US20050070446A1 - Boron free automotive gear oil - Google Patents

Boron free automotive gear oil Download PDF

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Publication number
US20050070446A1
US20050070446A1 US10/670,580 US67058003A US2005070446A1 US 20050070446 A1 US20050070446 A1 US 20050070446A1 US 67058003 A US67058003 A US 67058003A US 2005070446 A1 US2005070446 A1 US 2005070446A1
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Prior art keywords
oil
additive package
lubricating
oil soluble
test
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US10/670,580
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Chip Hewette
Jeffrey Milner
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Afton Chemical Corp
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Afton Chemical Corp
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Priority to US10/670,580 priority Critical patent/US20050070446A1/en
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Assigned to ETHYL PETROLEUM ADDITIVES, INC. reassignment ETHYL PETROLEUM ADDITIVES, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HEWETTE, CHIP, MILNER, JEFFREY L.
Assigned to SUNTRUST BANK, AS ADMINISTRATIVE AGENT reassignment SUNTRUST BANK, AS ADMINISTRATIVE AGENT SECURITY AGREEMENT Assignors: ETHYL PETROLEUM ADDITIVES, INC.
Priority to CA002480114A priority patent/CA2480114A1/en
Priority to AU2004210592A priority patent/AU2004210592A1/en
Priority to EP04077548A priority patent/EP1518919A1/en
Priority to JP2004272174A priority patent/JP2005097615A/en
Priority to MXPA04009160A priority patent/MXPA04009160A/en
Priority to SG200405365A priority patent/SG110161A1/en
Assigned to AFTON CHEMICAL CORPORATION reassignment AFTON CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: ETHYL PETROLEUM ADDITIVES, INC.
Publication of US20050070446A1 publication Critical patent/US20050070446A1/en
Priority to US11/552,733 priority patent/US20070054813A1/en
Assigned to SUNTRUST BANK reassignment SUNTRUST BANK SECURITY AGREEMENT Assignors: AFTON CHEMICAL CORPORATION
Assigned to AFTON CHEMICAL CORPORATION reassignment AFTON CHEMICAL CORPORATION RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: SUNTRUST BANK
Priority to JP2011270247A priority patent/JP2012046769A/en
Abandoned legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating 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
    • C10M169/04Mixtures of base-materials and additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/223Five-membered rings containing nitrogen and carbon only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28Amides; Imides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/024Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106Thiadiazoles
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40Low content or no content compositions
    • C10N2030/42Phosphor free or low phosphor content compositions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40Low content or no content compositions
    • C10N2030/44Boron free or low content boron compositions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/04Oil-bath; Gear-boxes; Automatic transmissions; Traction drives

Definitions

  • the present invention is in the field of lubricant additives and lubricant formulations. Specifically, the present invention relates to a boron-free lubricant additive package that is capable of passing tests for which the presence of boron was thought to be essential to passing.
  • boron-containing lubricants have been used to attain satisfactory performance against standard industry tests. Two such industry tests are the ISOT and the L60-1. However, boron imparts certain undesirable properties to the lubricant such as moisture sensitivity and increased price. Thus, it is desirable to have a lubricant that can provide the performance demanded by industry while reducing or eliminating the presence of boron. Recently, a boron-free lubricant additive package has been developed that unexpectedly passes both the ISOT standard test and the L60-1 standard test.
  • the present invention provides a lubricating additive package that is capable of passing both the ISOT standard test and the L60-1 standard test. More specifically, the present invention in an embodiment provides an oil soluble lubricant additive package comprising: (a) a succinimide dispersant, (b) an antiwear agent, (c) an extreme pressure additive, wherein the weight ratio of said dispersant to said extreme pressure additive is from about 1:7 to about 1:2, and wherein the package is boron-free, and wherein the total phosphorus content of the package is not more than about 500 ppm.
  • a lubricating oil comprising: (a) a base oil; and (b) the oil soluble lubricant additive package taught herein.
  • the base oils useful herein include natural lubricating oils, synthetic lubricating oils, and mixtures thereof. Suitable lubricating oils also include basestocks obtained by isomerization of synthetic wax and slack wax, as well as basestocks produced by hydrocracking the aromatic and polar components of the crude. In general, both the natural and synthetic lubricating oils will each have a kinematic viscosity ranging from about 1 to about 40 mm 2 /s (cSt) at 100° C., although typical applications will require each of the base oils to have a viscosity ranging from about 1 to about 16 mm 2 /s (cSt) at 100° C., preferably 2 to 15 mm 2 /s (cSt) at 100° C. Natural lubricating oils include animal oils, vegetable oils (e.g., castor oil and lard oil), petroleum oils, mineral oils, and oils derived from coal or shale. The preferred natural lubricating oil comprises mineral oil.
  • the mineral oils useful in this invention can include but are not limited to all common mineral oil base stocks. This would include oils that are naphthenic or paraffinic in chemical structure. Oils that are refined by conventional methodology using acid, alkali, and clay or other agents such as aluminum chloride, or be extracted oils produced, for example, by solvent extraction with solvents such as phenol, sulfur dioxide, furfural, dichlorodiethyl ether, etc. They may be hydrotreated or hydrorefined, dewaxed by chilling or catalytic dewaxing processes, or hydrocracked. The mineral oil may be produced from natural crude sources or be composed of isomerized wax materials or residues of other refining processes.
  • the oil of lubricating viscosity is a hydrotreated, hydrocracked and/or iso-dewaxed mineral oil having a Viscosity Index (VI) of greater than 80, preferably greater than 90; greater than 90 volume % saturates and less than 0.03 wt. % sulfur.
  • VI Viscosity Index
  • Group II and Group III basestocks are also particularly suitable for use in the present invention, and are typically prepared from conventional feedstocks using a severe hydrogenation step to reduce the aromatic, sulfur and nitrogen content, followed by dewaxing, hydrofinishing, extraction and/or distillation steps to produce the finished base oil.
  • base oils known as Group III, ⁇ 0.03 wt. % sulfur, and ⁇ 90 vol % saturates, viscosity index >120; and Group IV, poly-alpha-olefins. Hydrotreated basestocks and catalytically dewaxed basestocks, because of their low sulfur and aromatics content, generally fall into the Group II and Group III categories.
  • the base oil comprises a mineral oil having a VI of at least 110.
  • the lubricating oils may be derived from refined, re-refined oils, or mixtures thereof.
  • Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar sands bitumen) without further purification or treatment.
  • Examples of unrefined oils include shale oil obtained directly from a retorting operation, petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment.
  • Refined oils are similar to the unrefined oils except that refined oils have been treated in one or more purification steps to improve one or more properties.
  • Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art.
  • Re-refined oils are obtained by treating used oils in processes similar to those used to obtain the refined oils. These re-refined oils are also known as reclaimed or reprocessed oils and are often additionally processed by techniques for removal of spent additives and oil breakdown products.
  • Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as oligomerized, polymerized, and interpolymerized olefins; alkylbenzenes; polyphenyls; and alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologs thereof, and the like.
  • Preferred synthetic oils are oligomers of ⁇ -olefins, particularly oligomers of 1-decene, having a viscosity ranging from about 1 to about 12, preferably 2 to 8, mm 2 /s (cSt) at 100° C. These oligomers are known as poly- ⁇ -olefins or PAOs.
  • Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers, and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc.
  • This class of synthetic oils is exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide; the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polypropylene glycol having a molecular weight of 100-1500); and mono- and poly-carboxylic esters thereof (e.g., the acetic acid esters, mixed C 3 -C 8 fatty acid esters, and C 12 oxo acid diester of tetraethylene glycol).
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, subric acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoethers, propylene glycol, etc.).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, subric acid, sebasic acid, fumaric acid, adipic acid,
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl isothalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebasic acid with two moles of tetraethylene glycol and two moles of 2-ethyl-hexanoic acid, and the like.
  • a preferred type of oil from this class of synthetic oils is adipates of C 4 to C 12 alcohols.
  • Esters useful as synthetic lubricating oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane pentaeythritol, dipentaerythritol, tripentaerythritol, and the like.
  • Silicon-based oils (such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils. These oils include tetra-ethyl silicate, tetra-isopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-pentoxy)-disiloxane, poly(methyl)-siloxanes and poly (methylphenyl) siloxanes, and the like.
  • oils include tetra-ethyl silicate, tetra-isopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-
  • Other synthetic lubricating oils include liquid esters of phosphorus containing acids (e.g., tricresyl phosphate, trioctylphosphate, and diethyl ester of decylphosphonic acid), polymeric tetra-hydrofurans, poly-alpha-olefins, and the like.
  • liquid esters of phosphorus containing acids e.g., tricresyl phosphate, trioctylphosphate, and diethyl ester of decylphosphonic acid
  • polymeric tetra-hydrofurans e.g., polymeric tetra-hydrofurans, poly-alpha-olefins, and the like.
  • Dispersants derived from polyisobutylene (PIB) or mixed butane-substituted succinimides are among the succinimide dispersants useful herein, where the molecular weight range of the PIB is approximately 900-2100, most especially MW range 1200-1500.
  • the succinimide is malienated to a succinic anhydride to PIB ratio of approximately 1.0-1.25.
  • the polyisobutylene succinic anhydride intermediate can be further reacted with a suitable amine including any mono-, di-, or polyamine.
  • the dispersant may comprise one or more of various types of ashless dispersants including succinimides, succinamides, succinic esters, and succinic ester-amides.
  • the ashless dispersant may comprise one or more alkenyl succinimides of an amine having at least one primary amino group capable of forming an imide group.
  • the alkenyl succinimides may be formed by conventional methods such as by heating an alkenyl succinic anhydride, acid, acid-ester, acid halide, or lower alkyl ester with an amine containing at least one primary amino group.
  • the alkenyl succinic anhydride may be made readily by heating a mixture of polyolefin and maleic anhydride to about 180°-220° C.
  • the polyolefin may be a polymer or copolymer of a lower monoolefin such as ethylene, propylene, isobutene and the like, having a number average molecular weight in the range of about 700 to about 2100 as determined by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • Amines which may be employed in forming the ashless dispersant include without limitation any that have at least one primary amino group which can react to form an imide group and at least one additional primary or secondary amino group and/or at least one hydroxyl group.
  • a few representative examples are: N-methyl-propanediamine, N-dodecylpropanediamine, N-aminopropyl-piperazine, ethanolamine, N-ethanol-ethylenediamine, N-phenylenediamine, and the like.
  • Suitable amines may include alkylene polyamines, such as propylene diamine, dipropylene triamine, di-(1,2-butylene)triamine, and tetra-(1,2-propylene)pentamine.
  • alkylene polyamines such as propylene diamine, dipropylene triamine, di-(1,2-butylene)triamine, and tetra-(1,2-propylene)pentamine.
  • a further example includes the ethylene polyamines which can be depicted by the formula H 2 N(CH 2 CH 2 NH) n H, wherein n may be an integer from about one to about ten. These include: ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and the like, including mixtures thereof in which case n is the average value of the mixture.
  • ethylene polyamines have a primary amine group at each end so they may form mono-alkenylsuccinimides and bis-alkenylsuccinimides.
  • Commercially available ethylene polyamine mixtures may contain minor amounts of branched species and cyclic species such as N-aminoethyl piperazine, N,N′-bis(aminoethyl)piperazine, N,N′-bis(piperazinyl)ethane, and like compounds.
  • the commercial mixtures may have approximate overall compositions falling in the range corresponding to diethylene triamine to tetraethylene pentamine.
  • the molar ratio of polyalkenyl succinic anhydride to polyalkylene polyamines may be from about 1:1 to about 2.4:1.
  • the ashless dispersant may comprise the products of the reaction of a polyethylene polyamine, e.g. triethylene tetramine or tetraethylene pentamine, with a hydrocarbon substituted carboxylic acid or anhydride made by reaction of a polyolefin, such as polyisobutene, of suitable molecular weight, with an unsaturated polycarboxylic acid or anhydride, e.g., maleic anhydride, maleic acid, fumaric acid, or the like, including mixtures of two or more such substances.
  • a polyethylene polyamine e.g. triethylene tetramine or tetraethylene pentamine
  • a hydrocarbon substituted carboxylic acid or anhydride made by reaction of a polyolefin, such as polyisobutene, of suitable molecular weight
  • an unsaturated polycarboxylic acid or anhydride e.g., maleic anhydride, maleic acid, fumaric acid, or the like, including mixtures
  • the dispersant may contain at least one polyalkylene moiety.
  • the dispersant may comprise at least two polyalkylene moieties.
  • the polyalkylene moiety may have a molecular weight of from about 900 amu to about 3000 amu.
  • the polyalkylene moiety polyalkylene moiety may, for example, have a molecular weight of from about 1300 amu to about 2100 amu.
  • the polyalkylene moiety may have a molecular weight of about 2100 amu.
  • the polyalkylene moiety may comprise a polybutenyl group.
  • the dispersant may be dissolved in oil of suitable viscosity for ease of handling. It should be understood that the weight percentages given here are for neat dispersant, without any diluent oil added.
  • the dispersant may be further reacted with an organic acid, an anhydride, and/or an aldehyde/phenol mixture. Such a process may enhance compatibility with elastomer seals, for example.
  • the dispersant may further comprise a mixture of dispersants.
  • the dispersant may comprise nitrogen and/or may be free of phosphorus.
  • the dispersant may be present in an embodiment in the lubricating fluid in an amount of about 1 wt % to about 5 wt %.
  • the dispersant used in some embodiments of the present disclosure may comprise a succinimide prepared from an alkenyl succinic acid or anhydride and ammonia.
  • the succinimide may comprise the reaction product of a succinic anhydride and ammonia.
  • the alkenyl group of the alkenyl succinic acid may be a short chain alkenyl group, for example, the alkenyl group may comprise about 12 to about 36 carbon atoms.
  • the succinic anhydride may comprise a C 12 to about C 36 aliphatic hydrocarbyl succinimide.
  • the succinic anhydride may comprise a C 16 to about C 28 aliphatic hydrocarbyl succinimide.
  • the succinic anhydride may comprise a C 18 to about C 24 aliphatic hydrocarbyl succinimide.
  • the succinimide may be prepared from a succinic anhydride and ammonia as described in European Patent 0 020 037, herein incorporated by reference. Further, the succinimide may comprise HiTEC® 3191 friction modifier, available from Ethyl Corporation. In some embodiments, no non-metallic friction modifier other than the succinimide disclosed herein is included.
  • the succinimide may comprise one or more of a compound having the following structure: wherein Z may have the structure:
  • One embodiment utilizes a poly-amine of the type tetra ethyl pentamine.
  • examples can include but are not limited to HiTEC® 646 Dispersant, available from Ethyl Corporation, and similar succinimide dispersants.
  • Extreme pressure agents known to those skilled in the art are useful in the lubricant additive packages, lubricating oil, lubricated machines, and methods of the present invention. Also useful herein as extreme pressure agents are sulfurized olefins, including but not limited to sulfurized isobutylene, alkylpolysulfides and sulfurized fatty acid esters.
  • Corrosion inhibitors of the thiadiazole and triazole classes are suitable for use in this invention.
  • Alkyl substituted thiadiazoles as well as alkyl substituted triazoles are useful in this invention.
  • Antiwear and siloxane-containing polymer antifoam agents can also be employed in the lubricant additive packages and finished lubricating oils of the present invention.
  • a variety of oil-soluble sulphur-containing antiwear and/or extreme pressure additives can be used in the practice of this invention. Examples are included within the categories of dihydrocarbyl polysulphides; sulphurized olefins; sulphurized fatty acid esters of both natural and synthetic origins; trithiones; sulphurized thienyl derivatives; sulphurized terpenes; sulphurized oligomers of C 2 -C 8 monoolefins; and sulphurized Dieis-Alder adducts such as those disclosed in U.S. reissue patent Re 27,331.
  • Specific examples include sulphurized polyisobutene of Mn 1,100, sulfurized isobutylene, sulphurized diisobutylene, sulphurized triisobutylene, dicyclohexyl polysulphide, diphenyl polysulphide, dibenzyl polysulphide, dinonyl polysulphide, and mixtures of di-tert-butyl polysulphide such as mixtures of di-tert-butyl trisulphide, di-tert-butyl tetrasulphide and di-tert-butyl pentasulphide, among others.
  • Combinations of such categories of sulphur-containing antiwear and/or extreme pressure agents can also be used, such as a combination of sulphurized isobutylene and di-tert-butyl trisulphide, a combination of sulphurized isobutylene and dinonyl trisulphide, a combination of sulphurized tall oil and dibenzyl polysulphide, and the like.
  • a component which contains both phosphorus and sulphur in its chemical structure is deemed a phosphorus-containing antiwear and/or extreme pressure agent rather than a sulphur-containing antiwear and/or extreme pressure agent.
  • phosphorus- and nitrogen-containing antiwear and/or extreme pressure additives which can be employed in the practice of this invention are the phosphorus- and nitrogen-containing compositions of the type described in G.B. 1,009,913; G.B. 1,009,914; U.S. Pat. No. 3,197,405 and/or U.S. Pat. No. 3,197,496.
  • compositions are formed by forming an acidic intermediate by the reaction of a hydroxy-substituted triester of a phosphorothioic acid with an inorganic phosphorus acid, phosphorus oxide or phosphorus halide, and neutralizing a substantial portion of said acidic intermediate with an amine or hydroxy-substituted amine.
  • Another type of phosphorus- and nitrogen-containing antiwear and/or extreme pressure additive which can be used in the compositions of this invention is the amine salts of hydroxy-substituted phosphetanes or the amine salts of hydroxy-substituted thiophosphetanes.
  • this general type of antiwear and/or extreme pressure agent include the amine salts hydroxyphosphetanes and the amine salts of hydroxy-thiophosphetanes typified by Irgalube 295 additive (Ciba-Geigy Corporation).
  • Another useful category of phosphorus- and nitrogen-containing antiwear and/or extreme pressure agents is comprised of the amine salts of partial esters of phosphoric and thiophosphoric acids.
  • EP 531 585 referred to above.
  • the formulations of the present invention have a total phosphorus content of not more than about 500 ppm.
  • the formulations are also boron-free.
  • boron-free herein is meant substantially free of boron whereby trace amounts of or contamination with low or unintended levels of boron are to be included.
  • Boron-free can herein include low levels of boron up to about 25 ppm.
  • substantially free of boron herein is meant less than about 50 ppm of boron.
  • An example of an oil soluble lubricant additive package formulation of the present invention is outlined in the table below: COmponent Wt % Sulfurized olefin 30-50 Primary amine 0.1-5 Acid phosphate 0.5-5.0 Rust Inhibitor 0.01-1 Antifoamant 0.2-2.0 Corrosion Inhibitor 0.2-2.0 Diluent Oil 30-40 Dispersant 2-15.0
  • a finished oil comprising the preferred boron-free oil soluble lubricant additive package was manufactured for testing purposes.
  • the finished oil was then tested by the L60-1 and the ISOT standard tests. It was unexpected that a lubricant additive package could pass both the L60-1 and ISOT standard tests without the inclusion of a boron source in the formulation.
  • the L60-1 test requires at least a 7.5 carbon/varnish (C/V) rating or higher to pass, and at least a 9.4 sludge rating or higher to pass.
  • the L60-1 rating is based on a merit system with 10 indicating no carbon/varnish and zero representing the worst rating.
  • the ISOT test conversely, requires at most a 3.0 for varnish on the glass beaker and for varnish on the glass rod to indicate clean gear performance.
  • the ISOT rating is based on a demerit system with the best ISOT rating zero indicating no varnish and 9 representing the worst varnish rating. This rating may also be described as thinly to lightly adhering lacquer in the ISOT procedure. Note that prior art formulations containing phosphorus and boron pass both tests. Formulations with low phosphorus alone do not pass both tests. Only the formulations of the present invention with both low phosphorus and a dispersant pass both tests without boron.
  • the formulations of the present invention are especially effective in the lubrication of vehicular axle gears and vehicular transmission gears.
  • the vehicles can be passenger cars, light duty trucks, heavy duty trucks, buses, recreation vehicles, marine craft, and the like.

Abstract

The present invention provides a boron-free oil soluble lubricant additive package having a succinimide dispersant, an antiwear agent, and an extreme pressure agent, with a total phosphorus content of 500 ppm or less. The lubricating oils of this invention can pass both the ISOT and L60-1 tests, even in the absence of boron.

Description

    TECHNICAL FIELD OF THE INVENTION
  • The present invention is in the field of lubricant additives and lubricant formulations. Specifically, the present invention relates to a boron-free lubricant additive package that is capable of passing tests for which the presence of boron was thought to be essential to passing.
  • BACKGROUND OF THE INVENTION
  • Historically, boron-containing lubricants have been used to attain satisfactory performance against standard industry tests. Two such industry tests are the ISOT and the L60-1. However, boron imparts certain undesirable properties to the lubricant such as moisture sensitivity and increased price. Thus, it is desirable to have a lubricant that can provide the performance demanded by industry while reducing or eliminating the presence of boron. Recently, a boron-free lubricant additive package has been developed that unexpectedly passes both the ISOT standard test and the L60-1 standard test.
  • SUMMARY OF THE INVENTION
  • The present invention provides a lubricating additive package that is capable of passing both the ISOT standard test and the L60-1 standard test. More specifically, the present invention in an embodiment provides an oil soluble lubricant additive package comprising: (a) a succinimide dispersant, (b) an antiwear agent, (c) an extreme pressure additive, wherein the weight ratio of said dispersant to said extreme pressure additive is from about 1:7 to about 1:2, and wherein the package is boron-free, and wherein the total phosphorus content of the package is not more than about 500 ppm.
  • In another embodiment is provided a lubricating oil comprising: (a) a base oil; and (b) the oil soluble lubricant additive package taught herein.
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)
  • In accordance with the foregoing summary, the following presents a detailed description of one embodiment of the invention that is currently considered to be the best mode.
  • We begin with a discussion of the various components employed in certain embodiments of the present invention. Then we present a lubricant additive package of the present invention and an example of a lubricant oil comprising the inventive lubricant additive package. We conclude with a discussion of the L60-1 and ISOT test performance attained by the inventive lubricant additive package.
  • Base Oil
  • The base oils useful herein include natural lubricating oils, synthetic lubricating oils, and mixtures thereof. Suitable lubricating oils also include basestocks obtained by isomerization of synthetic wax and slack wax, as well as basestocks produced by hydrocracking the aromatic and polar components of the crude. In general, both the natural and synthetic lubricating oils will each have a kinematic viscosity ranging from about 1 to about 40 mm2/s (cSt) at 100° C., although typical applications will require each of the base oils to have a viscosity ranging from about 1 to about 16 mm2/s (cSt) at 100° C., preferably 2 to 15 mm2/s (cSt) at 100° C. Natural lubricating oils include animal oils, vegetable oils (e.g., castor oil and lard oil), petroleum oils, mineral oils, and oils derived from coal or shale. The preferred natural lubricating oil comprises mineral oil.
  • The mineral oils useful in this invention can include but are not limited to all common mineral oil base stocks. This would include oils that are naphthenic or paraffinic in chemical structure. Oils that are refined by conventional methodology using acid, alkali, and clay or other agents such as aluminum chloride, or be extracted oils produced, for example, by solvent extraction with solvents such as phenol, sulfur dioxide, furfural, dichlorodiethyl ether, etc. They may be hydrotreated or hydrorefined, dewaxed by chilling or catalytic dewaxing processes, or hydrocracked. The mineral oil may be produced from natural crude sources or be composed of isomerized wax materials or residues of other refining processes. In one embodiment, the oil of lubricating viscosity is a hydrotreated, hydrocracked and/or iso-dewaxed mineral oil having a Viscosity Index (VI) of greater than 80, preferably greater than 90; greater than 90 volume % saturates and less than 0.03 wt. % sulfur.
  • Group II and Group III basestocks are also particularly suitable for use in the present invention, and are typically prepared from conventional feedstocks using a severe hydrogenation step to reduce the aromatic, sulfur and nitrogen content, followed by dewaxing, hydrofinishing, extraction and/or distillation steps to produce the finished base oil. Also useful herein are base oils known as Group III, ≦0.03 wt. % sulfur, and ≧90 vol % saturates, viscosity index >120; and Group IV, poly-alpha-olefins. Hydrotreated basestocks and catalytically dewaxed basestocks, because of their low sulfur and aromatics content, generally fall into the Group II and Group III categories.
  • There is no limitation as to the chemical composition of the various basestocks used in the present invention. For example, the proportions of aromatics, paraffinics, and naphthenics in the various Group I, Group II and Group III oils can vary substantially. The degree of refining and the source of the crude used to produce the oil generally determine this composition. In one embodiment, the base oil comprises a mineral oil having a VI of at least 110.
  • The lubricating oils may be derived from refined, re-refined oils, or mixtures thereof. Unrefined oils are obtained directly from a natural source or synthetic source (e.g., coal, shale, or tar sands bitumen) without further purification or treatment. Examples of unrefined oils include shale oil obtained directly from a retorting operation, petroleum oil obtained directly from distillation, or an ester oil obtained directly from an esterification process, each of which is then used without further treatment. Refined oils are similar to the unrefined oils except that refined oils have been treated in one or more purification steps to improve one or more properties. Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration, and percolation, all of which are known to those skilled in the art. Re-refined oils are obtained by treating used oils in processes similar to those used to obtain the refined oils. These re-refined oils are also known as reclaimed or reprocessed oils and are often additionally processed by techniques for removal of spent additives and oil breakdown products.
  • Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as oligomerized, polymerized, and interpolymerized olefins; alkylbenzenes; polyphenyls; and alkylated diphenyl ethers, alkylated diphenyl sulfides, as well as their derivatives, analogs, and homologs thereof, and the like. Preferred synthetic oils are oligomers of α-olefins, particularly oligomers of 1-decene, having a viscosity ranging from about 1 to about 12, preferably 2 to 8, mm2/s (cSt) at 100° C. These oligomers are known as poly-α-olefins or PAOs.
  • Synthetic lubricating oils also include alkylene oxide polymers, interpolymers, copolymers, and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. This class of synthetic oils is exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide; the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polypropylene glycol having a molecular weight of 100-1500); and mono- and poly-carboxylic esters thereof (e.g., the acetic acid esters, mixed C3-C8 fatty acid esters, and C12 oxo acid diester of tetraethylene glycol).
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, subric acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoethers, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl isothalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebasic acid with two moles of tetraethylene glycol and two moles of 2-ethyl-hexanoic acid, and the like. A preferred type of oil from this class of synthetic oils is adipates of C4 to C12 alcohols.
  • Esters useful as synthetic lubricating oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane pentaeythritol, dipentaerythritol, tripentaerythritol, and the like.
  • Silicon-based oils (such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils) comprise another useful class of synthetic lubricating oils. These oils include tetra-ethyl silicate, tetra-isopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-pentoxy)-disiloxane, poly(methyl)-siloxanes and poly (methylphenyl) siloxanes, and the like. Other synthetic lubricating oils include liquid esters of phosphorus containing acids (e.g., tricresyl phosphate, trioctylphosphate, and diethyl ester of decylphosphonic acid), polymeric tetra-hydrofurans, poly-alpha-olefins, and the like.
  • Dispersants
  • Dispersants derived from polyisobutylene (PIB) or mixed butane-substituted succinimides are among the succinimide dispersants useful herein, where the molecular weight range of the PIB is approximately 900-2100, most especially MW range 1200-1500. In one embodiment, the succinimide is malienated to a succinic anhydride to PIB ratio of approximately 1.0-1.25. The polyisobutylene succinic anhydride intermediate can be further reacted with a suitable amine including any mono-, di-, or polyamine.
  • The dispersant may comprise one or more of various types of ashless dispersants including succinimides, succinamides, succinic esters, and succinic ester-amides.
  • Methods for the production of the foregoing types of ashless dispersants are known to those skilled in the art and are reported in the patent literature. For example, the synthesis of various ashless dispersants of the foregoing types is described in such patents as U.S. Pat. Nos. 2,459,112; 2,962,442, 2,984,550; 3,036,003; 3,163,603; 3,166,516; 3,172,892; 3,184,474; 3,202,678; 3,215,707; 3,216,936; 3,219,666; 3,236,770; 3,254,025; 3,271,310; 3,272,746; 3,275,554; 3,281,357; 3,306,908; 3,311,558; 3,316,177; 3,331,776; 3,340,281; 3,341,542; 3,346,493; 3,351,552; 3,355,270; 3,368,972; 3,381,022; 3,399,141; 3,413,347; 3,415,750; 3,433,744; 3,438,757; 3,442,808; 3,444,170; 3,448,047; 3,448,048; 3,448,049; 3,451,933; 3,454,497; 3,454,555; 3,454,607; 3,459,661; 3,461,172; 3,467,668; 3,493,520; 3,501,405; 3,522,179; 3,539,633; 3,541,012; 3,542,680; 3,543,678; 3,558,743; 3,565,804; 3,567,637; 3,574,101; 3,576,743; 3,586,629; 3,591,598; 3,600,372; 3,630,904; 3,632,510; 3,632,511; 3,634,515; 3,649,229; 3,697,428; 3,697,574; 3,703,536; 3,704,308; 3,725,277; 3,725,441; 3,725,480; 3,726,882; 3,736,357; 3,751,365; 3,756,953; 3,793,202; 3,798,165; 3,798,247; 3,803,039; 3,804,763; 3,836,471; 3,862,981; 3,936,480; 3,948,800; 3,950,341; 3,957,854; 3,957,855; 3,980,569; 3,991,098; 4,071,548; 4,173,540; 4,234,435; 5,137,980 and Re 26,433, herein incorporated by reference.
  • In some embodiments, the ashless dispersant may comprise one or more alkenyl succinimides of an amine having at least one primary amino group capable of forming an imide group. The alkenyl succinimides may be formed by conventional methods such as by heating an alkenyl succinic anhydride, acid, acid-ester, acid halide, or lower alkyl ester with an amine containing at least one primary amino group. The alkenyl succinic anhydride may be made readily by heating a mixture of polyolefin and maleic anhydride to about 180°-220° C. The polyolefin may be a polymer or copolymer of a lower monoolefin such as ethylene, propylene, isobutene and the like, having a number average molecular weight in the range of about 700 to about 2100 as determined by gel permeation chromatography (GPC).
  • Amines which may be employed in forming the ashless dispersant include without limitation any that have at least one primary amino group which can react to form an imide group and at least one additional primary or secondary amino group and/or at least one hydroxyl group. A few representative examples are: N-methyl-propanediamine, N-dodecylpropanediamine, N-aminopropyl-piperazine, ethanolamine, N-ethanol-ethylenediamine, N-phenylenediamine, and the like.
  • Suitable amines may include alkylene polyamines, such as propylene diamine, dipropylene triamine, di-(1,2-butylene)triamine, and tetra-(1,2-propylene)pentamine. A further example includes the ethylene polyamines which can be depicted by the formula H2N(CH2CH2NH)nH, wherein n may be an integer from about one to about ten. These include: ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and the like, including mixtures thereof in which case n is the average value of the mixture. These depicted ethylene polyamines have a primary amine group at each end so they may form mono-alkenylsuccinimides and bis-alkenylsuccinimides. Commercially available ethylene polyamine mixtures may contain minor amounts of branched species and cyclic species such as N-aminoethyl piperazine, N,N′-bis(aminoethyl)piperazine, N,N′-bis(piperazinyl)ethane, and like compounds. The commercial mixtures may have approximate overall compositions falling in the range corresponding to diethylene triamine to tetraethylene pentamine. The molar ratio of polyalkenyl succinic anhydride to polyalkylene polyamines may be from about 1:1 to about 2.4:1.
  • In some embodiments, the ashless dispersant may comprise the products of the reaction of a polyethylene polyamine, e.g. triethylene tetramine or tetraethylene pentamine, with a hydrocarbon substituted carboxylic acid or anhydride made by reaction of a polyolefin, such as polyisobutene, of suitable molecular weight, with an unsaturated polycarboxylic acid or anhydride, e.g., maleic anhydride, maleic acid, fumaric acid, or the like, including mixtures of two or more such substances.
  • The dispersant may contain at least one polyalkylene moiety. As a further example, the dispersant, may comprise at least two polyalkylene moieties. The polyalkylene moiety may have a molecular weight of from about 900 amu to about 3000 amu. The polyalkylene moiety polyalkylene moiety may, for example, have a molecular weight of from about 1300 amu to about 2100 amu. As a further example, the polyalkylene moiety may have a molecular weight of about 2100 amu. The polyalkylene moiety may comprise a polybutenyl group.
  • The dispersant may be dissolved in oil of suitable viscosity for ease of handling. It should be understood that the weight percentages given here are for neat dispersant, without any diluent oil added.
  • The dispersant may be further reacted with an organic acid, an anhydride, and/or an aldehyde/phenol mixture. Such a process may enhance compatibility with elastomer seals, for example. The dispersant may further comprise a mixture of dispersants. As a further example, the dispersant may comprise nitrogen and/or may be free of phosphorus. The dispersant may be present in an embodiment in the lubricating fluid in an amount of about 1 wt % to about 5 wt %.
  • The dispersant used in some embodiments of the present disclosure may comprise a succinimide prepared from an alkenyl succinic acid or anhydride and ammonia. For example, the succinimide may comprise the reaction product of a succinic anhydride and ammonia. The alkenyl group of the alkenyl succinic acid may be a short chain alkenyl group, for example, the alkenyl group may comprise about 12 to about 36 carbon atoms. Further, the succinic anhydride may comprise a C12 to about C36 aliphatic hydrocarbyl succinimide. As a further example, the succinic anhydride may comprise a C16 to about C28 aliphatic hydrocarbyl succinimide. As an even further example, the succinic anhydride may comprise a C18 to about C24 aliphatic hydrocarbyl succinimide.
  • The succinimide may be prepared from a succinic anhydride and ammonia as described in European Patent 0 020 037, herein incorporated by reference. Further, the succinimide may comprise HiTEC® 3191 friction modifier, available from Ethyl Corporation. In some embodiments, no non-metallic friction modifier other than the succinimide disclosed herein is included.
  • The succinimide may comprise one or more of a compound having the following structure:
    Figure US20050070446A1-20050331-C00001

    wherein Z may have the structure:
    Figure US20050070446A1-20050331-C00002
      • wherein R1 and R2 may be independently hydrogen or straight or branched chain hydrocarbon groups containing from about 1 to about 34 carbon atoms such that the total number of carbon atoms in R1 and R2 is from about 11 to about 35; and
      • wherein, in addition to or in the alternative, the succinimide may be formed by reacting maleic acid, anhydride, or ester with an internal olefin containing about 12 to about 36 carbon atoms, said internal olefin being formed by isomerizing the olefinic double bond of a linear α-olefin or mixture thereof to obtain a mixture of internal olefins.
  • One embodiment utilizes a poly-amine of the type tetra ethyl pentamine. Examples can include but are not limited to HiTEC® 646 Dispersant, available from Ethyl Corporation, and similar succinimide dispersants.
  • Extreme Pressure Additives
  • Extreme pressure agents known to those skilled in the art are useful in the lubricant additive packages, lubricating oil, lubricated machines, and methods of the present invention. Also useful herein as extreme pressure agents are sulfurized olefins, including but not limited to sulfurized isobutylene, alkylpolysulfides and sulfurized fatty acid esters.
  • Corrosion Inhibitors
  • Corrosion inhibitors of the thiadiazole and triazole classes are suitable for use in this invention. Alkyl substituted thiadiazoles as well as alkyl substituted triazoles are useful in this invention.
  • Other Agents
  • Antiwear and siloxane-containing polymer antifoam agents, well known to those skilled in the art and as taught in, for example, U.S. Pat. No. 5,492,638, can also be employed in the lubricant additive packages and finished lubricating oils of the present invention.
  • A variety of oil-soluble sulphur-containing antiwear and/or extreme pressure additives can be used in the practice of this invention. Examples are included within the categories of dihydrocarbyl polysulphides; sulphurized olefins; sulphurized fatty acid esters of both natural and synthetic origins; trithiones; sulphurized thienyl derivatives; sulphurized terpenes; sulphurized oligomers of C2-C8 monoolefins; and sulphurized Dieis-Alder adducts such as those disclosed in U.S. reissue patent Re 27,331. Specific examples include sulphurized polyisobutene of Mn 1,100, sulfurized isobutylene, sulphurized diisobutylene, sulphurized triisobutylene, dicyclohexyl polysulphide, diphenyl polysulphide, dibenzyl polysulphide, dinonyl polysulphide, and mixtures of di-tert-butyl polysulphide such as mixtures of di-tert-butyl trisulphide, di-tert-butyl tetrasulphide and di-tert-butyl pentasulphide, among others.
  • Combinations of such categories of sulphur-containing antiwear and/or extreme pressure agents can also be used, such as a combination of sulphurized isobutylene and di-tert-butyl trisulphide, a combination of sulphurized isobutylene and dinonyl trisulphide, a combination of sulphurized tall oil and dibenzyl polysulphide, and the like.
  • Reference should be had to EP 531 585 referred to above for further details concerning this component.
  • For purposes of this invention a component which contains both phosphorus and sulphur in its chemical structure is deemed a phosphorus-containing antiwear and/or extreme pressure agent rather than a sulphur-containing antiwear and/or extreme pressure agent.
  • One such type of phosphorus- and nitrogen-containing antiwear and/or extreme pressure additives which can be employed in the practice of this invention are the phosphorus- and nitrogen-containing compositions of the type described in G.B. 1,009,913; G.B. 1,009,914; U.S. Pat. No. 3,197,405 and/or U.S. Pat. No. 3,197,496. In general, these compositions are formed by forming an acidic intermediate by the reaction of a hydroxy-substituted triester of a phosphorothioic acid with an inorganic phosphorus acid, phosphorus oxide or phosphorus halide, and neutralizing a substantial portion of said acidic intermediate with an amine or hydroxy-substituted amine.
  • Another type of phosphorus- and nitrogen-containing antiwear and/or extreme pressure additive which can be used in the compositions of this invention is the amine salts of hydroxy-substituted phosphetanes or the amine salts of hydroxy-substituted thiophosphetanes. Examples of this general type of antiwear and/or extreme pressure agent include the amine salts hydroxyphosphetanes and the amine salts of hydroxy-thiophosphetanes typified by Irgalube 295 additive (Ciba-Geigy Corporation).
  • Another useful category of phosphorus- and nitrogen-containing antiwear and/or extreme pressure agents is comprised of the amine salts of partial esters of phosphoric and thiophosphoric acids. For further details concerning this component, reference should be had to EP 531 585 referred to above.
  • The formulations of the present invention have a total phosphorus content of not more than about 500 ppm. The formulations are also boron-free. By “boron-free” herein is meant substantially free of boron whereby trace amounts of or contamination with low or unintended levels of boron are to be included. Boron-free can herein include low levels of boron up to about 25 ppm. By “substantially free of boron” herein is meant less than about 50 ppm of boron.
  • NOTE: Current Boronated packages offered by Ethyl contain 125-150 ppm of Boron. I think the above levels are too high.
  • Example Formulation
  • An example of an oil soluble lubricant additive package formulation of the present invention is outlined in the table below:
    COmponent Wt %
    Sulfurized olefin 30-50
    Primary amine 0.1-5  
    Acid phosphate 0.5-5.0
    Rust Inhibitor 0.01-1  
    Antifoamant 0.2-2.0
    Corrosion Inhibitor 0.2-2.0
    Diluent Oil 30-40
    Dispersant   2-15.0
  • A finished oil comprising the preferred boron-free oil soluble lubricant additive package was manufactured for testing purposes. The finished oil was then tested by the L60-1 and the ISOT standard tests. It was unexpected that a lubricant additive package could pass both the L60-1 and ISOT standard tests without the inclusion of a boron source in the formulation.
    Phosphorus Boron L-60-1 ISOT
    Additive Dispersant ppm ppm C/V Sludge Beaker Rod
    Package A Yes 1,425 158 9.25 9.59 2.5 1
    Package B Yes 870 132
    Package C Yes 680 0 8.0 9.0
    Package D Yes 576 150 9.10 9.64 2.0 2.0
    Package E Yes 525 195 9.10 9.54 2.5 2.5
    Package F Yes 525 0 8.15 9.50
    Package G NO 525 0 3.40 8.68 7.0 9.0
    Package H NO 300 0 7.60 9.46 8.0 9.0
    Invention Yes 300 0 9.44 9.52 1.5 2.0
  • The L60-1 test requires at least a 7.5 carbon/varnish (C/V) rating or higher to pass, and at least a 9.4 sludge rating or higher to pass. The L60-1 rating is based on a merit system with 10 indicating no carbon/varnish and zero representing the worst rating.
  • The ISOT test, conversely, requires at most a 3.0 for varnish on the glass beaker and for varnish on the glass rod to indicate clean gear performance. The ISOT rating is based on a demerit system with the best ISOT rating zero indicating no varnish and 9 representing the worst varnish rating. This rating may also be described as thinly to lightly adhering lacquer in the ISOT procedure. Note that prior art formulations containing phosphorus and boron pass both tests. Formulations with low phosphorus alone do not pass both tests. Only the formulations of the present invention with both low phosphorus and a dispersant pass both tests without boron.
  • The formulations of the present invention are especially effective in the lubrication of vehicular axle gears and vehicular transmission gears. The vehicles can be passenger cars, light duty trucks, heavy duty trucks, buses, recreation vehicles, marine craft, and the like.
  • While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiment(s), but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims, which are incorporated herein by reference.

Claims (45)

1. An oil soluble lubricant additive package comprising:
(a) a succinimide dispersant,
(b) an antiwear agent,
(c) an extreme pressure additive, wherein the weight ratio of said dispersant to said extreme pressure additive is from about 1:7 to about 1:2, and wherein the package is boron-free, and wherein the total phosphorus content of the package is not more than about 500 ppm.
2. The oil soluble lubricant additive package according to claim 1, wherein said dispersant is selected from the group consisting of: one or more of succinimide dispersants, succinamides, succinic esters, and succinic ester-amides.
3. The oil soluble lubricant additive package according to claim 1, wherein said extreme pressure additive is selected from the group consisting of sulfurized olefins, sulfurized fatty acid esters, and alkyl polysulfides.
4. A lubricating oil comprising:
(a) a base oil; and
(b) the oil soluble lubricant additive package of claim 1.
5. The lubricating oil according to claim 4, wherein said lubricating oil achieves a satisfactory score on at least one test selected from the group consisting of: ISOT test and L60-1 test.
6. A machine lubricated by the lubricating oil of claim 4.
7. The machine according to claim 6, wherein said machine is selected from the group consisting of vehicular axle gears and vehicular transmission gears.
8. A vehicle comprising the oil soluble lubricating additive package of claim 1.
9. A method for lubricating an axle assembly, said method comprising the steps of:
at least partially filling said axle assembly with a lubricant comprising the oil soluble lubricant additive package of claim 1.
10. A method for lubricating at least one moving part, said method comprising the steps of:
contacting at least one said moving part with a lubricant comprising the oil soluble lubricant additive package of claim 1.
11. An oil soluble lubricant additive package comprising:
(a) a dispersant comprising no more than about 500 ppm of phosphorus, wherein said dispersant is substantially free of boron; and
(b) at least one inhibitor, wherein the weight ratio of said inhibitor to said dispersant is from about 1:17 to about 4:5.
12. The oil soluble lubricant additive package according to claim 11, wherein said dispersant is selected from the group consisting of: one or more of various types of ashless dispersants including succinimides, succinamides, succinic esters, and succinic ester-amides.
13. The oil soluble lubricant additive package according to claim 11, wherein at least one said inhibitor is selected from the group consisting of: corrosion inhibitors and oxidation inhibitors.
14. The oil soluble lubricant additive package according to claim 11, wherein at least one said inhibitor is selected from the group consisting of thiadiazoles and triazoles.
15. A lubricating oil comprising:
(a) a base oil; and
(b) the oil soluble lubricant additive package of claim 11.
16. The lubricating oil according to claim 15, wherein said lubricating oil achieves a satisfactory score on at least one test selected from the group consisting of: ISOT test and L60-1 test.
17. A machine lubricated by the lubricating oil of claim 15.
18. The machine according to claim 17, wherein said machine is selected from the group consisting of automotive gear assemblies and automotive transmission assemblies.
19. A vehicle comprising the oil soluble lubricating additive package of claim 11.
20. A method for lubricating an axle assembly, said method comprising the steps of:
at least partially filling said axle assembly with a lubricant comprising the oil soluble lubricant additive package of claim 11.
21. A method for lubricating at least one moving part, said method comprising the steps of:
contacting at least one said moving part with a lubricant comprising the oil soluble lubricant additive package of claim 11.
22. An oil soluble lubricant additive package comprising:
(a) a dispersant comprising no more than about 500 ppm of phosphorus, wherein said dispersant is substantially free of boron; and
(b) at least one antiwear agent, wherein the weight ratio of said dispersant to said antiwear agent is from about 10:1 to about 2:1.
23. The oil soluble lubricant additive package according to claim 22, wherein said dispersant is selected from the group consisting of: one or more of various types of ashless dispersants including succinimides, succinamides, succinic esters, and succinic ester-amides.
24. The oil soluble lubricant additive package according to claim 22, wherein at least one antiwear agent is selected from the group consisting of: dihydrocarbyl polysulphides; sulphurized olefins; sulphurized fatty acid esters of both natural and synthetic origins; trithiones; sulphurized thienyl derivatives; sulphurized terpenes; sulphurized oligomers of C2-C8 monoolefins; and sulphurized Dieis-Alder adducts.
25. A lubricating oil comprising:
(a) a base oil; and
(b) the oil soluble lubricant additive package of claim 22.
26. The lubricating oil according to claim 25, wherein said lubricating oil achieves a satisfactory score on at least one test selected from the group consisting of: ISOT test and L60-1 test.
27. A machine lubricated by the lubricating oil of claim 25.
28. The machine according to claim 27, wherein said machine is selected from the group consisting of vehicular axle gears and vehicular transmission gears.
29. A vehicle comprising the oil soluble lubricating additive package of claim 22.
30. A method for lubricating an axle assembly, said method comprising the steps of:
at least partially filling said axle assembly with a lubricant comprising the oil soluble lubricant additive package of claim 22.
31. A method for lubricating at least one moving part, said method comprising the steps of:
contacting at least one said moving part with a lubricant comprising the oil soluble lubricant additive package of claim 22.
32. An oil soluble lubricant additive package comprising:
(a) a dispersant comprising no more than about 500 ppm of phosphorus, wherein said dispersant is substantially free of boron; and
(b) at least one antifoam agent, wherein the weight ratio of said dispersant to said antifoam agent is from about 30:1 to about 5:1.
33. The oil soluble lubricant additive package according to claim 32, wherein said dispersant is selected from the group consisting of: one or more of various types of ashless dispersants including succinimides, succinamides, succinic esters, and succinic ester-amides.
34. The oil soluble lubricant additive package according to claim 32, wherein at least one antifoam agent is selected from the group consisting of siloxane-containing polymers.
35. A lubricating oil comprising:
(a) a base oil; and
(b) the oil soluble lubricant additive package of claim 32.
36. The lubricating oil according to claim 35, wherein said lubricating oil achieves a satisfactory score on at least one test selected from the group consisting of: ISOT test and L60-1 test.
37. A machine lubricated by the lubricating oil of claim 35.
38. The machine according to claim 37, wherein said machine is selected from the group consisting of: vehicular axle gears and vehicular transmission gears.
39. A vehicle comprising the oil soluble lubricating additive package of claim 32.
40. A method for lubricating an axle assembly, said method comprising the steps of:
at least partially filling said axle assembly with a lubricant comprising the oil soluble lubricant additive package of claim 32.
41. A method for lubricating at least one moving part, said method comprising the steps of:
contacting at least one said moving part with a lubricant comprising the oil soluble lubricant additive package of claim 32.
42. The lubricating oil according to claim 4, wherein said lubricating oil achieves a satisfying score on the ISOT test and the L60-1 test.
43. The lubricating oil according to claim 15, wherein said lubricating oil achieves a satisfying score on the ISOT test and the L60-1 test.
44. The lubricating oil according to claim 25, wherein said lubricating oil achieves a satisfying score on the ISOT test and the L60-1 test.
45. The lubricating oil according to claim 35, wherein said lubricating oil achieves a satisfying score on the ISOT test and the L60-1 test.
US10/670,580 2003-09-25 2003-09-25 Boron free automotive gear oil Abandoned US20050070446A1 (en)

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US10/670,580 US20050070446A1 (en) 2003-09-25 2003-09-25 Boron free automotive gear oil
CA002480114A CA2480114A1 (en) 2003-09-25 2004-09-03 Boron free automotive gear oil
AU2004210592A AU2004210592A1 (en) 2003-09-25 2004-09-10 Boron free automotive gear oil
EP04077548A EP1518919A1 (en) 2003-09-25 2004-09-15 Boron free automotive gear oil
JP2004272174A JP2005097615A (en) 2003-09-25 2004-09-17 Boron-free automotive gear oil
MXPA04009160A MXPA04009160A (en) 2003-09-25 2004-09-21 Boron free automotive gear oil.
SG200405365A SG110161A1 (en) 2003-09-25 2004-09-24 Boron free automotive gear oil
US11/552,733 US20070054813A1 (en) 2003-09-25 2006-10-25 Boron free automotive gear oil
JP2011270247A JP2012046769A (en) 2003-09-25 2011-12-09 Boron-free oil-soluble lubricant additive package

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