EP2109659B1 - Dispersant combination for improved transmission fluids - Google Patents

Dispersant combination for improved transmission fluids Download PDF

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Publication number
EP2109659B1
EP2109659B1 EP08728000.4A EP08728000A EP2109659B1 EP 2109659 B1 EP2109659 B1 EP 2109659B1 EP 08728000 A EP08728000 A EP 08728000A EP 2109659 B1 EP2109659 B1 EP 2109659B1
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EP
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composition
meth
dispersant
nitrogen
percent
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German (de)
English (en)
French (fr)
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EP2109659A2 (en
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Calvin A. James
Craig D. Tipton
William D. Abraham
Edward J. Konzman
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Lubrizol Corp
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Lubrizol Corp
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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
    • 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
    • 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
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero ring
    • 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
    • C10M2223/043—Ammonium or amine salts 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
    • 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
    • C10M2223/049—Phosphite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/76—Reduction of noise, shudder, or vibrations
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/045—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for continuous variable transmission [CVT]
    • 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
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • 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
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • the present invention relates to the field of additives for fluids such as automatic transmission fluids, traction fluids, fluids for continuously variable transmissions (CVTs), dual clutch automatic transmission fluids, farm tractor fluids, and engine lubricants.
  • fluids such as automatic transmission fluids, traction fluids, fluids for continuously variable transmissions (CVTs), dual clutch automatic transmission fluids, farm tractor fluids, and engine lubricants.
  • the fluids may also be used for lubricating devices such as gear boxes, transfer cases, and chains.
  • DVMs dispersant-viscosity modifiers
  • Other additives include succinimide dispersants as disclosed, in US2005/0202981 and EP-A-0355895 .
  • Additives and formulations for lubricating automatic transmissions have been described in a great number of patents and patent applications, including, US2006/0172899 .
  • US5,665,685 discloses a gear or transmission lubricant comprising an oil-soluble copolymer of an alkyl (meth)acrylate and N,N-diaminoalkyl(meth)acrylate with improved sludge dispersibility.
  • the present invention therefore, solves the problem of achieving such a balance by employing in such a formulation a high nitrogen-content dispersant viscosity modifier in combination with a succinimide dispersant prepared by a "direct alkylation" process, described below.
  • Such formulations may also impart good friction and high temperature oxidation performance at a relatively low treat rate
  • a lubricant composition comprising:
  • Natural oils useful in making the inventive lubricants and functional fluids include animal oils and vegetable oils as well as mineral lubricating oils such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic/-naphthenic types which may be further refined by hydrocracking and hydrofinishing processes.
  • Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins, also known as polyalphaolefins; polyphenyls; alkylated diphenyl ethers; alkyl- or dialkylbenzenes; and alkylated diphenyl sulfides; and the derivatives, analogs and homologues thereof. Also included are alkylene oxide polymers and interpolymers and derivatives thereof, in which the terminal hydroxyl groups may have been modified by esterification or etherification.
  • esters of dicarboxylic acids with a variety of alcohols or esters made from C5 to C12 monocarboxylic acids and polyols or polyol ethers.
  • Other synthetic oils include silicon-based oils, liquid esters of phosphorus-containing acids, and polymeric tetrahydrofurans.
  • Unrefined, refined and rerefined oils can be used in the lubricants of the present invention.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • Refined oils have been further treated in one or more purification steps to improve one or more properties. They can, for example, be hydrogenated, resulting in oils of improved stability against oxidation.
  • the oil of lubricating viscosity is an API Group II, Group III, Group IV, or Group V oil, including a synthetic oil, or mixtures thereof. These are classifications established by the API Base Oil Interchangeability Guidelines. Both Group II and Group III oils contain ⁇ 0.03 percent sulfur and > 99 percent saturates. Group II oils have a viscosity index of 80 to 120, and Group III oils have a viscosity index > 120. Polyalphaolefins are categorized as Group IV. The oil can also be an oil derived from hydroisomerization of wax such as slack wax or a Fischer-Tropsch synthesized wax.
  • Group V is encompasses "all others" (except for Group I, which contains > 0.03% S and/or ⁇ 90% saturates and has a viscosity index of 80 to 120).
  • the present invention may be used in Group II oils, which may especially reveal its benefits.
  • the oils of the present invention can encompass oils of a single viscosity range or a mixture of high viscosity and low viscosity range oils.
  • the oil exhibits a 100°C kinematic viscosity of 1 or 2 to 8 or 10 mm 2 /sec (cSt).
  • the overall lubricant composition may be formulated using oil and other components such that the viscosity at 100°C is 1 or 1.5 to 10 or 15 or 20 mm 2 /sec and the Brookfield viscosity (ASTM-D-2983) at -40°C is less than 20 or 15 Pa-s (20,000 cP or 15,000 cP), or less than 10 Pa-s, even 5 or less.
  • a dispersant viscosity modifier in particular, a dispersant viscosity modifier comprising a polyacrylate or polymethacrylate (hereinafter referred to as "poly(meth)acrylate") copolymer containing a nitrogen-containing monomer
  • Such materials typically include monomer-derived units from a monomer composition comprising one or more (meth)acrylates (that is, acrylates or methacrylates) of the formula (I), in which R denotes hydrogen or methyl and R 1 denotes hydrogen or a linear or branched alkyl radical having 1 to 40 carbon atoms.
  • Suitable monomers according to formula (I) include (meth)acrylates which are derived from saturated alcohols, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, 2-tert-butylheptyl (meth)acrylate, octyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth
  • the monomer composition may comprise one or more (meth)acrylates of the formula (I) in which R denotes hydrogen or methyl and R 1 denotes an alkyl radical substituted by an OH group and having 2 to 20 carbon atoms or denotes an alkoxylated radical of the formula (II) in which R 3 and R 4 independently represent hydrogen or methyl, R 5 represents hydrogen or an alkyl radical having 1 to 40 carbon atoms and n represents an integer from 1 to 90.
  • Such (meth)acrylates are known to a person skilled in the art and include hydroxyalkyl (meth)acrylates, such as 3-hydroxypropyl methacrylate, 3,4-dihydroxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,5-dimethy1-1,6-hexanediol (meth)acrylate, 1.10-decanediol (meth)acrylate, 1,2-propanediol (meth)acrylate; polyoxyethylene and polyoxypropylene derivatives of (meth)acrylic acid, such as triethylene glycol (meth)acrylate, tetraethylene glycol (meth)acrylate and tetrapropylene glycol (meth)acrylate. (The products from the polyols are believed to comprises largely the mono(meth)acrylates).
  • the poly(meth)acrylate backbone may comprise acrylic or methacrylic ester monomers having an alcohol-derived moiety of the ester having 1 to 40 or 1 to 30 carbon atoms, or 2 to 24 carbon atoms, or mixtures thereof.
  • Certain esters include methyl esters, ethyl, butyl, C9-11, and C12-18 esters.
  • a suitable (meth)acrylate is methyl methacrylate.
  • mixtures of alcohols of 2 to 11 (or 9 to 11) or 1 to 4 carbon atoms, alone or further in combination with alcohols of 12 to 24 (or 12 to 18) carbon atoms may be used, as described in US Patents 6,881,780 or 6,124,249 .
  • Suitable nitrogen-containing monomers for use in the DVM include nitrogen-containing (meth)acrylate (that is, acrylate or methacrylate) monomers such as amides or nitrogen-containing esters.
  • Suitable amides include the condensation products of (meth)acrylic acid with ammonia, monoamines, diamines, or polyamines.
  • the amine used to form the amide will normally contain at least one, and in certain embodiments exactly one, N-H group capable of condensing with carboxylic acid functionality, to form nitrogen-containing carboxylic derivatives with dispersant functionality.
  • Suitable amines include aromatic amines wherein a carbon atom of the aromatic ring structure is attached directly to the amino nitrogen.
  • the amines may be monoamines or polyamines.
  • the aromatic ring will typically be a mononuclear aromatic ring (i.e., one derived from benzene) but can include fused aromatic rings, especially those derived from naphthalene.
  • aromatic amines also include amino-substituted aromatic compounds and amines in which the amine nitrogen is a part of an aromatic ring, such as 3-aminoquinoline, 5-aminoquinoline, and 8-aminoquinoline. Also included are aromatic amines such as 2-aminobenzimidazole, which contains one secondary amino group attached directly to the aromatic ring and a primary amino group attached to the imidazole ring.
  • aromatic amines include 3-amino-N-(4-anilinophenyl)-N-isopropyl butanamide, and N-(4-anilinophenyl)-3- ⁇ (3-aminopropyl)-(cocoalkyl)amino ⁇ butanamide.
  • Other aromatic amines include various aromatic amine dye intermediates containing multiple aromatic rings linked by, for example, amide structures. Examples include materials of the general structure ⁇ -CONH- ⁇ -NH 2 where the phenyl groups may be further substituted.
  • Aromatic amines include those in which the amine nitrogen is a substituent on an aromatic carboxylic compound, that is, the nitrogen is not sp 2 hybridized within an aromatic ring. Certain aromatic amines, such as alkylated diphenylamines, may be used as antioxidants. To the extent that these materials will condense with a carboxylic functionality, they may also be suitable
  • Aromatic amines can be used alone or in combination with each other or in combination with or aliphatic or cycloaliphatic amines.
  • the amount of such an aliphatic or cycloaliphatic amine may, in some embodiments, be a minor amount compared with the amount of the aromatic amine.
  • Aliphatic or cycloaliphatic amines include monoamines having, e.g., 1 to 8 carbon atoms, such as methylamine, ethylamine, and propylamine, as well as various higher amines. Aliphatic diamines or polyamines can also be used, and in certain embodiments they will have only a single primary or secondary amino group.
  • Examples include dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylamino-ethylamine, dibutylaminoethylamine, 1-(2-aminoethyl)piperidine, 1-(2-aminoethyl)pyrrolidone, aminoethylmorpholine, and aminopropylmorpholine.
  • the nitrogen-containing monomer units may also include one or more (meth)acrylates or (meth) acrylamides of the formula (III), in which R denotes hydrogen or methyl, X denotes oxygen or an amino group of the formula --NHor -NR 7 --, in which R 7 represents an alkyl radical having 1 to 40 carbon atoms, and R 6 denotes a linear or branched alkyl radical substituted by at least one-NR 8 R 9 group and having 2 to 20, or 2 to 6, carbon atoms, R 8 and R 9 independently representing hydrogen or an alkyl radical having 1 to 20 or 1 to 6 carbon atoms, or in which R 8 and R 9 , including the nitrogen atom and optionally a further nitrogen or oxygen atom, form a 5- or 6-membered ring which optionally may be substituted by a C1-C6-alkyl group.
  • R denotes hydrogen or methyl
  • X denotes oxygen or an amino group of the formula --NHor -NR 7 --
  • R 7 represents an
  • ethylenically unsaturated and copolymerizable monomers may be used along with or in place of the (meth)acrylic monomer.
  • maleic acid or maleic anhydride can be reacted with a reactive amine to provide an amide (half amide or bis-amide) or an imide and may similarly be reacted with various aminoalcohols to provide any of a variety of ester or amide or imide compounds.
  • maleic anhydride itself may be copolymerized or grafted onto a polymer chain to give a succinic anhydride moiety which may be further reacted with an amine or aminoalcohol.
  • Other monomers that may be reacted with amines or aminoalcohols to provide a nitrogen-containing monomer include vinyl substituted nitrogen heterocyclic monomers such as N-vinyl imidazole, N-vinyl pyrrolidinone, and N-vinyl caprolactam; dialkylaminoalkyl (meth)acrylate monomers, in which the alkyl or amino alkyl groups may independently contain 1 to 8 carbon atoms; dialkylaminoalkyl (meth)acrylamide monomers, and teriary alkyl (meth)acrylamides such as t-butyl acrylamide.
  • vinyl substituted nitrogen heterocyclic monomers such as N-vinyl imidazole, N-vinyl pyrrolidinone, and N-vinyl caprolactam
  • dialkylaminoalkyl (meth)acrylate monomers in which the alkyl or amino alkyl groups may independently contain 1 to 8 carbon atoms
  • monomers include piperazine N-alkylmethacrylamide, morpholine N-alkylacrylamide, N-2-aminoethyl-N'-hydroxyethyl methacrylamide, and N-2-aminoethyl-N'-pyridinyl methacylamide.
  • the monomer composition may comprise other monomers such as styrene compounds.
  • styrene substituted styrenes having an alkyl substituent in the side chain, such as alpha-methylstyrene and alpha-ethylstyrene, substituted styrenes having an alkyl substituent on the ring, such as vinyltoluene and p-methylstyrene, halogenated styrenes, such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.
  • the amount of the nitrogen-containing monomer may be an amount suitable to provide at least 0.4 percent by weight of nitrogen to the dispersant viscosity modifier or alternatively 0.4 to 2 percent or to 1.5 percent or to 1.2 percent or to 1.0 percent, or alternatively 0.5 to 0.8 percent.
  • the amount of nitrogen-containing monomer required to deliver this amount of nitrogen to the polymer will depend, of course, on the particular monomer and its nitrogen content.
  • the monomer dimethylaminopropyl methacrylamide, having two nitrogens is itself about 16.5 percent by weight nitrogen. Suitable amounts of such monomers generally within the copolymer may thus be 1 to 10 percent by weight, or 2.5 to 6 percent or 3 to 5 percent or about 4 percent.
  • the dispersant viscosity modifier may be prepared by several different processes.
  • the nitrogen-containing copolymer is obtained by reacting, together, (meth)acrylate ester monomers and the nitrogen-containing monomer.
  • the nitrogen-containing monomer is grafted onto a preformed (meth)acrylate copolymer backbone, or maleic anhydride may be grafted and subsequently reacted with amine.
  • the polymer can be prepared by reacting a suitable amine with a (meth)acrylate copolymer, liberating the alcohol functionality from a portion of the ester groups.
  • the dispersant viscosity modifier may be prepared in an organic diluent, and specific amounts and types of diluent can affect the low temperature viscosity properties of lubricants containing them.
  • the molecular weight (number average molecular weight, M n ) of the dispersant viscosity modifier may be 10,000 to 300,000, or 20,000 to 150,000, or 30,000 to 100,000.
  • the amount of the dispersant viscosity modifier employed in final lubricating compositions may be 0.5 to about 10 weight percent, or 0.6 to 5% or 0.75 to 4.0% or 1 to 3.5% or 1.5 to 3.35%. In a concentrate, the amount of the dispersant viscosity modifier will be correspondingly greater, e.g., 2 to 50 or 5 to 45 or 10 to 35 percent by weight.
  • Another component of the present invention is a succinimide dispersant prepared by a certain method, sometimes referred to as "direct alkylation.”
  • Succinimide dispersants generally are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain.
  • Typical alkenyl succinimides have a variety of chemical structures including typically where each R 1 is independently an alkyl group, frequently a polyisobutyl group with a molecular weight of 500-5000, and R 2 are alkylene groups, commonly ethylene (C 2 H 4 ) groups.
  • Such molecules are commonly derived from reaction of an alkenyl acylating agent with a polyamine, and a wide variety of linkages between the two moieties is possible beside the simple imide structure shown above, including a variety of amides and quaternary ammonium salts. Also, a variety of modes of linkage of the R 1 groups onto the imide structure are possible, including various cyclic linkages. Succinimide dispersants are more fully described in U.S. Patents 4,234,435 and 3,172,892 .
  • the succinimide dispersants of the present invention are prepared from hydrocarbyl-subsituted succinic acylating agents which are in turn prepared by the so-called “direct alkylation” or “thermal” route, as contrasted with the so-called “chlorine” route. These routes differ in the method by which a polyalkylene (typically polyisobutylene, but also copolymers including ethylene copolymer) substituent is prepared and by which it is affixed to a maleic, that is, succinic acid or anhydride moiety.
  • a polyalkylene typically polyisobutylene, but also copolymers including ethylene copolymer
  • isobutylene is polymerized in the presence of AlCL3 to produce a mixture of polymers comprising predominantly trisubstituted olefin (III) and tetrasubstituted olefin (IV) end groups, with only a very small amount (for instance, less than 20 percent) of chains containing a terminal vinylidene group (I).
  • isobutylene is polymerized in the presence of BF3 catalyst to produce a mixture of polymers comprising predominantly (for instance, at least 70 percent) terminal vinylidene groups, with smaller amounts of tetrasubstituted end groups and other structures.
  • BF3 catalyst BF3 catalyst
  • a thermal process for preparing polyisobutene-substituted maleic anhydride is described in European patent publication EP 0 355 895 A2 .
  • the intermediate polyisobutene materials from a non-chlorine process sometimes referred to as "high vinylidene PIB," are also described in U.S.
  • Patent 6,165,235 Table 1 of which is summarized below: TABLE 1 PIB (a) Typical Percent in (b) Typical Percent in Terminal Groups Conventional PIB High Vinylidene PIB 4-5% 50-90% I 0-2% 6-35% II 63-67%, tri-substituted absent or minor III 22-28% tetrasubstituted IV and IVA 1-15% IV IVA 5-8%) 0-4% V OTHER 0-10% Note - Structure I may also be present in high-vinylidene PIB at 70-90%. In other embodiments, the invention may usefully use polyisobutylene containing at least 70%, e.g., 70 to 90%, of structures I and II, combined.
  • a certain amount of mono-reacted cyclic material can also be present, as shown: and, in one instance, the hydrocarbyl-substituted succinic anhydride of (a) contains on average 1.1 or 1.3 to 1.8 succinic anhydride moieties per hydrocarbyl group. It is also believed that a minor amount (e.g., up to 7 or 15 or 18 percent, e.g., 7 to 15 percent) of the product may contain a succinic anhydride moiety attached to the hydrocarbyl group by one sort or another of non-cyclic linkage.
  • high vinylidene polyisobutylene which is typically used in the present invention is believed to react with maleic anhydride in the absence of chlorine by a series of thermal "ene” reactions to produce a mixture of mono- and di-succininated polymeric material, the latter believed to have predominantly the general structure (VII): (non-cyclic disuccinated polymeric material) the double bond being located at either position about the central carbon atom.
  • VII general structure
  • acylating agents from polyisobutylene made from a BF 3 process and their reaction with amines is disclosed in U.S. Patent 4,152,499 .
  • Similar adducts can be made using polymers other than polyisobutylene; for instance U.S.
  • Patent 5,275,747 discloses derivatized ethylene alpha-olefin polymers with terminal ethenylidene unsaturation which can be substituted with mono-or dicarboxylic acid producing moieties. These materials from the direct alkylation or thermal process may also contain a small amount of materials with cyclic structure. The subsequently formed dispersant may contain at least one succinic moiety which is attached to the hydrocarbyl substituent through a non-cyclic linkage.
  • the hydrocarbyl substituents on the succinic anhydride component should normally be of sufficient length to provide a desired degree of solubility in a lubricating oil.
  • Such substituent will typically have a molecular weight of at least 300, at least 800, or at least 1200. Typical upper limits to the molecular weight may be determined by considerations of solubility, cost, or other practical considerations, and may be up to 5000 or up to 2500. Thus, for instance, the hydrocarbyl substituents can have a molecular weight of 300 to 5000 or 800 to 2500.
  • the hydrocarbyl-substituted succinic anhydride (or reactive equivalent thereof) is condensed an amine (or a mixture of amines) to form the succinimide dispersant.
  • Amines which can be used in preparing such dispersants include polyamines, such as aliphatic, cycloaliphatic, heterocyclic or aromatic polyamines. Examples of the polyamines include alkylene polyamines, hydroxy containing polyamines, arylpolyamines, and heterocyclic polyamines.
  • Alkylene polyamines are represented by the formula wherein n typically has an average value 1, or 2 to 10, or to 7, or to 5, and the "Alkylene" group has 1, or 2 to 10, or to 6, or to 4 carbon atoms.
  • Each R 5 is independently hydrogen, or an aliphatic or hydroxy-substituted aliphatic group of up to 30 carbon atoms.
  • alkylenepolyamines include polymethylenepolyamines, ethylenepolyamines, butylenepolyamines, propylenepolyamines, and pentylenepolyamines. The higher homologs and related heterocyclic amines such as piperazines and N-aminoalky1-substituted piperazines are also included.
  • polyamines examples include ethylenediamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tris-(2-aminoethyl(amine, propylenediamine, trimethylenediamine, tripropylenetetramine, tetraethylenepentamine (TEPA), hexaethyleneheptamine, and pentaethylenehexamine.
  • DETA diethylenetriamine
  • TETA triethylenetetramine
  • TEPA tetraethylenepentamine
  • hexaethyleneheptamine hexaethyleneheptamine
  • pentaethylenehexamine hexaethyleneheptamine
  • polyamine mixtures are those resulting from stripping of the above-described polyamine mixtures to leave as residue what is often termed polyamine bottoms or, more specifically, polyethyleneamine bottoms.
  • Another useful polyamine is a condensation reaction between a hydroxy compound and a polyamine reactant containing at least one primary or secondary amino group, as. described in U.S. Patent 5,053,152 and PCT publication WO86/05501 .
  • the dispersants described herein may be post-treated by reaction with any of a variety of agents. Among these are urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids such as terephthalic acid, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, and phosphorus compounds. References detailing such treatment are listed in U.S. Patent 4,654,403 .
  • borated dispersants may be prepared by reacting the dispersant with a boron compound such as boric acid or an alkali or mixed alkali metal and alkaline earth metal borate.
  • metal borates are generally a hydrated particulate metal borate which are known in the art.
  • Alkali metal borates include mixed alkali and alkaline metal borates. These metal borates are available commercially.
  • the boron content of the succinimide dispersant, if borated, may be 0.1 to about 1 weight percent or 0.2 to 0.6 or to 0.5 weight percent.
  • the nitrogen content of the dispersant may be 1 to 10 percent by weight, or 1 to 5%, or 1.5 to 3%, or 3 to 8 %, or 5 to 6 % (on an active chemical or diluent-free basis).
  • the dispersant may have a total base number (TBN) of 5 to 180 or 10 to 170 or 15 to 150 or 40 to 130 or 60 to 120, again, on an active chemical basis (factoring out the presence of any diluent).
  • the amount of the dispersant in compositions of the present invention may be 0.1 to 10 weight percent, or 0.5 to 7 % or 1 to 5% or 2 to 3%. These amounts are particularly suitable for fully formulated lubricants. In concentrates, the amounts may be correspondingly greater, e.g., 5 to 70 or 10 to 50 or 15 to 35 or 20 to 30 percent by weight.
  • Suitable materials include antioxidants (such as dialkyl diarylamines, sulfur compounds such as hydroxyalkyl alkyl sulfides (e.g., 1-(tert-dodecylthio)-2-propanol), and hindered phenols including hindered phenolic esters such as those represented by the formula: wherein R 11 is a straight chain or branched chain alkyl group containing 2 to 22 carbon atoms, e.g., 2 to 8, 2 to 6, or 4 to 8 carbon such as 4 or 8 carbon atoms. R 11 may be desirably a 2-ethylhexyl group or an n-butyl group.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • General Details Of Gearings (AREA)
EP08728000.4A 2007-01-30 2008-01-22 Dispersant combination for improved transmission fluids Active EP2109659B1 (en)

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US88719207P 2007-01-30 2007-01-30
PCT/US2008/051589 WO2008094781A2 (en) 2007-01-30 2008-01-22 Dispersant combination for improved transmission fluids

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Publication number Priority date Publication date Assignee Title
US20140274835A1 (en) * 2013-03-13 2014-09-18 Raymond F. Watts Method of providing high coefficients of friction across oil-lubricating friction clutches
EP3981863A1 (en) * 2013-05-14 2022-04-13 The Lubrizol Corporation Lubricating composition and method of lubricating a transmission
JP6775605B2 (ja) * 2016-05-18 2020-10-28 エボニック オペレーションズ ゲーエムベーハー 耐摩耗コポリマーおよび潤滑剤組成物
US10899980B2 (en) * 2017-08-18 2021-01-26 Championx Usa Inc. Kinetic hydrate inhibitors for controlling gas hydrate formation in wet gas systems

Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021357A (en) 1972-03-10 1977-05-03 Texaco Inc. Multifunctional tetrapolymer lube oil additive
US4036767A (en) 1976-06-14 1977-07-19 Texaco Inc. Polymethacrylate additives and lubricating compositions thereof
US4450087A (en) 1974-07-12 1984-05-22 Askew Herbert F Vapor lock resistant hydraulic fluids
EP0355895A2 (en) 1988-08-05 1990-02-28 Shell Internationale Researchmaatschappij B.V. Process for the preparation of succinic anhydride derivatives
US5175255A (en) 1987-03-23 1992-12-29 Amgen Inc. Methods for purification of platelet-derived growth factor
US5665685A (en) 1994-06-02 1997-09-09 Sanyo Chemical Industries, Ltd. Gear and transmission lubricant compositions of improved sludge-dispersibility, fluids comprising the same
US6077909A (en) 1997-02-13 2000-06-20 The Lubrizol Corporation Low chlorine content compositions for use in lubricants and fuels
US20020086965A1 (en) 1995-06-19 2002-07-04 Sivik Matthew R. Dispersant-viscosity improvers for lubricating oil compositions
US20030032293A1 (en) 2001-08-07 2003-02-13 Korean Institute Of Science And Technology High sensitive micro-cantilever sensor and fabricating method thereof
US6586375B1 (en) 2002-04-15 2003-07-01 The Lubrizol Corporation Phosphorus salts of nitrogen containing copolymers and lubricants containing the same
US20040077509A1 (en) 2002-08-02 2004-04-22 Tsuyoshi Yuki Viscosity index improver and lube oil containing the same
US20050124509A1 (en) 2003-12-04 2005-06-09 Antonio Gutierrez Lubricating oil compositions
US20050202981A1 (en) 2003-08-01 2005-09-15 The Lubrizol Corporation Mixed dispersants for lubricants
WO2005116174A1 (en) 2004-05-18 2005-12-08 The Lubrizol Corporation Polymeric dispersant viscosity modifier composition
WO2007044820A1 (en) * 2005-10-11 2007-04-19 The Lubrizol Corporation Product of amines with hydroxy acid as friction modifiers suitable for automatic transmission fluids
WO2007070845A2 (en) 2005-12-15 2007-06-21 The Lubrizol Corporation Engine lubricant for improved fuel economy
JP2007197509A (ja) 2006-01-24 2007-08-09 Sanyo Chem Ind Ltd 潤滑油用スラッジ分散剤
WO2007127615A2 (en) 2006-04-24 2007-11-08 The Lubrizol Corporation Star polymer lubricating composition
EP2053117A1 (en) 2006-08-03 2009-04-29 Idemitsu Kosan Co., Ltd. Lubricant composition
US20120135898A1 (en) 2006-07-27 2012-05-31 The Lubrizol Corporation Multi-Dispersant Lubricating Composition

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3930142A1 (de) * 1989-09-09 1991-03-21 Roehm Gmbh Dispergierwirksame viskositaets-index-verbesserer
EP0439254A3 (en) * 1990-01-23 1992-02-12 Rohm And Haas Company Dispersant polymethacrylate viscosity index improvers
US5969068A (en) * 1995-06-19 1999-10-19 The Lubrizol Corporation Dispersant-viscosity improvers for lubricating oil compositions
US5843874A (en) * 1996-06-12 1998-12-01 Ethyl Corporation Clean performing gear oils
JP3980146B2 (ja) * 1998-01-13 2007-09-26 シェブロンジャパン株式会社 潤滑油添加剤組成物及び潤滑油組成物
CN101031633B (zh) * 2004-07-30 2010-11-10 卢布里佐尔公司 润滑配备有废气再循环的柴油机的方法
US7439213B2 (en) * 2004-10-19 2008-10-21 The Lubrizol Corporation Secondary and tertiary amines as friction modifiers for automatic transmission fluids
JP4583138B2 (ja) * 2004-10-22 2010-11-17 Ｊｘ日鉱日石エネルギー株式会社 変速機用潤滑油組成物

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021357A (en) 1972-03-10 1977-05-03 Texaco Inc. Multifunctional tetrapolymer lube oil additive
US4450087A (en) 1974-07-12 1984-05-22 Askew Herbert F Vapor lock resistant hydraulic fluids
US4036767A (en) 1976-06-14 1977-07-19 Texaco Inc. Polymethacrylate additives and lubricating compositions thereof
US5175255A (en) 1987-03-23 1992-12-29 Amgen Inc. Methods for purification of platelet-derived growth factor
EP0355895A2 (en) 1988-08-05 1990-02-28 Shell Internationale Researchmaatschappij B.V. Process for the preparation of succinic anhydride derivatives
US5665685A (en) 1994-06-02 1997-09-09 Sanyo Chemical Industries, Ltd. Gear and transmission lubricant compositions of improved sludge-dispersibility, fluids comprising the same
US20020086965A1 (en) 1995-06-19 2002-07-04 Sivik Matthew R. Dispersant-viscosity improvers for lubricating oil compositions
US6077909A (en) 1997-02-13 2000-06-20 The Lubrizol Corporation Low chlorine content compositions for use in lubricants and fuels
US20030032293A1 (en) 2001-08-07 2003-02-13 Korean Institute Of Science And Technology High sensitive micro-cantilever sensor and fabricating method thereof
US6586375B1 (en) 2002-04-15 2003-07-01 The Lubrizol Corporation Phosphorus salts of nitrogen containing copolymers and lubricants containing the same
US20040077509A1 (en) 2002-08-02 2004-04-22 Tsuyoshi Yuki Viscosity index improver and lube oil containing the same
US20050202981A1 (en) 2003-08-01 2005-09-15 The Lubrizol Corporation Mixed dispersants for lubricants
US20050124509A1 (en) 2003-12-04 2005-06-09 Antonio Gutierrez Lubricating oil compositions
WO2005116174A1 (en) 2004-05-18 2005-12-08 The Lubrizol Corporation Polymeric dispersant viscosity modifier composition
WO2007044820A1 (en) * 2005-10-11 2007-04-19 The Lubrizol Corporation Product of amines with hydroxy acid as friction modifiers suitable for automatic transmission fluids
WO2007070845A2 (en) 2005-12-15 2007-06-21 The Lubrizol Corporation Engine lubricant for improved fuel economy
JP2007197509A (ja) 2006-01-24 2007-08-09 Sanyo Chem Ind Ltd 潤滑油用スラッジ分散剤
WO2007127615A2 (en) 2006-04-24 2007-11-08 The Lubrizol Corporation Star polymer lubricating composition
US20120135898A1 (en) 2006-07-27 2012-05-31 The Lubrizol Corporation Multi-Dispersant Lubricating Composition
EP2053117A1 (en) 2006-08-03 2009-04-29 Idemitsu Kosan Co., Ltd. Lubricant composition

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
"Chemistry and Technology of Lubricants", 1 January 2010, SPRINGER, article MORTIER ROY M, ET AL: "Viscosity Index Improvers and Thickeners", pages: 1 - 12, XP055806932
"LUBRICANT ADDITIVES, CHEMISTRY AND APPLICATIONS", 1 January 2003, MARCEL DEKKER, INC., , article LESLIE R. RUDNICK: "LUBRICANT ADDITIVES, CHEMISTRY AND APPLICATIONS /Passage/", pages: 8 - 8, XP093022593
"Lubricant Additives, Chemistry and Applications", 1 January 2010, article RUDNICK LESLIE: "Dispersants", pages: 153 - 157,331, XP055806930
LESLIE R. RUDNICK: "LUBRICANT ADDITIVES, CHEMISTRY AND APPLICATIONS", 2003, MARCEL DEKKER, INC.,, pages: 2pp, 342-344, 394 - 396, XP055706749
NIFANT’EV ILYA, VINOGRADOV ALEXANDER, VINOGRADOV ALEXEY, IVCHENKO PAVEL: "DFT Modeling of the Alternating Radical Copolymerization and Alder-Ene Reaction between Maleic Anhydride and Olefins", POLYMERS, vol. 12, no. 4, pages 744, XP055806934, DOI: 10.3390/polym12040744
THEO MANG, WILFRIED DRESEL: "LUBRICANTS AND LUBRICATION, Second Edition", 2007, WILEY-VCH VERLAG, article "6.4.3 Ashless Dispersants (AD)", pages: 2pp, 103, XP055706780
VACLAV STEPINA, VACLAV VESELY: "LUBRICANTS AND SPECIAL FLUIDS,", 1992, ELSEVIER, pages: 2pp, 316 - 319, XP055706757
XIONG ET AL.: "Polyacrylamide degradation and its implications in environmental systems", NPJ CLEAN WATER, vol. 1, 2018, pages 1 - 9, XP055706768

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CA2676290A1 (en) 2008-08-07
WO2008094781A3 (en) 2008-10-16
CA2676290C (en) 2015-03-10
EP2109659A2 (en) 2009-10-21
JP5414537B2 (ja) 2014-02-12
US20100099588A1 (en) 2010-04-22
WO2008094781A2 (en) 2008-08-07

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