EP2707470B1 - Imides aromatiques comme additifs de lubrifiant - Google Patents

Imides aromatiques comme additifs de lubrifiant Download PDF

Info

Publication number
EP2707470B1
EP2707470B1 EP12722998.7A EP12722998A EP2707470B1 EP 2707470 B1 EP2707470 B1 EP 2707470B1 EP 12722998 A EP12722998 A EP 12722998A EP 2707470 B1 EP2707470 B1 EP 2707470B1
Authority
EP
European Patent Office
Prior art keywords
composition
carbon atoms
acid
friction
percent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP12722998.7A
Other languages
German (de)
English (en)
Other versions
EP2707470A1 (fr
Inventor
Daniel J. Saccomando
Richard J. Vickerman
Stuart L. Bartley
Jody A. Kocsis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lubrizol Corp
Original Assignee
Lubrizol Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lubrizol Corp filed Critical Lubrizol Corp
Publication of EP2707470A1 publication Critical patent/EP2707470A1/fr
Application granted granted Critical
Publication of EP2707470B1 publication Critical patent/EP2707470B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/44—Five-membered ring containing nitrogen and carbon only
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/16—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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/72—Esters of polycarboxylic acids
    • 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
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • 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
    • C10M2207/285—Esters of aromatic polycarboxylic acids
    • 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
    • C10M2207/289—Partial esters containing free hydroxy 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086—Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C10M2215/224—Imidazoles
    • 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
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon 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
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • C10M2227/061—Esters derived from boron
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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
    • C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual 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
    • C10N2040/25—Internal-combustion engines

Definitions

  • the present technology relates to the field of additives for fluids such as automatic transmission fluids, traction fluids, fluids for continuously variable transmission fluids (CVTs), dual clutch automatic transmission fluids, farm tractor fluids, engine lubricants, industrial gear lubricants, greases, and hydraulic fluids, as well as for lubricants such as engine oils.
  • fluids such as automatic transmission fluids, traction fluids, fluids for continuously variable transmission fluids (CVTs), dual clutch automatic transmission fluids, farm tractor fluids, engine lubricants, industrial gear lubricants, greases, and hydraulic fluids, as well as for lubricants such as engine oils.
  • V sliding speed
  • a fluid which allows the vehicle to operate without vibration or shudder is said to have good anti-shudder performance.
  • the fluid should maintain those characteristics over its service lifetime.
  • the longevity of the anti-shudder performance in the vehicle is commonly referred to as "anti-shudder durability.”
  • the variable speed friction tester measures the coefficient of friction with respect to sliding speed simulating the speeds, loads, and friction materials found in transmission clutches and correlates to the performance found in actual use. The procedures are well documented in the literature; see for example Society of Automotive Engineers publication #941883.
  • PCT Publication WO2010/132318, November 18, 2010 discloses a condensation product of a hydroxy-polycarboxylic acid with an N,N-di(hydrocarbyl) alkylenediamine, where each hydrocarbyl group independently comprises 1 to about 22 carbon atoms.
  • the product may be an amide or an imide.
  • U.S. Patent Application 2008/0051307 Li, February 28, 2008 , discloses a lubricating composition containing (a) a major amount of an ester of a polycarboxylic acylating agent; and (b) at least one compound from (i) a metal hydrocarbyl dithiophosphate, or (ii) a viscosity modifier.
  • the composition is suitable for high temperature engines.
  • the polycarboxylic acylating agent may be, among others, pyromellitic acid.
  • U.S. Patent Application 2006/0183647 discloses tartrates, tartrimides, tartramides or combinations thereof useful as additives for lubricants.
  • Various compositions including automatic transmission fluids are said to benefit therefrom.
  • materials disclosed are oleyl tartrimide and tridecyl-propoxyamine tartrimide.
  • the alkyl groups of the amines may be linear or branched.
  • U.S. Patent 3,251,853, Hoke, May 17, 1966 discloses an oil-soluble acylated amine.
  • reactants can xylyl-stearic acid or heptylphenyl-heptanoic acid, with tetraethylene pentamine or dodecylamine or N-2-aminoethyloctadecylamine.
  • An example is the condensation product of N-2-aminoethyloctadecylamine with xylyl-stearic acid.
  • U.S. Patent publication 2009/0005277, Watts et al., January 1, 2009 discloses lubricating oil compositions said to have excellent friction stability, comprising, among other components, a polyalkylene polyamine-based friction modifier that has been reacted with an acylating agent to convert at least one secondary amine group into an amide.
  • the disclosed technology therefore, in certain embodiments, provides a friction modifier suitable for providing a transmission fluid, such as an automatic transmission fluid, with a high coefficient of friction or a durable positive slope in a ⁇ -V curve, or both.
  • a transmission fluid such as an automatic transmission fluid
  • US 3078228 A discloses novel chemical products and novel improved lubricating compositions. More particularly, the invention provides novel chemical compounds comprising imides and metal salts of certain of these imides, novel reaction products of metal alcoholates with imides, including certain of the stated novel imides, and a method of making the same, and novel lubricating compositions comprising an oleaginous base and the novel products provided by this invention.
  • US 2010/009876 A1 discloses a lubricating oil composition
  • a lubricating oil composition comprising a base oil for a lubricating oil, (A) a fatty acid partial ester compound, 0.5 to 1.5% by mass of (B) (b1) an aliphatic amine compound and/or (b2) an acid amide compound, 0.01 to 0.1% by mass of (C) a specific benzotriazole derivative and a specific amount of (D) a specific succinimide compound.
  • the lubricating oil composition is used for internal combustion engines such as gasoline engines, diesel engines, engines using dimethyl ether for fuel, gas engines and the like, which does not contain Mo base friction reducing agents.
  • the disclosed technology provides one or more of antiwear performance and corrosion inhibition when used to lubricate a mechanical device.
  • the present invention provides a composition
  • a composition comprising (a) an oil of lubricating viscosity and (b) 0.0001 to 10 weight percent based on the weight of the composition of a condensation product of (i) pyromellitic anhydride with (ii) an aliphatic primary amine, containing 6 to 80 carbon atoms, wherein the aliphatic primary amine is an N,N-dialkyl-1,3-propanediamine, said condensation product comprising an imide.
  • the aliphatic primary amine or alcohol comprises a primary amine containing 12 to 60 carbon atoms.
  • the disclosed technology further provides a method for lubricating a mechanical device, comprising supplying thereto any of the above-described compositions.
  • the mechanical device comprises an automatic transmission.
  • the composition imparts useful frictional properties when lubricating an automatic transmission.
  • Figure 1 shows the coefficient of friction over 30,000 test cycles provided by a lubricant containing a pyromellitic diimide of the disclosed technology.
  • One component which is used in certain embodiments of the disclosed technology is an oil of lubricating viscosity, which can be present in a major amount, for a lubricant composition, or in a concentrate forming amount, for a concentrate.
  • Suitable oils include natural and synthetic lubricating oils and mixtures thereof.
  • the oil of lubricating viscosity is generally present in a major amount (i.e. an amount greater than 50 percent by weight).
  • the oil of lubricating viscosity is present in an amount of 75 to 95 percent by weight, and often greater than 80 percent by weight of the composition.
  • 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 technology (that is, of the presently disclosed technology).
  • 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 I, Group II, Group III, Group IV, or Group V oil, including a synthetic oil, or mixtures thereof.
  • the oil is Groups II, III, IV, or V. These are classifications established by the API Base Oil Interchangeability Guidelines. Group III oils contain ⁇ 0.03 percent sulfur and ⁇ 90 percent saturates and have a viscosity index of ⁇ 120. Group II oils have a viscosity index of 80 to 120 and contain ⁇ 0.03 percent sulfur and ⁇ 90 percent saturates. 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.
  • wax such as slack wax or a Fischer-Tropsch synthesized wax.
  • Such oils are typically characterized as Group III.
  • 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).
  • At least 50% by weight of the oil of lubricating viscosity is a polyalphaolefin (PAO).
  • PAO polyalphaolefin
  • the polyalphaolefins are derived from monomers having from 4 to 30, or from 4 to 20, or from 6 to 16 carbon atoms.
  • Examples of useful PAOs include those derived from 1-decene. These PAOs may have a viscosity of 1.5 to 150 mm 2 /s (cSt) at 100°C.
  • PAOs are typically hydrogenated materials.
  • the oils of the present technology 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 to 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 to 15 or to 20 mm /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), such as less than 10 Pa-s, even 5 or less.
  • the present technology provides, as one component, a condensation product of (i) an aromatic polycarboxylic acid or mixtures thereof, the aromatic polycarboxylic acid comprising an aromatic ring substituted by at least one succinic acid or succinic anhydride group; with (ii) an aliphatic primary amine, containing 6 to 80 carbon atoms, wherein the aliphatic primary amine is an N,N-dialkyl-1,3-propanediamine, said condensation product comprising an imide.
  • the term "aliphatic” may, in some embodiments, include both cyclic and non-cyclic groups (i.e., "alicyclic"), and in other embodiments, it may be limited to non-cyclic groups.
  • these materials are useful as friction modifiers, particularly for lubricating automatic transmissions.
  • these materials are useful as antiwear agents or corrosion inhibitors, particularly for lubricating internal combustion engines.
  • the aromatic polycarboxylic acid may be a diacid, a triacid, a tetraacid, or a higher acid (or reactive equivalents). If the reaction product is a monoimide, the polycarboxylic acid will contain at least two acid (or equivalent) groups. If the reaction product is a diimide, the polycarboxylic acid will contain at least four acid (or equivalent) groups.
  • the acid groups are situated so as to permit formation of a 5-membered or 6-membered cyclic imide, which means that they may be, for instance, in positions ortho to each other on an aromatic ring, or having other relationships as described in greater detail below (e.g., two carbonyl groups may be attached to two adjacent carbon atoms, or to two carbon atoms which in turn are separated by one atom, but not generally attached in positions meta to each other on an aromatic ring).
  • this language should not be interpreted to require that that a cyclic imide is necessarily formed in each instance.
  • carboxylic acid may be used in this document for simplicity to refer designate a carboxylic acid or a reactive equivalent thereof.
  • anhydrides especially cyclic anhydrides, are often used. Cyclic anhydrides would typically have their carboxylic groups situated so as to permit formation of a cyclic imide having 5 or 6 carbon atoms in a cyclic structure, since cyclic anhydrides themselves would normally constitute a cyclic structure of 5 or 6 atoms.
  • the condensation products of the present technology may have, but will not necessarily have, a cyclic imide structure.
  • the reaction product of an anhydride with an amine is usually termed a condensation product, even though a small molecule such as water may not be generated by reaction under all circumstances.
  • the carboxylic acid groups may be attached directly to an aromatic group, or they may be indirectly attached through intervening carbon atoms.
  • An example of a material of the latter sort would be an aromatic ring substituted by at least one succinic acid (or anhydride) group, with other ring substituents also optionally present, such as phenylsuccinic acid or anhydride: This material has two carboxylic groups situated so as to permit formation of a cyclic imide having 5 carbon atoms in the cyclic structure.
  • the aromatic polycarboxylic acid may comprise an aromatic group with at least two carboxylic groups bonded directly to at least two aromatic carbon atoms.
  • the aromatic groups may be simple (one ring) or condensed rings.
  • the carboxylic acid groups may be on adjacent positions on an aromatic ring (e.g., ortho to each other) or they may be appropriately situated on different aromatic rings. Examples include phthalic anhydride, pyromellitic anhydride, and naphthalene-1,8-dioic anhydride.
  • the former have groups on a benzene ring; the latter has groups on a naphthalene (i.e., condensed) ring.
  • the latter is an example of a material having two carboxylic acid groups located on positions 1 and 8 and capable of forming a cyclic imide with 6 atoms in the ring:
  • aromatic rings There may be additional substituents on any of the aromatic rings, including additional carboxylic acid groups, hydrocarbyl groups, hydroxy groups, ether groups, and additional aromatic groups (including fused or non-fused rings). Additionally, one carboxylic group may be directly attached to an aromatic ring and a second may be joined through one or more carbon atoms, e.g., 2-carboxymethylbenzoic anhydride.
  • the aromatic polycarboxylic acid will be condensed with an aliphatic primary amine or alcohol containing 6 to 80 carbon atoms, wherein the aliphatic primary amine is an N,N-dialkyl-1,3-propane diamine.
  • the type of condensation product obtained comprises an imide. More severe conditions are typically required to form the cyclic imide.
  • the condensation product comprises an imide, and in certain cases a diimide.
  • the condensation product comprises a pyromellitic diimide.
  • the reaction product is a condensation product with an aliphatic primary amine, wherein the aliphatic primary amine is an N,N-dialkyl-1,3-propane diamine.
  • the product comprises an imide, and the imide may be a cyclic imide.
  • the primary amine may contain 6 to 80 carbon atoms, or 8 to 70 carbon atoms, or 12 to 60 carbon atoms, or 16 to 50 carbon atoms, or 18 to 40 carbon atoms.
  • the carbon atom that would normally be at position 3, 4, 5, 6, or 7 in the carbon chain of the amine is replaced by an oxygen or nitrogen atom. In some embodiments this replacement atom is at position 4.
  • the aliphatic primary amine of the above structure is an N,N-dialkyl-1,3-propanediamine, which may comprise, for instance, N,N-di-hydrogenatedtallow-1,3-propanediamine, N,N-dicoco-1,3-propanediamine, or N,N-diisostearyl-1,3-propanediamine.
  • the hydrocarbyl group or groups within the amine may comprise a mixture of individual groups on the same or different molecules having a variety of carbon numbers falling generally within the range of carbon numbers set forth above, although molecules with hydrocarbyl groups falling outside this range may also be present. If a mixture of hydrocarbyl groups is present, they may be primarily of even carbon number (e.g., 12, 14, 16, 18, 20, or 22) as is characteristic of groups derived from many naturally-occurring materials, or they may be a mixture of even and odd carbon numbers or, alternatively, an odd carbon number or a mixture of odd numbers. They may be branched, linear, or cyclic and may be saturated or unsaturated, or combinations thereof.
  • the hydrocarbyl groups may contain 16 to 18 carbon atoms, and sometimes predominantly 16 or predominantly 18.
  • specific examples include mixed “coco” groups from cocoamine (predominantly C12 and C14 amines) and mixed “tallow” groups from tallowamine (predominantly C16 and C18 groups), “isostearyl” groups (e.g., isooctadecyl or 16-methylheptadecyl groups), and 2-ethylhexyl groups.
  • Diamines suitable for preparing such products include those in the DuomeenTM series, available from AkzoNobel, having a general structure such as Such polyamines may be prepared by the addition of the monoamine R 1 R 2 NH to acrylonitrile, to prepare the alkyl nitrile amine (cyanoalkyl amine), followed by catalytic reduction of the nitrile group using, e.g., H 2 over Pd/C catalyst, to give the diamine.
  • each of R 1 and R 3 may be independently an alkyl group of 10 to 22 carbon atoms and each of R 2 and R 4 may be independently an alkyl group of 1 to 22 carbon atoms, provided that the total number of carbon atoms in R 1 and R 2 is at least 13 and the total number of carbon atoms in R 3 and R 4 is at least about 13.
  • R 1 , R 2 , R 3 , and R 4 are independently alkyl groups characteristic of tallowamine (including hydrogenated "tallow" groups) or cocoamine.
  • the amount of the condensation product in a fully formulated lubricant is 0.0001 to 10 percent by weight.
  • suitable amounts include 0.05 to 10 percent by weight, or 0.1 to 10 percent, or 0.3 to 5 percent, or 0.5 to 6 percent or 0.5 to 2.5 percent, or 0.8 to 4 percent, or 1 to 2.5 percent, or 0.8 to 2 percent
  • suitable amounts include 0.0001 to 0.1 percent by weight, or 0.001 to 0.05 percent or 0.002 to 0.03 percent.
  • dispersant is a dispersant. It may be described as "other than a condensation product as described above" in the event that some of the products described above may exhibit dispersant characteristics. Examples of dispersants are described in many U.S. Patents including the following: 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022, 3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,743, 3,632,511, 4,234,435, Re 26,433, and 6,165,235.
  • Succinimide dispersants a species of carboxylic dispersants, are prepared by the reaction of a hydrocarbyl-substituted succinic anhydride (or reactive equivalent thereof, such as an acid, acid halide, or ester) with an amine, as described above.
  • the hydrocarbyl substituent group generally contains an average of at least 8, or 20, or 30, or 35 up to 350, or to 200, or to 100 carbon atoms.
  • the hydrocarbyl group is derived from a polyalkene.
  • a polyalkene can be characterized by an M n (number average molecular weight) of at least 500.
  • the polyalkene is characterized by an M n of 500, or 700, or 800, or 900 up to 5000, or to 2500, or to 2000, or to 1500.
  • M n varies from 500, or 700, or 800, to 1200 or to 1300.
  • the polydispersity ( M w / M n ) is at least 1.5.
  • the polyalkenes include homopolymers and inter-polymers of polymerizable olefin monomers of 2 to 16 or to 6, or to 4 carbon atoms.
  • the olefins may be monoolefins such as ethylene, propylene, 1-butene, isobutene, and 1-octene; or a polyolefinic monomer, such as diolefinic monomer, such 1,3-butadiene and isoprene.
  • the inter-polymer is a homo-polymer.
  • An example of a polymer is a polybutene. In one instance about 50% or at least 50% of the polybutene is derived from isobutylene.
  • the polyalkenes can be prepared by conventional procedures.
  • the succinic acylating agents are prepared by reacting a polyalkene with an excess of maleic anhydride to provide substituted succinic acylating agents wherein the number of succinic groups for each equivalent weight of substituent group is at least 1.3, e.g., 1.5, or 1.7, or 1.8.
  • the maximum number of succinic groups per substituent group generally will not exceed 4.5, or 2.5, or 2.1, or 2.0.
  • the preparation and use of substituted succinic acylating agents wherein the substituent is derived from such polyolefins are described in U.S. Patent 4,234,435 .
  • the substituted succinic acylating agent can be reacted with an amine, including those amines described above and heavy amine products known as amine still bottoms.
  • the amount of amine reacted with the acylating agent is typically an amount to provide a mole ratio of CO:N of 1:2 to 1:0.25, or 1:2 to 1:0.75. If the amine is a primary amine, complete condensation to the imide can occur. Varying amounts of amide product, such as the amidic acid, may also be present. If the reaction is, rather, with an alcohol, the resulting dispersant will be an ester dispersant.
  • ester-amide dispersants If both amine and alcohol functionality are present, whether in separate molecules or in the same molecule (as in the above-described condensed amines), mixtures of amide, ester, and possibly imide functionality can be present. These are the so-called ester-amide dispersants.
  • Ammonium dispersants are reaction products of relatively high molecular weight aliphatic or alicyclic halides and amines, such as polyalkylene polyamines. Examples thereof are described in the following U.S. Patents: 3,275,554 , 3,438,757 , 3,454,555 , and 3,565,804 .
  • Mannich dispersants are the reaction products of alkyl phenols in which the alkyl group contains at least 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines).
  • aldehydes especially formaldehyde
  • amines especially polyalkylene polyamines.
  • the materials described in the following U.S. Patents are illustrative: 3,036,003 , 3,236,770 , 3,414,347 , 3,448,047 , 3,461,172, 3,539,633, 3,586,629, 3,591,598, 3,634,515, 3,725,480, 3,726,882, and 3,980,569.
  • Post-treated dispersants are also part of the present technology. They are generally obtained by reacting carboxylic, amine or Mannich dispersants with reagents such as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds such as boric acid (to give “borated dispersants”), phosphorus compounds such as phosphorus acids or anhydrides, or 2,5-dimercaptothiadiazole (DMTD). Exemplary materials of this kind are described in the following U.S.
  • Patents 3,200,107 , 3,282,955 , 3,367,943 , 3,513,093 , 3,639,242 , 3,649,659 , 3,442,808 , 3,455,832 , 3,579,450 , 3,600,372 , 3,702,757 , and 3,708,422 .
  • the amount of dispersant or dispersants, if present in formulations of the present technology, is generally 0.3 to 10 percent by weight. In other embodiments, the amount of dispersant is 0.5 to 7 percent or 1 to 10 percent or 1 to 5 percent or 1.5 to 9 percent or 2 to 8 percent of the final blended fluid formulation. In a concentrate, the amounts will be proportionately higher.
  • Viscosity modifiers and dispersant viscosity modifiers (DVM) are well known.
  • VMs and DVMs may include polymethacrylates, polyacrylates, polyolefins, styrenemaleic ester copolymers, and similar polymeric substances including homopolymers, copolymers and graft copolymers.
  • the DVM may comprise a nitrogen-containing methacrylate polymer, for example, a nitrogen-containing methacrylate polymer derived from methyl methacrylate and dimethylaminopropyl amine.
  • Examples of commercially available VMs, DVMs and their chemical types may include the following: polyisobutylenes (such as IndopolTM from BP Amoco or ParapolTM from ExxonMobil); olefin copolymers (such as LubrizolTM 7060, 7065, and 7067 from Lubrizol and LucantTM HC-2000L and HC-600 from Mitsui); hydrogenated styrene-diene copolymers (such as ShellvisTM 40 and 50, from Shell and LZ® 7308, and 7318 from Lubrizol); styrene/maleate copolymers, which are dispersant copolymers (such as LZ® 3702 and 3715 from Lubrizol); polymethacrylates, some of which have dispersant properties (such as those in the ViscoplexTM series from RohMax, the HitecTM series of viscosity index improver from Afton, and LZ 7702TM, LZ 7727TM, LZ 7725TM
  • AstericTM polymers from Lubrizol methacrylate polymers with radial or star architecture.
  • Viscosity modifiers that may be used are described in U.S. patents 5,157,088 , 5,256,752 and 5,395,539 .
  • the VMs and/or DVMs may be used in the functional fluid at a concentration of up to 20% by weight. Concentrations of 1 to 12%, or 3 to 10% by weight may be used.
  • Another component that may be used in the composition used in the present technology is a supplemental friction modifier.
  • These friction modifiers are well known to those skilled in the art.
  • a list of friction modifiers that may be used is included in U.S. Patents 4,792,410 , 5,395,539 , 5,484,543 and 6,660,695 .
  • U.S. Patent 5,110,488 discloses metal salts of fatty acids and especially zinc salts, useful as friction modifiers.
  • a list of supplemental friction modifiers may include: fatty phosphites borated alkoxylated fatty amines fatty acid amides metal salts of fatty acids fatty epoxides sulfurized olefins borated fatty epoxides fatty imidazolines fatty amines other than the fatty amines discussed above condensation products of carboxylic acids and polyalkylene-polyamines glycerol esters metal salts of alkyl salicylates borated glycerol esters amine salts of alkylphosphoric acids alkoxylated fatty amines ethoxylated alcohols oxazolines imidazolines hydroxyalkyl amides polyhydroxy tertiary amines dialkyl tartrates molybdenum compounds - and mixtures of two or more thereof.
  • fatty phosphites may be generally of the formula (RO) 2 PHO or (RO)(HO)PHO where R may be an alkyl or alkenyl group of sufficient length to impart oil solubility.
  • Suitable phosphites are available commercially and may be synthesized as described in U.S. Patent 4,752,416 .
  • Borated fatty epoxides that may be used are disclosed in Canadian Patent No. 1,188,704 . These oil-soluble boron- containing compositions may be prepared by reacting a boron source such as boric acid or boron trioxide with a fatty epoxide which may contain at least 8 carbon atoms. Non-borated fatty epoxides may also be useful as supplemental friction modifiers.
  • a boron source such as boric acid or boron trioxide
  • Non-borated fatty epoxides may also be useful as supplemental friction modifiers.
  • Borated amines that may be used are disclosed in U.S. Patent 4,622,158 .
  • Borated amine friction modifiers (including borated alkoxylated fatty amines) may be prepared by the reaction of a boron compounds, as described above, with the corresponding amines, including simple fatty amines and hydroxy containing tertiary amines.
  • the amines useful for preparing the borated amines may include commercial alkoxylated fatty amines known by the trademark "ETHOMEEN” and available from Akzo Nobel, such as bis[2-hydroxyethyl]-coco-amine, polyoxyethylene[10]cocoamine, bis[2-hydroxyethyl] soyamine, bis[2-hydroxyethyl] -tallow-amine, polyoxyethylene- [5] tallowamine, bis[2-hydroxyethyl]oleyl-amine, bis[2-hydroxyethyl]octadecylamine, and polyoxyethylene[15]octadecylamine.
  • ETHOMEEN commercial alkoxylated fatty amines known by the trademark "ETHOMEEN” and available from Akzo Nobel, such as bis[2-hydroxyethyl]-coco-amine, polyoxyethylene[10]cococoamine, bis[2-hydroxyethyl] soyamine, bis[2-hydroxyethyl] -tallow-amine,
  • Alkoxylated fatty amines and fatty amines themselves may be useful as friction modifiers. These amines are commercially available.
  • Borated fatty acid esters of glycerol may be prepared by borating a fatty acid ester of glycerol with a boron source such as boric acid.
  • Fatty acid esters of glycerol themselves may be prepared by a variety of methods well known in the art. Many of these esters, such as glycerol monooleate and glycerol tallowate, are manufactured on a commercial scale.
  • Commercial glycerol monooleates may contain a mixture of 45% to 55% by weight monoester and 55% to 45% by weight diester.
  • Fatty acids may be used in preparing the above glycerol esters; they may also be used in preparing their metal salts, amides, and imidazolines, any of which may also be used as friction modifiers.
  • the fatty acids may contain 6 to 24 carbon atoms, or 8 to 18 carbon atoms.
  • a useful acid may be oleic acid.
  • the amides of fatty acids may be those prepared by condensation with ammonia or with primary or secondary amines such as diethylamine and diethanolamine.
  • Fatty imidazolines may include the cyclic condensation product of an acid with a diamine or polyamine such as a polyethylenepolyamine.
  • the friction modifier may be the condensation product of a C8 to C24 fatty acid with a polyalkylene polyamine, for example, the product of isostearic acid with tetraethylenepentamine.
  • the condensation products of carboxylic acids and polyalkylenepolyamines may be imidazolines or amides.
  • the fatty acid may also be present as its metal salt, e.g., a zinc salt.
  • These zinc salts may be acidic, neutral, or basic (overbased).
  • These salts may be prepared from the reaction of a zinc containing reagent with a carboxylic acid or salt thereof.
  • a useful method of preparation of these salts is to react zinc oxide with a carboxylic acid.
  • Useful carboxylic acids are those described hereinabove. Suitable carboxylic acids include those of the formula RCOOH where R is an aliphatic or alicyclic hydrocarbon radical. Among these are those wherein R is a fatty group, e.g., stearyl, oleyl, linoleyl, or palmityl.
  • zinc salts wherein zinc is present in a stoichiometric excess over the amount needed to prepare a neutral salt.
  • Salts wherein the zinc is present from 1.1 to 1.8 times the stoichiometric, e.g., 1.3 to 1.6 times the stoichiometric amount of zinc, may be used.
  • These zinc carboxylates are known in the art and are described in U.S. Pat. 3,367,869 .
  • Metal salts may also include calcium salts. Examples may include overbased calcium salts.
  • Sulfurized olefins are also well known commercial materials used as friction modifiers.
  • a suitable sulfurized olefin is one which is prepared in accordance with the detailed teachings of U.S. Patents 4,957,651 and 4,959,168 . Described therein is a cosulfurized mixture of 2 or more reactants selected from the group consisting of at least one fatty acid ester of a polyhydric alcohol, at least one fatty acid, at least one olefin, and at least one fatty acid ester of a monohydric alcohol.
  • the olefin component may be an aliphatic olefin, which usually will contain 4 to 40 carbon atoms. Mixtures of these olefins are commercially available.
  • the sulfurizing agents useful in the process of the present technology include elemental sulfur, hydrogen sulfide, sulfur halide plus sodium sulfide, and a mixture of hydrogen sulfide and sulfur or sulfur dioxide.
  • Metal salts of alkyl salicylates include calcium and other salts of long chain (e.g. C12 to C16) alkyl-substituted salicylic acids.
  • Amine salts of alkylphosphoric acids include salts of oleyl and other long chain esters of phosphoric acid, with amines such as tertiary-aliphatic primary amines, sold under the trade name PrimeneTM.
  • the amount of the supplemental friction modifier may be 0.1 to 1.5 percent by weight of the lubricating composition, such as 0.2 to 1.0 or 0.25 to 0.75 percent. In some embodiments, however, the amount of the supplemental friction modifier is present at less than 0.2 percent or less than 0.1 percent by weight, for example, 0.01 to 0.1 percent.
  • compositions of the present technology can also include a detergent.
  • Detergents as used herein are salts of organic acids (typically metal salts, although various ammonium salts including quaternary ammonium salts are known).
  • the organic acid portion of the detergent may be a sulfonate, carboxylate, phenate, or salicylate.
  • the metal portion of the detergent may be an alkali or alkaline earth metal. Suitable metals include sodium, calcium, potassium, and magnesium.
  • the detergents are overbased, meaning that there is a stoichiometric excess of metal base over that needed to form the neutral metal salt.
  • Suitable overbased organic salts include the sulfonate salts having a substantially oleophilic character and which are formed from organic materials.
  • Organic sulfonates are well known materials in the lubricant and detergent arts.
  • the sulfonate compound should contain on average 10 to 40 carbon atoms, such as 12 to 36 carbon atoms or 14 to 32 carbon atoms on average.
  • the phenates, salicylates, and carboxylates have a substantially oleophilic character.
  • the carbon atoms While the present technology allows for the carbon atoms to be either aromatic or in paraffinic configuration, in certain embodiments alkylated aromatics are employed. While naphthalene based materials may be employed, the aromatic of choice is the benzene moiety.
  • Suitable compositions thus include an overbased monosulfonated alkylated benzene such as a monoalkylated benzene.
  • Alkyl benzene fractions may be obtained from still bottom sources and are mono- or di-alkylated. It is believed, in the present technology, that the mono-alkylated aromatics are superior to the dialkylated aromatics in overall properties.
  • a mixture of mono-alkylated aromatics e.g., benzene
  • the mono-alkylated salt benzene or toluene sulfonate
  • the mixtures wherein a substantial portion of the composition contains polymers of propylene as the source of the alkyl groups assist in the solubility of the salt.
  • mono-functional (e.g., mono-sulfonated) materials avoids crosslinking of the molecules with less precipitation of the salt from the lubricant.
  • the salt may be "overbased."
  • overbasing it is meant that a stoichiometric excess of the metal base be present over that required for the anion of the neutral salt.
  • the excess metal from overbasing has the effect of neutralizing acids which may build up in the lubricant.
  • the excess metal will be present over that which is required to neutralize the anion at in the ratio of up to 30:1, such as 5:1 to 18:1 on an equivalent basis.
  • the amount of the overbased salt utilized in the composition is typically 0.025 to 3 or to 5 weight percent on an oil free basis, such as 0.1 to 1.0 percent or 0.2 to 4 percent.
  • the final lubricating composition may contain no detergent or substantially no detergent or only a low amount of detergent. That is, for a calcium overbased detergent for instance, the amount may be such as to provide less than 250 parts per million calcium, e.g., 0 to 250 or 1 to 200 or 10 to 150 or 20 to 100 or 30 to 50 parts per million calcium, or less than any of the foregoing non-zero amounts.
  • Such low amounts of detergent may be particularly suitable for automatic transmission applications. This is in contrast with more conventional automatic transmission formulations which may contain sufficient calcium detergent to provide 300 to 600 ppm calcium.
  • Formulations suitable for lubricating an internal combustion engine will typically have non-zero amounts of detergents, e.g., 0.1 to 5 percent.
  • the overbased salt is usually made in up to about 50% oil and has a TBN range of 10-800 or 10-600 on an oil free basis. Borated and non-borated overbased detergents are described in U.S. Patents 5,403,501 and 4,792,410 .
  • compositions of the present technology can also include at least one phosphorus compound such as organic or inorganic phosphorus acids, organic or inorganic phosphorus acid salt, organic phosphorus acid esters, or derivatives thereof including sulfur-containing analogs which may, in certain embodiments, be in an amount of 0.002-1.0 weight percent.
  • the amount of such phosphorus compound may be those that will supply 0.025 to 0.085 percent or 0.02 to 0.08 percent phosphorus to the composition.
  • the phosphorus acids, salts, esters or derivatives thereof include phosphoric acid, phosphorous acid, phosphorus acid esters or salts thereof, phosphites, phosphorus-containing amides, phosphorus-containing carboxylic acids or esters, phosphorus-containing ethers, and mixtures thereof. Some phosphorus materials may serve as antiwear agents.
  • the phosphorus acid, ester, or derivative can be an organic or inorganic phosphorus acid, phosphorus acid ester, phosphorus acid salt, or derivative thereof.
  • the phosphorus acids include the phosphoric, phosphonic, phosphinic, and thiophosphoric acids including dithiophosphoric acid as well as the mono-thiophosphoric, thiophosphinic and thiophosphonic acids.
  • One group of phosphorus compounds are alkylphosphoric acid mono alkyl primary amine salts as represented by the formula where R 1 , R 2 , R 3 are alkyl or hydrocarbyl groups or one of R 1 and R 2 can be H.
  • the materials are usually a 1:1 mixture of dialkyl and monoalkyl phosphoric acid esters. Compounds of this type are described in U.S. Patent 5,354,484 .
  • Eighty-five percent phosphoric acid is a suitable material for addition to the fully-formulated compositions and can be included at a level of 0.01 to 0.3 weight percent based on the weight of the composition, such as 0.03 to 0.2 or to 0.1 percent.
  • the phosphoric acid may form a salt with a basic component such as a succinimide dispersant.
  • phosphorus-containing materials that may be present include dialkyl phosphites (sometimes referred to as dialkyl hydrogen phosphonates) such as dibutyl phosphite.
  • phosphorus materials include phosphorylated hydroxy-substituted triesters of phosphorothioic acids and amine salts thereof, as well as sulfur-free hydroxy-substituted di-esters of phosphoric acid, sulphur-free phosphorylated hydroxy-substituted di- or tri-esters of phosphoric acid, and amine salts thereof. These materials are further described in U.S. patent application US 2008-0182770 .
  • antioxidants that is, oxidation inhibitors
  • antioxidants including hindered phenolic antioxidants, secondary aromatic amine antioxidants such as dinonyldiphenylamine as well as such well-known variants as monononyldiphenylamine and diphenylamines with other alkyl substituents such as mono- or di-octyl, sulfurized phenolic antioxidants, oil-soluble copper compounds, phosphorus-containing antioxidants, and organic sulfides, disulfides, and polysulfides such as 2-hydroxyalkyl, alkyl thioethers or 1-t-dodecylthio-2-propanol or sulfurized 4-carbobutoxycyclohexene or other sulfurized olefins.
  • the amount of antioxidant may be 0.1 to 5 percent by weight or 0.15 to 2.5 percent or
  • corrosion inhibitors such as tolyl triazole and dimercaptothiadiazole and oil-soluble derivatives of such materials.
  • seal swell agents such as isodecyl sulfolane or phthalate esters, which are designed to keep seals pliable.
  • pour point depressants such as alkylnaphthalenes, polymethacrylates, vinyl acetate/fumarate or /maleate copolymers, and styrene/maleate copolymers.
  • anti-wear agents such as zinc dialkyldithiophosphates, tridecyl adipate, and various long-chain derivatives of hydroxy carboxylic acids, such as tartrates, tartramides, tartrimides, and citrates as described in US Application 2006-0183647 .
  • These optional materials are known to those skilled in the art, are generally commercially available, and are described in greater detail in published European Patent Application 761,805 .
  • corrosion inhibitors e.g., tolyltriazole, dimercaptothiadiazoles
  • dyes e.g., fluidizing agents, odor masking agents, and antifoam agents.
  • Organic borate esters and organic borate salts can also be included.
  • the above components can be in the form of a fully-formulated lubricant or in the form of a concentrate within a smaller amount of lubricating oil. If they are present in a concentrate, their concentrations will generally be directly proportional to their concentrations in the more dilute form in the final blend.
  • the presently described compositions may be used in a method for lubricating a mechanical device, comprising supply to the mechanical device any of the lubricant compositions described herein.
  • the mechanical device may be an automatic transmission such as found in a vehicle such as an automobile.
  • Automatic transmissions include continuously variable transmissions and dual clutch transmissions, as well as transmissions for gasoline, diesel, and hybrid engines of various types (including gasoline/electric hybrids).
  • Mechanical devices also include internal combustion engines, including two-stroke cycle and four-stroke cycle engines, gasoline-fueled engines, diesel-fueled engines, spark ignited engines, compression ignited engines, sump-lubricated engines, and engines in which the lubricant is supplied in admixture with fuel.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include:
  • Duomeen®2HT is a tradename of Akzo Nobel for the diamine which may be represented by (HTallow) 2 N-(CH 2 ) 3 NH 2 , where HTallow represents hydrogenated tallow, being a mixture of about 64% C18 groups, 31% C16 groups, 4% C14 groups, and 1% C12 groups.
  • a 2 L round-bottom flange flask is equipped with a stirrer, nitrogen inlet, thermocouple, Dean-Stark trap, and condenser.
  • To the flask is charged 56.7 g pyromellitic dianhydride and 750 mL xylene.
  • the mixture is heated to about 110 °C with stirring, and 300 g of Duomeen®2HT is added dropwise over about 2 hours.
  • the mixture is heated to 145 °C and stirred for 4 hours, then further heated to 190 °C for 1 hour under vacuum, allowing solvent and any remaining water to be removed by distillation, and then allowed to cool.
  • the resulting diimide is obtained in an amount of 332 g.
  • Comparative Preparative Example B Reaction of 2-ethylhexanol with pyromellitic dianhydride. Pyromellitic dianhydride, 21.2 g, and 2-ethylhexanol, 25.6 g, are added to a 250 mL 4-necked flask equipped with a mechanical stirrer, nitrogen inlet, thermocouple, and Dean-Stark trap topped with a condenser. The reaction mixture is heated to 150 °C over 30 minutes and held at temperature for 2 hours.
  • Base formulation I is prepared with the following components:
  • Base formulation II is prepared with the following components:
  • Lubricants for testing are prepared by adding one of the test materials identified in the tables below, to the indicated base formulation.
  • the resulting lubricants are subjected to a VSFT test, which is a variable speed friction test.
  • the VSFT apparatus consists of a disc that can be metal or another friction material which is rotated against a metal surface.
  • the friction materials employed in the particular tests are various commercial friction materials commonly used in automatic transmission clutches, as indicated in the Tables.
  • the test is run over three temperatures and two load levels.
  • the coefficient of friction measured by the VSFT is plotted against the sliding speed (50 and 200 r.p.m.) over a number speed sweeps at a constant pressure.
  • results are sometimes presented as slope of the ⁇ -V curve as a function of time, reported for 40, 80, and 120 °C and 24 kg and 40 kg (235 and 392 N) force, determined at 4 hour intervals from 0 to 52 hours.
  • the slope will initially be positive, with a certain amount of variability, and may gradually decrease, possibly becoming negative after a certain period of time. Longer duration of positive slope is desired.
  • the data is initially collected as a table of slope values as a function of time, for each run.
  • each formulation at each temperature is assigned a "slope score.”
  • A the fraction of slope values within the first 7 time measurements (0 to 24 hours) at 24 kg and of the first 7 measurements at 40 kg (thus 14 measurements total) that are positive, as a percent.
  • B The fraction of the slope values at the two pressures (14 measurements total) within the second 24 hours (28-52 hours) that are positive are denoted as "B”.
  • the slope score is defined as A + 2B.
  • the extra weighting given to the latter portion of the test is to reflect the greater importance (and difficulty) of preparing a durable fluid that retains a positive slope in the latter stages of the test.
  • the maximum score of 300 denotes a fluid that exhibits a consistently positive slope through the entire test.
  • Friction Mat'1 a Slope Score 40°C 80°C 120°C 1* none - I 6100 0 28.57 78.57 2 A 1 I 6100 78.57 171.43 235.72 3 A 2.5 I 6100 85.74 221.44 264.28 4* none - II 6100 0 21.43 128.57 5 A 1 II 6100 71.43 114.29 157.14 6 A 2.5 II 6100 185.71 271.43 300 7* none - II 4211 0 14.29 200 8 A 2.5 II 4211 271.43 292.86 300 * A reference or comparative example a. Friction materials: RaybestosTM 4211 or Borg WarnerTM 6100, as indicated
  • results show desirable frictional performance by materials of the present technology, in particular as compared to the base formulation from which they are absent.
  • the results also indicate that better performance is sometimes obtained at relatively higher concentrations of 2.5% compared with 1.0%.
  • Example 3 containing 2.5% of the pyromellitic dimide of Preparative Example A in Base Formulation I, is subjected to a Ford 30K durability dynamic friction test (DynaxTM D-0530-31). Friction between steel and friction plates of a lubricated clutch is measured during the engagement process. The midpoint dynamic coefficient of friction is determined during the 50 ms interval centrally located at 1800 r.p.m. between 400 and 30,000 engagement cycles, repeated at 4 cycles per minute. Lubricant temperature is 135 °C.
  • FIG. 1 A plot of midpoint coefficients of friction is shown in Figure 1 .
  • the upper, solid line, indicated by diamond shapes, represents the coefficient of friction for the fluid of Example 3, containing the pyromellitic diimide.
  • the lower, dashed line, indicated by the open circles, represents the same baseline fluid without the pyromellitc diimide.
  • the present technology will also impart good antishudder durability to the lubrication of a wet clutch as typically found in an automatic transmission.
  • a series of lubricant formulations is prepared containing additive components typically used in heavy duty diesel engine lubricants.
  • the base formulation contains, in a 100-120N mineral oil, 7.6% of an olefin copolymer viscosity modifier (including 92% diluent oil), 0.15% of a pour point depressant (oil diluted), 5.1% of a succinimide dispersant (47% diluent oil), 0.63% zinc dialkyldithiophosphates (9% oil), 2.2% of a mixture of antioxidants, 1.53% overbased calcium sulfonate detergents (42% oil), 0.1% oleamide, and 90 ppm commercial antifoam agent.
  • lubricant formulations are subjected to a copper and lead coupon corrosion test. In this test, 50 g of lubricant sample, containing Cu and Pb coupons, is bubbled with 50 cm 3 air, typically at 135 °C, for typically 216 hours.
  • Glycerol monooleate is known to lead to excessive lead corrosion. This excessive corrosion is significantly reduced by the presence of pyromellitic ester. Copper corrosion, as evaluated by visual rating, is typically improved by the presence of pyromellitic ester, especially when molybdenum is also present. (Copper corrosion as measured by ppm Cu is not significantly affected.)
  • a lubricant composition suitable for use as an engine lubricant is prepared with the following components, in weight percents: 1.0% tetraester of pyromellitic acid and 2-ethylhexanol as from Comparative Prep. Ex. B
  • the lubricant composition of comparative Example 17 will exhibit one or more of good antiwear performance and good coefficient of friction.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (10)

  1. Composition comprenant
    (a) une huile de viscosité lubrifiante et
    (b) de 0,0001 à 10 % en poids sur la base du poids de la composition d'un produit de condensation
    (i) d'anhydride pyromellitique ; avec
    (ii) une amine primaire aliphatique, contenant 6 à 80 atomes de carbone, dans laquelle l'amine primaire aliphatique est une N,N-dialkyl-1,3-propanediamine,
    ledit produit de condensation comprenant un imide.
  2. Composition selon la revendication 1, dans laquelle l'amine primaire aliphatique est une amine primaire contenant 12 à 60 atomes de carbone.
  3. Composition selon l'une quelconque des revendications 1 à 2, dans laquelle le produit de condensation comprend un imide cyclique.
  4. Composition selon l'une quelconque des revendications 1 à 3, dans laquelle le produit de condensation comprend un diimide.
  5. Composition selon l'une quelconque des revendications 1 à 4, dans laquelle le produit de condensation comprend un diimide pyromellitique.
  6. Composition selon la revendication 1, dans laquelle la N,N-dialkyl-1,3-propanediamine comprend la N,N-di-(suif hydrogéné)-1,3-propanediamine, la N,N-dicoco-1,3-propanediamine ou la N,N-diisostéaryl-1,3-propanediamine.
  7. Composition selon l'une quelconque des revendications 1 à 6, dans laquelle le produit de condensation comprend un matériau représenté par
    Figure imgb0011
     où R1 et R3 représentent chacun indépendamment un groupe alkyle de 8 à 22 atomes de carbone et R2 et R4 représentent chacun indépendamment un groupe alkyle de 1 à 22 atomes de carbone, à condition que le nombre total d'atomes de carbone dans R1 et R2 soit d'au moins 13 et le nombre total d'atomes de carbone dans R3 et R4 est d'au moins 13.
  8. Composition selon la revendication 7, dans laquelle R1, R2, R3, et R4 sont des groupes alkyle caractéristiques de la suifamine, la cocoamine ou l'isostéarylamine.
  9. Composition selon l'une quelconque des revendications 1 à 8, comprenant en outre au moins un additif choisi dans le groupe constitué par les esters de borate organiques, les sels de borate organiques, les esters de phosphore organiques, les sels de phosphore organiques, les sels de phosphore inorganiques et les acides de phosphore inorganiques.
  10. Procédé de lubrification d'un dispositif mécanique, comprenant la fourniture de la composition selon l'une quelconque des revendications 1 à 9.
EP12722998.7A 2011-05-12 2012-05-08 Imides aromatiques comme additifs de lubrifiant Active EP2707470B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161485247P 2011-05-12 2011-05-12
PCT/US2012/036867 WO2012154708A1 (fr) 2011-05-12 2012-05-08 Imides et esters aromatiques utilisés comme additifs de lubrifiant

Publications (2)

Publication Number Publication Date
EP2707470A1 EP2707470A1 (fr) 2014-03-19
EP2707470B1 true EP2707470B1 (fr) 2021-04-21

Family

ID=46147726

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12722998.7A Active EP2707470B1 (fr) 2011-05-12 2012-05-08 Imides aromatiques comme additifs de lubrifiant

Country Status (9)

Country Link
US (1) US20140107001A1 (fr)
EP (1) EP2707470B1 (fr)
JP (1) JP6100243B2 (fr)
KR (1) KR101951396B1 (fr)
CN (1) CN103534341B (fr)
AU (2) AU2012253694A1 (fr)
BR (1) BR112013029108A2 (fr)
CA (1) CA2834072A1 (fr)
WO (1) WO2012154708A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9243203B2 (en) * 2012-11-30 2016-01-26 Chevron Oronite Company Llc Copolymers of polyaminopolyolefins and polyanhydrides and methods of their preparation
CA2967334C (fr) 2014-11-12 2023-03-21 The Lubrizol Corporation Esters phosphores mixtes pour des applications de lubrifiant
EP3280787B1 (fr) 2015-04-09 2023-09-06 The Lubrizol Corporation Lubrifiants contenant des composés d'ammonium quaternaire
CN110088255A (zh) 2016-12-16 2019-08-02 路博润公司 具有在滚针轴承上的减少的磨损的自动变速器的润滑
CA3074318A1 (fr) * 2017-09-18 2019-03-21 Chevron Oronite Company Llc Dispersants de polyimide et leur procedes de fabrication et d'utilisation
CN111492043B (zh) * 2017-11-30 2023-06-09 路博润公司 受阻胺封端的丁二酰亚胺分散剂和含有其的润滑组合物
US10822569B2 (en) * 2018-02-15 2020-11-03 Afton Chemical Corporation Grafted polymer with soot handling properties
US10851324B2 (en) 2018-02-27 2020-12-01 Afton Chemical Corporation Grafted polymer with soot handling properties
US20190352575A1 (en) * 2018-05-18 2019-11-21 Chevron Japan Ltd. Lubricating oils for wet clutch systems
US10899989B2 (en) 2018-10-15 2021-01-26 Afton Chemical Corporation Amino acid grafted polymer with soot handling properties
JP7274277B2 (ja) 2018-10-24 2023-05-16 出光興産株式会社 潤滑油組成物
US11046908B2 (en) 2019-01-11 2021-06-29 Afton Chemical Corporation Oxazoline modified dispersants

Family Cites Families (64)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3159637A (en) * 1964-12-01 Process for the preparation of
US3036003A (en) 1957-08-07 1962-05-22 Sinclair Research Inc Lubricating oil composition
US3078228A (en) * 1959-11-06 1963-02-19 Houghton & Co E F Imide compounds and lubricants containing the same
US3236770A (en) 1960-09-28 1966-02-22 Sinclair Research Inc Transaxle lubricant
US3200107A (en) 1961-06-12 1965-08-10 Lubrizol Corp Process for preparing acylated amine-cs2 compositions and products
US3251853A (en) 1962-02-02 1966-05-17 Lubrizol Corp Oil-soluble acylated amine
DE1271877B (de) 1963-04-23 1968-07-04 Lubrizol Corp Schmieroel
US3282955A (en) 1963-04-29 1966-11-01 Lubrizol Corp Reaction products of acylated nitrogen intermediates and a boron compound
US3513093A (en) 1963-06-17 1970-05-19 Lubrizol Corp Lubricant containing nitrogen-containing and phosphorus-containing succinic derivatives
US3455832A (en) 1963-09-09 1969-07-15 Monsanto Co Schiff bases
GB1053577A (fr) 1963-11-01
US3414347A (en) 1965-03-30 1968-12-03 Edroy Products Company Inc Binocular with pivoted lens plate
GB1142195A (en) 1965-06-18 1969-02-05 British Petroleum Co Alkaline lubricating oil
US3539633A (en) 1965-10-22 1970-11-10 Standard Oil Co Di-hydroxybenzyl polyamines
US3442808A (en) 1966-11-01 1969-05-06 Standard Oil Co Lubricating oil additives
US3461172A (en) 1966-11-22 1969-08-12 Consolidation Coal Co Hydrogenation of ortho-phenolic mannich bases
US3702757A (en) 1967-03-09 1972-11-14 Chevron Res Phosphate ester amine salts useful as fuel detergents and anti-icing agents
US3448047A (en) 1967-04-05 1969-06-03 Standard Oil Co Lube oil dispersants
US3600372A (en) 1968-06-04 1971-08-17 Standard Oil Co Carbon disulfide treated mannich condensation products
US3586629A (en) 1968-09-16 1971-06-22 Mobil Oil Corp Metal salts as lubricant additives
US3591598A (en) 1968-11-08 1971-07-06 Standard Oil Co Certain condensation products derived from mannich bases
US3726882A (en) 1968-11-08 1973-04-10 Standard Oil Co Ashless oil additives
US3634515A (en) 1968-11-08 1972-01-11 Standard Oil Co Alkylene polyamide formaldehyde
US3725480A (en) 1968-11-08 1973-04-03 Standard Oil Co Ashless oil additives
US3639242A (en) 1969-12-29 1972-02-01 Lubrizol Corp Lubricating oil or fuel containing sludge-dispersing additive
US3649659A (en) 1970-03-24 1972-03-14 Mobil Oil Corp Coordinated complexes of mannich bases
US3708422A (en) 1971-01-29 1973-01-02 Cities Service Oil Co Electric discharge machining fluid
US3980569A (en) 1974-03-15 1976-09-14 The Lubrizol Corporation Dispersants and process for their preparation
US4234435A (en) 1979-02-23 1980-11-18 The Lubrizol Corporation Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation
US4237022A (en) 1979-10-01 1980-12-02 The Lubrizol Corporation Tartarimides and lubricants and fuels containing the same
JPS5653191A (en) * 1979-10-09 1981-05-12 Nippon Oil Co Ltd Lubricating oil composition
US4661277A (en) * 1981-01-16 1987-04-28 Mobil Oil Corporation Anti-rust compositions
CA1188704A (fr) 1981-05-26 1985-06-11 Kirk E. Davis Compositions a teneur de bore destinees a servir d'additifs pour lubrifiants
US4622158A (en) 1983-11-09 1986-11-11 The Lubrizol Corporation Aqueous systems containing organo-borate compounds
US4789493A (en) 1986-02-05 1988-12-06 Mobil Oil Co Lubricants containing n-alkylalkylenediamine amides
US4741848A (en) 1986-03-13 1988-05-03 The Lubrizol Corporation Boron-containing compositions, and lubricants and fuels containing same
EP0309481B1 (fr) 1986-06-13 1994-03-16 The Lubrizol Corporation Compositions lubrifiantes et de fluide fonctionnel contenant du phosphore
US5110488A (en) 1986-11-24 1992-05-05 The Lubrizol Corporation Lubricating compositions containing reduced levels of phosphorus
US4752416A (en) 1986-12-11 1988-06-21 The Lubrizol Corporation Phosphite ester compositions, and lubricants and functional fluids containing same
US4792410A (en) 1986-12-22 1988-12-20 The Lubrizol Corporation Lubricant composition suitable for manual transmission fluids
IN172215B (fr) 1987-03-25 1993-05-08 Lubrizol Corp
US5157088A (en) 1987-11-19 1992-10-20 Dishong Dennis M Nitrogen-containing esters of carboxy-containing interpolymers
US4957651A (en) 1988-01-15 1990-09-18 The Lubrizol Corporation Mixtures of partial fatty acid esters of polyhydric alcohols and sulfurized compositions, and use as lubricant additives
US4959168A (en) 1988-01-15 1990-09-25 The Lubrizol Corporation Sulfurized compositions, and additive concentrates and lubricating oils containing same
DE68912307T2 (de) 1988-10-24 1994-05-05 Exxon Chemical Patents Inc Amid enthaltende reibungsmodifizierungsmittel zur verwendung bei leistungstransmissionsfluiden.
BR9007186A (pt) 1990-01-05 1992-01-28 Lubrizol Corp Composicao lubrificante e metodo de lubrificacao de transmissoes e conjuntos de engrenagens
JPH06136374A (ja) * 1992-07-01 1994-05-17 Kao Corp 潤滑油組成物
AU710294B2 (en) 1995-09-12 1999-09-16 Lubrizol Corporation, The Lubrication fluids for reduced air entrainment and improved gear protection
JP3520198B2 (ja) * 1998-05-08 2004-04-19 東燃ゼネラル石油株式会社 潤滑油組成物
US6150306A (en) * 1999-03-04 2000-11-21 Morton Internatioanl Inc. Fluorescent tracer dyes
WO2002024840A1 (fr) * 2000-09-20 2002-03-28 Exxonmobil Research And Engineering Company Composition lubrifiante pour moteur diesel
JP3555891B2 (ja) * 2002-02-22 2004-08-18 新日本石油株式会社 低摩擦摺動材料及びこれに用いる潤滑油組成物
US6660695B2 (en) 2002-03-15 2003-12-09 Infineum International Ltd. Power transmission fluids of improved anti-shudder properties
US7429554B2 (en) * 2004-01-07 2008-09-30 The Lubrizol Corporation Automatic transmission fluids with phthalic acid corrosion inhibitor
US20080051307A1 (en) 2004-07-27 2008-02-28 The Lubrizol Corporation Lubricating Compositions Containing An Ester Of A Polycarboxylic Acylating Agent
US7807611B2 (en) 2004-10-12 2010-10-05 The Lubrizol Corporation Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof
JP4677359B2 (ja) * 2005-03-23 2011-04-27 アフトン・ケミカル・コーポレーション 潤滑組成物
FR2885139B1 (fr) 2005-04-29 2010-12-24 Agronomique Inst Nat Rech Preparation de complexes solubles proteine n-proteine p tronquee ou de proteine n soluble d'un virus de la famille des paramyxoviridae et leurs utilisations vaccinales
CA2625029C (fr) * 2005-10-11 2014-12-23 The Lubrizol Corporation Produit d'amines et d'acide hydroxy utilise comme modificateur de frottement adaptes aux liquides de transmission automatique
IN2009CN02056A (fr) * 2006-10-17 2015-08-07 Idemitsu Kosan Co
JP2008127435A (ja) * 2006-11-17 2008-06-05 Idemitsu Kosan Co Ltd 潤滑油添加剤および潤滑油組成物
US20080182770A1 (en) 2007-01-26 2008-07-31 The Lubrizol Corporation Antiwear Agent and Lubricating Compositions Thereof
US20090005277A1 (en) 2007-06-29 2009-01-01 Watts Raymond F Lubricating Oils Having Improved Friction Stability
KR101703368B1 (ko) * 2009-05-13 2017-02-06 더루우브리졸코오포레이션 윤활제의 마찰 조정제로서의 이미드 및 비스-아미드

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
AU2012253694A1 (en) 2013-11-07
CN103534341A (zh) 2014-01-22
KR101951396B1 (ko) 2019-02-22
US20140107001A1 (en) 2014-04-17
JP2014517106A (ja) 2014-07-17
CA2834072A1 (fr) 2012-11-15
JP6100243B2 (ja) 2017-03-22
WO2012154708A1 (fr) 2012-11-15
KR20140037853A (ko) 2014-03-27
AU2017202845A1 (en) 2017-05-18
CN103534341B (zh) 2015-12-09
EP2707470A1 (fr) 2014-03-19
AU2017202845B2 (en) 2019-01-17
BR112013029108A2 (pt) 2017-02-07

Similar Documents

Publication Publication Date Title
AU2017202845B2 (en) Aromatic imides and esters as lubricant additives
US8778858B2 (en) Amine derivatives as friction modifiers in lubricants
EP2398876B1 (fr) Bis-amides d'acide oxalique ou amide-ester en tant que modificateurs de frottement dans des lubrifiants
US9006156B2 (en) Imides and bis-imides as friction modifiers in lubricants
US8501674B2 (en) Amine derivatives as friction modifiers in lubricants
EP3161114B1 (fr) Mélanges de modificateurs de coefficient de frottement pour conférer de bonne performances au frottement à des liquides pour transmission

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20131118

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20180614

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20201116

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602012075294

Country of ref document: DE

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1384653

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210515

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1384653

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210421

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20210421

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210722

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210821

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210823

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602012075294

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210531

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210531

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210508

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20210531

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20220124

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210821

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210531

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20220527

Year of fee payment: 11

Ref country code: FR

Payment date: 20220525

Year of fee payment: 11

Ref country code: DE

Payment date: 20220527

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20120508

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230516

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602012075294

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20230508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20231201

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230531