Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
  • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • C10M169/042—Mixtures of base-materials and additives the additives being compounds of unknown or incompletely defined constitution only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
  • C10M159/12—Reaction products
  • C10M159/123—Reaction products obtained by phosphorus or phosphorus-containing compounds, e.g. P x S x with organic 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
  • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
• • 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
  • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
• • 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
  • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
  • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
• • 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
  • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
  • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
  • C10M2219/106—Thiadiazoles
• • 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
  • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2221/041—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving sulfurisation of macromolecular compounds, e.g. polyolefins
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/043—Ammonium or amine salts thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/047—Thioderivatives not containing metallic elements
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/049—Phosphite
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives

Definitions

• the present disclosure relates to a single lubricating composition suitable for wet brakes, gears, and differentials having improved characteristics for extreme pressure, friction, and copper corrosion.
• wet brakes, gears, differentials, and axles are often lubricated from a common fluid provided via a single reservoir that must meet the extreme pressure requirements for lubricating the gears, transmissions, and axles but must also meet the friction requirements of a clutch and/or wet brake.
• axles, transfer cases, and/or differentials in heavy duty or industrial applications have a variety of mechanisms to provide power and/or torque transfer from, for instance, an input pinion gear to opposing wheels of an axle shaft.
• lubricants for such applications require that the fluid have proper extreme pressure performance and suitable copper corrosion performance suitable to the heavy duty loads experienced by the equipment.
• a number of additives may be included in the lubricant to achieve desired extreme pressure performance.
• such lubricants may often include a sulfurized additive to protect gears and other components from wear and scoring.
• a sulfurized additive may provide good extreme pressure and wear-scar performance for the desired application, prior sulfurized additives tend to be detrimental to copper and copper alloys leading to unacceptable copper corrosion and friction.
• Heavy duty and industrial equipment may also use a wet clutch and/or a wet brake where the same fluid used to lubricant the gears and axle may also be used in the wet clutch or braking system.
• a wet clutch or braking system the frictional performance must be controlled and additives suitable for extreme pressure and general lubrication are not always suitable for improved friction performance.
• a lubricating composition including one or more base oils of lubricating viscosity; up to about 3 weight percent of sulfur provided by an extreme pressure agent; a first phosphorous-containing component including a hydrocarbyl phosphonate monoester, wherein in some embodiments the first phosphorus-containing component is substantially amine-free or substantially amine free (e.g., less than about 0.05 weight percent of amine components, less than about 0.02 weight percent of amine components, less than about 0.01 weight percent of amine components, or no functional levels of any amine components), a second phosphorus-containing component including an amine salt of a dialkyl hydrogen thiophosphite; and a third phosphorus-containing component prepared by reacting a dialkyl phosphorodithioic acid (preferably O,O'-di (4-methyl-2-pentanyl) phosphorodithioic acid) with ethylene and/or propylene oxide to provide a first reaction product and further reacting said first reaction product
• the lubricating composition includes about 0.1 to about 0.5 weight percent of total amine compounds provided from the second phosphorus-containing component, the third phosphorus-containing component, and the hydrocarbylamine compound; and wherein about 15 to about 25 weight percent of the total amine compounds are provided by the hydrocarbylamine compound, greater than 50 weight percent of the total amine compounds are provided by the second phosphorus-containing component, and about 20 to about 30 weight percent of the total amine compounds are provided by the third phosphorus containing component.
• the extreme pressure agent provides about 1.5 to about 3 weight percent sulfur and, in embodiments, is provided by a blend of organic sulfide compounds, wherein each organic sulfide compound in the blend, independently, has a structure of the formula R 1 -S x -R 2 wherein R 1 and R 2 , independently, are a C2 to C20 hydrocarbyl group and x is an integer of 2 to 6, wherein the blend of organic sulfide compounds provides about 14,000 ppm to about 16,000 ppm of sulfur from organic sulfide compounds having S 2 and S 3 moieties and no more than about 3000 ppm of sulfur from organic sulfide compounds having S 4 , S 5 , and/or S 6 moieties in the organic sulfide compounds;
• the lubricating composition described in the previous paragraph may include other features or embodiments in any combination. These other features or embodiments may include one or more of the following: wherein a weight ratio of the hydrocarbyl phosphonate monester to the total amine compounds is about 0.7:1 to about 1.8:1; and/or wherein the lubricating composition includes about 1.3 to about 3 weight percent of total sulfur, at least about 90 weight percent of the total sulfur is provided by the extreme pressure agent as a blend of organic sulfide compounds, where the blend has about 10 to about 15 weight percent of organic sulfide compounds with a S 2 moiety, about 60 to about 70 weight percent of compounds with a S 3 moiety, and about 12 to about 20 weight percent of compounds with a S 4 moiety; and/or wherein the blend of organic sulfide compounds are provided by a first organic sulfide reaction product and a second organic sulfide reaction product; and/or wherein the hydrocarbylamine compound is
• any embodiment of the lubricating composition of this Summary is described to achieve about 100 mm 2 or less damage in a FZG sprung test at 90°C at load stage 9 or above when compared to a reference fluid and about 200 mg or less copper corrosion pursuant to ASTM D130 and with the hydrocarbyl phosphonate monoester solubilized in the one or more base oils and, in particular, the use of a lubricating composition including up to about 3 weight percent sulfur from an extreme pressure agent; a first phosphorous-containing component including a hydrocarbyl phosphonate monoester, wherein the first phosphorus-containing component is preferably substantially amine-free or amine-free as described above, a second phosphorus-containing component including an amine salt of a dialkyl hydrogen thiophosphite; and a third phosphorus-containing component prepared by reacting a dialkyl phosphorodithioic acid (preferably an O,O'-di (4-methyl
• the extreme pressure agent includes a blend of organic sulfide compounds, wherein each organic sulfide compound in the blend, independently, has a structure of the formula R 1 -S x -R 2 wherein R 1 and R 2 , independently, are a C2 to C20 hydrocarbyl group and x is an integer of 2 to 6, wherein the blend of organic sulfide compounds provides about 14,000 ppm to about 16,000 ppm of sulfur from organic sulfide compounds having S 2 and S 3 moieties and no more than about 3000 ppm of sulfur from organic sulfide compounds having S 4 , S 5 , and/or S 6 moieties in the organic sulfide compounds.
• the fluids herein have balanced performance for extreme pressure suitable for the gear applications as well as friction performance suitable for the wet-cutch and/or wet-brake applications.
• the lubricating compositions herein include at least one or more base oils of lubricating viscosity; an extreme pressure agent contributing up to about 3 weight percent sulfur, up to about 2 weight percent sulfur, or greater than about 1.5 weight percent sulfur and no more than 3 weight percent sulfur (in some embodiments, the extreme pressure agent is provided by a blend of organic sulfide compounds); at least three distinct phosphorus-containing components where one is preferably amine free and the other two are preferably amine-containing phosphorus components; and a hydrocarbylamine compound; and a thiadiazole or derivative thereof selected from a mono hydrocarbyl thiol-substituted thiadiazole, a bishydrocarbyl thiol-substituted thiadiazole, or combinations thereof. As shown by the Examples below, such compounds provide sufficient extreme pressure performance.
• the lubricants herein include an extreme pressure agent as a blend of organic sulfide compounds to provide the extreme pressure performance.
• each organic sulfide compound in the blend independently, has a structure of the formula R 1 -S x -R 2 wherein R 1 and R 2 , independently, are a C2 to C20 hydrocarbyl group and x is an integer of 2 to 6.
• the blend of organic sulfide compounds provides about 14,000 ppm to about 16,000 ppm of sulfur from organic sulfide compounds having S 2 and S 3 moieties and have less than 3000 ppm, and preferably about 2500 to about 3000 ppm, of sulfur from organic sulfide compounds having S 4 , S 5 , and/or S 6 moieties in the organic sulfide compounds.
• the lubricants herein also include at least three distinct phosphorus-containing components as friction modifiers.
• the three phosphorus-containing components include (1) a first phosphorous-containing component in the form of a hydrocarbyl phosphonate monoester, and preferably the first phosphorus-containing component is substantially amine free or amine free as defined above, (2) a second phosphorus-containing component in the form of an amine salt of a dialkyl hydrogen thiophosphite; and (3) a third phosphorus-containing component prepared by reacting a dialkyl phosphorodithioic acid (preferably, an O,O'-di (4-methyl-2-pentanyl) phosphorodithioic acid) with ethylene and/or propylene oxide to provide a first reaction product and further reacting said first reaction product with phosphorus pentoxide to provide a second reaction product and neutralizing said second reaction product with one or more aliphatic primary amines (preferably tertiary alipha
• the lubricants herein also include a hydrocarbylamine compound.
• the hydrocarbylamine compound is an aliphatic tertiary primary amine.
• the lubricants herein include less than about 0.1 weight percent of the hydrocarbylamine compound (and any additive packages or additive concentrates includes less than about 10 weight percent of the hydrocdarbylamine compound).
• the lubricating compositions herein also include about 0.1 to about 0.5 weight percent of total amine compounds contributed from the second phosphorus-containing component, the third phosphorus-containing component, and the hydrocarbylamine compound combined. In another approach or embodiment, about 15 to about 25 weight percent of the total amine compounds are provided by the hydrocarbylamine compound, greater than 50 weight percent of the total amine compounds are provided by the second phosphorus-containing component, and about 20 to about 30 weight percent of the total amine compounds are provided by the third phosphorus-containing component.
• the lubricating compositions herein include an extreme pressure agent contributing up to about 3 weight percent sulfur, up to about 2 weight percent sulfur, or about 1 weight percent to about 3 weight percent, about 1.5 weight percent to about 3 weight percent, or about 1.5 weight percent to about 2 weight percent sulfur.
• the extreme pressure agent is a blend of organic sulfide compounds that, in an embodiment or approach, is provided by a combination of two or more different organic sulfide compounds.
• the combined first and second organic sulfide compounds provide up to about 3 weight percent sulfur (preferably, up to 3 weight percent sulfur) and, preferably about 1 to about 3 weight percent sulfur in the composition (preferably, about 1 to about 3 weight percent or about 1.5 to about 3 weight percent sulfur, or about 1.5 to about 2 weight percent sulfur).
• the blend of organic sulfide compounds provides at least about 90 weight percent or more of the total sulfur in the lubricating composition and, in other approaches, the combined organic sulfide compounds provide about 90 to about 99 weight percent of the total sulfur in the lubricating composition, or about 95 to about 98 weight percent of the total sulfur in the lubricating composition.
• each organic sulfide compound in the blend is obtained from a reaction product including a certain combination/ratio of different organic sulfide compounds with a specific contribution of sulfur provided from S 2 -S 6 moieties in the compound. More specifically, each organic sulfide compound in the blend herein is a dihydrocarbyl sulfide compound having a structure of the formula R 1 -S x -R 2 (Formula I) wherein R 1 and R 2 of Formula I, independently, are a C2 to C20 hydrocarbyl group and x is an integer of at least 2 (and preferably, 2 to 6, 2 to 5, or 2 to 4) suitable to achieve the sulfur contributions, ratios, and profiles herein.
• each hydrocarbyl group of the organic sulfide independently, has 2 to 20 carbon atoms, preferably from 3 to 10 carbon atoms, or more preferably, 3 to 4 carbon atoms.
• each hydrocarbyl group of the organic sulfide compound may be aromatic or aliphatic, preferably, the hydrocarbyl groups may be aliphatic groups such as alkyl, alkenyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, cycloalkenyl, or the like, and most preferably, the hydrocarbyl groups are alkyl groups.
• Suitable alkyl groups may be propyl, iso-propyl, butyl, iso-butyl, and/or tert-butyl groups.
• each hydrocarbyl group may be derived from olefins.
• the olefin may have from 2 to 20 carbon atoms or other ranges are set forth above.
• Suitable olefins for preparing each of organic sulfide compounds herein may be mono or disubstituted monoolefins that include 2 to 12 carbon atoms.
• a disubstituted monoolefins is an olefin having at least one double bonded carbon atom having two alkyl substituents.
• Suitable olefins for deriving the organic sulfides include ethylene, propylene, butylene, isobutylene, 2-methyl-2-pentene, 2-methyl2-butene, 2- methyl-1-butene, diisobutylene, triisobutylene, and mixtures thereof as well as dimers, trimers, tetramers, and mixtures thereof may be suitable hydrocarbyl groups for each of the organic sulfides herein.
• Each of the organic sulfide compounds herein may be prepared by reacting, optionally under super-atmospheric pressure, one or more of the above hydrocarbyl or olefin compounds with a source of sulfur (preferably, elemental sulfur or molten sulfur) in the presence, or absence, of a catalyst, such as an optional alkyl amine catalyst, followed by removal of low boiling materials.
• a source of sulfur preferably, elemental sulfur or molten sulfur
• the source of sulfur is substantially devoid of sulfur chlorides, hydrogen sulfides, and combinations thereof and, in this context, reactions herein have about 0.1 weight percent or less, about 0.05 weight percent or less, about 0.01 weight percent or less, or no sulfur chlorides, hydrogen sulfides, or the like.
• suitable organic sulfides herein may be obtained, for example, with an olefin or hydrocarbyl compound combined or reacted with elemental sulfur in ratios of about 2:1 to about 1:2 moles of olefin/hydrocarbyl to grams of sulfur in an autoclave or other reaction vessel that is suitable for conducting super-atmospheric pressure and elevated temperature reactions.
• the reaction can be carried out at temperatures from about 100°C to about 200°C, pressures from about 250 to about 1,000 psi, and for reaction times of about 2 to about 30 hours as needed to achieve the desired sulfur levels for each additive of the mixture.
• the reaction can be carried with or without a catalyst.
• suitable catalysts may include amines and sulfur compounds such as dithiocarbamate salts and mercaptans such as, but not limited to, n-butylamine, n-octylamine, triethylamine, tetramethylthiuram disulfide, and mercaptobenzothiazole, and the like.
• the catalysts may be used, if needed, in amounts of about 0.01 to about 5.0 weight percent of the reaction mixture or other amounts suitable for the particular application and sulfur levels.
• the reaction may be carried out in the absence of oxygen.
• the above sulfurized olefin or sulfurized hydrocarbyl intermediate may then be treated with an aqueous solution of caustic and/or alkali metal sulfide, such as sodium or potassium sulfide and, in some instances, sodium sulfide, which can be prepared, for example, by mixing aqueous sodium hydrosulfide and caustic solutions (such as aqueous sodium hydroxide) in amounts effective to produce the desired sulfide profiles/ratios (e.g., -S x - groups) of each reaction product.
• the solution can contain co-solvents such as methanol.
• the sodium sulfide solution and the sulfurized intermediate may be combined in a stirred reactor and heated under an inert atmosphere such as nitrogen at temperatures up to about 100°C, such as about 50°C to about 100°C for about 30 minutes to about 4 hours and, in some instances, about 1 to about 2 hours.
• the reaction mixture is then allowed to cool and the organic product separated on top of the aqueous layer may be recovered.
• the amount of caustic may be varied as needed to form each of the organic sulfide compounds and to provide the sulfur contributions from the noted sulfur profiles/ratios thereof.
• a first organic sulfide compound may having a high level of S 3 sulfur groups may be processed with higher levels of caustic and a second organic sulfide compound having a balanced mix of S 3 and S 4 groups may be processed with lower amounts of caustic.
• the first organic sulfide compound is processed with at least 2x the amount of caustic than the second organic sulfide compound.
• the blend of organic sulfide compounds of the lubricating compositions herein provides about 14,000 ppm to about 16,000 ppm of sulfur from organic sulfide compounds having S 2 and S 3 moieties and about 2500 to about 3000 ppm of sulfur from organic sulfide compounds having S 4 or greater sulfur moieties, and preferably S 4 , S 5 , and/or S 6 moieties in the organic sulfide compound.
• about 12 to about 20 weight percent of the organic sulfide compounds in blend have an S 2 moiety (in other approaches, about 12 to about 16 weight percent), about 60 to about 75 weight percent of organic sulfide compounds in blend have a S 3 moiety (in other approaches, about 65 to about 75 weight percent), about 12 to about 20 weight percent of organic sulfide compounds in the blend have an S 4 moiety (in other approaches, about 12 to about 18 weight percent), about 0.5 to about 5 weight percent of organic sulfide compounds in blend have an S 5 moiety (in other approaches, about 0.5 to about 3 weight percent), and no more than about 1 weight percent of organic sulfide compounds in the blend have an S 6 moiety (in other approaches, no more than about 0.5 weight percent or no functional amounts).
• This blend of total organic sulfide compounds are preferably provided by at least two reaction products of different organic sulfide combinations.
• the organic sulfide compounds in the blend is a combination of organic sulfide compounds having a select weight ratios of the S 3 moieties to the S 4 moieties, such as a weight ratio of S 3 to S 4 moieties of about 3:1 to about 6:1 (in other approaches, about 4: 1 to about 5.5:1).
• a first organic sulfide compound is a reaction product of organic sulfide compounds includes high amounts of compounds with a S 3 moiety and, preferably, includes a combination of organic sulfide compounds with about 12 to 18 about weight percent organic sulfide compounds with an S 2 moiety (in other embodiments, about 12 to about 16 weight percent), about 70 to about 90 weight percent of organic sulfide compounds with a S 3 moiety (in other embodiments, about 80 to about 90 weight percent), about 1 to about 6 weight percent of organic sulfide compounds with an S 4 moiety (in other embodiments, about 2 to about 5 weight percent), no more than about 1 weight percent of organic sulfide compounds with an S 5 moiety (in other embodiments, no more than about 0.5 weight percent or no functional amounts), and no more than about 1 weight percent of organic sulfide compounds having an S 6 moiety (in other embodiments, no more than about 0.5 weight percent or no functional amounts).
• the first reaction product of organic sulfide compounds includes
• the second organic sulfide compound is a second reaction product of organic sulfide compounds including a more balanced blend of compounds with a S 3 and S 4 moieties and, preferably, includes a combination of organic sulfide compounds with about 12 to about 18 percent organic sulfide compounds with an S 2 moiety (in other embodiments, about 12 to about 16 weight percent), about 50 to about 60 weight percent of organic sulfide compounds with a S 3 moiety (in other embodiments, about 55 to about 60 weight percent), about 20 to about 30 weight percent of organic sulfide compounds with an S 4 moiety (in other embodiments, about 20 to about 26 weight percent), about 1 to about 5 weight percent of organic sulfide compounds with an S 5 moiety (in other embodiments, about 1 to about 4 weight percent), and no more than about 1 weight percent of organic sulfide compounds having an S 6 moiety (in other embodiments, no more than about 0.5 weight percent or no functional amounts).
• the lubricating compositions herein may include treat rates of the organic sulfide compounds provided by (1) about 1.5 to about 2.8 weight percent of the first reaction product of organic sulfide compounds (in other approaches, about 1.6 to about 2.2 weight percent), and (2) about 1.5 to about 2.8 weight percent of the second reaction product of organic sulfur compounds (in other approaches, about 1.6 to about 2.2 weight percent).
• the amounts of each reaction product will depend on the make-up of the sulfur compounds within each reaction product.
• it is preferred that the final fluid include no more than 3 weight percent of sulfur compounds with S 5 sulfur groups, greater than about 60 weight percent of sulfur compounds with S 3 groups, and/or less than 20 weight percent of sulfur compounds with S 4 groups.
• the lubricating compositions may have a weight ratio of the first organic sulfide reaction product to the second organic sulfide reaction product of about 0.8:1 to about 1:0.8.
• compositions herein include the specific profile/ratios of organic sulfur compounds, the compositions can surprisingly include higher levels of total sulfur yet achieve better copper corrosion performance than comparative fluids having lower levels of sulfur but not falling with the certain sulfur profiles identified herein.
• the lubricating compositions herein include a first phosphorus-containing component in the form of an amine-free or substantially amine-free, hydrocarbyl phosphonate monoester (that is, contributing less than about 0.05 weight percent amine compounds, less than 0.02 weight percent amine compounds, less than about 0.01 amine compounds, or no functional levels of any amine compounds).
• the amine-free, hydrocarbyl phosphonate monoester has a structure of Formula II wherein R 5 , the hydrocarbyl moiety, of Formula II is a linear or branched C12 to C30 hydrocarbyl chain; R 6 , the monoester moiety, of Formula II is a linear or branched C1 to C4 alkyl group; and R ' is hydrogen or an alkyl group such as a C1 to C30 alkyl group.
• R 6 is a methyl or ethyl group and R' is hydrogen.
• the amount of the phosphonate monoester is about 0.1 to about 1 weight percent based on a total weight of the lubricating oil composition, in other approaches, about 0.1 to about 0.7 percent, in yet further approaches, or about 0.1 to about 0.5 weight percent.
• Suitable phosphonates may also include primary alkyl acyclic hydrocarbyl phosphonates in which the primary alkyl group includes 1 to 4 carbon atoms and in which the acyclic hydrocarbyl group bonded to the phosphorus atom contains 12 to 30 carbon atoms and, in some approaches, is a linear hydrocarbyl group free of acetylenic unsaturation. In other approaches, the acyclic hydrocarbyl group includes 12 to 24 carbon atoms, and in yet further approaches, 12 to 20 carbon atoms.
• Exemplary phosphonate compounds for the first phosphorus-containing component herein include methyl hydrocarbyl phosphonates, ethyl hydrocarbyl phosphonates, propyl hydrocarbyl phosphonates, butyl hydrocarbyl phosphonates, iso-butyl hydrocarbyl phosphonates, and wherein, in each case, the hydrocarbyl group is preferably linear, saturated, or contains one or more olefinic double bonds with each double bond preferably being an internal double bond.
• Other suitable compounds include those in which the hydrocarbyl group bonded to the phosphorus atom contains 16 to 20 carbon atoms or 18 to 20 carbon atoms.
• a particularly suitable phosphonate monoester compound may be ethyl octadecyl phosphonate or methyl octadecyl phosphonate.
• suitable phosphonate monoesters include, but are not limited to, methyl triacontyl phosphonate, methyl triacontenyl phosphonate, methyl eicosyl phosphonate, methyl hexadecyl phosphonate, methyl hexadecenyl phosphonate, methyl tetracontenyl phosphonate, methyl hexacontyl phosphonate, methyl dodecyl phosphonate, methyl dodecenyl phosphonate, ethyl triacontyl phosphonate, ethyl triacontenyl phosphonate, ethyl eicosyl phosphonate, ethyl hexadecyl phosphonate
• the lubricating compositions herein include a second phosphorus-containing component in the form of an amine salt of a dihydrocarbyl hydrogen thiophosphite.
• the second phosphorus-containing component provides amine compounds to the lubricant from the amine salt.
• Suitable compounds for the second phosphorus-continuing component include, in some embodiments, an organic ester of phosphoric acid, phosphorous acid, or amine salts thereof.
• the second phosphorus-containing component may include one or more of a dihydrocarbyl phosphite, a trihydrocarbyl phosphite, a dihydrocarbyl phosphate, a trihydrocarbyl phosphate, any sulfur analogs thereof, and any amine salts thereof. More specifically, the second phosphorus-containing component may include, in some preferred embodiments, at least one an amine salt of a dibutyl hydrogen thiophosphite. In approaches or embodiments herein, the lubricating compositions include about 0.1 to about 0.8 weight percent of the second amine-containing phosphorus component (in other approaches, about 0.2 to about 0.8 weight percent, or about 0.4 to about 0.8 weight percent).
• the second phosphorus-containing component also provides amine compounds to the lubricants herein, and in embodiments, is preferably salted with a hydrocarbyl amine.
• the hydrocarbyl amine salt contributes about 0.1 to about 0.3 weight percent of an amine compound to the lubricating compositions herein (in other embodiments, about 0.2 to about 0.3 weight percent of an amine compound).
• the amine salt is a linear aliphatic primary amine having a C6 to a C30 hydrocarbyl group, or in other approaches, a C10 to a C20 hydrocarbyl group.
• suitable amines for salting the second phosphorus-containing component herein include aliphatic amines, aromatic amines, cycloaliphatic amines, heterocyclic amines, carbocylic amines, or combinations thereof.
• the amine is a linear aliphatic tertiary amine.
• the amines may have 4 to 30 carbon atoms.
• the amines may include an aliphatic primary amine containing at least about 8 carbon atoms and may have the structure R 14 NH 2 , wherein R 14 is, for example, an aliphatic group such as tert-octyl, tert-dodecyl, tert-tetradecyl, tert-octadecyl, cetyl, behenyl, stearyl, eicosyl, docosyl, tetracosyl, hexatriacontanyl, and pentahexacontanyl.
• R 14 is, for example, an aliphatic group such as tert-octyl, tert-dodecyl, tert-tetradecyl, tert-octadecyl, cetyl, behenyl, stearyl, eicosyl, docosyl, tetracosyl, hexatriacontany
• suitable amines may be a C11 to C20 tertiary alkyl primary amine and, more preferably, a C11 to C14 tertiary alkyl primary amine.
• Further amines may include, but are not limited to, cyclohexyl amine, n-hexylamine, dodecylamine, di-dodecylamine, tri-dodecylamine, N-methyl-octylamine, butylamine, oleyl amine, myristyl amine, N-dodecyl trimethylene diamine, aniline, o-toluidine, benzidine, phenylene diamine, N,N'-di-sec-butylphenylene diamine, beta-naphthylamine, alpha-naphthylamine, morpholine, piperazine, methane diamine, cyclopentyl amine, ethylene diamine, hexamethylene
• the third phosphorus-containing component of the lubricating compositions herein is an amine-containing and phosphorus-containing component in the form of a reaction product made by reacting a dialkyl phosphorodithioc acid, such as O,O-dihydrocarbyl phosphorodithioic acid, and an epoxide to produce a first reaction product.
• This first reaction product is then reacted with phosphorus pentoxide to provide a second reaction product.
• the second reaction product is then neutralized with an amine compound to provide the third phosphorus-containing component of the lubricants herein.
• starting phosphorodithioic acids for producing the third phosphorus product may have the general structure of Formula III wherein R 8 and R 9 of Formula III may be a C1 to C30 hydrocarbyl group and, preferably, butyl, lauryl, 4-methyl-2-pentyl groups and the like linear or branched alkyl groups.
• the starting acid of Formula III may be prepared by reacting phosphorus pentasulfide with a suitable alcohol or a phenol. In one example, the alcohol or phenol may be reacted with phosphorus pentasulfide at about 50°C to about 200°C.
• suitable epoxides used to form the first reaction product include those of Formula IV wherein R 10 , R 11 , R 12 , and R 13 of Formula IV are each, independently, hydrogen or any C 1 -C 30 hydrocarbyl group and may preferably include ethylene oxide, propylene oxide, styrene oxide, alpha-methylstyrene oxide, combination thereof, and the like oxides.
• Preferred oxides include ethylene and/or propylene oxide.
• suitable amine compounds for neutralizing the second reaction product include aliphatic amines, aromatic amines, cycloaliphatic amines, heterocyclic amines, carbocylic amines, or combinations thereof.
• the amines may have 4 to 30 carbon atoms.
• the amines may include an aliphatic primary amine containing at least about 8 carbon atoms and may have the structure R 14 NH 2 , wherein R 14 is, for example, an aliphatic group such as tert-octyl, tert-dodecyl, tert-tetradecyl, tert-octadecyl, cetyl, behenyl, stearyl, eicosyl, docosyl, tetracosyl, hexatriacontanyl, and pentahexacontanyl.
• R 14 is, for example, an aliphatic group such as tert-octyl, tert-dodecyl, tert-tetradecyl, tert-octadecyl, cetyl, behenyl, stearyl, eicosyl, docosyl, tetracosyl, hexatriacontany
• suitable amines may be tertiary aliphatic primary amines, such as a C11 to C20 tertiary alkyl primary amine and, more preferably, a C11 to C14 tertiary alkyl primary amine.
• Further amines may include, but are not limited to, cyclohexyl amine, n-hexylamine, dodecylamine, di-dodecylamine, tri-dodecylamine, N-methyl-octylamine, butylamine, oleyl amine, myristyl amine, N-dodecyl trimethylene diamine, aniline, o-toluidine, benzidine, phenylene diamine, N,N'-di-sec-butylphenylene diamine, beta-naphthylamine, alpha-naphthylamine, morpholine, piperazine, methane diamine, cyclopentyl amine, ethylene diamine, hexamethylene tetramine, octamethylene diamine, and N,N'-dibutylphenylene diamine.
• the lubricating compositions include about 0.1 to about 0.8 weight percent of the third phosphorus-containing component (in other approaches, about 0.2 to about 0.8 weight percent, or about 0.4 to about 0.8 weight percent).
• the third phosphorus compound herein may contribute about 0.1 to about 0.3 weight percent of the amine compound to the lubricating compositions herein (in other approaches, about 0.1 to about 0.2 weight percent).
• hydroxy-substituted amines may also be used in neutralizing the second reaction product.
• exemplary hydroxyl-substituted amines may include ethanolamine, diethanolamine, triethanolamine, isopropanolamine, para-aminophenol, 4-amino-naphthol-1, 8-amino-naphthol-1, beta-aminoalizarin, 2-amino-2-ethyl-1,3-propandiol, 4-amino-4'-hydroxy-diphenyl ether, 2-amino-resorcinol, N-4-hydroxybutyl-dodecyl amine, N-2-hydroxyethyl-n-octylamine, N-2-hydroxypropyl dinonylamine, N,N-di-(3-hydroxypropyl)-tert-dodecyl amine, N-hydroxytriethoxyethyl-tert-tetradecyl amine, N-hydroxy
• the first phosphorus-containing component in the form of a phosphonate monoester may drop out of solution or result in a small amount of precipitate. If needed, limited amounts of additional hydrocarbylamine compounds are further added to the lubricating compositions herein.
• Such hydrocarbylamine compounds preferably include linear aliphatic tertiary amines.
• the lubricating combinations include less than about 0.1 weight percent of the hydrocarbyl amine compounds (preferably, about 0.099 weight percent or less, and more preferably, about 0.098 weight percent or less), and any additive concentrate includes less than about 10 weight percent of the hydrocarbylamine compounds.
• Possible minimum amounts for the hydrocarbyl amine compounds in the lubricating composition of the invention are 0.01, 0.02, 0.04 and 0.06 weight percent. Possible ranges include 0.01 to 1 (or 0.099 or 0.098), 0.02 to 1 (or 0.099 or 0.098), 0.04 to 1 (or 0.099 or 0.098), 0.06 to 1 (or 0.099 or 0.098) weight percent.
• Exemplary hydrocarbyl amine compounds include dihydrocarbyl (mono)thiophosphate amines and may include those with a hydrocarbyl portion being saturated or unsaturated groups, alkyl groups, alkenyl groups and/or aromatic hydrocarbon groups of 2 to 24 carbons.
• suitable hydrocarbylamine compounds may be primary hydrocarbyl amines containing 4 to 30 carbon atoms.
• Fatty amines may also be used and may include alkyl amines such as n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-octadecylamine (stearyl amine), and the like.
• the hydrocarbyl amines may be those derived from tertiary-aliphatic primary amines having 4 to 30 carbon atoms in the alkyl group. Mixtures of amines may also be beneficial, such as mixtures of C11-C14 tertiary alkyl primary amines and/or mixtures of C18-C22 tertiary alkyl primary amines.
• the lubricating compositions herein include a total amount of amine compounds contributed from three sources including the hydrocarbylamine compounds, the amine compounds contributed by the second phosphorus-containing component, and then amine compounds contributed by the third phosphorus-containing component.
• the lubricating compositions herein include about 0.1 to about 0.5 weight percent of total amine compounds provided from the second amine-containing phosphorus component, the third amine-containing phosphorus component, and the hydrocarbylamine compounds combined.
• the total amine compounds in the lubricating compositions herein include about 15 to about 25 weight percent of the total amine compounds provided by the hydrocarbylamine compound (in other approaches, about 18 to about 22 weight percent), greater than 50 weight percent of the total amine compounds provided by the second phosphorus-containing component (in other approaches, about 50 to about 60 weight percent), and about 20 to about 30 weight percent of the total amine compounds provided by the third phosphorus-containing component (in other approaches, about 25 to about 30 weight percent).
• a certain portion of the amines contributed by the second and third phosphorus-containing components may aid in solubilizing the first phosphorus-containing component, but such amounts are not sufficient to keep the first phosphorus-containing component in solution.
• less than 0.1 weight percent of the additional hydrocarbylamine compounds combines with at least portions of the amine compounds from the first and second phosphorus-containing components to keep the first phosphorus-containing component is solution.
• a weight ratio of the first phosphorus-containing component, and preferably the hydrocarbyl phosphonate monoester, to the total amine compounds is about 0.7: 1 to about 1.8:1, and in other approaches, about 1:1 to about 1.5:1.
• the lubricating compositions herein may also be free of or substantially free of certain other phosphorus friction modifiers. While not wishing to be limited by theory, it is believed that phosphonate diesters, such as dialkyl hydrocarbyl phosphonate (and in particular dimethyl octadecyl phosphonate), may negatively impact copper corrosion. It is believed, for instance, that such phosphonate diesters may react or interact with the thiadiazole additives of the compositions herein leading to undesired reaction products or other impurities that may degrade copper corrosion.
• phosphonate diesters such as dialkyl hydrocarbyl phosphonate (and in particular dimethyl octadecyl phosphonate)
• phosphonate diesters may react or interact with the thiadiazole additives of the compositions herein leading to undesired reaction products or other impurities that may degrade copper corrosion.
• the lubricating compositions herein may be, in some approaches or embodiments, free of or substantially free of phosphonate diesters, such as less than about 0.8 weight percent, less than 0.5 weight percent, less, than about 0.25 weight percent, less than about 0.1 weight percent, or include no functional amounts of phosphonate diesters.
• the lubricating compositions herein may also include a thiadiazole or derivative thereof.
• the lubricating compositions may include about 0.1 weight percent or more of the thiadiazole or derivative thereof.
• the lubricating compositions may include about 0.1 weight percent to about 1 weight percent, or about 0.1 weight to about 0.5 weight percent of the thiadiazole or derivative thereof.
• the thiadiazole or derivative thereof may be a mixture of thiadiazole compounds and/or hydrocarbyl-substituted derivatives thereof.
• the thiadiazole or derivative thereof provides at least about 350 ppm sulfur to the lubricating composition, in other approaches, at least about 380 ppm sulfur, at least about 400 ppm sulfur, at least about 500 ppm sulfur, at least about 600 ppm sulfur, or at least about 700 ppm sulfur to about 2500 ppm or less, about 2000 ppm or less, about 1500 ppm or less, or about 1000 ppm or less.
• the thiadiazole or derivative thereof includes one or more compounds having a structure of Formula I: wherein each R 3 is independently hydrogen or sulfur, each R 4 is independently an alkyl group, n is an integer of 0 or 1 and if R 3 is hydrogen then the integer n of the adjacent R 4 moiety is 0 and if R 3 is sulfur then the n of the adjacent R 4 moiety is 1, and with the proviso that at least one R 3 is sulfur.
• the thiadiazole additive is a blend of compounds of Formula Ia and Formula Ib shown below: wherein within Formula Ia each integer n is 1, each R 3 is sulfur, and each R 4 is a C5 to C15 alkyl group, preferably a C8 to C12 alkyl group; and wherein within Formula Ib one integer n is 1 with the associated R 4 group being a C5 to C15 alkyl group (preferably a C8 to C12 alkyl group) and the associated R 3 group being sulfur and the other integer n is 0 with the associated R 3 group being hydrogen.
• the thiadiazole or derivative thereof includes a blend of Formula Ia and Ib with Formula Ia being a majority of the blend and in other approaches, the blend of Ia and Ib is about 75 to about 90 weight percent of Ia and about 10 to about 25 weight percent of Ib (or other ranges therewithin).
• the thiadiazole is a 2,5 dimercapto 1,3,4 thiadiazole including a blend of 2,5-bis-(nonyldithio)-1,3,4-thiadiazole (such as about 75 to about 90%) and 2,5-mono-(nonyldithio)-1,3,4-thiadiazole (such as about 10 to about 25%).
• examples of the thiadiazole compounds that may be used in the fluids herein include 2-mercapto-5-hydrocarbylthio-1,3,4-thiadiazole; 2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazole; 2,5-bis(hydrocarbylthio)-1,3,4-thiadiazole; 2,5-bis(hydrocarbyldithio)-1,3,4-thiadiazoles, variations thereof, or combinations thereof.
• the 1,3,4-thiadiazoles are generally synthesized from hydrazine and carbon disulfide by known procedures. See, for example, U.S. Pat. Nos.
• suitable base oils for use in the lubricating composition or gear fluids herein include mineral oils, synthetic oils, and include all common mineral oil basestocks.
• the mineral oil may be naphthenic or paraffinic.
• the mineral oil may be refined by conventional methodology using acid, alkali, and clay or other agents such as aluminium chloride, or may be an extracted oil produced, e.g. by solvent extraction with solvents such as phenol, sulfur dioxide, furfural or dichlorodiethyl ether.
• the mineral oil may be hydrotreated or hydrofined, dewaxed by chilling or catalytic dewaxing processes, or hydrocracked, such as the Yubase ® family of hydrockracked base oils from SK Innovation Co., Ltd. (Seoul, Korea).
• the mineral oil may be produced from natural crude sources or be composed of isomerized wax materials or residues of other refining processes.
• the base oil or base oil of lubricating viscosity used in the compositions herein may be selected from any suitable base oil for driveline or gear oil applications.
• Examples include the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. These three base oil groups are as follows: TABLE 1: Base oil Types Base Oil Category Sulfur (%) Saturates (%) Viscosity Index Group I > 0.03 and/or ⁇ 90 80 to 120 Group II ⁇ 0.03 and ⁇ 90 80 to 120 Group III ⁇ 0.03 and ⁇ 90 ⁇ 120 Group IV All polyalphaolefins (FAGs) Group V All others not included in Groups I, II, III, or IV
• Groups I, II, and III are mineral oil process stocks and may be preferred for the driveline or gear fluids of the present application. It should be noted that although Group III base oils are derived from mineral oil, the rigorous processing that these fluids undergo causes their physical properties to be very similar to some true synthetics, such as PAOs. Therefore, oils derived from Group III base oils may be referred to as synthetic fluids in the industry. Suitable oils may be derived from hydrocracking, hydrogenation, hydrofinishing, unrefined, refined, and re-refined oils, and mixtures thereof.
• the base oil may be a blend of Group I and Group II oils and the blend may be about 0% to about 100% of the Group I oil, about 0% to about 100% of the Group II oil, about 0% to about 100% of the Group III oil, or various blends of Group I and II, Group I and III, or Group II and III oil blends.
• Unrefined oils are those derived from a natural, mineral, or synthetic source without or with little further purification treatment. Refined oils are similar to the unrefined oils except that they have been treated in one or more purification steps, which may result in the improvement of one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, and the like. Oils refined to the quality of an edible may or may not be useful. Edible oils may also be called white oils. In some embodiments, lubricating oil compositions are free of edible or white oils.
• Re-refined oils are also known as reclaimed or reprocessed oils. These oils are obtained similarly to refined oils using the same or similar processes. Often these oils are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
• Mineral oils may include oils obtained by drilling or from plants and animals or any mixtures thereof.
• oils may include, but are not limited to, castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil, and linseed oil, 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.
• Such oils may be partially or fully hydrogenated, if desired. Oils derived from coal or shale may also be useful.
• the major amount of base oil included in the gear fluids herein may be selected from the group consisting of Group I, Group II, a Group III, and a combination of two or more of the foregoing, and wherein the major amount of base oil is other than base oils that arise from provision of additive components or viscosity index improvers in the composition.
• the major amount of base oil included in a lubricating composition may be selected from the group consisting of Group I, a Group II, and a combination of two or more of the foregoing, and wherein the major amount of base oil is other than base oils that arise from provision of additive components or viscosity index improvers in the composition.
• the base oil may also be any of the synthetic base oils.
• Useful synthetic lubricating oils may include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers); poly(1-hexenes), poly(1-octenes), trimers or oligomers of 1-decene, e.g., poly(1-decenes), such materials being often referred to as ⁇ -olefins, and mixtures thereof; alkyl-benzenes (e.g.
• dodecylbenzenes dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); diphenyl alkanes, alkylated diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof or mixtures thereof.
• Polyalphaolefins are typically hydrogenated materials.
• oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans.
• Synthetic oils may be produced by Fischer-Tropsch reactions and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as well as other gas-to-liquid oils.
• the amount of the base oil of lubricating viscosity in the compositions herein may be the balance remaining after subtracting from 100 wt% the sum of the amount of the performance additives.
• the oil of lubricating viscosity that may be present in a finished fluid may be a "major amount,” such as greater than about 50 wt%, greater than about 60 wt%, greater than about 70 wt%, greater than about 80 wt%, greater than about 85 wt%, greater than about 90 wt%, or greater than about 95 wt%.
• a preferred base oil or base oil of lubricating viscosity has less than about 25 ppm sulfur, a viscosity index greater than about 120 ppm, and a kinematic viscosity at about 100°C of about 2to about8 cSt.
• the base oil of lubricating viscosity has less than about 25 ppm sulfur, a viscosity index greater than 120, and a kinematic viscosity at 100°C of about 4 cSt.
• the base oil may have CP (paraffinic carbon content) of greater than 40%, greater than 45%, greater than 50%, greater than 55%, or greater than 90%.
• the base oil may have a CA (aromatic carbon content) of less than 5%, less than 3%, or less than 1%.
• the base oil may have a CN (naphthenic carbon content) of less than 60%, less than 55%, less than 50%, or less than 50% and greater than 30%.
• the base oil may have a ratio of 1 ring naphthenes to 2-6 ring naphthenes of less than 2 or less than 1.5 or less than 1.
• a suitable driveline or gear lubricant composition herein may include additive components in the ranges listed in the following Table 2.
• Table 2 Suitable and Preferred Driveline or Gear Fluid Compositions Component wt% (Suitable Embodiments) wt% (Other Embodiments) First organic sulfide reaction product 1.5 - 3.2 1.6 - 2.2 Second organic sulfide reaction product 1.5 - 3.2 1.6 - 2.2 Thiadiazole or derivative thereof 0.1 - 1.0 0.1 - 0.5 Phosphorous-containing components 0.1 - 2.0 0.5 - 1.6 Antioxidant(s) 0.1 - 5.0 0.01 - 40 Detergent(s) 0.0 - 150 1.0 - 80 Corrosion inhibitor(s) 0.0 - 5.0 0.1 - 3.0 Ash-free phosphorus compound(s) 0.0 - 15.0 0.1 - 5.0 Antifoaming agent(s) 0.0 - 1.0 0.001 -0.5 Antiwear agent(s) 0.0 -
• the percentages of each component above represent the weight percent of each component, based upon the weight of the total final additive or lubricating oil composition.
• the balance of the lubricating oil composition consists of one or more base oils or solvents. Additives used in formulating the compositions described herein may be blended into the base oil or solvent individually or in various sub-combinations. However, it may be suitable to blend all of the components concurrently using an additive concentrate (i.e., additives plus a diluent, such as a hydrocarbon solvent).
• the lubricating composition described herein may be formulated to provide lubrication, enhanced friction performance properties, and improved copper corrosion for various applications.
• the driveline lubricating compositions herein may be used for lubricating a machine part, such as a gear.
• Lubricating fluids according to the present disclosure can be used in gear applications, such as industrial gear applications, automotive gear applications, axles, and stationary gearboxes.
• Gear-types can include, but are not limited to, spur, spiral, worm, rack and pinion, involute, bevel, helical, planetary, and hypoid gears and as well as limited-slip applications and differentials.
• the driveline lubricating compositions disclosed herein are also suitable for automatic or manual transmissions, including step automatic transmissions, continuously variable transmissions, semi-automatic transmissions, automated manual transmissions, toroidal transmissions, and dual clutch transmissions.
• the driveline lubricating compositions herein are particularly suited for use in axles, transfer cases, differentials, such as straight differentials, turning differentials, limited-slip differentials, clutch-type differentials, and locking differentials, and the like.
• the lubricant including such additives noted above may also include one or more optional components so long as such components and amounts thereof do not impact the performance characteristics as described in the above paragraphs. These optional components are described in the following paragraphs.
• the lubricant composition herein may comprise one or more phosphorus-containing compounds that may impart anti-wear benefits to the fluid.
• the one or more phosphorus-containing compounds may be present in the lubricating oil composition in an amount ranging from about 0 wt% to about 15 wt%, or about 0.01 wt% to about 10 wt%, or about 0.05 wt% to about 5 wt%, or about 0.1 wt% to about 3 wt% of the lubricating oil composition.
• the phosphorus-containing compound may provide up to 5000 ppm phosphorus, or from about 50 to about 5000 ppm phosphorus, or from about 300 to about 1500 ppm phosphorus, or up to 600 ppm phosphorus, or up to 900 ppm phosphorus to the lubricant composition.
• the one or more phosphorus-containing compounds may include ashless phosphorus-containing compounds.
• suitable phosphorus-containing compound include, but are not limited to, thiophosphates, dithiophosphates, phosphates, phosphoric acid esters, phosphate esters, phosphites, phosphonates, phosphorus-containing carboxylic esters, ethers, or amides salts thereof, and mixtures thereof.
• Phosphorus containing anti-wear agents are more fully described in European Patent 0612839 .
• phosphonate and phosphite are used often interchangeably in the lubricant industry.
• dibutyl hydrogen phosphonate is often referred to as dibutyl hydrogen phosphite.
• inventive lubricant composition to include a phosphorus-containing compound that may be referred to as either a phosphite or a phosphonate.
• the compound may have about 5 to about 20 weight percent phosphorus, or about 5 to about 15 weight percent phosphorus, or about 8 to about 16 weight percent phosphorus, or about 6 to about 9 weight percent phosphorus.
• the inclusion of the phosphorus-containing compound in combination with the above described dispersant to a lubricant compositions unexpectedly imparts positive frictional characteristics, such as a low friction coefficient, to the lubricant composition.
• the inventive effect is even further pronounced in some cases where the phosphorus-containing compound, on its own, imparts negative frictional characteristics to the fluid.
• the lubricant composition has an improved, i.e., lower, friction coefficient. That is, the dispersants herein tend to transform fluids containing phosphorus-containing compounds having relatively poor friction coefficients into fluids with improved frictional properties.
• Another type of phosphorus-containing compound that when combined with the olefin copolymer dispersant herein imparts improved frictional characteristics to a lubricating composition is an ashless (metal free) phosphorus-containing compound.
• the ashless phosphorus-containing compound may be dialkyl dithiophosphate ester, amyl acid phosphate, diamyl acid phosphate, dibutyl hydrogen phosphonate, dimethyl octadecyl phosphonate, salts thereof, and mixtures thereof.
• the ashless phosphorus-containing compound may be have the formula: wherein R 1 of Formula XIV is S or O; R2 is -OR, -OH, or -R"; R3 is -OR", -OH, or SR′′′C(O)OH; R4 is -OR"; R′′′ is C1 to C3 branched or linear alkyl chain; and R" is a C1 to C18 hydrocarbyl chain.
• the phosphorous-containing compound has the structure shown in Formula XIV, the compound may have about 8 to about 16 weight percent phosphorus.
• the lubricant composition comprises a phosphorus-containing compound of Formula XIV wherein R1 is S; R2 is -OR"; R3 is S R′′′COOH; R4 is -OR"; R′′′ is C3 branched alkyl chain; R" is C4; and wherein the phosphorus-containing compound is present in an amount to deliver between 80-900 ppm phosphorus to the lubricant composition.
• the lubricant composition comprises a phosphorus-containing compound of Formula XIV wherein R1 is O; R2 is -OH; R3 is -OR" or -OH; R4 is -OR"; R" is C5; and wherein phosphorus-containing compound is present in an amount to deliver between 80-1500 ppm phosphorus to the lubricant composition.
• the lubricant composition comprises a phosphorus-containing compound of Formula XIV wherein R1 is O; R2 is OR"; R3 is H; R4 is -OR"; R" is C4; and wherein the one or more phosphorus-containing compound(s) is present in an amount to deliver between 80-1550 ppm phosphorus to the lubricant composition.
• the lubricant composition comprises a phosphorus-containing compound of Formula XIV wherein R1 is O; R2 is -R"; R3 is -OCH3 or -OH; R4 is -OCH3; R" is C18; and wherein the one or more phosphorus-containing compound(s) is present in an amount to deliver between 80-850 ppm phosphorus to the lubricant composition.
• the phosphorus-containing compound has the structure shown in Formula XIV and delivers about 80 to about 4500 ppm phosphorus to the lubricant composition. In other embodiments, the phosphorus-containing compound is present in an amount to deliver between about 150 and about 1500 ppm phosphorus, or between about 300 and about 900 ppm phosphorus, or between about 800 to 1600 ppm phosphorus, or about 900 to about 1800 ppm phosphorus, to the lubricant composition.
• the lubricant composition may also include other anti-wear agents that are non-phosphorus-containing compounds.
• antiwear agents include borate esters, borate epoxides, thiocarbamate compounds (including thiocarbamate esters, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl)disulfides, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides, and mixtures thereof), sulfurized olefins, tridecyl adipate, titanium compounds, and long chain derivatives of hydroxyl carboxylic acids, such as tartrate derivatives, tartramides, tartrimides, citrates, and mixtures thereof.
• a suitable thiocarbamate compound is molybdenum dithiocarbamate.
• Suitable tartrate derivatives or tartrimides may contain alkyl-ester groups, where the sum of carbon atoms on the alkyl groups may be at least 8.
• the tartrate derivative or tartrimide may contain alkyl-ester groups, where the sum of carbon atoms on the alkyl groups may be at least 8.
• the antiwear agent may in one embodiment include a citrate.
• the additional anti-wear agent may be present in ranges including about 0 wt% to about 15 wt%, or about 0.01 wt% to about 10 wt%, or about 0.05 wt% to about 5 wt%, or about 0.1 wt% to about 3 wt% of the lubricating oil composition.
• the lubricant compositions of the disclosure may also contain other extreme pressure agent(s) so long as the lubricating compositions herein include the noted amounts and profiles set forth herein.
• the optional extreme pressure agent may contain sulfur and may contain at least 12 percent by weight sulfur.
• the extreme pressure agent added to the lubricating oil is sufficient to provide at least 350 ppm sulfur, 500 ppm sulfur, 760 ppm sulfur, from about 350 to about 2,000 ppm sulfur, from about 2,000 to about 30,000 ppm sulfur, or from about 2,000 to about 4,800 ppm sulfur, or about 4,000 to about 25,000 ppm sulfur to the lubricant composition.
• sulfur-containing extreme pressure agents include sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfurized olefins (see, for example U.S. Pat. Nos.
• organo-sulfur compounds selected from sulfurized olefins, sulfur-containing amino heterocyclic compounds, ,5-dimercapto-1,3,4-thiadiazole, polysulfides having a majority of S3 and S4 sulfides, sulfurized fatty acids, sulfurized branched olefins, organic polysulfides, and mixtures thereof.
• the extreme pressure agent is present in the lubricating composition in an amount of up to about 3.0 wt% or up to about 5.0 wt%. In other embodiments, the extreme pressure agent is present from about 0.05 wt% to about 0.5 wt%, based on the total lubricant composition. In other embodiments, the extreme pressure agent is present from about 0.1 wt% to about 3.0 wt%, based on the total lubricant composition. In other embodiments the extreme pressure agent is present in an amount between about 0.6 wt% and about 1 wt%, based on the total lubricant composition. In yet other embodiments, the detergent is present in an amount of about 1.0 wt%, based on the total lubricant composition.
• One suitable class of extreme pressure agents are polysulfides composed of one or more compounds represented by the formula: Ra-Sx-Rb where Ra and Rb are hydrocarbyl groups each of which may contain 1 to 18, and in other approaches, 3 to 18 carbon atoms and x is may be in the range of from 2 to 8, and typically in the range of from 2 to 5, especially 3. In some approaches, x is an integer from 3 to 5 with about 30 to about 60 percent of x being an integer of 3 or 4.
• the hydrocarbyl groups can be of widely varying types such as alkyl, cycloalkyl, alkenyl, aryl, or aralkyl.
• Tertiary alkyl polysulfides such as di-tert-butyl trisulfide, and mixtures comprising di-tert-butyl trisulfide (e.g., a mixture composed principally or entirely of the tri, tetra-, and pentasulfides) may be used.
• Examples of other useful dihydrocarbyl polysulfides include the diamyl polysulfides, the dinonyl polysulfides, the didodecyl polysulfides, and the dibenzyl polysulfides.
• Sulfurized isobutenes made by reacting an olefin, such as isobutene, with sulfur.
• Sulfurized isobutene SIB
• SIB sulfurized polyisobutylene
• Various methods have been disclosed in the prior art for the preparation of sulfurized olefins. See, for example, U.S. Pat. No.
• Methods for preparing sulfurized olefins generally involve formation of a material, typically referred to as an adduct", in which an olefin is reacted with a sulfur halide, for example, sulfur monochloride. The adduct is then reacted with a sulfur source to provide the sulfurized olefin.
• the quality of a sulfurized olefin is generally measured by various physical properties, including, for example, viscosity, sulfur content, halogen content and copper corrosion test weight loss.
• U.S. Patent No. 4,966,720 relates to sulfurized olefins useful as extreme pressure additives in lubrication oils and to a two stage reaction for their preparation.
• the lubricating oil compositions herein also may optionally contain one or more antioxidants.
• Antioxidant compounds are known and include for example, phenates, phenate sulfides, sulfurized olefins, phosphosulfurized terpenes, sulfurized esters, aromatic amines, alkylated diphenylamines (e.g., nonyl diphenylamine, di-nonyl diphenylamine, octyl diphenylamine, di-octyl diphenylamine), phenyl-alpha-naphthylamines, alkylated phenyl-alpha-naphthylamines, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, macromolecular antioxidants, or mixtures thereof. Antioxidant compounds may be used alone or in combination.
• the hindered phenol antioxidant may contain 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 and/or a bridging group linking to a second aromatic group.
• Suitable hindered phenol antioxidants 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, or 4-dodecyl-2,6-di-tert-butylphenol.
• the hindered phenol antioxidant may be an ester and may include, e.g., Irganox ® L-135 available from BASF or an addition product derived from 2,6-di-tert-butylphenol and an alkyl acrylate, wherein the alkyl group may contain about 1 to about 18, or about 2 to about 12, or about 2 to about 8, or about 2 to about 6, or about 4 carbon atoms.
• Another commercially available hindered phenol antioxidant may be an ester and may include Ethanox ® 4716 available from Albemarle Corporation.
• Useful antioxidants may include diarylamines and phenols.
• the lubricating oil composition may contain a mixture of a diarylamine and a phenol, such that each antioxidant may be present in an amount sufficient to provide up to about 5 wt%, based on the weight of the lubricant composition.
• the antioxidant may be a mixture of about 0.3 wt% to about 1.5 wt% diarylamine and about 0.4 wt% to about 2.5 wt% phenol, based on the lubricant composition.
• Suitable olefins that may be sulfurized to form a sulfurized olefin include propylene, butylene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene or mixtures thereof.
• hexadecene, heptadecene, octadecene, nonadecene, eicosene or mixtures thereof and their dimers, trimers and tetramers are especially useful olefins.
• the olefin may be a Diels-Alder adduct of a diene such as 1,3-butadiene and an unsaturated ester, such as, butylacrylate.
• sulfurized olefin includes sulfurized fatty acids and their esters.
• the fatty acids are often obtained from vegetable oil or animal oil and typically contain about 4 to about 22 carbon atoms.
• suitable fatty acids and their esters include triglycerides, oleic acid, linoleic acid, palmitoleic acid or mixtures thereof.
• the fatty acids are obtained from lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil or mixtures thereof.
• Fatty acids and/or ester may be mixed with olefins, such as ⁇ -olefins.
• the one or more antioxidant(s) may be present in ranges about 0 wt% to about 20 wt%, or about 0.1 wt% to about 10 wt%, or about 1 wt% to about 5 wt%, of the lubricating oil composition.
• Dispersants contained in the lubricant composition may include, but are not limited to, an oil soluble polymeric hydrocarbon backbone having functional groups that are capable of associating with particles to be dispersed.
• the dispersants comprise amine, alcohol, amide, or ester polar moieties attached to the polymer backbone often via a bridging group.
• Dispersants may be selected from Mannich dispersants as described in U.S. Pat. Nos. 3,634,515 , 3,697,574 and 3,736,357 ; ashless succinimide dispersants as described in U.S. Pat. Nos. 4,234,435 and 4,636,322 ; amine dispersants as described in U.S. Pat. Nos.
• the additional dispersant may be derived from a polyalphaolefin (PAO) succinic anhydride, an olefin maleic anhydride copolymer.
• PAO polyalphaolefin
• the additional dispersant may be described as a poly-PIBSA.
• the additional dispersant may be derived from an anhydride which is grafted to an ethylene-propylene copolymer.
• Another additional dispersant may be a high molecular weight ester or half ester amide.
• the additional dispersant if present, can be used in an amount sufficient to provide up to about 10 wt%, based upon the final weight of the lubricating oil composition.
• Another amount of the dispersant that can be used may be about 0.1 wt% to about 10 wt%, or about 0.1 wt% to about 10 wt%, or about 3 wt% to about 8 wt%, or about 1 wt% to about 6 wt%, based upon the final weight of the lubricating oil composition.
• the lubricant compositions herein also may optionally contain one or more viscosity index improvers.
• Suitable viscosity index improvers may include polyolefins, olefin copolymers, ethylene/propylene copolymers, polyisobutenes, hydrogenated styrene-isoprene polymers, styrene/maleic ester copolymers, hydrogenated styrene/butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkyl styrenes, hydrogenated alkenyl aryl conjugated diene copolymers, or mixtures thereof.
• Viscosity index improvers may include star polymers and suitable examples are described in US Publication No. 20120101017A1 , which is incorporated herein by reference.
• the lubricating oil compositions herein also may optionally contain one or more dispersant viscosity index improvers in addition to a viscosity index improver or in lieu of a viscosity index improver.
• Suitable viscosity index improvers may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with the reaction product of an acylating agent (such as maleic anhydride) and an amine; polymethacrylates functionalized with an amine, or esterified maleic anhydride-styrene copolymers reacted with an amine.
• the total amount of viscosity index improver and/or dispersant viscosity index improver may be about 0 wt% to about 20 wt%, about 0.1 wt% to about 15 wt%, about 0.1 wt% to about 12 wt%, or about 0.5 wt% to about 10 wt%, about 3 wt% to about 20 wt%, about 3 wt% to about 15 wt%, about 5 wt% to about 15 wt%, or about 5 wt% to about 10 wt%, of the lubricating oil composition.
• the viscosity index improver is a polyolefin or olefin copolymer having a number average molecular weight of about 10,000 to about 500,000, about 50,000 to about 200,000, or about 50,000 to about 150,000.
• the viscosity index improver is a hydrogenated styrene/butadiene copolymer having a number average molecular weight of about 40,000 to about 500,000, about 50,000 to about 200,000, or about 50,000 to about150,000.
• the viscosity index improver is a polymethacrylate having a number average molecular weight of about 10,000 to about 500,000, about 50,000 to about 200,000, or about 50,000 to about 150,000.
• additives may be selected to perform one or more functions required of lubricant composition. Further, one or more of the mentioned additives may be multi-functional and provide functions in addition to or other than the function prescribed herein.
• the other additives may be in addition to specified additives of the present disclosure and/or may comprise one or more of metal deactivators, viscosity index improvers, ashless TBN boosters, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, seal swelling agents and mixtures thereof.
• fully-formulated lubricating oil will contain one or more of these additives.
• Suitable metal deactivators may include 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 optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides.
• benzotriazoles typically tolyltriazole
• dimercaptothiadiazole derivatives 1,2,4-triazoles
• benzimidazoles 2-alkyldithiobenzimidazoles
• Suitable foam inhibitors include silicon-based compounds, such as siloxane.
• Suitable pour point depressants may include a polymethylmethacrylates or mixtures thereof. Pour point depressants may be present in an amount sufficient to provide from about 0 wt% to about 1 wt%, about 0.01 wt% to about 0.5 wt%, or about 0.02 wt% to about 0.04 wt% based upon the final weight of the lubricating oil composition.
• Suitable rust inhibitors may be a single compound or a mixture of compounds having the property of inhibiting corrosion of ferrous metal surfaces.
• Non-limiting examples of rust inhibitors useful herein include oil-soluble high molecular weight organic acids, such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid, as well as oil-soluble polycarboxylic acids including dimer and trimer acids, such as those produced from tall oil fatty acids, oleic acid, and linoleic acid.
• oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, and cerotic acid
• oil-soluble polycarboxylic acids including dimer and trim
• Suitable corrosion inhibitors include long-chain alpha, omega-dicarboxylic acids in the molecular weight range of about 600 to about 3000 and alkenylsuccinic acids in which the alkenyl group contains about 10 or more carbon atoms such as, tetrapropenylsuccinic acid, tetradecenylsuccinic acid, and hexadecenylsuccinic acid.
• alkenylsuccinic acids include the half esters of alkenyl succinic acids having about 8 to about 24 carbon atoms in the alkenyl group with alcohols such as the polyglycols. The corresponding half amides of such alkenyl succinic acids are also useful.
• a useful rust inhibitor is a high molecular weight organic acid.
• an engine oil is devoid of a rust inhibitor.
• the rust inhibitor if present, can be used in optional amount sufficient to provide about 0 wt% to about 5 wt%, about 0.01 wt% to about 3 wt%, about 0.1 wt% to about 2 wt%, based upon the final weight of the lubricating oil composition.
• the lubricant composition may also include corrosion inhibitors (it should be noted that some of the other mentioned components may also have copper corrosion inhibition properties). Suitable inhibitors of copper corrosion include ether amines, polyethoxylated compounds such as ethoxylated amines and ethoxylated alcohols, imidazolines, monoalkyl and dialkyl thiadiazole, and the like.
• Thiazoles, triazoles and thiadiazoles may also be used in the lubricants.
• Examples include benzotriazole, tolyltriazole, octyltriazole, decyltriazole; dodecyltriazole, 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-5-hydrocarbylthio-1,3,4-thiadiazoles, and 2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazoles.
• the lubricant composition includes a 1,3,4-thiadiazole, such as 2-hydrocarbyldithio-5-mercapto-1,3,4-dithiadiazole.
• Anti-foam/Surfactant agents may also be included in a fluid according to the present invention.
• Various agents are known for such use.
• Copolymers of ethyl acrylate and hexyl ethyl acrylate, such as PC-1244, available from Solutia may be used.
• silicone fluids, such as 4% DCF may be included.
• Mixtures of anti-foam agents may also be present in the lubricant composition.
• gear fluids are for use in extreme pressure situations such as for transmissions and gear drive components having metal-on-metal contact situations, for instance, in a transmission and/or a limited-slip differential and/or wet brakes and/or wet clutches.
• 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 a predominantly hydrocarbon character.
• Each hydrocarbyl group is independently selected from hydrocarbon substituents, and substituted hydrocarbon substituents containing one or more of halo groups, hydroxyl groups, alkoxy groups, mercapto groups, nitro groups, nitroso groups, amino groups, pyridyl groups, furyl groups, imidazolyl groups, oxygen and nitrogen, and wherein no more than two non-hydrocarbon substituents are present for every ten carbon atoms in the hydrocarbyl group.
• percent by weight or "wt%”, unless expressly stated otherwise, means the percentage the recited component represents to the weight of the entire composition. All percent numbers herein, unless specified otherwise, is weight percent.
• soluble oil-soluble
• dispenser dispensers
• soluble dissolvable, miscible, or capable of being suspended in the oil in all proportions.
• the foregoing terms do mean, however, that they are, for instance, soluble, suspendable, dissolvable, or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed.
• additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
• alkyl refers to straight, branched, cyclic, and/or substituted saturated chain moieties from about 1 to about 200 carbon atoms.
• alkenyl refers to straight, branched, cyclic, and/or substituted unsaturated chain moieties from about 3 to about 30 carbon atoms.
• aryl refers to single and multi-ring aromatic compounds that may include alkyl, alkenyl, alkylaryl, amino, hydroxyl, alkoxy, halo substituents, and/or heteroatoms including, but not limited to, nitrogen, and oxygen.
• the molecular weight is determined by gel permeation chromatography (GPC) using commercially available polystyrene standards (with a Mn of about 180 to about 18,000 as the calibration reference).
• Mn molecular weight
• the molecular weight (Mn) for any embodiment herein may be determined with a gel permeation chromatography (GPC) instrument obtained from Waters or the like instrument and the data processed with Waters Empower Software or the like software.
• the GPC instrument may be equipped with a Waters Separations Module and Waters Refractive Index detector (or the like optional equipment).
• the GPC operating conditions may include a guard column, 4 Agilent PLgel columns (length of 300 ⁇ 7.5 mm; particle size of 5 ⁇ , and pore size ranging from 100-10000 ⁇ ) with the column temperature at about 40 °C. Un-stabilized HPLC grade tetrahydrofuran (THF) may be used as solvent, at a flow rate of 1.0 mL/min.
• THF Un-stabilized HPLC grade tetrahydrofuran
• the GPC instrument may be calibrated with commercially available polystyrene (PS) standards having a narrow molecular weight distribution ranging from 500 - 380,000 g/mol. The calibration curve can be extrapolated for samples having a mass less than 500 g/mol.
• PS polystyrene
• Samples and PS standards can be in dissolved in THF and prepared at concentration of 0.1-0.5 weight percent and used without filtration.
• GPC measurements are also described in US 5,266,223 , which is incorporated herein by reference.
• the GPC method additionally provides molecular weight distribution information; see, for example, W. W. Yau, J. J. Kirkland and D. D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wiley and Sons, New York, 1979 , also incorporated herein by reference.
• any sulfur moiety distributions, amounts, or ratios of the organic sulfide compounds were determined using CNMR via a Bruker Avance-3 HD 500MHz instrument equipped with a 5mm BBO Prodigy probe (or equivalent).
• Samples were dissolved in chloroform-d, about 3% wt/wt for the 1 H NMR one-dimensional (1D) and two-dimensional (2D) homonuclear experiments and about 30% wt/wt for the 13 C 1D and 2D heteronuclear experiments.
• the experiments were conducted at ambient temperature.
• An exemplary organic polysulfide reaction product may be prepared as follows: a 300 mL stainless steel autoclave was charged with sulfur (67.2g, 1.92 gram atoms) and 0.1 mL n-butylamine (1.0 mmol). The autoclave was cooled in a dry ice isopropyl alcohol bath and sparged (4 ⁇ 100 psi) with N 2 . Isobutylene (58.8g, 1.05 mole) was condensed into the autoclave. The autoclave was sealed and heated to 140°C under an autogeneous pressure of 550 psi for 26.5 hours. After standing overnight the autoclave was vented to a caustic trap and a condenser cooled in dry ice and then heated to 10°C and sparged with N 2 for 0.5 hours.
• Example 3A a 100 mL round bottom flask equipped with an over-head stirrer and reflux condenser was charged with sodium hydrosulfide (10.8g, 46% aq) and sodium hydroxide (12.0g, 50% aq), and the sulfurized product prepared in Example 3A (20g). The solution was vigorously stirred and heated to 80°C for 2 hours and 100°C for 2 hours. After cooling, the solution was taken up in diethyl ether and poured into a separatory funnel.
• Organic Sulfide Reaction Product A the first organic sulfide reaction product had about 15 weight percent of compounds with an S 2 moiety, about 82 weight percent of compounds with a S 3 moiety, about 3 weight percent of compounds with a S 4 moiety, and no compounds with either a S 5 or S 6 moiety Reaction product A had a weight ratio of S 3 to S 4 of about 27.3:1. Sulfide profiles were determined by CNMR as described above.
• Organic Sulfide Reaction Product B the second organic sulfide reaction product had about 15 weight percent of compounds with an S 2 moiety, about 59 weight percent of compounds with a S 3 moiety, about 24 weight percent of compounds with a S 4 moiety, about 3 weight percent of compounds with a S 5 moiety, and no compounds with a S 6 moiety Reaction product B had a weight ratio of S 3 to S 4 of about 2.5:1. Sulfide profiles were also determined by CNMR as described above.
• the organic sulfide reaction products A and B of Example 1 were evaluated in lubricating compositions of Table 3 when combined with various phosphorus-containing components and amine compounds.
• the lubricating compositions of Table 3 included about 0.13 weight percent of a thiadiazole or derivative thereof.
• the lubricating compositions also included the same amounts an additive package including the same detergents, friction modifiers, a viscosity modifier, an antioxidant, rust inhibitor, corrosion inhibitor, seal swell agent, and antifoam agents. All of the evaluated compositions also included the balance of base oils and/or process oils as needed to achieve a target KV100 viscosity of about 13 to 14 cSt.
• the second phosphorus-containing component of Table 3 was an amine salt of a dibutyl hydrogen thiophosphite.
• the third phosphorus-containing component of Table 3 was a phosphorus reaction product formed by (i) reacting an O,O-di(4-methyl-2-pentyl) phosphorodithioic acid with propylene oxide, to form a first reaction product, (ii) reacting the first reaction product with phosphorus pentoxide to produce an acid phosphate intermediate, and (iii) neutralizing at least a major portion of the intermediate with a C11-C14 tertiary alkyl primary amine.
• the hydrocarbylamine compound was an aliphatic tertiary primary amine.
• an antioxidant includes two or more different antioxidants.
• the term “include” and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items.
• each range disclosed herein is to be interpreted as a disclosure of each specific value within the disclosed range that has the same number of significant digits.
• a range from 1 to 4 is to be interpreted as an express disclosure of the values 1, 2, 3 and 4 as well as any range of such values.
• each lower limit of each range disclosed herein is to be interpreted as disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compounds, substituent or parameter.
• this disclosure to be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it is also further understood that any range between the endpoint values within the broad range is also discussed herein.
• a range from 1 to 4 also means a range from 1 to 3, 1 to 2, 2 to 4, 2 to 3, and so forth.

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