EP3134496A1 - Multigrade-schmiermittelzusammensetzung - Google Patents

Multigrade-schmiermittelzusammensetzung

Info

Publication number
EP3134496A1
EP3134496A1 EP15719586.8A EP15719586A EP3134496A1 EP 3134496 A1 EP3134496 A1 EP 3134496A1 EP 15719586 A EP15719586 A EP 15719586A EP 3134496 A1 EP3134496 A1 EP 3134496A1
Authority
EP
European Patent Office
Prior art keywords
lubricating
oil
viscosity
composition
lubricant
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.)
Granted
Application number
EP15719586.8A
Other languages
English (en)
French (fr)
Other versions
EP3134496B1 (de
Inventor
John G. Loop
Mary Galic Raguz
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
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Filing date
Publication date
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Application filed by Lubrizol Corp filed Critical Lubrizol Corp
Publication of EP3134496A1 publication Critical patent/EP3134496A1/de
Application granted granted Critical
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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular compounds
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
    • 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
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
    • 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
    • C10M2207/028—Overbased 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—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
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/54—Fuel economy
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines

Definitions

  • the disclosed technology relates to a lubricating composition for a heavy duty diesel engine that provides for improved fuel economy without reducing durability (i.e. anti-wear) performance of the engine. This may be achieved through the use of high viscosity index base oils in combination with ashless dispersants and overbased metal-containing detergents.
  • Lubricating oil compositions are used for the smooth operation of internal combustion engines.
  • the engine oils for internal combustion engines in particular serve to (i) lubricate various sliding interfaces between the piston ring and cylinder liner, in bearings of the crank shaft and the connecting rod, and in the valve driving mechanism including cams and valve lifters, (ii) cool the engine, (iii) clean and disperse the combustion products and (iv) prevent corrosion and consequent rust formation.
  • the stringent requirements for high performance engines in recent years has meant greater demand from lubricants used in such engines.
  • the viscosity index is commonly evaluated as the viscosity- temperature characteristic of lubricating base oils and lubricating compositions, while the properties evaluated for the low-temperature viscosity characteristics are generally the pour point, cloud point and freezing point. Polymeric viscosity index improvers have also been implicated in deposit formation.
  • the objectives of the invention described herein include providing improved fuel economy while also providing at least one of (i) reduced wear (such as cam wear or lifter wear), (ii) decreased deposit formation, (iii) improved soot handling, (iv) reduced lead or copper corrosion, (v) increased oxidation resistance, and/or (vi) improved seal compatibility in an internal combustion engine.
  • the objectives of the present invention includes providing improved fuel economy while also providing at least one of (i) reduced wear or (ii) decreased deposit formation, especially in compression ignition (i.e. diesel) engines.
  • the invention described herein provides a multigrade lubricating composition that includes an oil of lubricating viscosity having a viscosity index of at least 1 10 or 120 to 140 or 150; an ashless dispersant; and an overbased metal detergent wherein the lubricating composition contains less than 0.01 weight percent of a polymeric viscosity index improver.
  • the lubricant composition has a SAE viscosity grade of XW-Y, wherein X may be 0, 5, or 10; and Y may be 16, 20, 26, 30, or 40.
  • the invention further provides a lubricating composition as described herein wherein the multigrade crankcase lubricant is a SAE OW-16, OW-20, OW-26, 5W-16, 5W-20, 5W-26, 5W-30, 1 OW-16, 10W-30, or 10W-40 lubricant.
  • the multigrade crankcase lubricant is a SAE OW-16, OW-20, OW-26, 5W-16, 5W-20, 5W-26, 5W-30, 1 OW-16, 10W-30, or 10W-40 lubricant.
  • the invention further provides a lubricating composition as described herein in which the ashless dispersant is derived from a polyolefin having a number average molecular weight of 500 to 5000.
  • the invention further provides a lubricating composition as described herein in which the metal- containing overbased detergent includes one or more of a calcium sulfonate, a calcium phenate, a magnesium sulfonate or a magnesium phenate.
  • the invention further provides a lubricating composition as described herein in which the metal-containing overbased detergent is present in an amount to deliver at least 4 TBN to the composition.
  • the invention further provides a lubricating composition as described herein in which the lubricating composition has a viscosity index of at least 130 or at least 135.
  • the lubricating composition has a viscosity index of 130 to 230, 135 to 195, or 140 to 175.
  • the invention further provides a lubricating composition as described herein in which the oil of lubricating viscosity has a viscosity index of at least 124.
  • the invention further provides a lubricating composition as described herein in which the oil of lubricating viscosity includes from 0.1 weight percent to 20 weight percent of an oil derived from hydroisomerization of a high wax-containing feed stream.
  • the invention further provides a lubricating composition as described herein in which the oil of lubricating viscosity includes from 0.5 weight percent to 5 weight percent of an oil derived from hydroisomerization of a high wax -containing feed stream.
  • the invention further provides a method of lubricating a compression- ignition internal combustion engine including supplying the engine a lubricant composition as described herein.
  • the invention further provides a method of improving fuel economy of a compression-ignition internal combustion engine including supplying to the engine a SAE OW-16, OW-20, OW-26, 5W-16, 5W-20, 5W-30, 10W-16, 10W-30 or 10W-40 lubricant in which the lubricant includes an oil of lubricating viscosity having a viscosity index of at least 1 15, an ashless dispersant, and an overbased metal detergent, wherein the lubricating composition contains less than 0.01 weight percent of a polymeric viscosity modifier.
  • the invention further provides a multigrade crankcase lubricant composition having a viscosity index of at least 130 as described herein including an oil of lubricating viscosity having a viscosity index of at least 1 15, and an ashless dispersant, an overbased metal detergent, in which the lubricating composition contains less than 0.1 weight percent of an ethylene-olefm-based copolymer.
  • the invention further provides a lubricant composition as described herein in which in the ethylene-based copolymer, ethylene makes up from 50 percent to 90 percent of the monomer used to prepare the copolymer on a molar basis.
  • the invention further provides a lubricant composition as described herein in which the ethylene-olefin copolymer has a molecular weight from 5,000 to 40,000 Mn.
  • the invention further provides a lubricant composition as described herein in which no more than 50% of the overbased metal detergent contains a salicylate soap.
  • the oil of lubricating viscosity of the invention may be defined as an API Group 11+ base oil.
  • API Group 11+ base oils are known and described for example in SAE publication entitled “Design Practice: Passenger Car Automatic Transmissions", fourth Edition, AE-29, published 2012, page 12-9.
  • US 8,216,448 also defines a API Group 11+ as a "Group II plus base oil” having a viscosity index greater than or equal to 1 10 and less than 120.
  • the oil of lubricating viscosity of the invention may have a viscosity index (VI) of at least 1 10 or 1 15 or 120 to 140 or 150.
  • the viscosity index may be at least 130, or at least 135. In another embodiment, the viscosity index may be at least 124.
  • Examples of an oil of lubricating viscosity of the present invention include base oils sold under the registered trade names of Ultra-S, Nexbase®, Yubase®, Petrocanada, and Chevron neutral oil 1 10RLV.
  • the oil of lubricating viscosity of the invention may be present at 60 wt % to 97.5 wt %, or 70 wt % to 95 wt %, or 80 wt % to 95 wt % of the lubricating composition.
  • the oil of lubricating viscosity of the invention may also be blended with a conventional oil of lubricating viscosity (i. e., an oil of lubricating viscosity other than that defined by the present invention) with the proviso that the base oil mixture continues to exhibit a viscosity index as described above.
  • a conventional oil of lubricating viscosity i. e., an oil of lubricating viscosity other than that defined by the present invention
  • the conventional oil of lubricating viscosity may be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines.
  • the five base oil groups are as follows: Group I (sulfur content >0.03 wt %, and/or ⁇ 90 wt % saturates, viscosity index 80-120); Group II (sulfur content ⁇ 0.03 wt %, and >90 wt % saturates, viscosity index 80-120); Group III (sulfur content ⁇ 0.03 wt %, and >90 wt % saturates, viscosity index >120); Group IV (all polyalphaolefins (PAOs)); and Group V (all others not included in Groups I, II, III, or IV).
  • the oil of lubricating viscosity comprises an API Group I, Group II (other than the oil of lubricating viscosity defined by the present invention), Group III, Group IV, Group V oil or mixtures thereof.
  • the conventional oil of lubricating viscosity is an API Group I, Group II (other than the oil of lubricating viscosity defined by the present invention), Group III, Group IV oil or mixtures thereof.
  • the conventional oil of lubricating viscosity is often an API Group II (other than the oil of lubricating viscosity defined by the present invention), Group III or Group IV oil or mixtures thereof.
  • Groups I, II and III are mineral oil base stocks.
  • the oil of lubricating viscosity can include natural or synthetic oils and mixtures thereof. Mixture of mineral oil and synthetic oils, e.g., polyalphaolefm oils and/or polyester oils, may be used.
  • Base oils of API Group II and Group III are subjected to hydrotreating to reduce/remove aromatics and raise viscosity index.
  • Group III base oils are subjected to severe hydrotreating process conditions in order to produce oils with viscosity index of at least 120.
  • the lubricating composition of the invention comprises a severely hydrotreated base oil with a viscosity index of at least 1 10, at least 120, at least 130, or even at least 140.
  • the lubricating composition comprises a Group III base oil.
  • Some high viscosity index Group III base oils are produced in part by inclusion of high wax containing feed streams that are subjected to hydroisomerization to produce high viscosity index isoparaffmic base oils.
  • Natural oils include animal oils and vegetable oils (e.g. vegetable acid esters) 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. Hydrotreated or hydrocracked oils are also useful oils of lubricating viscosity. Oils of lubricating viscosity derived from coal or shale are also useful.
  • Synthetic oils include hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized and interpolymerized olefins and mixtures thereof, alkylbenzenes, polyphenyl, alkylated diphenyl ethers, and alkylated diphenyl sulfides and their derivatives, analogs and homologues thereof.
  • Alkylene oxide polymers and interpolymers and derivatives thereof, and those where terminal hydroxyl groups have been modified by, e.g., esterification or etherification, are other classes of synthetic lubricating oils.
  • suitable synthetic lubricating oils comprise esters of dicarboxylic acids and those made from C5 to C 12 monocarboxylic acids and polyols or polyol ethers.
  • Other synthetic lubricating oils include liquid esters of phosphorus- containing acids, polymeric tetrahydrofurans, silicon-based oils such as poly-alkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils, and silicate oils.
  • oils include those produced by Fischer-Tropsch reactions, typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes.
  • oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
  • the base oil of lubricating viscosity contains 0.1 weight percent to 20 weight percent of a base oil fraction derived from hydroisomerization of a high wax-containing feed stream and/or base oil derived from hydroisomerization of a Fischer-Tropsch wax feed stream. In one embodiment, the oil of lubricating viscosity contains 0.5 weight percent to 5 weight percent of a base oil fraction derived from hydroisomerization of a high wax-containing feed stream and/or base oil derived from hydroisomerization of a Fischer-Tropsch wax feed stream. In one embodiment, the lubricating composition is free of (or substantially free of) a hydroisomerized wax- derived base oil.
  • Unrefined, refined, and rerefined oils either natural or synthetic (as well as mixtures thereof) of the types disclosed hereinabove can used.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
  • Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Rerefined oils often are additionally processed to remove spent additives and oil breakdown products.
  • the amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 wt % the sum of the amount of performance additives of the present invention.
  • the lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the performance additives of this invention are in the form of a concentrate (which may be combined with additional oil to form, in whole or in part, a finished lubricant), the ratio of the performance additives to the oil of lubricating viscosity and/or to diluent oil include the ranges of 1 :99 to 99: 1 by weight, or 80:20 to 10:90 by weight.
  • Dispersants generally, are well known in the field of lubricants and include primarily what is known as ashless dispersants and polymeric dispersants. Ashless dispersants are so-called because, as supplied, they do not contain metal and thus do not normally contribute to sulfated ash when added to a lubricant. However, they may interact with ambient metals once they are added to a lubricant which includes a metal- containing species. Ashless dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long chain alkenyl succinimides, having a variety of chemical structures, including those represented by Formula (I):
  • each R is independently an alkyl group, frequently a polyisobutylene group with a molecular weight (M n ) of 500-5000 based on the polyisobutylene precursor, and R 2 are alkylene groups, commonly ethylene (C2H4) 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.
  • the amine portion is shown as an alkylene polyamine, although other aliphatic and aromatic mono- and polyamines may also be used. Also, a variety of modes of linkage of the R 1 groups onto the imide structure are possible, including various cyclic linkages.
  • the ratio of the carbonyl groups of the acylating agent to the nitrogen atoms of the amine may be 1 :0.5 to 1 :3, and in other instances 1 : 1 to 1 :2.75 or 1 : 1.5 to 1 :2.5.
  • Succinimide dispersants are more fully described in U.S. Patents 4,234,435 and 3,172,892 and in EP 0355895.
  • the dispersant is prepared by a process that involves the presence of small amounts of chlorine or other halogen, as described in U.S. Patent 7,615,521 (see, e.g., col. 4, lines 18-60 and preparative example A). Such dispersants typically have some carbocyclic structures in the attachment of the hydrocarbyl substituent to the acidic or amidic "head” group.
  • the dispersant is prepared by a thermal process involving an "ene" reaction, without the use of any chlorine or other halogen, as described in U.S. Patent 7,615,521 ; dispersants made in this manner are often derived from high vinylidene (i.e.
  • the dispersant is prepared by free radical catalyzed polymerization of high-vinylidene polyisobutylene with an ethylenically unsaturated acylating agent, as described in United States Patent 8,067,347.
  • Dispersants may be derived from, as the polyolefm, high vinylidene polyisobutylene, that is, having greater than 50, 70, or 75% terminal vinylidene groups (a and ⁇ isomers).
  • the succinimide dispersant may be prepared by the direct alkylation route. In other embodiments it may comprise a mixture of direct alkylation and chlorine -route dispersants.
  • Suitable dispersants for use in the compositions of the present invention include succinimide dispersants.
  • the dispersant may be present as a single dispersant.
  • the dispersant may be present as a mixture of two or three different dispersants, wherein at least one may be a succinimide dispersant.
  • the succinimide dispersant may be a derivative of an aliphatic polyamine, or mixtures thereof.
  • the aliphatic polyamine may be aliphatic polyamine such as an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or mixtures thereof.
  • the aliphatic polyamine may be ethylenepolyamine.
  • the aliphatic polyamine may be selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.
  • the succinimide dispersant may be a derivative of an aromatic amine, an aromatic polyamine, or mixtures thereof.
  • the aromatic amine may be 4- aminodiphenylamine (ADPA) (also known as N-phenylphenylenediamine), derivatives of ADPA (as described in United States Patent Publications 201 1/0306528 and 2010/0298185), a nitroaniline, an aminocarbazole, an amino- indazolinone, an aminopyrimidine, 4-(4-nitrophenylazo)aniline, or combinations thereof.
  • ADPA 4- aminodiphenylamine
  • the dispersant is derivative of an aromatic amine wherein the aromatic amine has at least three non-continuous aromatic rings.
  • the succinimide dispersant may be a derivative of a polyether amine or polyether polyamine.
  • Typical polyether amine compounds contain at least one ether unit and will be chain terminated with at least one amine moiety.
  • the polyether polyamines can be based on polymers derived from C2-C6 epoxides such as ethylene oxide, propylene oxide, and butylene oxide. Examples of polyether polyamines are sold under the Jeffamine® brand and are commercially available from Hunstman Corporation located in Houston, Texas.
  • Another class of ashless dispersant is high molecular weight esters. These materials are similar to the above-described succinimides except that they may be seen as having been prepared by reaction of a hydrocarbyl acylating agent and a polyhydric aliphatic alcohol such as glycerol, pentaerythritol, or sorbitol. Such materials are described in more detail in U.S. Patent 3,381 ,022. Aromatic succinate esters may also be prepared as described in United States Patent Publication 2010/0286414.
  • a succinic-based dispersant may be formed by reacting maleic anhydride or a reactive equivalent thereof, such as an acid or ester, with a hydrocarbon chain by any method such as those disclosed above (e.g., chlorine-based process or thermal process).
  • Other acids or equivalents thereof may be used in place of the maleic anhydride. These include fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citaconic anhydride, and cinnamic acid as well as other ethylenically unsaturated acids such as acrylic or methacrylic acid; and their reactive equivalents.
  • Mannich bases are materials which are formed by the condensation of a higher molecular weight, alkyl substituted phenol, an alkylene polyamine, and an aldehyde such as formaldehyde. Such materials may have the general structure as represented by Formula (II)
  • Another class of ashless dispersants include dispersants comprising a quaternary ammonium salt.
  • Quaternary ammonium salts include the reaction product of: (i) a compound comprising at least one tertiary amino group; and (ii) a quaternizing agent suitable for converting the tertiary amino group of compound (i) to a quaternary nitrogen.
  • quaternary ammonium salts examples include (i) imide quaternary ammonium salts, (ii) Mannich quaternary ammonium salts, (iii) polyalkene substituted amine quaternary ammonium salts, (iv) amide quaternary ammonium salts, (v) ester quaternary ammonium salts, (vi) polyester quaternary ammonium salts, or (vii) any combination thereof.
  • imide quaternary ammonium salts examples include (i) imide quaternary ammonium salts, (ii) Mannich quaternary ammonium salts, (iii) polyalkene substituted amine quaternary ammonium salts, (iv) amide quaternary ammonium salts, (v) ester quaternary ammonium salts, (vi) polyester quaternary ammonium salts, or (vii) any combination thereof.
  • each of the different types of quaternary ammonium salts described uses a different non-quaternized nitrogen- containing compound in its preparation, but generally the non-quaternized nitrogen- containing compound contains a tertiary nitrogen capable of being quaternized (or a primary or secondary nitrogen atom that can be alkylated to a tertiary nitrogen that can then be quaternized) and a hydrocarbyl substituent group.
  • a tertiary nitrogen capable of being quaternized (or a primary or secondary nitrogen atom that can be alkylated to a tertiary nitrogen that can then be quaternized) and a hydrocarbyl substituent group.
  • the preparation and use of quaternized ammonium dispersants is described in detail in United States Patent 7,951 ,21 1 and United States Patent 7,906,470.
  • the dispersant may also be post-treated by conventional methods by a reaction with any of a variety of agents.
  • agents include boron compounds, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds.
  • the dispersant may also exhibit basicity, as measured by Total Base Number (TBN).
  • TBN may be determined by ASTM D2896. This will particularly be the case if the dispersant is prepared with an amine, such as a polyamine, and the amine contains one or more amino groups that have not reacted with acidic groups of the dispersant.
  • the TBN of the dispersant may be 1 to 1 10, or 5 to 50, or 10 to 40 or 30 to 70.
  • the dispersant may not exhibit basicity (that is, have a TBN of 0 or nearly 0).
  • the dispersant has a TBN of zero as measured by D2896. Such could be the case if no basic nitrogen is present on the dispersant.
  • the dispersant may be present at 0.01 wt % to 20 wt %, or 0.1 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 0.5 wt % to 8 wt % , or 1.0 wt % to 6.5 wt % of the lubricating composition.
  • Metal overbased detergents otherwise referred to as overbased detergents, metal-containing overbased detergents or superbased salts, are characterized by a metal content in excess of that which would be necessary for neutralization according to the stoichiometry of the metal and the particular acidic organic compound, i.e. the substrate, reacted with the metal.
  • the overbased detergent may comprise one or more of non-sulfur containing phenates, sulfur containing phenates, sulfonates, salicylates, and mixtures thereof.
  • the amount of excess metal is commonly expressed in terms of substrate to metal ratio.
  • the terminology "metal ratio" is used in the prior art and herein to define the ratio of the total chemical equivalents of the metal in the overbased salt to the chemical equivalents of the metal in the salt which would be expected to result from the reaction between the hydrocarbyl substituted organic acid; the hydrocarbyl- substituted phenol or mixtures thereof to be overbased, and the basic metal compound according to the known chemical reactivity and the stoichiometry of the two reactants.
  • a normal or neutral salt i.e. soap
  • the metal ratio is one and, in an overbased salt, the metal ratio is greater than one, especially greater than 1.3.
  • the overbased detergent of the invention may have a metal ratio of 5 to 30, or a metal ratio of 7 to 22, or a metal ratio of at least 1 1.
  • the metal-containing detergent may also include "hybrid" detergents formed with mixed surfactant systems including phenate and/or sulfonate components, e.g. phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, as described, for example, in US Patents 6,429,178; 6,429, 179; 6,153,565; and 6,281 , 179.
  • phenate/salicylates e.g. phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, as described, for example, in US Patents 6,429,178; 6,429, 179; 6,153,565; and 6,281 , 179.
  • hybrid detergent would be considered equivalent to amounts of distinct phenate and sulfonate detergents introducing like amounts of phenate and sulfonate soaps, respectively.
  • Overbased phenates and salicylates typically have a total base number of 180 to 450 TBN.
  • Overbased sulfonates typically have a total base number of 250 to 600, or 300 to 500.
  • Overbased detergents are known in the art.
  • Alkylphenols are often used as constituents in and/or building blocks for overbased detergents.
  • Alkylphenols may be used to prepare phenate, salicylate, salixarate, or saligenin detergents or mixtures thereof.
  • Suitable alkylphenols may include para-substituted hydrocarbyl phenols.
  • the hydrocarbyl group may be linear or branched aliphatic groups of 1 to 60 carbon atoms, 8 to 40 carbon atoms, 10 to 24 carbon atoms, 12 to 20 carbon atoms, or 16 to 24 carbon atoms.
  • the alkylphenol overbased detergent is prepared from an alkylphenol or mixture thereof that is free of or substantially free of (i.e.
  • the lubricating composition of the invention contains less than 0.1 weight percent) p-dodecylphenol. In one embodiment, the lubricating composition of the invention contains less than 0.3 weight percent of alkylphenol, less than 0.1 weight percent of alkylphenol, or less than 0.05 weight percent of alkylphenol.
  • the overbased metal-containing detergent may be alkali metal or alkaline earth metal salts.
  • the overbased detergent may be sodium salts, calcium salts, magnesium salts, or mixtures thereof of the phenates, sulfur-containing phenates, sulfonates, salixarates and salicylates.
  • the overbased detergent is a calcium detergent, a magnesium detergent or mixtures thereof.
  • the overbased calcium detergent may be present in an amount to deliver at least 500 ppm calcium by weight and no more than 3000 ppm calcium by weight, or at least 1000 ppm calcium by weight, or at least 2000 ppm calcium by weight, or no more than 2500 ppm calcium by weight to the lubricating composition.
  • the overbased detergent may be present in an amount to deliver no more than 500 ppm by weight of magnesium to the lubricating composition, or no more than 330 ppm by weight, or no more than 125 ppm by weight, or no more than 45 ppm by weight.
  • the lubricating composition is essentially free of (i.e. contains less than 10 ppm) magnesium resulting from the overbased detergent.
  • the overbased detergent may be present in an amount to deliver at least 200 ppm by weight of magnesium, or at least 450 ppm by weight magnesium, or at least 700 ppm by weight magnesium to the lubricating composition.
  • both calcium and magnesium containing detergents may be present in the lubricating composition. Calcium and magnesium detergents may be present such that the weight ratio of calcium to magnesium is 10: 1 to 1 : 10, or 8:3 to 4:5, or 1 : 1 to 1 :3.
  • the overbased detergent is free of or substantially free of sodium.
  • the sulfonate detergent may be predominantly a linear alkylbenzene sulfonate detergent having a metal ratio of at least 8 as is described in paragraphs [0026] to [0037] of US Patent Publication 2005/065045 (and granted as US 7,407,919).
  • the linear alkylbenzene sulfonate detergent may be particularly useful for assisting in improving fuel economy.
  • the linear alkyl group may be attached to the benzene ring anywhere along the linear chain of the alkyl group, but often in the 2, 3 or 4 position of the linear chain, and in some instances, predominantly in the 2 position, resulting in the linear alkylbenzene sulfonate detergent.
  • Salicylate detergents and overbased salicylate detergents may be prepared in at least two different manners. Carbonylation (also referred to as carboxylation) of a p-alkylphenol is described in many references including US Patent 8,399,388. Carbonylation may be followed by overbasing to form overbased salicylate detergent. Suitable p-alkylphenols include those with linear and/or branched hydrocarbyl groups of 1 to 60 carbon atoms. Salicylate detergents may also be prepared by alkylation of salicylic acid, followed by overbasing, as described in US Patent 7,009,072.
  • Salicylate detergents prepared in this manner may be prepared from linear and/or branched alkylating agents (usually 1 -olefins) containing 6 to 50 carbon atoms, 10 to 30 carbon atoms, or 14 to 24 carbon atoms.
  • the overbased detergent of the invention is a salicylate detergent.
  • the salicylate detergent of the invention is free of unreacted p-alkylphenol (i.e. contains less than 0.1 weight percent).
  • the salicylate detergent of the invention is prepared by alkylation of salicylic acid.
  • the overbased detergent may be present at 0.2 wt % to 15 wt %, or 0.3 wt % to 10 wt %, or 0.3 wt % to 8 wt %, or 0.4 wt % to 3 wt %.
  • the detergent may be present at 2 wt % to 3 wt % of the lubricating composition.
  • the detergent may be present at 0.2 wt % to 1 wt % of the lubricating composition.
  • Metal-containing overbased detergents often provide TBN to the lubricating composition.
  • the overbased detergent is present in an amount to deliver at least 4 mg KOH/g of TBN to the lubricating composition, or 4 to 15 mg KOH/g, or 5 to 9 mg KOH/g of TBN to the lubricating composition.
  • Metal-containing detergents contribute sulfated ash to a lubricating composition.
  • Sulfated ash may be determined by ASTM D874.
  • the lubricating composition of the invention comprises a metal-containing detergent in an amount to deliver at least 0.4 weight percent sulfated ash to the total composition.
  • the metal-containing detergent is present in an amount to deliver at least 0.6 weight percent sulfated ash, or at least 0.75 weight percent sulfated ash, or even at least 0.9 weight percent sulfated ash to the lubricating composition.
  • overbased detergents contribute detergent soap, also referred to as neutral detergent salt, to the lubricating composition.
  • Soap being a metal salt of the substrate, may act as a surfactant in the lubricating composition.
  • the lubricating composition comprises 0.05 weight percent to 1.5 weight percent detergent soap, or 0.1 weight percent to 0.9 weight percent detergent soap.
  • the lubricating composition contains no more than 0.5 weight percent detergent soap.
  • the overbased detergent may have a weight ratio of ash:soap of 5 : 1 to 1 :2.3, or 3.5 : 1 to 1 :2, or 2.9: 1 to 1 : 1 :7.
  • compositions of the invention may optionally comprise one or more additional performance additives.
  • additional performance additives may include one or more metal deactivators, detergents, friction modifiers, antiwear agents, corrosion inhibitors, soot-dispersing additives, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, pour point depressants, seal swelling agents, and any combination or mixture thereof.
  • fully-formulated lubricating oil will contain one or more of these performance additives, and often a package of multiple performance additives.
  • the invention provides a lubricating composition further comprising an antiwear agent, a dispersant viscosity modifier, a friction modifier, a viscosity modifier, an antioxidant, an overbased detergent, a dispersant (different from that of the invention), or a combination thereof, where each of the additives listed may be a mixture of two or more of that type of additive.
  • the invention provides a lubricating composition further comprising an antiwear agent, a dispersant viscosity modifier, a friction modifier, a viscosity modifier (typically an olefin copolymer such as an ethylene-propylene copolymer), an antioxidant (including phenolic and aminic antioxidants), an overbased detergent (including overbased sulfonates and phenates), or a combination thereof, where each of the additives listed may be a mixture of two or more of that type of additive.
  • an antiwear agent typically an olefin copolymer such as an ethylene-propylene copolymer
  • an antioxidant including phenolic and aminic antioxidants
  • an overbased detergent including overbased sulfonates and phenates
  • antiwear agent Another additive is an antiwear agent.
  • anti-wear agents include phosphorus-containing antiwear/extreme pressure agents such as metal thiophosphates, phosphoric acid esters and salts thereof, phosphorus-containing carboxylic acids, esters, ethers, and amides, and phosphites.
  • a phosphorus antiwear agent may be present in an amount to deliver 0.01 to 0.2 or 0.015 to 0.15 or 0.02 to 0.1 or 0.025 to 0.08 percent phosphorus.
  • the antiwear agent is a zinc dialkyldithiophosphate (ZDP).
  • Zinc dialkyldithiophosphates may be described as primary zinc dialkyldithiophosphates or as secondary zinc dialkyldithiophosphates, depending on the structure of the alcohol used in its preparation.
  • the compositions of the invention include primary zinc dialkyldithiophosphates.
  • the compositions of the invention include secondary zinc dialkyldithiophosphates.
  • the compositions of the invention include a mixture of primary and secondary zinc dialkyldithiophosphates.
  • component (b) is a mixture of primary and secondary zinc dialkyldithiophosphates where the ratio of primary zinc dialkyldithiophosphates to secondary zinc dialkyldithiophosphates (one a weight basis) is at least 1 : 1 , or even at least 1 : 1.2, or even at least 1 : 1.5 or 1 :2, or 1 : 10. In some embodiments component (b) is a mixture of primary and secondary zinc dialkyldithiophosphates that is at least 50 percent by weight primary, or even at least 60, 70, 80, or even 90 percent by weight primary. In some embodiments component (b) is free of primary zinc dialkyldithiophosphates.
  • the phosphorus antiwear agent may be present at 0 wt % to 3 wt %, or 0.1 wt % to 1.5 wt %, or 0.5 wt % to 0.9 wt % of the lubricating composition.
  • Another class of anti-wear additives includes oil-soluble titanium compounds as disclosed in U.S. Pat. No. 7,727,943 and US20060014651.
  • the oil- soluble titanium compounds may function as antiwear agents, friction modifiers, antioxidants, deposit control additives, or more than one of these functions.
  • the oil soluble titanium compound may be a titanium (IV) alkoxide.
  • the titanium alkoxide may be formed from a monohydric alcohol, a polyol or mixtures thereof.
  • the monohydric alkoxides may have 2 to 16, or 3 to 10 carbon atoms.
  • the titanium alkoxide may be titanium (IV) isopropoxide.
  • the titanium alkoxide may be titanium (IV) 2-ethylhexoxide.
  • the titanium compound comprises the alkoxide of a vicinal 1 ,2-diol or polyol.
  • the 1 ,2-vicinal diol comprises a fatty acid mono-ester of glycerol, often the fatty acid may be oleic acid.
  • the oil soluble titanium compound may be a titanium carboxylate.
  • the titanium (IV) carboxylate may be titanium neodecanoate.
  • the oil soluble titanium compound may be present in the lubricating composition in an amount necessary to provide for 10 ppm to 1500 ppm titanium by weight or 25 ppm to 150 ppm titanium by weight.
  • the invention provides a lubricating composition which further comprises ashless antioxidant.
  • Ashless antioxidants may comprise one or more of arylamines, diarylamines, alkylated arylamines, alkylated diaryl amines, phenols, hindered phenols, sulfurized olefins, or mixtures thereof.
  • the lubricating composition includes an antioxidant, or mixtures thereof.
  • the antioxidant may be present at 0 wt % to 15 wt %, or 0.1 wt % to 10 wt %, or 0.5 wt % to 5 wt %, or 0.5 wt % to 3 wt %, or 0.3 wt % to 1.5 wt % of the lubricating composition.
  • the diarylamine or alkylated diarylamine may be a phenyl-a- naphthylamine (PANA), an alkylated diphenylamine, or an alkylated phenylnapthylamine, or mixtures thereof.
  • the alkylated diphenylamine may include di-nonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine, di- octylated diphenylamine, di-decylated diphenylamine, decyl diphenylamine and mixtures thereof.
  • the diphenylamine may include nonyl diphenylamine, dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine, or mixtures thereof.
  • the alkylated diphenylamine may include nonyl diphenylamine, or dinonyl diphenylamine.
  • the alkylated diarylamine may include octyl, di-octyl, nonyl, di-nonyl, decyl or di-decyl phenylnapthylamines.
  • the diarylamine antioxidant of the invention may be present on a weight basis of the lubrication composition at 0.1% to 10%, 0.35%> to 5%>, or even 0.5%> to 2%.
  • the phenolic antioxidant may be a simple alkyl phenol, a hindered phenol, or coupled phenolic compounds.
  • the hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
  • the phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and/or a bridging group linking to a second aromatic group.
  • hindered phenol antioxidants examples include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert- butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4- butyl-2,6-di-tert-butylphenol, 4-dodecyl-2,6-di-tert-butylphenol, or butyl 3 -(3, 5- ditert-butyl-4-hydroxyphenyl)propanoate.
  • the hindered phenol antioxidant may be an ester and may include, e.g., IrganoxTM L-135 from Ciba.
  • Coupled phenols often contain two alkylphenols coupled with alkylene groups to form bisphenol compounds.
  • suitable coupled phenol compounds include 4,4'- methylene bis-(2,6-di-tert-butyl phenol), 4-methyl-2,6-di- tert-butylphenol, 2,2'-bis-(6-t-butyl-4-heptylphenol); 4,4'-bis(2,6-di-t-butyl phenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 2,2'-methylene bis(4-ethyl-6-t- butylphenol).
  • Phenols of the invention also include polyhydric aromatic compounds and their derivatives.
  • suitable polyhydric aromatic compounds include esters and amides of gallic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, l ,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxynaphthoic acid, 3,7-dihydroxy naphthoic acid, and mixtures thereof.
  • the phenolic antioxidant comprises a hindered phenol.
  • the hindered phenol is derived from 2,6-ditertbutyl phenol.
  • the lubricating composition of the invention comprises a phenolic antioxidant in a range of 0.01 wt % to 5 wt %, or 0.1 wt % to 4 wt %, or 0.2 wt % to 3 wt %, or 0.5 wt % to 2 wt % of the lubricating composition.
  • Sulfurized olefins are well known commercial materials, and those which are substantially nitrogen-free, that is, not containing nitrogen functionality, are readily available.
  • the olefinic compounds which may be sulfurized are diverse in nature. They contain at least one olefinic double bond, which is defined as a non- aromatic double bond; that is, one connecting two aliphatic carbon atoms. These materials generally have sulfide linkages having 1 to 10 sulfur atoms, for instance, 1 to 4, or 1 or 2.
  • Ashless antioxidants may be used separately or in combination.
  • two or more different antioxidants are used in combination, such that there is at least 0.1 weight percent of each of the at least two antioxidants and wherein the combined amount of the ashless antioxidants is 0.5 to 5 weight percent. In one embodiment, there may be at least 0.25 to 3 weight percent of each ashless antioxidant.
  • the invention provides a lubricating composition further comprising a molybdenum compound.
  • the molybdenum compound may be selected from the group consisting of molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, amine salts of molybdenum compounds, molybdenum-containing dispersants, and mixtures thereof. Examples of commercially available molybdenum compounds include Sakura-lubeTM 525 and Sakura-lubeTM 710, both available from Adeka Corporation; and Molyvan ® 855 available from Vanderbilt Chemicals, LLC.
  • the molybdenum compound may provide the lubricating composition with 0 to 1000 ppm, or 5 to 1000 ppm, or 10 to 750 ppm, or 5 ppm to 300 ppm, or 20 ppm to 250 ppm of molybdenum.
  • the molybdenum compound is a molybdenum dithio carbamate compound present in an amount to provide 300 ppm to 750 ppm molybdenum to the lubricating composition.
  • the lubricating composition of the invention further comprises a soot dispersing additive.
  • the soot dispersing additive may be present at 0 wt % to 5 wt %, or 0 wt % to 4 wt %, or 0.05 wt % to 2 wt % of the lubricating composition.
  • Suitable soot dispersing additives include functionalized low molecular weight polyolefins, for example, ethylene-propylene copolymers with a number average molecular weight (Mn) of less than 20,000 that have been functionalized with an acylating agent such as maleic anhydride and an amine, preferably an aromatic amine.
  • an acylating agent such as maleic anhydride and an amine, preferably an aromatic amine.
  • Other soot dispersing additives may be prepared from acylated polyisobutylene that has been functionalized with aromatic (poly)amines. More detailed description of soot-dispersing additives are disclosed in U.S. Patents 4,863,623; 5, 182,041 ; 7,790,661 ; 8,557,753; and 8,637,437.
  • the soot dispersing additive may include those described in U.S. Patent 7,790,661 or in U.S. Patent 8,557,753.
  • the invention provides a lubricating composition further comprising a friction modifier.
  • friction modifiers include long chain fatty acid derivatives of amines, fatty esters, or epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty esters, amides, and/or imides of a- hydroxy-carbonyl compounds such as tartaric acid, malic acid, citric acid, glycolic acid, lactic acid and mandelic acid.
  • fatty as used herein, can mean having a C8-22 linear alkyl group.
  • Friction modifiers may also encompass materials such as sulfurized fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil or monoester of a polyol and an aliphatic carboxylic acid.
  • the friction modifier may be selected from the group consisting of long chain fatty acid derivatives of amines, long chain fatty esters, or long chain fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; and fatty alkyl tartramides.
  • the friction modifier may be present at 0 wt % to 6 wt %, or 0.05 wt % to 4 wt %, or 0.1 wt % to 2 wt % of the lubricating composition.
  • the friction modifier may be a long chain fatty acid ester.
  • the long chain fatty acid ester may be a mono-ester or a diester or a mixture thereof, and in another embodiment the long chain fatty acid ester may be a triglyceride.
  • corrosion inhibitors include those described in paragraphs 5 to 8 of US Application US05/038319, published as WO2006/047486, octyl octanamide, condensation products of dodecenyl succinic acid or anhydride and a fatty acid such as oleic acid with a polyamine.
  • the corrosion inhibitors include the Synalox® (a registered trademark of The Dow Chemical Company) corrosion inhibitor.
  • the Synalox® corrosion inhibitor may be a homopolymer or copolymer of propylene oxide.
  • the Synalox® corrosion inhibitor is described in more detail in a product brochure with Form No. 1 18-01453-0702 AMS, published by The Dow Chemical Company.
  • the product brochure is entitled "SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications.”
  • the lubricating composition may further include metal deactivators, including derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole derivatives, 1 ,2,4-triazoles, benzimidazoles, 2- alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors, including copolymers of ethyl acrylate and 2-ethylhexylacrylate and copolymers of ethyl acrylate and 2-ethylhexylacrylate and vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; and pour point depressants, including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides.
  • metal deactivators including derivatives of benzotriazoles (typicallyltri
  • the lubricating composition may further comprise a polyether compound.
  • the polyether compound may be a polyether, a polyetheramine, a (poly)alkoxylated amine, an ethoxylated alcohol, or mixtures thereof.
  • the polyether can be represented by the formula RO[CH 2 CH(R 1 )0] x H where R is a hydrocarbyl group; R 1 is selected from the group consisting of hydrogen, alkyl groups of 1 to 14 carbon atoms, and mixtures thereof; and x is a number from 2 to 50.
  • the hydrocarbyl group R is a univalent hydrocarbon group, has one or more carbon atoms, and includes alkyl and alkyl-phenyl groups having 7 to 30 total carbon atoms, such as 9 to 25 total carbon atoms, or 1 1 to 20 total carbon atoms.
  • the repeating oxyalkylene units may be derived from ethylene oxide, propylene oxide, or butylene oxide.
  • the number of oxyalkylene units x may be 10 to 35, or 18 to 27.
  • the polyether of the present invention can be prepared by various well-known methods including condensing one mole of an alcohol or alkylphenol with two or more moles of an alkylene oxide, mixture of alkylene oxides, or with several alkylene oxides in sequential fashion, usually in the presence of a base catalyst.
  • U.S. Pat. No. 5,094,667 provides reaction conditions for preparing a polyether.
  • Suitable polyethers are commercially available from Dow Chemicals, Huntsman, ICI and include the Actaclear ® series from Bayer.
  • Suitable ethoxylates include Surfonic ® ethoxylates, for example Surfonic L24-5, available from Huntsman International LLC.
  • Polymeric viscosity modifiers may be present with the proviso that they do not exceed, in one embodiment, 0.1 weight percent of the lubricating composition. In one embodiment the polymeric viscosity modifier is present in an amount less than 0.01 weight percent of the lubricating composition.
  • Suitable viscosity modifiers include ethylene-olefin co-polymers, especially ethylene-propylene; maleic anhydride-styrene alternating copolymers and esters thereof, polymethacrylates (including random, block and star architectures), hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-isoprene radial and/or block copolymers, or mixtures thereof.
  • the polymeric viscosity modifier includes an ethylene-olefin based copolymer.
  • the ethylene makes up from 50 weight percent to 90 weight percent or from 65 weight percent to 85 weight percent, on a molar basis of the monomer used to prepare the copolymer of the ethylene-olefin-based copolymer.
  • the ethylene makes up at least 70 weight percent of the monomer used to prepare the copolymer.
  • the ethylene-olefin copolymer has a molecular weight from 5,000 to 40,000 Mn.
  • Pour point depressants that may be useful in the compositions of the invention further include polyalphaolefins, esters of maleic anhydride-styrene, poly(meth)acrylates, polyacrylates or polyacryl amides.
  • the invention provides for a method of lubricating an internal combustion engine comprising supplying to the internal combustion engine a lubricating composition as disclosed herein.
  • the lubricant is added to the lubricating system of the internal combustion engine, which then delivers the lubricating composition to the critical parts of the engine, during its operation, that require lubrication.
  • the lubricating compositions described above may be utilized in an internal combustion engine.
  • the engine components may have a surface of steel or aluminum (typically a surface of steel), and may also be coated for example with a diamond-like carbon (DLC) coating.
  • DLC diamond-like carbon
  • An aluminum surface may be comprised of an aluminum alloy that may be a eutectic or hyper-eutectic aluminum alloy (such as those derived from aluminum silicates, aluminum oxides, or other ceramic materials).
  • the aluminum surface may be present on a cylinder bore, cylinder block, or piston ring having an aluminum alloy, or aluminum composite.
  • the internal combustion engine may be fitted with an emission control system, an oil mist separator or a turbocharger.
  • emission control system examples include diesel particulate filters (DPF), or systems employing selective catalytic reduction (SCR).
  • the internal combustion engine of the present invention is distinct from a gas turbine.
  • individual combustion events translate from a linear reciprocating force into a rotational torque through the rod and crankshaft.
  • a gas turbine which may also be referred to as a jet engine
  • a continuous combustion process generates a rotational torque continuously without translation, and can also develop thrust at the exhaust outlet.
  • the lubricant composition for an internal combustion engine may be suitable for any engine lubricant irrespective of the sulfur, phosphorus or sulfated ash (ASTM D-874) content.
  • the sulfur content of the engine oil lubricant may be 1 wt % or less, or 0.8 wt % or less, or 0.5 wt % or less, or 0.3 wt % or less. In one embodiment, the sulfur content may be in the range of 0.001 wt % to 0.5 wt %, or 0.01 wt % to 0.3 wt %.
  • the phosphorus content may be 0.2 wt % or less, or 0.12 wt % or less, or 0.1 wt % or less, or 0.085 wt % or less, or 0.08 wt % or less, or even 0.06 wt % or less, 0.055 wt % or less, or 0.05 wt % or less.
  • the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm.
  • the total sulfated ash content may be 2 wt % or less, or 1.5 wt % or less, or 1.1 wt % or less, or 1 wt % or less, or 0.8 wt % or less, or 0.5 wt % or less, or 0.4 wt % or less.
  • the sulfated ash content may be 0.05 wt % to 0.9 wt %, or 0.1 wt % to 0.2 wt % or to 0.45 wt %.
  • the lubricating composition may be an engine oil, wherein the lubricating composition may be characterized as having at least one of (i) a sulfur content of 0.5 wt % or less, (ii) a phosphorus content of 0.1 wt % or less, (iii) a sulfated ash content of 1.5 wt % or less, or combinations thereof.
  • compositions are prepared according to Table 1 below. Compositions are prepared by blending components as shown in Table 1 into a lubricant. The amounts in Table 1 are on an oil-free basis.
  • additives include metal passivators, surfactant, ashless antioxidants, and foam inhibitor
  • the lubricating compositions are evaluated for wear protection in GM 6.5L Roller Follower Wear Test (RFWT) (ASTM D5966). This test measures wear on camshaft roller follower pins to determine the ability of an engine oil to control wear in the presence of soot-laden oil. The results obtained are summarized in Table 2, below.
  • RWT Roller Follower Wear Test
  • Table 2 The results obtained are summarized in Table 2, below.
  • HVES 540 The baseline lubricant was a commercial SAE 15W-40 API CJ-4 Heavy-Duty Diesel Engine Oil. The results obtained are summarized in Table 2, below.
  • 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. Examples of hydrocarbyl groups include:
  • hydrocarbon substituents that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-, aliphatic-, and alicyclic- substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
  • aliphatic e.g., alkyl or alkenyl
  • alicyclic e.g., cycloalkyl, cycloalkenyl
  • aromatic-, aliphatic-, and alicyclic- substituted aromatic substituents as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form a ring);
  • substituted hydrocarbon substituents that is, substituents containing non- hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);
  • hetero substituents that is, substituents which, while having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
  • Heteroatoms include sulfur, oxygen, and nitrogen.
  • no more than two, or no more than one, non- hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; alternatively, there may be no non-hydrocarbon substituents in the hydrocarbyl group.
  • the transitional term "comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps.
  • the term also encompass, as alternative embodiments, the phrases “consisting essentially of and “consisting of,” where “consisting of excludes any element or step not specified and “consisting essentially of permits the inclusion of additional un-recited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.

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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)
EP15719586.8A 2014-04-25 2015-04-24 Multigrade-schmiermittelzusammensetzung Active EP3134496B1 (de)

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US201461984232P 2014-04-25 2014-04-25
PCT/US2015/027416 WO2015164682A1 (en) 2014-04-25 2015-04-24 Multigrade lubricating compositions

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CN106459818A (zh) 2017-02-22
CA2946865C (en) 2023-03-28
CA2946865A1 (en) 2015-10-29
US20170044460A1 (en) 2017-02-16
WO2015164682A1 (en) 2015-10-29
CN115093893A (zh) 2022-09-23

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