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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
  • C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
• • 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
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/12—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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/40—Low content or no content compositions
  • C10N2030/43—Sulfur free or low sulfur content compositions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
  • C10N2060/10—Chemical after-treatment of the constituents of the lubricating composition by sulfur or a compound containing sulfur

Definitions

• the exemplary embodiment relates to lubricating compositions and finds particular application in connection with a lubricating composition containing a phenolic antioxidant and a sulfurized organic compound that is low in active sulfur, which is able to provide both antioxidancy and reduced corrosion.
• a lubricating composition containing a phenolic antioxidant and a sulfurized organic compound that is low in active sulfur, which is able to provide both antioxidancy and reduced corrosion.
• Ashless additives additives that produce little or no ash when burnt
• Basic ashless additives such as amines, are frequently employed as antioxidants.
• hydrocarbyl substituted diphenylamines such as octyl diphenylamine, di-octyl diphenylamine, and dinonyl diphenylamine
• octyl diphenylamine di-octyl diphenylamine
• dinonyl diphenylamine hydrocarbyl substituted diphenylamines
• a lubricating composition includes an oil of lubricating viscosity, a phenolic antioxidant, a sulfurized organic compound with an active sulfur content of no more than 8 wt. %, and optionally, one or more performance additives selected from: a succinimide dispersant, and a detergent.
• the lubricating composition may be at least substantially free of substituted diphenylamine (SDPA) antioxidants.
• SDPA substituted diphenylamine
• the lubricating composition may be at least substantially free of aminic antioxidants.
• the phenolic antioxidant may be at least 0.1 wt. %, or at least 0.5 wt.
• the phenolic antioxidant may be no more than 8 wt. 4760-01 % of the lubricating composition, or no more than 6 wt. %, or no more than 5 wt. %, or no more than 4 wt. % or no more than 3 wt. % of the lubricating composition.
• the phenolic antioxidant may be selected from a hindered phenol, a hindered alkyl phenol ester, a hindered alkoxy phenol, a hindered phenol acetate, a hindered bisphenol, a polyphenol, a 4-tert-butylphenol- formaldehyde condensate, a 4-tert-butylphenol-acetaldehyde condensate, and mixtures thereof.
• the phenolic antioxidant may be selected from: a mixture of C7-C9 branched alkyl esters of 3,5-bis(1,1-dimethyl-ethyl)- 4-hydroxy-benzenepropanoic acid; a C4 alkyl ester of 3,5-bis(1,1-dimethyl- ethyl)-4-hydroxy-benzenepropanoic acid, and 2,2'-thiodiethylene bis[3-(3,5- di-tert-butyl-4-hydroxyphenyl)propionate].
• the sulfurized organic compound is generally one which is low in active sulfur.
• a sulfurized organic compound which is low in active sulfur has either a low weight percent of active sulfur or a low weight % active sulfur in the total sulfur in the sulfurized organic compound, or both.
• the sulfurized organic compound may have an active sulfur content of no more than 8 wt. %, or no more than 6 wt. %, or no more than 4.0 wt. %, or no more than 3 wt. %, or no more than 2.5 wt.%, or no more than 2 wt. %.
• the sulfurized organic compound may have a total sulfur content of at least 0.1 wt. %, or at least 1 wt. %, or at least 1.5 wt. %, or at least 2 wt.
• the active sulfur may account for no more than 25 wt. %, or no more than 22 wt. %, or no more than 20 wt. %, or no more than 19 wt., or at least 1 wt. %, or at least 1.5 wt. % of the total sulfur in the sulfurized organic compound.
• the sulfurized organic compound may provide at least 0.01 wt.%, or at least 0.03 wt.%, or at least 0.05 wt.
• the sulfurized organic compound may provide no more than 0.02 wt. % of active sulfur, or no more than 0.018 wt. %, or no more than 0.015 wt. %, or no more than 0.013 wt. % of active sulfur in the lubricating composition. 4760-01 [0015]
• the sulfurized organic compound may be at least 0.1 wt. %, or at least 0.15 wt. % or at least 0.2 wt. % of the lubricating composition.
• the sulfurized organic compound may be up to 1 wt. %, or up to 0.8 wt.
• the sulfurized organic compound may be selected from an oligomeric polysulfide, an alkyl polysulfide, a sulfurized ester, a sulfurized cycloaliphatic dialkylester, a sulfurized cycloaliphatic dialkenyl ester, and mixtures thereof.
• the sulfurized organic compound may be selected from an oligomeric polysulfide of Formula I: R 1 ⁇ S x ⁇ [(C(R') v H 2-v ) n ⁇ S x ] p ⁇ R 2 Formula I, where R 1 and R 2 are each independently a C2-C20 alkyl, e.g., a C3 or C4 or higher alkyl, or a C16 or lower alkyl; each R' is independently a C1-C20 alkyl, or a C6 or lower alkyl; each n is independently at least 1, or at least 2, or up to 8, e.g., 3-5, such as 3 or 4; p is independently at least 1, or at least 2, or up to 8; each v is from 0-2, e.g., v is 0; and each x is independently at least 1.
• R 1 and R 2 are each independently a C2-C20 alkyl, e.g., a C3 or C4 or higher alkyl
• the sulfurized organic compound may include an alkyl polysulfide of Formula II: R 1 ⁇ S x ⁇ R 2 , where R 1 and R 2 are each independently a C2-C20 alkyl, or a C3-C8 alkyl, such as a C4 alkyl; and each x is independently at least 1.
• the sulfurized organic compound may include a sulfurized fatty acid ester of an aliphatic alcohol.
• the sulfurized fatty acid ester of an aliphatic alcohol may include a sulfurized triglyceride.
• the sulfurized organic compound may include at least one of a cycloaliphatic dialkylester and a cycloaliphatic dialkenyl ester of Formula V: , 4760-01 where each of R 13 and R 14 is independently a C2 or higher alkyl or alkenyl group; and x is at least 1.
• the succinimide dispersant may be at least 0.2 wt. %, or at least 0.5 wt. %, or at least 1.0 wt. %, or up to 7.0 wt. %, or up to 6.0 wt. of the lubricating composition.
• the succinimide dispersant may provide no more than 0.1 wt. % nitrogen to the lubricating composition.
• the detergent may be at least 0.1 wt. %, or at least 0.2 wt. %, or at least 0.25 wt. %, or at least 0.4 wt. %, or up to 3.0 wt. %, or up to 2.0 wt. %, or up to 1.5 wt. %, or up to 1.25 wt. % of the lubricating composition.
• the detergent may provide the lubricating composition with at least 0.005 wt. % of boron, or at least 0.03 wt. % boron, or up to 0.06 wt. %, or up to 0.04 wt.% of boron.
• the detergent may provide the lubricating composition with at least 0.04 wt. %, or at least 0.08 wt. %, or up to 0.4 wt.%, or up to 0.3 wt. % of calcium.
• the detergent may be selected from an alkaline earth metal sulfonate, an alkaline earth metal salicylate, an alkaline earth metal saligenin, an alkaline earth metal salixarate, an alkaline earth metal hydrocarbyl- substituted hydroxybenzoate, and mixtures thereof.
• the oil of lubricating viscosity may be at least 80 wt. % of the lubricating composition, or up to 94 wt. % of the lubricating composition.
• the lubricating composition may further include at least one of an antiwear agent, a corrosion inhibitor, a viscosity modifier, a pour point depressant, an antifoam agent, an extreme pressure agent, a friction modifier, and combinations thereof.
• the antiwear agent may provide the lubricating composition with 300 - 850 ppm phosphorus by weight, based upon a total weight of the lubricating composition.
• the viscosity modifier may include a dispersant viscosity modifier which includes at least one of a reaction product of an olefin polymer comprising a carboxylic acid functionality with 3-nitroaniline; and an amine functionalized aromatic maleic anhydride-styrene copolymer.
• the dispersant viscosity modifier may be at least 0.01 wt. %, or at least 0.1 wt. %, or at least 2 wt. %, or no more than 8 wt. %, or no more than 7 wt. % of the lubricating composition.
• Molybdenum may be less than 800 ppm, or less than 400 ppm, or less than 150 ppm, or less than 100 ppm, or less than 80 ppm, or less than 50 ppm, or less than 20 ppm, based upon a total weight of the lubricating composition.
• a method for improving oxidative stability of a lubricating oil in an engine may include supplying the lubricating composition described above to the engine.
• the kinematic viscosity at 40°C (KV40) increase from 300 hours to 360 hours may be less than 75 or less than 50.
• the oxidation at the end of test may be less than 125 A/cm, as measured by the IR peak height.
• the lubricating composition described above may be used for lubricating an engine, such as an internal combustion engine or a heavy duty diesel engine.
• a lubricating composition includes a sulfurized organic compound sufficient to provide, in the lubricating composition, at least 0.1 wt. % sulfur; at least 0.1 wt. % of a phenolic antioxidant; at least 0.1 wt. % of a detergent; and at least 2 wt. % of a dispersant.
• the lubricating composition contains no more than 0.04 wt. % of active sulfur.
• the detergent may include at least one of a calcium salicylate detergent and a calcium sulfonate detergent sufficient to provide at least 0.1 wt. %, or at least 0.12 wt.
• aspects of the exemplary embodiment relate to a lubricating composition and to a method of lubricating a mechanical device.
• the composition provides improved oxidative stability of a lubricating oil in the mechanical device while minimizing corrosion of conductive metals.
• the lubricating composition has a TBN of at least 5, or at least 7. In another embodiment the lubricating composition has a TBN of no more than 20, or no more than 15, or no more than 12, or no more than 10.
• An exemplary lubricating composition includes: a) an oil of lubricating viscosity, b) a phenolic antioxidant, i.e., one or more phenolic antioxidants, c) a sulfurized organic compound, i.e., one or more sulfurized organic compounds, the sulfurized organic compound selected to provide the lubricating composition with a low active sulfur content, and d) optionally, one or more performance additives, which may be selected from: i) a succinimide dispersant, i.e., one or more succinimide dispersants, and ii) a detergent, i.e., one or more detergents, such an alkaline earth metal salt of an alkyl sulfonate.
• a succinimide dispersant i.e., one or more succinimide dispersants
• a detergent i.e., one or more detergents, such an alkaline earth metal salt of an alkyl sulfonate.
• the lubricating composition may further include one or more other performance additives.
• active sulfur of a sulfur-containing compound refers to the relative ability of a sulfur-containing compound to react chemically with a metal surface to form a metal sulfide. As used herein, active sulfur is the weight percent of sulfur which is available for a reaction at 150°C, as determined by ASTM D1662-19, “Standard Test Method for Active Sulfur in Cutting Oils,” hereinafter, ASTM D1662.
• the active sulfur of a sulfur-containing compound is not merely a function of the mole percent of sulfur that it contains and that two sulfur-containing compounds may have very similar mole % (or weight %) of sulfur but distinctly different weight % of active sulfur.
• the balance of the sulfur is referred to as inactive sulfur. 4760-01 [0037]
• the lubricating composition is free, or substantially free, of substituted diphenylamines. By “substantially free” it is meant that the lubricating composition contains no more than 0.1 wt. %, or no more than 0.01 wt. % of substituted diphenylamines.
• Substituted diphenylamines are defined as phenyl amines having a substituent on one or more of the carbon atoms of the phenyl rings.
• the substituent(s) can be hydrocarbyl substituent(s) selected from aliphatic substituents (including cycloaliphatic), aromatic substituents, substituents with alkyl and aryl moieties, and mixtures thereof.
• the lubricating composition may have a kinematic viscosity at 100°C (KV_100) of at least 2 cSt (or mm 2 /s), or at least 10 cSt, or at least 12 cSt, or up to 25 cSt, or up to 20 cSt, as measured by ASTM D445-21e1, “Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and Calculation of Dynamic Viscosity)”, hereinafter, “D445”.
• the lubricating composition may be liquid, i.e., not a gel or semi-solid, at ambient temperatures (15-30°C).
• the lubricating composition comprises an oil of lubricating viscosity.
• suitable oils include natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydrofinishing, unrefined, refined, re-refined oils or mixtures thereof.
• Oils of lubricating viscosity may also be defined as specified in April 2008 version of “Appendix E - API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils”, section 1.3 Sub-heading 1.3. “Base Stock Categories”. The API Guidelines are also summarized in U.S. Pat. No. 7,285,516.
• the five base oil groups are as follows: Group I (sulfur content >0.03 wt. %, and/or ⁇ 90 wt. % saturates, viscosity index 80- 120); Group II (sulfur content ⁇ 0.03 wt. %, and >90 wt. % saturates, viscosity index 80-120); Group III (sulfur content ⁇ 0.03 wt. %, and >90 wt. % saturates, viscosity index >120); Group IV (all polyalphaolefins (PAOs)); and Group V (all others not included in Groups I, II, III, or IV).
• Group I sulfur content >0.03 wt. %, and/or ⁇ 90 wt. % saturates, viscosity index 80- 120
• Group II sulfur content ⁇ 0.03 wt. %, and >90 wt. % saturates, viscosity index 80-120
• the exemplary oil of 4760-01 lubricating viscosity includes an API Group I, Group II, Group III, Group IV, Group V oil, or mixtures thereof.
• the oil of lubricating viscosity is an API Group I, Group II, Group III, or Group IV oil, or mixtures thereof.
• the oil of lubricating viscosity is an API Group I, Group II, or Group III oil, or mixture thereof.
• the oil of lubricating viscosity may be an API Group II, Group III mineral oil, a Group IV synthetic oil, or mixture thereof. In some embodiments, at least 5 wt. %, or at least 10 wt.%, or at least 20 wt.%, or at least 40 wt.
• % of the lubricating composition is a polyalphaolefin (Group IV).
• Other groups have defined, from which the oil of lubricating viscosity may be selected, including API Group II+ base oils, which refers to a Group II base oil having a viscosity index ⁇ 110 and less than 120, and API Group III+ base oil, having a viscosity index ⁇ 130, as described in SAE publication “Design Practice: Passenger Car Automatic Transmissions,” fourth Edition, AE-29, 2012, pages 12-9.
• a Group II and/or Group III base oil is used.
• Unrefined, refined and re-refined oils, and natural and synthetic oils are described, for example, in WO2008/147704 and U.S. Pub. No. 2010/197536.
• Synthetic oils may also be produced by Fischer-Tropsch reactions and typically may be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. Oils may be prepared by a Fischer-Tropsch gas-to- liquid synthetic procedure as well as other gas-to-liquid procedures.
• Unrefined oils are those obtained directly from a natural or synthetic source generally without (or with little) further purification treatment.
• Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
• Natural oils include animal oils, vegetable oils (e.g., castor oil), 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 and oils derived from coal or shale or mixtures thereof.
• Example animal and vegetable oils include long chain fatty acid esters, such as linseed oil, sunflower oil, sesame seed oil, beef tallow oil, lard oil, palm oil, castor oil, cottonseed oil, corn oil, peanut oil, soybean oil, olive oil, whale oil, menhaden oil, sardine oil, coconut oil, palm kernel oil, babassu oil, rapeseed oil, and soya oil.
• 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.
• Exemplary synthetic oils include hydrocarbon oils, such as poly-alpha olefins, synthetic esters and polyesters, poly-acrylates and poly-methacrylates, liquid esters of phosphorus-containing acids, and polymeric tetrahydrofurans.
• hydrocarbon oils such as poly-alpha olefins, synthetic esters and polyesters, poly-acrylates and poly-methacrylates, liquid esters of phosphorus-containing acids, and polymeric tetrahydrofurans.
• Example synthetic esters include esters of a dicarboxylic acid (e.g., selected from phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, and alkenyl malonic acids) with an alcohol (e.g., selected from butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, and propylene glycol).
• a dicarboxylic acid e.g., selected from phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, lino
• esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
• Esters particularly useful as synthetic oils include those made from C5 to C12 monocarboxylic acids and polyols and from polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Esters can also be monoesters, such as are available under 4760-01 the trade name Priolube 1976TM (C 18 -alkyl ⁇ COO ⁇ C 20 alkyl). Synthetic esters useful herein may have a KV_100 of 2.5 mm 2 /s to 30 mm 2 /s.
• Exemplary synthetic hydrocarbon oils include polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene- isobutylene copolymers); poly(1-hexenes), poly(1-octenes), poly(1-decenes), and mixtures thereof; alkyl-benzenes (e.g.
• 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.
• Mixtures of such oils are contemplated, such as a mixture of Group II and Group III base oils, or a mixture of Group III and Group IV base oils.
• the oil of lubricating viscosity may have a kinematic viscosity at 100°C (KV_100), determined according to D445, of at least 1.8 cSt, or at least 4 cSt, depending on the desired SAE grade of the lubricating composition.
• This viscosity can be obtained by a mixture of base oils, for example containing mineral bases of Group I such as Neutral Solvent (for example 500 NS or 600 NS) and Bright Stock bases. Any other combination of mineral or synthetic bases or bases of vegetable origin having, in mixture with the additives, a viscosity compatible with the desired SAE grade can be used.
• the amount of the oil of lubricating viscosity present may be typically the balance remaining after subtracting from 100 wt. % the sum of the amount of the additives as described herein above, and any other performance additives.
• the lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant.
• a ratio of the components of the lubricating composition (other than the oil of lubricating viscosity) to the oil of lubricating viscosity may be from 20:80 to 90:10 by weight, or from 40:60 to 80:20 by weight.
• a ratio of the components of the lubricating composition (other than the oil of lubricating viscosity) to the oil of lubricating viscosity may be from 1:99 to 30:70 by weight, or from 5:95 to 20:80 by weight.
• the oil of lubricating viscosity (including diluent oil and oil present as a result of additives in the composition) is at least 20 wt. %, or at least 40 wt. %, or at least 60 wt. %, or at least 80 wt. %, or at least 82 wt.
• the phenolic antioxidant may be present in the lubricating composition at a total concentration of at least 0.1 wt. %, or at least 0.5 wt. %, or at least 1 wt. %, or at least 1.5 wt. %, or at least 2 wt. %, or up to 8 wt. %, or up to 6 wt. %, or up to 5 wt. %, or up to 4 wt. %, or up to 3 wt.
• Exemplary phenolic antioxidants include hindered phenols, including hindered phenol esters, such as phenol alkyl esters, hindered phenol acetates, hindered phenol alkoxides, bis- and polyphenols, condensates of phenols with formic acid and mixtures thereof.
• Hindered phenol antioxidants often 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 (typically linear or branched alkyl) and/or a bridging group linking to a second aromatic group.
• Example phenolic antioxidants that may be used include: - Hindered phenols, such as 2-tert-butylphenol, 2-tert-butyl-4- methylphenol, 2-tert-butyl-5-methylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert- butylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4-methoxyphenol, 3-tert-butyl-4-methoxyphenol, 2,5-di-tert- butylhydroquinone, 2,6-di-tert-butyl-4-ethylphenol; 4-methyl-2,6-di-tert- butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, 4-butyl-2,6-di-di-
• the hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
• the phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and/or a bridging group linking to a second aromatic group.
• hindered phenol antioxidants examples include 2,6-di-tert- butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, 4-butyl-2,6-di-tert-butylphenol, and 4- dodecyl-2,6-di-tert-butylphenol.
• the hindered phenol antioxidant is an ester and may include, e.g., IrganoxTM L 135 or L 115 from BASF.
• IrganoxTM L 135 is a high molecular weight phenolic antioxidant, specifically, a mixture of C7-C9 branched alkyl esters of 3,5-bis(1,1-dimethyl- ethyl)-4-hydroxy-benzenepropanoic acid.
• IrganoxTM L 115 is 2,6-di-tert- butylphenol.
• suitable ester-containing hindered phenol antioxidant chemistry is found in U.S. Pat. No.6,559,105.
• the hindered alkyl phenol is a C4 alkyl ester of 3,5-bis(1,1- dimethyl-ethyl)-4-hydroxy-benzenepropanoic acid.
• the hindered alkyl phenol is 2,2'-thiodiethylene bis[3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate].
• Coupled phenols useful herein may contain two alkylphenols coupled with alkylene groups to form bisphenol compounds.
• Suitable coupled phenol compounds include 4,4'-methylene bis(2,6-di-tert- butyl phenol); 4-methyl-2,6-di-tert-butylphenol; 2,2'-bis(6-tert-butyl-4- heptylphenol); 4,4'-bis(2,6-di-tert-butyl phenol); 2,2'-methylene bis(4-methyl- 6-tert-butylphenol), and 2,2'-methylene bis(4-ethyl-6-tert-butylphenol).
• Other phenolic antioxidants may include polyhydric aromatic compounds and their derivatives.
• suitable polyhydric aromatic compounds include esters and amides of gallic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 1,4-dihydroxy-2-naphthoic acid, 3,5- dihydroxynaphthoic acid, 3,7-dihydroxy naphthoic acid, and mixtures thereof.
• the phenolic antioxidant comprises a hindered phenol.
• the hindered phenol is derived from 2,6-di-tert-butyl phenol.
• the lubricating composition is free or substantially free of substituted diphenylamine (SDPA) antioxidants.
• Substituted diphenylamines of this type include mono-, di-, tri-, and poly- alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylamino, aryl, alkylaryl, and/or alkoxyaryl-substituted diphenylamines, e.g., C1-C24, particularly C6 and higher, alkyl-substituted diphenylamines, such as mono-octyl diphenylamine, di-octyl diphenylamine, mono-butyl-mono-octyl diphenylamine, nonyl diphenylamine, di-nonyl diphenylamine, tri
• Aryl-substituted diphenylamines include phenyl- ⁇ - naphthylamine (PANA) and alkylated phenyl naphthylamines.
• PANA phenyl- ⁇ - naphthylamine
• Other aminic antioxidants which may be excluded or substantially free of, include 2,6-di-tert-butyl- ⁇ -dimethylamino-p-cresol.
• the lubricating composition is free or substantially free (less than 0.01 wt. %, or less than 0.001 wt. % or 0 wt. %) of all aminic antioxidants.
• the Sulfurized Organic Compound helps to control wear in a lubricated device, such as an engine, particularly for extreme pressure conditions in automobile, truck and industrial engines. They can also have very good thermal oxidation stability and rust inhibition properties.
• Sulfurized organic compounds include those that are substantially nitrogen-free, that is, do not contain nitrogen functionality.
• They may be 4760-01 formed by sulfurizing an organic compound containing at least one olefinic double bond (a non-aromatic double bond), that is, one connecting two aliphatic carbon atoms.
• the organic compounds to be sulfurized may, in some cases, include metal cations (e.g., from Group I or II, e.g., sodium, potassium, barium, calcium); halogen groups (e.g., chloro, bromo, or iodo); and/or oxygen-containing groups, such as ester groups.
• Example sulfurized organic compounds include dibenzyl mono- and disulfides, sulfurized isobutylene, sulfurized methyl esters of oleic acid, sulfurized alkylphenols, sulfurized dipentene, sulfurized terpenes, and sulfurized Diels-Alder adducts, and phosphosulfurized hydrocarbons such as the reaction product of phosphorus sulfide with turpentine or methyl oleate, and the like.
• the sulfurized organic compound or mixture of compounds particularly useful herein contain(s) little or no active sulfur. Active sulfur compounds include a chain of at least two connected sulfur atoms.
• the chain of sulfur atoms allows the molecule to break easily between sulfur atoms and the reactive sulfur species formed can cause corrosion of some metals, such as copper.
• Inactive sulfur compounds contain fewer than two connected sulfur atoms, i.e., each sulfur atom is connected to an atom other than sulfur. Some compounds may include both active sulfur and inactive sulfur, with some of the sulfur content being in a chain of two or more sulfur atoms while the remainder of the sulfur occurs as single sulfur atoms.
• the sulfurized organic compound or mixture of sulfurized organic compounds, where two or more such compounds are used, may have an active sulfur content, as determined at 150°C by ASTM D1662, of no more than 8 wt. %, or no more than 6 wt.
• the active sulfur is at least 0.1 wt. %, or at least 0.5 wt. %, or at least 1.0 wt. %, or at least 1.5 wt. %, or at least 1.8 wt. %, of the sulfurized organic compound or mixture of sulfurized organic compounds.
• the active sulfur content is the average (weighted mean) active sulfur content.
• the sulfurized organic compound or mixture of sulfurized organic compounds, where two or more such compounds are used may have a total sulfur content, as determined in accordance with ASTM D1552-16 (2021), “Standard Test Method for Sulfur in Petroleum Products by High Temperature Combustion and Infrared (IR) Detection or Thermal Conductivity Detection (TCD),” hereinafter D1552, of at least 1 wt. %, or at least 1.5 wt. %, or at least 2 wt. %, or no more than 18 wt. %, or no more than 15 wt.
• the total sulfur content is the average (weighted mean) sulfur content.
• the percentage, by weight, of the total sulfur (as determined by ASTM D1552) in the sulfurized organic compound that is active sulfur (as determined by ASTM D1662) may be no more than 25 wt. %, or no more than 22 wt. %, or no more than 20 wt. %, or no more than 19 wt. %, and may be as little as 0 wt.
• a ratio by weight of active sulfur to sulfur which is not active sulfur in the sulfurized organic compound may be no more than 25:75, or no more than 22:82, or no more than 20:80.
• the sulfurized organic compound(s) may be present in a sufficient amount to provide the lubricating composition with at least 0.01 wt.%, or at least 0.03 wt.%, or at least 0.05 wt.%, or up to 0.12 wt.%, or up to 0.09 wt. %, or up to 0.07 wt.% sulfur. Other sources of sulfur in the lubricating composition may provide additional amounts of sulfur. [0072] The sulfurized organic compound(s) may be present in a sufficient amount to provide the lubricating composition with no more than 0.04 wt. % of active sulfur, or no more than 0.03 wt. %, or no more than 0.025 wt.
• the sulfurized organic compound(s) are the only sources of active sulfur in the lubricating composition.
• the sulfurized organic compound may be selected from oligomeric polysulfides, alkyl polysulfides, sulfurized esters, sulfurized alpha olefins, sulfurized fats, and sulfurized soybean oil.
• Oligomeric polysulfides can be of the general form shown in Formula I: R 1 ⁇ Sx ⁇ [(C(R')vH2-v)n ⁇ Sx]p ⁇ R 2 Formula I, where R 1 and R 2 are each independently a C2-C20 alkyl, e.g., a C3, or C4 or higher alkyl, or a C16 or lower alkyl, each R' is independently a C1-C20 alkyl, or a C6 or lower alkyl; each n is independently at least 1, or at least 2, or up to 8, e.g., 3-5, such as 3 or 4; p is independently at least 1, or at least 2, or up to 8; each v is from 0-2, e.g., v is 0; and each x is independently at least 1, and in some cases may be at least 2, or up to 3, or higher, with the proviso that the limits noted above on active sulfur of the sulfurized organic compound(s) are met.
• R 1 and R 2 are each independently
• the values of x are no more than 1.
• the lubricating composition may thus be substantially free of compounds Formula (I) where x is 4 or higher. “Substantially free” in this context, means that x is 4 or higher in no more than 5%, or no more than 2%, or no more than 1%, or no more than 0.5% of the S x groups.
• the total sulfur content (ASTM D1552) of such oligomeric polysulfides and mixtures thereof may range from 5-45 wt. %, or at least 10 wt. %.
• Alkyl polysulfides can be of the general form shown in Formula II: 4760-01 R 1 ⁇ S x ⁇ R 2 Formula II, where R 1 and R 2 are each independently a C2-C20 alkyl, e.g., a C3 or higher alkyl, or a C16 or lower alkyl; and each x is independently at least 1, and in some cases may be at least 2, or up to 3, or higher, with the proviso that the limits noted above on active sulfur of the sulfurized organic compound(s) are met.
• the value of x is no more than 1.5, or no more than 1.2, on average, and that the lubricating composition is substantially free of compounds of Formula II where x is 4 or higher.
• the total sulfur content (ASTM D1552) of such alkyl polysulfides and mixtures thereof may range from 5-20 wt. %, or at least 10 wt. %.
• the active sulfur content (ASTM D1662) of such alkyl polysulfides and mixtures thereof may range from 0.5-45 wt. %, or up to 10 wt. %, or up to 9 wt. %, or up to 5 wt. %.
• the molecular weight may range from 200 to 2000 Dalton.
• R 3 , R 4 , and R 5 are each independently a C8 or higher alkyl or alkenyl group, or a C10 or higher alkyl or alkenyl group, or up to a C30 or up to a C24 alkyl or alkenyl group; and wherein at least one of R 3 , R 4 , and R 5 is linked to a sulfur atom of a sulfur-containing moiety, intermediate ends of the alkyl group.
• the total sulfur content (ASTM D1552) of the sulfurized triglyceride according to Formula IV may be at least 5 wt. %, or at least 7 wt. %, or up to 15 wt. %, or up to 12 wt. %. 4760-01 [0082]
• the active sulfur (ASTM D1662) of the sulfurized esters or mixture thereof may be less than 5 wt. %, e.g., from 3 – 4 wt. %.
• sulfurized esters include sulfurized cycloaliphatic dialkylesters and dialkenyl esters of the general form shown in Formula V: Formula V, where each of R 13 and R 14 is independently a C2 or higher alkyl group, such as a C3 or higher, or C4 or higher, or up to C10, or up to C6 alkyl or alkenyl group, e.g., a linear C4 alkyl group; and x is as described above, e.g., x is 1 or 2.
• the sulfur content of the sulfurized cycloaliphatic diester(s) may be at least 5 wt. % or at least 10 wt. % or up to 15 wt.
• Example sulfurized organic compounds include sulfurized olefins (sulfurized alkenes), which can be obtained by reacting a sulfurizing agent with an alkene, such as isobutylene, in the presence of a catalyst.
• Sulfurizing agents include elemental sulfur, hydrogen sulfide, sulfur halide, sodium sulfide, and a mixture of hydrogen sulfide and sulfur or sulfur dioxide.
• the amount of sulfurizing agent employed may be calculated based on the total olefinic unsaturation of the mixture. For example, 0.5 to 1.2 moles of sulfur are employed per mole of olefinic bonds.
• the olefinic compound may contain from 2 to 50 carbon atoms.
• Example sulfurized olefins can be obtained from isobutylene, sulfur and hydrogen sulfide, by catalytic processes using solid catalysts such as 4760-01 those described in U.S. Pat. Nos.
• 6,472,354B2 and 4,876,389A by reacting a mercaptan and sulfur in the presence of a basic catalyst. They can also be produced by a two-step process, as described in U.S. Pat. No. 4,937,385A, which includes synthesizing a mercaptan from an alkene and H 2 S in the presence of a solid catalyst and then bringing the mercaptan with sulfur and another heterogeneous catalyst together to form the sulfurized olefin. [0087] A sulfurized olefin as illustrated in Formula IV can be prepared as described in U.S. Pat. No. 4,957,651.
• the method employs a cosulfurized mixture of two or more reactants selected from (1) at least one fatty acid ester of a polyhydric alcohol, (2) at least one fatty acid, (3) at least one olefin, and (4) at least one fatty acid ester of a monohydric alcohol.
• Reactant (3), the olefin component includes at least one olefin.
• the olefin may be an aliphatic olefin, containing 4 to 40 carbon atoms, such as from 8 to 36 or 12 to 18 carbon atoms. Terminal olefins, or alpha-olefins, are particularly suitable, especially those having from 12 to 20 carbon atoms.
• a sulfurized organic compound as illustrated in Formula V can be the reaction product of a sulfurizing agent and at least one Diels-Alder adduct, in a molar ratio of at least 0.75:1.
• the molar ratio of sulfur source to Diels- Alder adduct may be from 0.75:1 to 1:1.2.
• the Diels-Alder adducts can be prepared from dienophiles having at least one carboxylic ester group represented by —C(O)O—R o , where R o is the residue of a saturated aliphatic alcohol of up to 40 carbon atoms, the aliphatic alcohol from which —Ro is derived being a mono or polyhydric alcohol, which may be selected from alkylene glycols, alkanols, alkoxy-substituted alkanols, ethanol, ethoxyethanol, propanol, butanol, beta-diethylamino-ethanol, dodecyl alcohol, diethylene glycol, tripropylene glycol, tetrabutylene glycol, hexanol, octanol, isooctyl alcohol and mixtures thereof.
• R o is the residue of a saturated aliphatic alcohol of up to 40 carbon atoms
• —C(O)O—Ro groups Generally, not more than two —C(O)O—Ro groups will be present, and in one embodiment, only one — C(O)O—Ro group.
• Such materials can also be described as cyclohexene compounds bearing ester substituents.
• An example sulfurized organic compound of this type is sulfurized 4-carbobutoxy cyclohexene.
• This and 4760-01 other sulfurized organic compounds can be further treated with other materials such as an aryl phosphate, e.g., triphenyl phosphite.
• the sulfurization reaction may be affected at an elevated temperature, e.g., 50-350° C or 100-200° C, with efficient agitation and often in an inert atmosphere such as nitrogen, optionally in the presence of an inert solvent.
• Performance additives i) Dispersants
• Dispersants include succinimide dispersants, Mannich dispersants, succinamide dispersants, and polyolefin succinic acid esters, amides, and ester-amides, and mixtures thereof.
• the dispersant includes at least one succinimide dispersant.
• the dispersant may be an N-substituted long chain alkenyl succinimide.
• An example of an N-substituted long chain alkenyl succinimide is polyisobutylene succinimide.
• the polyisobutylene from which polyisobutylene succinic anhydride is derived has a number average molecular weight Mn of at least 300, or at least 350, or at least 500, or at least 550, or at least 750, or at least 1000, and can be up to 5000, or up to 3000, or up to 2500.
• Such succinimides can be formed, for example, from high vinylidene polyisobutylene and maleic anhydride.
• the succinimide dispersant is a polyisobutylene succinimide dispersant derived from an 1800 to 2200 M n polyisobutylene, which includes 0.80-1.0 wt. % nitrogen.
• the dispersant may be a polyolefin succinic acid ester, amide, or ester-amide.
• a polyolefin succinic acid ester-amide may be a polyisobutylene succinic acid reacted with an alcohol (such as 4760-01 pentaerythritol) and a polyamine.
• Example polyolefin succinic acid esters include polyisobutylene succinic acid esters of pentaerythritol and mixture thereof.
• the exemplary dispersants may also be post-treated by conventional methods by a reaction with any of a variety of agents.
• boron compounds such as boric acid
• urea such as urea
• thiourea dimercaptothiadiazoles
• carbon disulfide aldehydes
• ketones such as carboxylic acids, such as terephthalic acid, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds.
• carboxylic acids such as terephthalic acid, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds.
• the post-treated dispersant is borated.
• the post-treated dispersant is reacted with dimercaptothiadiazoles.
• the post-treated dispersant is reacted with phosphoric or phosphorous acid.
• the post-treated dispersant is reacted with terephthalic acid and boric acid (as described, for example, in U.S. Pub. No.20090054278A1), which may be derived from an aliphatic polyamine, or mixtures thereof.
• the aliphatic polyamine may be an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or a mixture thereof.
• the aliphatic polyamine may be an ethylenepolyamine.
• the aliphatic polyamine may be chosen from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.
• the lubricating composition may include, in total, at least 0.01 wt. %, or at least 0.1 wt. %, or at least 0.2 wt. %, or at least 0.5 wt. %, or at least 1 wt. %, or at least 1.5 wt. %, or at least 2 wt. % or at least 3 wt. % dispersant, and in some embodiments, up to 15 wt. %, or up to 10 wt. %, or up to 8 wt.
• the lubricating composition includes at least 0.2 wt. %, or at least 0.5 wt. %, or at least 1.0 wt. %, or up to 7.0 wt. %, or up to 4760-01 6.0 wt. of a succinimide dispersant, which may be borated, or otherwise post- treated.
• the lubricating composition optionally further includes at least one detergent.
• a detergent is an additive that reduces formation of deposits on lubricated surfaces, for example high-temperature varnish and lacquer deposits on piston surfaces in engines.
• Exemplary detergents useful herein include metal-containing detergents, which may be neutral or overbased.
• the metal of the metal-containing detergent may be zinc, sodium, calcium, barium, or magnesium.
• the metal-containing detergent may be chosen from sulfonates, non-sulfur containing phenates, sulfur containing phenates, salixarates, salicylates, and mixtures thereof, or borated equivalents thereof.
• the metal-containing detergent may be borated with a borating agent such as boric acid.
• the metal-containing detergent may also include “hybrid” detergents formed with mixed surfactant systems including phenate and/or sulfonate components, e.g., phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, as described, for example, in U.S. Pat. Nos.6,429,178; 6,429,179; 6,153,565; and 6,281,179.
• phenate/salicylates e.g., phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, sulfonates/phenates/salicylates, as described, for example, in U.S. Pat. Nos.6,429,178; 6,429,179; 6,153,565; and 6,281,179.
• Example overbased metal-containing detergents include zinc, sodium, calcium, and magnesium salts of sulfonates, phenates (including sulfur-containing and non-sulfur containing phenates), salixarates, and hydroxybenzoates, such as salicylates, which may be hydrocarbyl substituted.
• Example sulfonate detergents include linear and branched alkylbenzene sulfonate detergents, and mixtures thereof, which may have a 4760-01 metal ratio of at least 8, as described, for example, in U.S. Pub. No. 2005065045.
• Linear alkyl benzenes may have the benzene ring attached anywhere on the linear chain, usually at the 2, 3, or 4 position, or be mixtures thereof.
• the alkylbenzene sulfonate detergent may be a branched alkylbenzene sulfonate, a linear alkylbenzene sulfonate, or a mixture thereof.
• the sulfonate detergent may be a metal salt of one or more oil-soluble alkyl toluene sulfonate compounds, as disclosed in U.S. Pub. No. 20080119378 A1.
• hydrocarbyl substituted hydroxybenzoate detergents include neutral and overbased alkaline earth metal C10 to C40 hydrocarbyl substituted hydroxybenzoates, in particular C10 to C40 hydrocarbyl substituted salicylates, as described, for example, in U.S. Pub.
• the detergent may include at one or more of an overbased calcium hydrocarbyl-substituted hydroxybenzoate detergent (e.g., a calcium salicylate detergent), an overbased calcium sulfonate detergent, and a magnesium sulfonate detergent.
• the calcium salicylate detergent may be present in sufficient amount to provide the lubricating composition with at least 0.02 wt. % Ca, such at least 0.04 wt. %, or up to 0.3 wt. % or up to 0.2 wt.%, or up to 0.15 wt. % Ca.
• the overbased calcium sulfonate detergent may be present in sufficient amount to provide at least 0.02 wt.
• the magnesium sulfonate detergent may neutral or overbased, such as an overbased sulfonate detergent having a metal ratio of 12 to 20, or 12 to 18, or 20 to 30, or 22 to 25.
• the magnesium sulfonate detergent may be present in sufficient amount to provide at least 0.01 wt. % Mg, such at least 0.02 wt. %, or up to 0.1 wt.%, or up to 0.06 wt. % Mg in the lubricating composition.
• the lubricating composition includes, in total, at least 0.1 wt. %, or at least 0.2 wt. %, or at least 0.25 wt. %, or at least 0.4 wt. 4760-01 %, or up to 3.0 wt. %, or up to 2.0 wt. %, or up to 1.5 wt. %, or up to 1.25 wt.
• the lubricating composition may further include one or more other performance additives, as follows: iii. Anti-wear Agents [0107]
• the lubricating composition optionally further includes at least one antiwear agent, other than the sulfurized organic compound.
• Suitable antiwear agents suitable for use herein include metal dihydrocarbyldithiophosphates (such as zinc dialkyldithiophosphates (ZDDPs)), titanium compounds, tartrates, tartrimides, oil soluble amine salts of phosphorus compounds, phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds, such as thiocarbamate esters, thiocarbamate amides, thiocarbamic ethers, alkylene-coupled thiocarbamates, and bis(S-alkyldithiocarbamyl) disulfides.
• ZDDPs zinc dialkyldithiophosphates
• the antiwear agent includes a zinc dialkyldithiophosphate.
• the alkyl groups of the dialkyldithiophosphate may be linear or branched and may contain 2 to 20 carbon atoms, provided that the total number of carbons is sufficient to make the zinc dialkyldithiophosphate oil soluble.
• ZDDPs zinc dialkyldithiophosphates
• ZDDPs zinc dialkyldithiophosphates
• ZDDPs zinc dialkyldithiophosphates
• ZDDPs zinc dialkyldithiophosphates
• ZDDPs prepared from mixed alcohols such as methylpropyl and amyl alcohols, 2- ethylhexyl and isopropyl alcohols, 4-methyl-2-p
• the ZDDP is at least 0.1 wt. % or at least 0.25 wt. %, or at least 0.5 wt. %, or up to 5 wt. %, or up to 4 wt. %, or up to 3 wt. % of the lubricating composition. 4760-01 [0110] In one embodiment, the ZDDP is present in sufficient amount to provide at least 0.03 wt. % or at least 0.06 wt. %, or up to 0.5 wt. % or up to 0.1 wt. % Zn in the lubricating composition.
• the antiwear agent may, in another embodiment, include a tartrate or tartrimide, as described in U.S. Pub. Nos. 2006/0079413; 2006/0183647; and 2010/0081592.
• the tartrate or tartrimide may contain alkyl-ester groups, where the sum of carbon atoms on the alkyl groups is at least 8.
• the antiwear agent may, in one embodiment, include a citrate as disclosed in U.S. Pub. No. 20050198894.
• the lubricating composition is free or substantially free of metal-containing antiwear agents. In other embodiments, the lubricating composition is free or substantially free of phosphorus- containing antiwear agents.
• phosphorus-containing antiwear agents are absent or, where present, are in an amount to provide the lubricating composition with no more than 0.8 wt. % phosphorus, or no more than 0.15 wt. % phosphorus.
• C3/6 mixed secondary ZDDP’s may be present at up to 1.2 wt. %, or up to 1 wt. %, or up to 0.5 wt. %.
• the lubricating composition may include at least 0.01 wt. %, or at least 0.1 wt. %, or at least 0.25 wt. %, or at least 0. 5 wt.
• the lubricating composition may include an extreme pressure agent in addition to the sulfurized organic compound that is low in active sulfur.
• non-sulfur EP agents include chlorinated wax; phosphorus esters, such as di-hydrocarbon and tri-hydrocarbon phosphites, e.g., dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite and polypropylene substituted phenol phosphite; and barium heptylphenol diacid; amine salts of alkyl and dialkylphosphoric acids and their derivatives including, for example, the amine salt of a reaction product of a 4760-01 dialkyldithiophosphoric acid with propylene oxide and subsequently followed by a further reaction with P2O5; and mixtures thereof.
• phosphorus esters such as di-hydrocarbon and tri-hydrocarbon
• the lubricating composition may include at least 0.01 wt. %, or at least 0.1 wt. %, or at least 0.5 wt. % extreme pressure agent, and in some embodiments, up to 3 wt. %, or up to 1.5 wt. %, or up to 0.9 wt. % of the extreme pressure agent(s).
• v. Foam Inhibitors The lubricating composition may include a foam inhibitor.
• Foam inhibitors that may be useful in the lubricant composition include polysiloxanes; copolymers of ethyl acrylate and 2-ethylhexylacrylate and optionally vinyl acetate; demulsifiers including fluorinated polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers.
• the lubricating composition may include at least 0.005 wt. %, or at least 0.08 wt. % of foam inhibitor(s), and in some embodiments, up to 3 wt. %, or up to 1.5 wt. %, or up to 0.4 wt.
• the lubricating composition may include a viscosity modifier.
• Viscosity modifiers also sometimes referred to as viscosity index improvers or viscosity improvers
• useful in the lubricant composition are usually polymers, including polyisobutenes, polymethacrylates (PMA) and polymethacrylic acid esters, diene polymers, polyalkylstyrenes, esterified styrene-maleic anhydride copolymers, hydrogenated alkenylarene- conjugated diene copolymers, such as styrene-butadiene copolymer resins (SBRs), and polyolefins also referred to as olefin copolymer or OCP.
• SBRs styrene-butadiene copolymer resins
• PMAs are prepared from mixtures of methacrylate monomers having different alkyl groups.
• the alkyl groups may be either straight chain or branched chain groups containing from 1 to 18 carbon atoms.
• Most PMAs are viscosity modifiers as well as pour point depressants.
• the viscosity 4760-01 modifier includes a styrene-butadiene resin.
• the viscosity modifier includes a polyolefin comprising ethylene and one or more higher olefin, such as propylene.
• the viscosity modifier includes one or more dispersant viscosity modifiers (DVMs). DVMs provide both dispersancy and viscosity modification.
• DVMs dispersant viscosity modifiers
• Example DVMs are made from polymers such as an olefin polymer (e.g., ethylene propylene copolymer) and/or vinyl aromatic polymers (e.g., polystyrene) that have been radically grafted with an ethylenically unsaturated carboxylic acid material, such as maleic anhydride, which is functionalized with one or more amines and/ or a pendent functional group which has sulfonate functionality.
• DVMs of this type are disclosed, for example, in U.S. Pat. Nos. 4,863,623; 5,264,140; 5,409,623; 6,107,257; 6,107,258; 6,117,825; U.S. Pub. Nos.
• the lubricating composition may include at least 0.01 wt. %, or at least 0.1 wt. %, or at least 0.2 wt. %, or at least 0.4 wt. % of viscosity modifier (including dispersant viscosity modifiers) and in some embodiments, up to 10 wt. %, or up 5 wt. %, or up to 4 wt. %, or up to 2 wt. % of such viscosity modifiers. In one embodiment, the lubricating composition includes at least 0.2 wt.
• the lubricating composition may include a corrosion inhibitor.
• Corrosion inhibitors/metal deactivators that may be useful in the exemplary lubricating composition include fatty amines, octylamine octanoate, condensation products of dodecenyl succinic acid or anhydride, and a fatty acid such as oleic acid with a polyamine, derivatives of benzotriazoles (e.g., tolyltriazole), 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles and 2-alkyldithiobenzothiazoles. 4760-01 [0123] When present, the lubricating composition may include at least 0.005 wt. %, or at least 0.01 wt.
• the lubricating composition may include a pour point depressant.
• Pour point depressants that may be useful in the exemplary lubricating composition include polyalphaolefins, esters of maleic anhydride-styrene copolymers, polymethacrylates, polyacrylates, and polyacrylamides.
• the pour point depressant is a maleic anhydride-styrene copolymer.
• the lubricating composition may include at least 0.005 wt. %, or at least 0.01 wt. %, or at least 0.1 wt. %, or at least 0.15 wt. % pour point depressant(s), and in some embodiments, up to 5 wt. %, or up to 2 wt. %, or up to 1 wt. % pour point depressant(s). In some embodiments, no pour point depressants are used.
• Friction Modifiers [0126]
• the lubricating composition may include a friction modifier.
• Friction modifiers that may be useful in the exemplary lubricating composition include fatty acid derivatives such as amines, esters, epoxides, fatty imidazolines, condensation products of carboxylic acids and polyalkylene-polyamines and amine salts of alkylphosphoric acids.
• the friction modifier may be an ash-free friction modifier.
• Such friction modifiers are those which typically do not produce any sulfated ash when subjected to the conditions of ASTM D874- 13a (2016).
• An additive is referred to as “non-metal containing” if it does not contribute metal content to the lubricant composition.
• the term “fatty alkyl” or “fatty” in relation to friction modifiers means a carbon chain having 8 to 30 carbon atoms, typically a straight carbon chain.
• the hydrocarbyl groups R 23 , R 24 , and R 25 may be linear or predominantly linear alkyl groups.
• the ash-free friction modifier is a fatty ester, amide, or imide of various hydroxy-carboxylic acids, such as tartaric acid, malic acid lactic acid, glycolic acid, and mandelic acid.
• suitable materials include tartaric acid di(2-ethylhexyl) ester (i.e., di(2- ethylhexyl)tartrate), di(C 8 -C 10 )tartrate, di(C 12-15 )tartrate, dioleyltartrate, oleyl tartrimide, and oleyl maleimide.
• the ash-free friction modifier may be chosen from long chain fatty acid derivatives of amines, fatty esters, or fatty epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; fatty alkyl tartramides; fatty phosphonates; fatty phosphites; borated phospholipids, borated fatty epoxides; glycerol esters; borated glycerol esters; fatty amines; alkoxylated 4760-01 fatty amines; borated alkoxylated fatty amines; hydroxyl and polyhydroxy fatty amines including tertiary hydroxy fatty amines; hydroxy alkyl amides; metal salts of fatty acids; metal salts of alkyl salicylates; fatty ox
• Friction modifiers may also encompass materials such as sulfurized fatty compounds and olefins, sunflower oil or soybean oil monoester of a polyol and an aliphatic carboxylic acid.
• the friction modifier may be a long chain fatty acid ester.
• the long chain fatty acid ester may be a mono-ester and in another embodiment the long chain fatty acid ester may be a triglyceride.
• the amount of the ash-free friction modifier in a lubricant may be 0.1 to 3 percent by weight (or 0.12 to 1.2 or 0.15 to 0.8 percent by weight).
• the material may also be present in a concentrate, alone or with other additives and with a lesser amount of oil.
• the amount of material may be two to ten times the above concentration amounts.
• the lubricating composition is free or substantially free of friction modifiers, e.g., contains no more than 0.001 wt. % of friction modifiers.
• the friction modifier(s) may be at least 0.01%, or at least 0.05 wt. %, or at least 0.1 wt. %, or up to 6 wt. %, or up to 4 wt. %, or up to 2 wt. % of the lubricating composition.
• Molybdenum compounds [0134] In one embodiment, the lubricating composition contains a molybdenum compound.
• Molybdenum compounds may serve in various functions in the lubricating composition, such as antiwear agents, friction modifiers, and antioxidants. [0135] For ease of description, the amounts of molybdenum compounds are not included in the amounts of antiwear agents, friction modifiers, and antioxidants, described elsewhere. 4760-01 [0136] Molybdenum-containing antiwear agents and antioxidants include molybdenum hydrocarbyldithiocarbamate, molybdenum hydrocarbyldithiocarbamate dimer complexes, and other compounds containing molybdenum and sulfur, as described, for example, in U.S. Pat. No.4,285,822.
• molybdenum-containing materials include molybdenum dihydrocarbyldithio-phosphates; molybdenum-amine compounds, as described in U.S. Pat. No.6,329,327; organomolybdenum compounds made from the reaction of a molybdenum source, fatty oil, and a diamine, as described in U.S. Pat. No. 6,914,037; and trinuclear molybdenum-sulfur complexes, as described in U.S. Pat. No. 6,232,276.
• Other molybdenum compounds are disclosed in U.S. Pub. No.20080280795.
• a primary, secondary or tertiary amine represented by the formula NR 29 R 30 R 31 , where each
• Suitable amines include monoalkyl (or alkenyl) amines such as tetradecylamine, stearylamine, oleylamine, beef tallow alkylamine, hardened beef tallow alkylamine, and soybean oil alkylamine; dialkyl(or alkenyl)amines such as N-tetradecylmethylamine, N- pentadecylmethylamine, N-hexadecylmethylamine, N-stearylmethylamine, N- 4760-01 oleylmethylamine, N-dodecyl(di)methylamine, N-beef tallow alkyl methylamine, N-hardened beef tallow alkyl methylamine, N-soybean oil alkyl methylamine, ditetradecylamine, dipentadecylamine, dihexadecylamine, distearylamine, dioleylamine, N-cocoyl methylamine,
• Suitable secondary amines have two alkyl (or alkenyl) groups with 14 to 18 carbon atoms.
• Examples of the compound containing the hexavalent molybdenum atom include molybdenum trioxides or hydrates thereof (MoO 3 ⁇ nH 2 O), molybdenum acid (H 2 MoO 4 ), alkali metal molybdates (Q 2 MoO 4 ) wherein Q represents an alkali metal such as sodium and potassium, ammonium molybdates (e.g., (NH4)2MoO4 or heptamolybdate (NH4)6[Mo7O24] ⁇ 4H2O), MoOCl4, MoO2Cl2, MoO2Br2, Mo2O3Cl6 and the like.
• the lubricating composition comprises a molybdenum amine compound.
• Other organomolybdenum compounds may be the reaction products of fatty oils, mono-alkylated alkylene diamines and a molybdenum source. Materials of this sort are generally made in two steps, a first step involving the preparation of an aminoamide/glyceride mixture at high temperature, and a second step involving incorporation of the molybdenum.
• fatty oils examples include cottonseed oil, groundnut oil, coconut oil, linseed oil, palm kernel oil, olive oil, corn oil, palm oil, castor oil, rapeseed oil (low or high erucic acids), soyabean oil, sunflower oil, herring oil, sardine oil, and tallow. These fatty oils are generally known as glyceryl esters of fatty acids, triacylglycerols or triglycerides.
• Examples of mono-alkylated alkylene diamines that may be used include methylaminopropylamine, methylaminoethylamine, butylaminopropylamine, butylaminoethylamine, octylaminopropylamine, octylaminoethylamine, dodecylaminopropylamine, dodecylaminoethylamine, hexadecylaminopropylamine, hexadecylaminoethylamine, octadecylaminopropylamine, octadecylaminoethylamine, isopropyloxypropyl- 1,3-diaminopropane, and octyloxypropyl-1,3-diaminopropane.
• Mono- alkylated alkylene diamines derived from fatty acids may also be used. Examples include N-coco alkyl-1,3-propanediamine (Duomeen®C), N-tall oil alkyl-1,3-propanediamine (Duomeen®T) and N-oleyl-1,3-propanediamine (Duomeen®O), all commercially available from Akzo Nobel.
• Sources of molybdenum for incorporation into the fatty oil/diamine complex are generally oxygen-containing molybdenum compounds include, similar to those above, ammonium molybdates, sodium molybdate, molybdenum oxides and mixtures thereof.
• molybdenum trioxide MoO3
• Nitrogen-containing molybdenum compounds which are commercially available include, for example, Sakura-lube® 710 available from Adeka which is a molybdenum amine compound, and Molyvan® 855, available from R.T. Vanderbilt.
• the nitrogen-containing molybdenum compound, where used, may be at least 0.001 wt. %, or at least 0.002 wt. % of the lubricating composition or up to 2 wt. %, or up to 1.0 wt. % of the composition.
• the molybdenum compound may provide the lubricant composition at least 5 ppm, or at least 10 ppm, 5 ppm, or up to 300 ppm, or up to 800 ppm of molybdenum.
• the lubricating composition contains less than 800 ppm molybdenum, or less than 400 ppm, or less than 150 ppm, or less than 100 ppm, or less than 80 ppm, or less than 50 ppm, or less than 20 ppm, or less than 2 ppm, or less than 1 ppm molybdenum, or 0 ppm.
• the molybdenum compound does not contain dithiocarbamate moieties or ligands. 4760-01 [0147]
• the lubricating composition may include a molybdenum compound in an amount to provide 40 to 1200 parts per million by weight molybdenum to the composition, or at least 50, or at least 60, or at least 100, or at least 300, or up to 1000, or up to 800, or up to 500, or up to 400, or up to 250, or up to 200 parts per million, by weight.
• the actual amount of the compound will depend in part on the nature and formula weight of the anion or complexing agent associated with the molybdenum, in a way that may be readily calculated.
• the molybdenum compound is present in the lubricating composition in an amount of 0 to 1.1 wt. %, or at least 0.01 wt. %, or at least 0.02 wt. %, or at least 0.03 wt. %, or at least 0.04 wt. %, or at least 0.07 wt. %, or up to 0.5 wt. %, or up to 0.35 wt. %, or up to 0.2 wt. %, or up to 0.18 wt. %.
• the lubricating composition may contain a deposit control additive or additives, which may be selected from an alkylaryl sulfonate, amine oxide, carboxylated alcohol ethoxylate, ethoxylated amine, ethoxylated amide, glycerol ester, glycol ester, imidazoline, lecithin, lecithin derivative, lignin, monoglyceride, monoglyceride derivative, olefin sulfonate, phosphate ester, phosphate ester derivative, propoxylated fatty acid, ethoxylated fatty acid, propoxylated alcohol or alkyl phenol, sucrose ester, sulfonate of dodecyl or tridecyl benzene, naphthalene sulfonate, petroleum sulfonate, tridecyl or dodecyl benzene sulfonic acid, sulfo
• alkoxylated hydrocarbyl-substituted phenolic compounds such as propoxylated polyisobutylene phenol, as described in WO2014/193543A1 may be used.
• Additional deposit control additives may be at least 0.01%, or at least 0.10 wt. %, or at least 0.5 wt. %, or up to 6 wt. %, or up to 3.0 wt.%.
• no deposit control additives are used.
• Demulsifiers useful herein include trialkyl phosphates, and various polymers and copolymers of ethylene glycol, ethylene oxide, propylene oxide, and mixtures thereof.
• the demulsifier, where present, may be at least 0.001%, or at least 0.01 wt. %, or up to 0.10 wt. %, of the lubricating composition.
• Seal Swell Agents [0153] Seal swell agents useful herein include sulfolene derivatives such as Exxon Necton-37TM (FN 1380) and Exxon Mineral Seal OilTM (FN 3200).
• Example Lubricating Compositions [0154] An engine lubricant may have a composition as illustrated in Table 1.
• Example Lubricating Compositions 4760-01 Use of the Lubricating Composition includes use as a cylinder lubricant for an internal combustion engine, e.g., for a passenger car, heavy, medium or light duty diesel vehicle, small engines such as motorcycle and tert-stroke oil engines, and 2-stroke marine diesel engines, but may also find use as an engine oil as a driveline lubricant, including gear and automatic transmission oils, and for other industrial oils, such as hydraulic lubricants.
• an internal combustion engine e.g., for a passenger car, heavy, medium or light duty diesel vehicle, small engines such as motorcycle and tert-stroke oil engines, and 2-stroke marine diesel engines, but may also find use as an engine oil as a driveline lubricant, including gear and automatic transmission oils, and for other industrial oils, such as hydraulic lubricants.
• An exemplary method of lubricating a mechanical device includes supplying the exemplary lubricating composition to the device.
• the lubricating composition is added to the lubricating system of an internal combustion engine, which then delivers the lubricating composition to the cylinder of the engine, during its operation, where minor amounts may be combusted with the fuel.
• the internal combustion engine may be a diesel-fueled engine, a gasoline-fueled engine, a natural gas-fueled engine, a mixed gasoline/alcohol-fueled engine, or a biodiesel-fueled engine.
• the internal combustion engine may be a 2-stroke or 4-stroke engine.
• the engine is a heavy-duty diesel engine.
• the lubricating composition may be suitable for use as a cylinder lubricant irrespective of the phosphorus, or sulfated ash (ASTM D874-13a (2016)) content of the fuel.
• ASTM D874-13a ASTM D874-13a (2018)
• the following examples illustrate preparation and evaluation of example lubricating compositions. 4760-01 Examples [0162] The following materials were obtained: [0163] Oils: 4-cSt Grp III Base oil, hydrotreated heavy paraffinic petroleum distillates, sold as Yubase 4, obtained from SK Lubricants Co., Ltd.
• 6-cSt Grp III Base oil, hydrotreated heavy paraffinic petroleum distillates, sold as Yubase 6, obtained from SK Lubricants Co., Ltd. Diluent Oil, Grp III.
• Antioxidants Hindered Phenolic Antioxidant (HPAO), IrganoxTM L 135, obtained from BASF (3,5-dibutyl-4-hydroxyphenyl) propionate).
• SDPA Diphenyl Amine
• Sulfurized Organic Compounds [0167] Sulfurized organic compounds denoted A-F were obtained from The Lubrizol Corporation, as shown in Table 2. Active Sulfur is determined by ASTM D1662. Total sulfur is determined by ASTM D1552.
• Dispersants [0169] Dispersants denoted A-F were obtained from The Lubrizol Corporation, as shown in Table 3. TABLE 3: Dispersants [0170] Detergents Overbased Calcium Salicylate Detergent with a TBN of ⁇ 300, obtained from Wuxi. Magnesium sulfonate detergent, with a TBN of ⁇ 690, obtained from The Lubrizol Corporation. Overbased calcium sulfonate detergent, with a TBN of ⁇ 170, obtained from The Lubrizol Corporation. [0171] Viscosity Modifiers Hydrogenated Styrene-b-butadiene copolymer resin viscosity modifier, LZ 7418A, obtained from The Lubrizol Corporation.
• Aromatic dispersant viscosity modifier A reaction product of an olefin polymer comprising a carboxylic acid functionality with 3-nitroaniline
• Aromatic dispersant viscosity modifier B amine functionalized aromatic maleic anhydride-styrene copolymer
• Other Additives Secondary ZDDP a combination of primary and secondary ZDDPs derived from C3 and C6 alcohols.
• Pour point depressant maleic anhydride/styrene copolymer ester, obtained from The Lubrizol Corporation.
• Foam inhibitor mixture of polydimethylsiloxanes.
• Propoxylated polyisobutylene phenol deposit control agent obtained by reaction of propylene oxide with polyisobutylene phenol and KOH as described in WO2014193543A1.
• Triazole derivative corrosion Inhibitor, IrgametTM 30 N,N-bis(2- ethylhexyl)-1-triazole-1-methyl amine, obtained from BASF.
• Lubricating Compositions suitable for use in a heavy-duty diesel engine were prepared in a Group III base oil of lubricating viscosity containing the sulfurized olefins described herein are prepared according to the formulations shown in Tables 3, 4, and 5. [0175] Weight % of all ingredients (except from the oil) are expressed on an actives (oil free) basis.
• Example 1 contains both a hindered phenolic antioxidant (HPAO) and a substituted diphenylamine (SDPA) antioxidant, while Example 2 has essentially the same formulation as Example 1, except that only the hindered phenolic antioxidant is used, with the amount being increased to maintain the same total amount of antioxidant.
• HPAO hindered phenolic antioxidant
• SDPA substituted diphenylamine
• a series of engine lubricants suitable for use in a heavy duty diesel engine are prepared in a Group III base oil of lubricating viscosity containing sulfurized olefin B, as described above, and aminic free antioxidants as well as polymeric viscosity modifiers, ashless succinimide dispersants, over-based detergents, antioxidants, zinc dialkyldithiophosphate (ZDDP), and other performance additives, as shown in TABLE 5.
• different amounts of the phenolic antioxidant are used.
• a series of engine lubricants suitable for use in a heavy-duty diesel engine are prepared in a Group III base oil of lubricating viscosity containing various sulfurized olefins are shown in TABLE 6. The amount of sulfurized olefin is adjusted to provide approximately the same total amount of sulfur.
• Kinematic Viscosity Kinematic viscosity at 100°C (KV_100) and at 40°C (KV_40) are measured according to ASTM D445-21e1.
• % SA % Sulfated Ash
• Viscosity Index is determined according to ASTM D2270-10 (2016), “Standard Practice for Calculating Viscosity Index from Kinematic Viscosity at 40 °C and 100 °C.”
• Apparent Viscosity is determined by the following methods: [0185] 1.
• CCS Cold Crank Simulator
• ASTM D5293-20 “Standard Test Method for Apparent Viscosity of Engine Oils and Base Stocks Between –10 °C and –35 °C Using Cold-Cranking Simulator,” in cP.
• ASTM D5481-21 “Standard Test Method for Measuring Apparent Viscosity at High-Temperature and High-Shear Rate by Multicell Capillary Viscometer,” (HTHS), in cP.
• CEC L-36-90 “High shear high temperature viscosity measurement,” 2019, for some examples.
• Oxidation properties are determined using the Renault Catalyst Oxidation Test (TOC-4) Procedure by BMW (RNES-B-00023). This test method assesses the resistance against oxidation of an engine lubricating oil composition and the method simulates changes in engine oils subjected to harsh conditions of increased load and regime, and hot casing.
• TOC-4 procedure four tubes each containing 150 g of oil containing anhydrous iron (III) acetylacetonate catalyst (360 ppm iron) are heated in a test cell at 170°C for 168 hours. During this time, air is blown through the oil in the tubes at a rate of 10 liters per hour.
• Samples of each oil (30 ml) are assessed for oxidative degradation after 24 hours, 120 hours, 136 hours, and 168 hours; the samples after 120 hours providing the average value for the TOC-4 procedure.
• a lower peak area increase indicates lower oxidative degradation.
• a peak area increase after 120 hours must be less than 400.
• TAN Total Acid Number
• ASTM D664-18e2 Standard Test Method for Acid Number of Petroleum Products by Potentiometric Titration.
• Oxidation Resistance determined by the Kinematic Viscosity Change at 170°C for the following: [0192] 1. Relative Change in KV_40 at 120hrs, as compared with fresh lubricating composition, % ( ⁇ 200 to meet the Renault RN-17 Specification). [0193] 2. Relative Change in KV_100 at a specified time (e.g., 120 hrs or 260 hrs), as compared with fresh lubricating composition, %.
• Oxidation stability (Volvo T-13 test) is determined in accordance with ASTM D8048-21ae1, “Standard Test Method for Evaluation of Diesel Engine Oils in T-13 Diesel Engine,” using a 2010 Volvo/Mack D13/D8, 505 Brake Horsepower, 13L, in-line 6-cylinder diesel engine with 6 electronic unit injectors, variable geometry turbocharger, with cooled exhaust gas recirculation (EGR). The test is operated for 360 hrs at 1500 RPM steady state conditions at a given fuel flow, producing approximately 2200 N m and 130°C oil temperature with 19-20% EGR to evaluate the oxidative stability of engine oils.
• Oxidation Induction Time Thin film antioxidancy is measured as the OIT, in minutes, which is determined according to CEC L-85-99: “Oxidative Stability of Lubricants by PDSC (Pressure Differential Scanning Calorimetry).” This represents the time after which oxygen uptake, as measured by a pressure drop, ceases. The longer the OIT, the better the antioxidancy.
• Deposit Control Deposit control is evaluated using the MHT TEOST and Komatsu Hot Tube Tests, as follows.
• MHT TEOST is measured according to ASTM D7097-19, “Standard Test Method for Determination of Moderately High Temperature Piston 4760-01 Deposits by Thermo-Oxidation Engine Oil Simulation Test—TEOST MHT.” The total deposits are reported in mg.
• Komatsu Hot Tube Test (280°C), KES_07.803 In this test, glass tubes are inserted through and heated by an aluminum heater block. The sample is pumped via a syringe pump through the glass tube for 16 hours, at a flow rate of 0.31 cm 3 /hr, along with an air flow of 10 cm 3 /min.
• Corrosion properties are evaluated according to ASTM D6594- 20e1- “Standard Test Method for Evaluation of Diesel Engine Oil at 135°C” and ASTM D130-19, “Standard Test Method for Corrosiveness to Copper from Petroleum Products by Copper Strip Test.”
• the ASTM D6594 test method covers testing diesel engine lubricants to determine their tendency to corrode various metals, specifically alloys of lead and copper commonly used in cam followers and bearings.
• TABLE 7 shows results from the Volvo T-13 test for Examples 1 and 2.
• Example 13 uses a sulfurized fatty acid ester of the type described in U.S. Pat. No. 11,136,652 B1.
• Example 13 did not perform as well as Examples 8, 9, and 10, which exhibit superior oxidative performance. These three samples include active sulfur at less than 0.015 wt. % of the lubricating composition and a sulfurized olefin in which active sulfur amounts to less than 20 wt. % of the total sulfur in sulfurized olefin. [0209] The results show that relatively high levels (2wt. % to 4wt. %) of an SDPA-free phenolic antioxidant can achieve oxidation performance that previously required relying on SDPA phenolic antioxidants and also provide lower corrosion rates. [0210] Each of the documents referred to above is incorporated herein by reference.

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