoric acid or a solid acid catalyst such as Amberlyst-15, Amberlyst-36, zeolites, mineral acid clay or tungsten polyphosphoric acid; at a temperature of from 0 to 300, preferably from 50 to 250° C.
• DEAD triphenylphosphine and diethyl azodicarboxylate
• a liquid acid catalyst such as sulfonic acid, e.g., dodecyl benzene sulfonic acid, paratol
• Ashless dispersants useful in the compositions of the present invention comprise an oil-soluble polymeric long chain backbone having functional groups capable of associating with particles to be dispersed.
• such dispersants comprise amine, alcohol, amide or ester polar moieties attached to the polymer backbone, often via a bridging group.
• the ashless dispersant may be, for example, selected from oil-soluble salts, esters, amino-esters, amides, imides and oxazolines of long chain hydrocarbon-substituted mono- and polycarboxylic acids or anhydrides thereof; thiocarboxylate derivatives of long chain hydrocarbons; long chain aliphatic hydrocarbons having polyamine moieties attached directly thereto; and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine.
• the ashless dispersant is a “high molecular weight” dispersant having a number average molecular weight ( M n ) greater than or equal to 4,000, such as between 4,000 and 20,000.
• M n number average molecular weight
• the precise molecular weight ranges will depend on the type of polymer used to form the dispersant, the number of functional groups present, and the type of polar functional group employed.
• a high molecular weight dispersant is one formed with a polymer backbone having a number average molecular weight of from 1680 to 5600.
• Typical commercially-available polyisobutylene-based dispersants contain polyisobutylene polymers having a number average molecular weight ranging from 900 to 2300, functionalized by maleic anhydride (MW98), and derivatized with polyamines having a molecular weight of from 100 to 350. Polymers of lower molecular weight may also be used to form high molecular weight dispersants by incorporating multiple polymer chains into the dispersant, which can be accomplished using methods that are known in the art.
• Polymer molecular weight specifically number average molecular weight ( M n ), can be determined by various known techniques.
• One convenient method is gel permeation chromatography (GPC), which additionally provides molecular weight distribution information (see W. W. Yau, J. J. Kirkland and D. D. Bly, “Modern Size Exclusion Liquid Chromatography”, John Wiley and Sons, New York. 1979).
• GPC gel permeation chromatography
• the degree of polymerization D p of a polymer is:
• the degree of polymerization for the polymer backbones used in the invention is at least 30, typically from 30 to 165, more preferably 35 to 100.
• the preferred hydrocarbons or polymers employed in this invention include homopolymers, interpolymers or lower molecular weight hydrocarbons.
• One family of useful polymers comprise polymers of ethylene and/or at least one C 3 to C 28 alpha-olefin having the formula H 2 C ⁇ CHR 1 , wherein R 1 is straight or branched chain alkyl radical comprising 1 to 26 carbon atoms and wherein the polymer contains carbon-to-carbon unsaturation, preferably a high degree of terminal ethenylidene unsaturation.
• One preferred class of such polymers employed in this invention comprise interpolymers of ethylene and at least one alpha-olefin of the above formula, wherein R 1 is alkyl of from 1 to 18 carbon atoms, and more preferably is alkyl of from 1 to 8 carbon atoms, and more preferably still of from 1 to 2 carbon atoms.
• useful alpha-olefin monomers and comonomers include, for example, propylene, butene-1, hexene-1, octene-1,4-methylpentene-1, decene-1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, and mixtures thereof (e.g., mixtures of propylene and butene-1, and the like).
• Exemplary of such polymers are propylene homopolymers, butene-1 homopolymers, propylene-butene copolymers, ethylene-propylene copolymers, ethylene-butene-1 copolymers and the like, wherein the polymer contains at least some terminal and/or internal unsaturation.
• Preferred polymers are unsaturated copolymers of ethylene and propylene and ethylene and butene-1.
• the interpolymers of this invention may contain a minor amount, e.g. 0.5 to 5 mole % of a C 4 to C 18 non-conjugated diolefin comonomer.
• the polymers of this invention comprise only alpha-olefin homopolymers, interpolymers of alpha-olefin comonomers and interpolymers of ethylene and alpha-olefin comonomers.
• the molar ethylene content of the polymers employed in this invention is preferably in the range of 20 to 80, more preferably 30 to 70%.
• the ethylene content of such copolymers is most preferably between 45 and 65%, although higher or lower ethylene contents may be present.
• These polymers may be prepared by polymerizing alpha-olefin monomer, or mixtures of alpha-olefin monomers, or mixtures comprising ethylene and at least one C 3 to C 28 alpha-olefin monomer, in the presence of a catalyst system comprising at least one metallocene (e.g., a cyclopentadienyl-transition metal compound) and an alumoxane compound.
• a catalyst system comprising at least one metallocene (e.g., a cyclopentadienyl-transition metal compound) and an alumoxane compound.
• the percentage of polymer chains exhibiting terminal ethenylidene unsaturation may be determined by FTIR spectroscopic analysis, titration, or C 13 NMR.
• Interpolymers of this latter type may be characterized by the formula POLY-C(R 1 ) ⁇ CH 2 wherein R 1 is C 1 to C 26 alkyl, preferably C 1 to C 18 alkyl, more preferably C 1 to C 8 alkyl, and most preferably C 1 to C 2 alkyl, (e.g., methyl or ethyl) and wherein POLY represents the polymer chain.
• the chain length of the R 1 alkyl group will vary depending on the comonomer(s) selected for use in the polymerization.
• a minor amount of the polymer chains can contain terminal ethenyl, i.e., vinyl, unsaturation, ice, POLY-CH ⁇ CH 2 , and a portion of the polymers can contain internal monounsaturation, e.g. POLY-CH ⁇ CH(R 1 ), wherein R 1 is as defined above.
• terminally unsaturated interpolymers may be prepared by known metallocene chemistry and may also be prepared as described in U.S. Pat. Nos. 5,498,809; 5,663,130; 5,705,577; 5,814,715; 6,022,929 and 6,030,930.
• Another useful class of polymers comprises polymers prepared by cationic polymerization of isobutene, styrene, and the like.
• Common polymers from this class include polyisobutenes obtained by polymerization of a C 4 refinery stream having a butene content of 35 to 75% by wt., and an isobutene content of 30 to 60% by wt., in the presence of a Lewis acid catalyst, such as aluminum trichloride or boron trifluoride.
• a preferred source of monomer for making poly-n-butenes is petroleum feed streams such as Raffinate II. These feedstocks are disclosed in the art such as in U.S. Pat. No. 4,952,739.
• Polyisobutylene is a most preferred backbone of the present invention because it is readily available by cationic polymerization from butene streams (e.g., using AlCl 3 or BF 3 catalysts). Such polyisobutylenes generally contain residual unsaturation in amounts of one ethylenic double bond per polymer chain, positioned along the chain.
• polyisobutylene polymers employed are generally based on a hydrocarbon chain of from 900 to 2,300.
• Methods for making polyisobutylene are known.
• Polyisobutylene can be functionalized by halogenation (e.g. chlorination), the thermal “ene” reaction, or by fee radical grafting using a catalyst (e.g. peroxide), as described below.
• the polymer or hydrocarbon may be functionalized, for example, with carboxylic acid producing moieties (preferably acid or anhydride) by reacting the polymer or hydrocarbon under conditions that result in the addition of functional moieties or agents, i.e., acid, anhydride, ester moieties, etc., onto the polymer or hydrocarbon chains primarily at sites of carbon-to-carbon unsaturation (also referred to as ethylenic or olefinic unsaturation) using the halogen assisted functionalization (e.g. chlorination) process or the thermal “ene” reaction.
• carboxylic acid producing moieties preferably acid or anhydride
• the functionalization is randomly effected along the polymer chain.
• Selective functionalization can be accomplished by halogenating, e.g., chlorinating or brominating the unsaturated ⁇ -olefin polymer to 1 to 8, preferably 3 to 7 wt. % chlorine, or bromine, based on the weight of polymer or hydrocarbon, by passing the chlorine or bromine through the polymer at a temperature of 60 to 250, preferably 110 to 160, e.g., 120 to 140° C. for 0.5 to 10, preferably 1 to 7, hours.
• the halogenated polymer or hydrocarbon (hereinafter backbones) can then be reacted with sufficient monounsaturated reactant capable of adding functional moieties to the backbone, e.g., monounsaturated carboxylic reactant, at 100 to 250, usually 180 to 235° C., for 0.5 to 10, e.g., 3 to 8, hours, such that the product obtained will contain the desired number of moles of the monounsaturated carboxylic reactant per mole of the halogenated backbones.
• the backbone and the monounsaturated carboxylic reactant can be mixed and heated while adding chlorine to the hot material.
• the hydrocarbon or polymer backbone can be functionalized, e.g., with carboxylic acid producing moieties (preferably acid or anhydride moieties) selectively at sites of carbon-to-carbon unsaturation on the polymer or hydrocarbon chains, or randomly along chains using the three processes mentioned above, or combinations thereof, in any sequence.
• carboxylic acid producing moieties preferably acid or anhydride moieties
• the preferred monounsaturated reactants that are used to functionalize the backbone comprise mono- and dicarboxylic acid material, i.e., acid, anhydride, or acid ester material, including (i) monounsaturated C 4 to C 10 dicarboxylic acid wherein (a) the carboxyl groups are vicinyl, (i.e., located on adjacent carbon atoms) and (b) at least one, preferably both, of said adjacent carbon atoms are part of said mono unsaturation; (ii) derivatives of (i) such as anhydrides or C 1 to C 5 alcohol derived mono- or diesters of (i); (iii) monounsaturated C 3 to C 10 monocarboxylic acid wherein the carbon-carbon double bond is conjugated with the carboxy group, i.e., of the structure —C ⁇ C—CO—; and (iv) derivatives of (iii) such as C 1 to C 5 alcohol derived mono- or diesters of (iii).
• Mixtures of monounsaturated carboxylic materials (i)-(iv) also may be used.
• the monounsaturation of the monounsaturated carboxylic reactant becomes saturated.
• maleic anhydride becomes backbone-substituted succinic anhydride
• acrylic acid becomes backbone-substituted propionic acid.
• Such monounsaturated carboxylic reactants are fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and lower alkyl (e.g., C 1 to C 4 alkyl) acid esters of the foregoing, e.g., methyl maleate, ethyl fumarate, and methyl fumarate.
• the monounsaturated carboxylic reactant, preferably maleic anhydride typically will be used in an amount ranging from 0.01 to 20, preferably 0.5 to 10 wt. %, based on the weight of the polymer or hydrocarbon.
• chlorination normally helps increase the reactivity of starting olefin polymers with monounsaturated functionalizing reactant, it is not necessary with the polymers or hydrocarbons contemplated for use in the present invention, particularly those preferred polymers or hydrocarbons which possess a high terminal bond content and reactivity.
• the backbone and the monounsaturated functionality reactant e.g., carboxylic reactant, are contacted at elevated temperature to cause an initial thermal “ene” reaction to take place. Ene reactions are known.
• the hydrocarbon or polymer backbone can be functionalized by random attachment of functional moieties along the polymer chains by a variety of methods.
• the polymer in solution or in solid form, may be grafted with the monounsaturated carboxylic reactant, as described above, in the presence of a free-radical initiator.
• the grafting takes place at an elevated temperature in the range of 100 to 260, preferably 120 to 240° C.
• free-radical initiated grafting is accomplished in a mineral lubricating oil solution containing, for example, 1 to 50, preferably 5 to 30 wt. % polymer based on the initial total oil solution.
• the free-radical initiators that may be used are peroxides, hydroperoxides, and azo compounds, preferably those that have a boiling point greater than 100° C. and decompose thermally within the grafting temperature range to provide free-radicals.
• Representative of these free-radical initiators are azobutyronitrile, bis-tertiary-butyl peroxide and dicumene peroxide.
• the initiator when used, typically is used in an amount of between 0.005 and 1% by weight based on the weight of the reaction mixture solution.
• the aforesaid monounsaturated carboxylic reactant material and free-radical initiator are used in a weight ratio range of from 1.0:1 to 30:1, preferably 3:1 to 6:1.
• the grafting is preferably carried out in an inert atmosphere, such as under nitrogen blanketing.
• the resulting grafted polymer is characterized by having carboxylic acid (or ester or anhydride) moieties randomly attached along the polymer chains, it being understood, of course, that some of the polymer chains remain ungrafted.
• the free radical grafting described above can be used for the other polymers and hydrocarbons of the present invention.
• the functionalized oil-soluble polymeric hydrocarbon backbone may then be 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., polyalkene and polyoxyalkylene polyamines of 2 to 60, such as 2 to 40 (e.g., 3 to 20), total carbon atoms having 1 to 12, such as 3 to 12, preferably 3 to 9, nitrogen atoms per 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, for example, 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-(1,2-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-(1,2-propylene)triamine.
• amine compounds include: alicyclic diamines such as 1,4-di(aminomethyl)cyclohexane and heterocyclic nitrogen compounds such as imidazolines.
• Another useful class of amines is the polyamido and related amido-amines as disclosed in U.S. Pat. Nos. 4,857,217; 4,956,107; 4,963,275; and 5,229,022.
• TAM tris(hydroxymethyl)amino methane
• Dendrimers, star-like amines, and comb-structured amines may also be used.
• condensed amines as described in U.S. Pat. No. 5,053,152.
• the functionalized polymer is reacted with the amine compound using conventional techniques as described, for example in U.S. Pat. Nos. 4,234,435 and 5,229,022, as well as in EP-A-208,560.
• the functionalized, oil-soluble polymeric hydrocarbon backbones may also be derivatized with hydroxy compounds such as monohydric and polyhydric alcohols, or with aromatic compounds such as phenols and naphthols.
• Preferred polyhydric alcohols include alkylene glycols in which the alkylene radical contains from 2 to 8 carbon atoms.
• Other useful polyhydric alcohols include glycerol, mono-oleate of glycerol, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, dipentaerythritol, and mixtures thereof.
• An ester dispersant may also be derived from unsaturated alcohols, such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, 1-cyclohexene-3-ol, and oleyl alcohol.
• unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, 1-cyclohexene-3-ol, and oleyl alcohol.
• Still other classes of alcohols capable of yielding ashless dispersants comprise ether-alcohols, including oxy-alkylene and oxy-arylene.
• Such ether-alcohols are exemplified by ether-alcohols having up to 150 oxy-alkylene radicals in which the alkylene radical contains from 1 to 8 carbon atoms.
• the ester dispersants may be di-esters of succinic acids or acid-esters, i.e., partially esterified succinic acids, as well as partially esterified polyhydric alcohols or phenols, i.e., esters having free alcohols or phenolic hydroxy radicals.
• An ester dispersant may be prepared by any one of several known methods as described, for example, in U.S. Pat. No. 3,381,022.
• Preferred groups of dispersant include polyamine-derivatized poly ⁇ -olefin, dispersants, particularly ethylene/butene alpha-olefin and polyisobutylene-based dispersants.
• Particularly preferred are ashless dispersants derived from polyisobutylene substituted with succinic anhydride groups and reacted with polyethylene amines, e.g., polyethylene diamine, tetraethylene pentamine; or a polyoxyalkylene polyamine, e.g., polyoxypropylene diamine, trimethylolaminomethane; a hydroxy compound, e.g., pentaerythritol; and combinations thereof.
• One particularly preferred dispersant combination is a combination of (A) polyisobutylene substituted with succinic anhydride groups and reacted with (B) a hydroxy compound, e.g., pentaerythritol; (C) a polyoxyalkylene polyamine, e.g., polyoxypropylene diamine, or (D) a polyalkylene diamine, e.g., polyethylene diamine and tetraethylene pentamine using 0.3 to 2 moles of (B), (C) and/or (D) per mole of (A).
• Another preferred dispersant combination comprises a combination of (A) polyisobutenyl succinic anhydride with (B) a polyalkylene polyamine, e.g., tetraethylene pentamine, and (C) a polyhydric alcohol or polyhydroxy-substituted aliphatic primary amine, e.g., pentaerythritol or trismethylolaminomethane, as described in U.S. Pat. No. 3,632,511.
• Mannich base condensation products Another class of ashless dispersants comprises Mannich base condensation products. Generally, these products are prepared by condensing about one mole of an alkyl-substituted mono- or polyhydroxy benzene with 1 to 2.5 moles of carbonyl compound(s) (e.g., formaldehyde and paraformaldehyde) and 0.5 to 2 moles of polyalkylene polyamine, as disclosed, for example, in U.S. Pat. No. 3,442,808.
• carbonyl compound(s) e.g., formaldehyde and paraformaldehyde
• Such Mannich base condensation products may include a polymer product of a metallocene catalyzed polymerization as a substituent on the benzene group, or may be reacted with a compound containing such a polymer substituted on a succinic anhydride in a manner similar to that described in U.S. Pat. No. 3,442,808.
• Examples of functionalized and/or derivatized olefin polymers synthesized using metallocene catalyst systems are described in the publications identified supra.
• the dispersant can be further post treated by a variety of conventional post treatments such as boration, as generally taught in U.S. Pat. Nos. 3,087,936 and 3,254,025. Boration of the dispersant is readily accomplished by treating an acyl nitrogen-containing dispersant with a boron compound such as boron oxide, boron halide boron acids, and esters of boron acids, in an amount sufficient to provide from 0.1 to 20 atomic proportions of boron for each mole of acylated nitrogen composition.
• Useful dispersants contain from 0.05 to 2.0, e.g., from 0.05 to 0.7, mass % boron.
• the boron which appears in the product as dehydrated boric acid polymers (primarily (HBO 2 ) 3 ), is believed to attach to the dispersant imides and diimides as amine salts, e.g., the metaborate salt of the diimide.
• Boration can be carried out by adding from 0.5 to 4, e.g., from 1 to 3 mass % (based on the mass of acyl nitrogen compound) of a boron compound, preferably boric acid, usually as a slurry, to the acyl nitrogen compound and heating with stirring at from 135 to 190, e.g., 140 to 170° C., for from 1 to 5 hours, followed by nitrogen stripping.
• the boron treatment can be conducted by adding boric acid to a hot reaction mixture of the dicarboxylic acid material and amine, while removing water. Other post-reaction processes commonly known in the art can also be applied.
• the dispersant may also be further post treated by reaction with a so-called “capping agent”.
• a so-called “capping agent” nitrogen-containing dispersants have been “capped” to reduce the adverse effect such dispersants have on the fluoroelastomer engine seals.
• Numerous capping agents and methods are known. Of the known “capping agents”, those that convert basic dispersant amino groups to non-basic moieties (e.g., amido or imido groups) are most suitable.
• alkyl acetoacetate e.g., ethyl acetoacetate (EAA)
• EAA ethyl acetoacetate
• the reaction of a nitrogen-containing dispersant and formic acid is described, for example, in U.S. Pat. No. 3,185,704.
• the reaction product of a nitrogen-containing dispersant and other suitable capping agents are described in U.S. Pat. No. 4.663,064 (glycolic acid); U.S. Pat. Nos. 4,612,132; 5,334,321; 5,356,552; 5,716,912; 5,849,676; 5,861,363 (alkyl and alkylene carbonates, e.g., ethylene carbonate); U.S. Pat. No. 5,328,622 (mono-epoxide); U.S. Pat. Nos.
• Oils of lubricating viscosity useful in the context of the present invention may be selected from natural lubricating oils, synthetic lubricating oils and mixtures thereof.
• the lubricating oil may range in viscosity from light distillate mineral oils to heavy lubricating oils such as gasoline engine oils, mineral lubricating oils and heavy duty diesel oils. Generally, the viscosity of the oil ranges from 2 to 40, especially from 4 to 20, centistokes as measured at 100° C.
• Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil); liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale also serve as useful base oils.
• Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes)); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and derivative, analogs and homologs thereof. Also useful are synthetic oils derived from a gas to liquid process from
• Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyiso-propylene glycol ether having a molecular weight of 1000 or diphenyl ether of poly-ethylene glycol having a molecular weight of 1000 to 1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3 -C 8 fatty acid esters and C 13 oxo acid diester of tetraethylene glycol.
• polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide
• alkyl and aryl ethers of polyoxyalkylene polymers e.
• Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
• dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linole
• esters includes dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
• Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
• Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils comprise another useful class of synthetic lubricants; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl)silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes.
• oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhex
• Other synthetic lubricating oils include liquid esters of phosphorous-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
• the oil of lubricating viscosity may comprise a Group I, Group II or Group III, base stock or base oil blends of the aforementioned base stocks.
• the oil of lubricating viscosity is a Group II or Group III base stock, or a mixture thereof, or a mixture of a Group I base stock and one or more a Group II and Group III.
• a major amount of the oil of lubricating viscosity is a Group II, Group III, Group IV or Group V base stock, or a mixture thereof.
• the base stock, or base stock blend preferably has a saturate content of at least 65, more preferably at least 75, such as at least 85%. Most preferably, the base stock, or base stock blend, has a saturate content of greater than 90%.
• the oil or oil blend will have a sulfur content of less than 1, preferably less than 0.6, most preferably less than 0.4% by weight.
• the volatility of the oil or oil blend is less than or equal to 30%, preferably less than or equal to 25%, more preferably less than or equal to 20%, most preferably less than or equal 16%.
• the viscosity index (VI) of the oil or oil blend is at least 85, preferably at least 100, most preferably from about 105 to 140.
• base stocks and base oils in this invention are the same as those found in the American Petroleum Institute (API) publication “Engine Oil Licensing and Certification System”, Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998. Said publication categorizes base stocks as follows:
• the mass:mass ratio of (B1) to (B2) is in the range from 1:3 to 9:1. Preferably it is in the range of 1:1 to 6:1 more preferably in the range of 3:1 to 6:1.
• the respective masses are in terms of active ingredient.
• the ratio of (B1) to (B2) may be expressed as the mass % of (B1), as active ingredient, to the mass % of nitrogen in (B2). For example, in these terms, it may be 30:1 to 750:1, such as 80:1 to 500:1, for example 250:1 to 500:1; preferably, it is 40:1 to 80:1.
• additive combination (B) constitutes from 0.04 to 5 mass % of the lubricating oil composition. Preferably, it constitutes from 0.2 to 2.5, more preferably from 0.4 to 2 mass %.
• the concentration of (B2) in the lubricating oil composition may be less than 0.03, such as less than 0.02, for example in the range of 0.002 to 0.01, such as in the range of 0.004 to 0.005 or to 0.01 mass %.
• the lubricating oil composition to be useful in a trunk piston or cross-head diesel engine, will contain at least one overbased metal detergent to provide the required TBN.
• Such detergents are well-known and established in the art and examples include alkali metal or alkaline earth metal additives such as overbased oil-soluble or oil-dispersible calcium, magnesium, sodium or barium salts of a surfactants selected from phenol, sulphonic acid, carboxylic acid, salicylic acid and naphthenic acid, wherein the overbasing is provided by oil-insoluble salts of the metal, e.g., carbonate, basic carbonate, acetate, formate, hydroxide or oxalate, which is stabilized by the oil-soluble salt of the surfactant.
• the metal of the oil-soluble surfactant salt may be the same or different from that of the metal of the oil-insoluble salt.
• the metal, whether the metal of the oil-soluble salt or oil-insoluble salt is calcium.
• the TBN of the detergent may be low, i.e. less than 50, medium, i.e. 50-150, or high, i.e. over 150.
• the TBN is medium or high, i.e. more than 50.
• the TBN is at least 60, more preferably at least 100, more preferably at least 150, and up to 500, such as up to 350.
• Surfactants for the surfactant system of the overbased detergent preferably contain at least one hydrocarbyl group, for example, as a substituent on an aromatic ring.
• hydrocarbyl as used herein means that the group concerned is primarily composed of hydrogen and carbon atoms and is bonded to the remainder of the molecule via a carbon atom but does not exclude the presence of other atoms or groups in a proportion insufficient to detract from the substantially hydrocarbon characteristics of the group.
• hydrocarbyl groups in surfactants for use in accordance with the invention are aliphatic groups, preferably alkyl or alkylene groups, especially alkyl groups, which may be linear or branched. The total number of carbon atoms in the surfactants should be at least sufficient to impart the desired oil-solubility.
• Anti-wear additives such as metal (e.g. Zn) salts of dihydrocarbyl dithiophosphates (e.g. in an amount of from 0.10 to 3.0 mass % of the lubricating oil composition); anti-oxidants, or oxidation inhibitors, for example in the form of aromatic amines or hindered phenols (e.g. in an amount of up to 3 mass % of the lubricating oil composition);
• pour point depressants such as pour point depressants, anti-foamants, metal rust inhibitors, pour point depressants and/or demulsifiers may be provided, if necessary.
• oil-soluble or ‘oil-dispersable’ as used herein do not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. These do mean, however, that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
• the lubricant compositions of this invention comprise defined individual (i.e. separate) components that may or may not remain the same chemically before and after mixing.
• additive package(s) may be prepared, although not essential, to prepare one or more additive packages or concentrates comprising the additives, whereby the additives can be added simultaneously to the oil of lubricating viscosity to form the lubricating oil composition. Dissolution of the additive package(s) into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential.
• the additive package(s) will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration, and/or to carry out the intended function in the final formulation when the additive package(s) is/are combined with a predetermined amount of base lubricant.
• the additives may be admixed with small amounts of base oil or other compatible solvents together with other desirable additives to form additive packages containing active ingredients in an amount, based oil the additive package, of, for example, from 2.5 to 90, preferably from 5 to 75, most preferably from 8 to 60 mass % of additives in the appropriate proportions, the remainder being base oil.
• M n was determined by GPC using polystyrene standard corrected with the elution volume of 2-(2-naphthyloxy)ethanol as internal standard. THF was used as eluent, ( M n of 1000 dalton). 1 H and 13 C NMR confirmed the structure. FDMS and MALDI-TOF indicates the product contains mixture of methylene-linked 2-(2-naphthyloxy)ethanol oligomer of Formula (I) containing from 2 to 24 2-(2-naphthyloxy)ethanol units (m is 1 to 23).
• Step 3 Reaction of Methylene-Linked 2-(2-naphthyloxy)ethanol oligomer and an Acylating Agent (PIBSA)
• the following examples use a centrifuge water shedding test which evaluates the ability of an oil to shed water from a prepared test mixture of oil and water.
• the test uses an Alfa Laval MAB103B 2.0 centrifuge coupled to a Watson Marlow peristaltic pump. The centrifuge is sealed with 800 ml of water. A measurement is made of the amount of deposits formed in the centrifuge during the test. Pre-measured amounts of water and the test oil are mixed together and then passed through the centrifuge at a rate of 2 litres/min. The test is run for an hour and a half, allowing the mixture to pass through the centrifuge about 10 times. The centrifuge is weighed before and after the test. A poor trunk piston diesel engine lubricant will produce a larger amount of deposits in the centrifuge system.
• Example 1 is an example of the invention. The key to the table is as follows:
• PIBSA/PAM a polyisobutenyl succinic anhydride/polyamine dispersant.
• PmNE the final product of Synthesis Example 1 above.
• Each formulation comprised a Group II base oil and a Group I bright stock, a zinc dihydrocarbyl dithiophosphate antiwear additive, and a detergent system in the form of a 225 TBN calcium salicylate and a 350 TBN calcium salicylate in the ratio (mass:mass) of 1.419:1. Additionally, each formulation contained one or both of a PIBSA/PAM and the PmNE in the amounts (mass %) given in the table below; otherwise the formulations are equivalent.
• Reference Example C contains a low total proportion of dispersant and therefore exhibits a good water shedding result as demonstrated by the low mass of deposits. Reference Example C, however, would exhibit poor soot handling properties because of its low total proportion of dispersant.
• Reference Examples A and B respectively containing PIBSA/PAM and PmNE as sole dispersants and, for Reference Example A, in a higher proportion than in Reference Example C, exhibit poor water shedding properties.
• Example 1 of the invention, contains both PIBSA/PAM and PmNE and exhibits much better water shedding performance than Reference Examples A and B at the same total dispersant treat rate. Also, because of its higher total dispersant treat rate, Example 1 would exhibit much better soot handling properties than Reference Example C.

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