Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
  • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
  • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
• • 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
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
  • C10M135/10—Sulfonic acids or derivatives 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
  • 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
  • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
  • C10M2215/064—Di- and triaryl amines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/28—Amides; Imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/046—Overbasedsulfonic acid salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
  • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
  • C10M2219/066—Thiocarbamic type compounds
  • C10M2219/068—Thiocarbamate metal salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
  • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
  • C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/12—Groups 6 or 16
• • 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
  • C10N2020/071—Branched chain compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/04—Detergent property or dispersant property
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/10—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
  • C10N2030/52—Base number [TBN]
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines

Definitions

• This disclosure relates to lubricating oil additives that disrupt oxidation and increase the useful life of lubricating oils. More particularly, this disclosure relates to lubricating oil compositions that include alkylated diphenylamine antioxidant and sulfonate detergent.
• Oxidation is a concern for in-service lubricating oils as it can cause thickening of the oil, sludge, varnish, acid number increase and corrosion. These outcomes are generally detrimental to proper operation of automotive engines and limit useful life of the lubricating oil. With continually evolving engine designs, operating conditions and oil performance expectations, oxidation continues to be an important ongoing technical challenge.
• antioxidants can also extend drain intervals, maintain viscosity, reduce deposit, reduce foam formation, protect against corrosion as well as protect the lubricating oil against high temperature.
• antioxidants there are many antioxidants that have varying degrees of effectiveness.
• Commercial lubricants are usually formulated with one or more antioxidants to protect the fluid under a wide range of conditions (e.g., temperature, time, air mixtures, pressure, etc.).
• alkylated diphenylamines are used as antioxidants.
• Widely- used alkylated diphenylamine antioxidants include nonylated (C9) diphenylamine which can be added into organic fluids such as engine oils, gear oils, hydraulic fluids, compressor oils, turbine oils, and grease.
• This disclosure relates to lubricating oil additives that disrupt oxidation and increase the useful life of lubricating oils. More particularly, this disclosure relates to compositions that include alkylated diphenylamines and sulfonate detergents.
• a lubricating oil composition comprising: a base oil; a primary antioxidant comprising alkylated diphenylamines having an alkyl group derived from propylene tetramers; and a sulfonate detergent.
• a method of improving oxidation stability of a lubricating oil comprising: supplying to an engine a lubricating oil composition comprising: a base oil; a primary antioxidant comprising alkylated diphenylamines having an alkyl group derived from propylene tetramers; and a sulfonate detergent.
• FIG. 1 illustrates a comparison of oxidative induction time of formulated oil samples as described in the Example.
• antioxidant or equivalent term (e.g., "oxidation stabilizer” or “oxidation inhibitor”) refers to a composition and its ability to resist deleterious attacks in an oxidizing environment. Antioxidants are often used in organic fluids (e.g., lubricating oil, gear oil, compressor oil, mineral oil, hydraulic fluid, etc.) to improve the oxidation stability of the organic fluid.
• organic fluids e.g., lubricating oil, gear oil, compressor oil, mineral oil, hydraulic fluid, etc.
• alkyl refers to a saturated hydrocarbon group, that can be linear, branched, cyclic, or a combination of cyclic, linear and/or branched.
• Olefin refers to a hydrocarbon that has at least one carbon- carbon double bond that is not part of an aromatic ring or ring system. Olefins may include aliphatic and aromatic, cyclic and acyclic, and/or linear and branched compounds having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system, unless specifically stated otherwise. Olefins having only one, only two, only three, etc., carbon-carbon double bonds can be identified by use of the term “mono,” “di,” “tri,” etc., within the name of the olefin. The olefins can be further identified by the position of the carbon-carbon double bond(s). Depending on the context, the term “olefin” may refer to an "olefin oligomer” or to an "olefin monomer” or both.
• An "olefin oligomer” is an oligomer made from oligomerization of "olefin monomers.”
• a “propylene oligomer” is made from the oligomerization of propylene monomers.
• propylene oligomers include propylene tetramer and propylene pentamer.
• a "propylene tetramer” is an olefin oligomer product resulting from the oligomerization of nominally 4 propylene monomers. These terms also can be used generically to describe homo-oligomers, co-oligomers, salts of oligomers, derivatives of oligomers, and the like.
• a “minor amount” or related term means less than 50 wt % of a composition, expressed in respect of the stated additive and in respect of the total weight of the composition, reckoned as active ingredient of the additive.
• a “major amount” or related term means an amount greater than 50 wt % based on the total weight of the composition.
• the present invention relates to antioxidant compositions that disrupt oxidation and increase the useful life of lubricating oils. More particularly, the present invention describes antioxidant compositions comprising a plurality of lubricant additives.
• the lubricant additives include at least one antioxidant and at least one detergent working together to provide enhanced oxidative performance.
• the enhanced performance is a result of a previously unknown synergy arising from the lubricant additive components of the present invention in lubricating oil compositions.
• Antioxidants and detergents compatible with the present invention will be described herein.
• the antioxidant composition comprises a primary antioxidant and one or more secondary antioxidants.
• the primary antioxidant of the present invention is an alkylated diphenylamine having one or more relatively long alkyl groups.
• Conventional alkylated diphenylamine antioxidants typically utilize relatively short alkyl groups. These include, for example, nonylated diphenylamine ("propylene trimer") which nominally has 9 carbons and can be formed from the oligomerization of propylene.
• the alkylated diphenylamines of the present invention have been alkylated by propylene tetramers (having nominally 12 carbons) or by a mixture comprising propylene tetramers, wherein the propylene tetramer is the predominant olefin oligomer alkylating agent.
• Propylene tetramers can be obtained by the oligomerization of 4 propylene monomers.
• propylene tetramer over propylene trimer including, but not limited to, increased oil solubility, cheaper cost, and superior stability against oxidation.
• the alkylated diphenylamine of the present invention may be present at about 0.4 wt % to about 20 wt % of the lubricating oil composition, such as from about 0.5 wt % to about 15 wt %, 0.1 wt % to about 10 wt %, 0.5 wt % to about 8 wt %, or 1 wt % to about 5 wt %.
• the propylene oligomers (i.e., propylene tetramers) of the present invention can be prepared by any compatible method known in the art.
• a process for preparing the propylene oligomers employs a liquid phosphoric acid oligomerization catalyst.
• Descriptions of liquid phosphoric acid-catalyzed propylene oligomerization process can be found in U.S. Pat. Nos. 2,592,428; 2,814,655; and 3,887,634, the relevant portions of which are hereby incorporated by reference.
• An unrefined product of oligomerization process typically includes a mixture of branched olefins having a distribution in number of carbons.
• olefin oligomers are subject to extreme conditions during the oligomerization process which results in cracking, recombination, isomerization and the like.
• Refined or processed oligomerization products typically have higher concentration of the desired product.
• the term "propylene tetramer" may not necessarily refer to a pure propylene tetramer product but a mixture of olefins or olefin oligomer products. Accordingly, the product of alkylation involving diphenylamine and propylene tetramer can have a distribution in number of carbons within the alkylated alkyl groups.
• Propylene tetramers can be obtained from the oligomerization of 4 propylene monomers.
• the propylene tetramer is a cost effective olefin to manufacture.
• As a product of oligomerization it features a highly branched chain of 10 to 15 carbons with high degree of methyl branching that imparts exceptional oil solubility and compatibility with other oil soluble lubricant additive components.
• the average carbon number can range from about 10 to about 15.
• the product of oligomerization can vary in degree of branching.
• the propylene tetramer can exhibit a total branching (i.e., sum of olefinic and aliphatic branching) ranging from 1 to 15.
• the average total branching can range from about 1 to about 15.
• the propylene tetramers of the present invention generally comprise at least 50 wt % of Cio to C15 carbon atoms. In an embodiment, the propylene tetramers contain a distribution of carbon atoms which comprise at least 60 wt % of Cio to C15 carbon atoms. In an embodiment, the propylene tetramers contain a distribution of carbon atoms which comprise at least 70 wt % of Cio to C15 carbon atoms. In an embodiment, the propylene oligomers contain a distribution of carbon atoms which comprise at least 80 wt % of Cio to C15 carbon atoms. In an embodiment, the propylene oligomers contain a distribution of carbon atoms which comprise at least 90 wt % of Cio to Ci5 carbon atoms.
• propylene oligomers employed herein may also contain a minor amount of lower molecular weight propylene oligomer(s) such as propylene trimer, as well as higher molecular weight propylene oligomer(s) such as propylene pentamer.
• the propylene tetramer of the present invention may be a mixture of olefinic hydrocarbons containing 0-1 wt % C9H18, 0-5 wt % C10H20, 0-10 wt % C11 H22, 50-90 wt % C12H24, I Q- 20 wt % C13H26, 5-15 wt % C14H28, and/or 1-10 wt % C15H30.
• the alkylated diphenylamine of the present invention can be obtained by any alkylation process compatible with the present invention.
• US 6,355,839 hereby incorporated by reference, describes the preparation of alkylated diphenylamine wherein the diphenylamine is alkylated with polyisobutylene.
• any suitable catalyst may be used.
• the alkylation of diphenylamine may proceed in the presence of a clay catalyst. Temperature of this reaction can range from 140°C to 200°C, more typically between 150°C to 190°C. In some embodiments, the temperature of the reaction ranges between 160°C to 180°C. The reaction can be carried out at a single temperature, or sequentially, at different temperatures.
• the propylene oligomer can be charged at a charge mole ratio (CMR) between 2:1 to 8:1 in relation to the diphenylamine charge. In some embodiments, the CMR is between 3:1 to 7:1 or between 4:1 and 6:1.
• the reaction product can be filtered to remove the catalyst and then distilled to remove unreacted olefin oligomers and diphenylamines.
• the use of clay as catalyst is disclosed in U.S. Pat. No. 3,452,056, which is hereby incorporated by reference.
• reaction conditions may vary significantly depending on the catalyst used. For example, reactions involving homogeneous acid catalysts may only require temperatures ranging between 75°C to 100°C.
• the alkylated diphenylamine product can have various relative amounts of mono-alkylated, di-alkylated, and/or tri- alkylated diphenylamine products. It should be apparent that for a given di- or tri- alkylated diphenylamine molecule, the two or more alkylated alkyl groups may be identical or different in accordance with this disclosure.
• the present invention employs one or more secondary antioxidants in combination with the primary antioxidant.
• the secondary antioxidant may be present at about 0.01 wt % to about 20 wt % of the lubricating oil composition, such as from about 0.05 wt % to about 15 wt %, 0.1 wt % to about 10 wt %, 0.5 wt % to about 8 wt %, or 1 wt % to about 5 wt %.
• a number of secondary antioxidants are compatible with the present invention.
• secondary antioxidants include molybdenum succinimides, dithiocarbamates and hindered phenols. These oil-soluble components are generally known.
• the mono and polysuccinimides that can be used to prepare the molybdenum complexes described herein are disclosed in numerous references and are well known in the art. Certain fundamental types of succinimides and the related materials encompassed by the term of art "succinimide" are taught in U.S. Pat. No's. 3,219,666; 3,172,892; and 3,272,746, the disclosures of which are hereby incorporated by reference.
• succinimide is understood in the art to include many of the amide, imide, and amidine species which may also be formed.
• the predominant product however is a succinimide and this term has been generally accepted as meaning the product of a reaction of an alkenyl substituted succinic acid or anhydride with a nitrogen-containing compound.
• Preferred succinimides because of their commercial availability, are those succinimides prepared from a hydrocarbyl succinic anhydride, wherein the hydrocarbyl group contains from about 24 to about 350 carbon atoms, and an ethylene amine, said ethylene amines being especially characterized by ethylene diamine, diethylene triamine, triethylene tetramine, and tetraethylene pentamine.
• Particularly preferred are those succinimides prepared from polyisobutenyl succinic anhydride of 70 to 128 carbon atoms and tetraethylene pentamine or triethylene tetramine or mixtures thereof.
• succinimide also included within the term “succinimide” are the cooligomers of a hydrocarbyl succinic acid or anhydride and a poly secondary amine containing at least one tertiary amino nitrogen in addition to two or more secondary amino groups. Ordinarily this composition has between 1,500 and 50,000 average molecular weight. A typical compound would be that prepared by reacting polyisobutenyl succinic anhydride and ethylene dipiperazine.
• Succinimides having an average molecular weight of 1000 or 1300 or 2300 and mixtures thereof are most preferred.
• Such succinimides can be post treated with boron or ethylene carbonate as known in the art.
• Suitable dithiocarbamates include, but are not limited to, dithiocarbamates wherein the metal is zinc, copper or molybdenum, ashless thiocarbamates or dithiocarbamates (i.e., essentially metal free) such as methylenebis(dialkyldithiocarbamate), ethylenebis(dialkyldithiocarbamate), and isobutyl disulfide-2, 2'-bis(dialkyldithiocarbamate) where the alkyl groups of the dialkyldithiocarbamate can preferably have from 1 to 6 carbon atoms.
• Examples of preferred ashless dithiocarbamates are methylenebis(dibutyldithiocarbamate), ethylenebis(dibutylthiocarbamate) and isobutyl disulfide-2, 2'- bis(dibutyldithiocarbamate).
• the secondary antioxidant employed in the lubricating oil of the present invention may be a sterically hindered phenol.
• the hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
• the phenol group is often further substituted with a hydrocarbyl group and/or a bridging group linking to a second aromatic group.
• Suitable hindered phenols include, but are not limited to, 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 antioxidant composition of the present invention includes one or more detergents.
• Detergents may be present at about 0.01 wt % to about 10 wt % of the lubricating oil composition, such as from about 0.05 wt % to about 8 wt %, 0.1 wt % to about 5 wt %, 0.5 wt % to about 4 wt %, or 1 wt % to about 3 wt %.
• Detergents are normally salts (e.g., overbased salts) and are single phase, homogeneous Newtonian systems characterized by a metal content in excess of that which would be present according to the stoichiometry of the metal and the particular acidic organic compound reacted with the metal.
• the detergents of the present invention include sulfonate detergents.
• Metallic detergents such as sulfonate detergents typically contain a polar head group and a hydrocarbon tail or an oleophilic group. In general, the hydrocarbon tail can range from about 3 carbons to 50 carbons in length.
• Sulfonate detergents may be natural or synthesized.
• the detergent may be neutral or overbased.
• Overbased detergents may range in degree of overbasing (as measured by ASTM D2896).
• Compatible overbased sulfonates include low overbased, medium overbased, high overbased, and high high overbased sulfonate detergents. In some embodiments, the detergent may be borated.
• sulfonate detergents include alkyl aryl sulfonates and the like. Specific examples include magnesium alkyltoluene sulfonates which are described in US20110136711. Other examples include calcium alkyl aryl sulfonates, calcium alkyltoluene sulfonates, and magnesium alkylbenzene sulfonates.
• Metals of detergents can also include alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium.
• alkali or alkaline earth metals e.g., barium, sodium, potassium, lithium, calcium, and magnesium.
• the most commonly used metals are calcium and magnesium, which both may be present in detergents used in lubricants, and mixtures of calcium and/or magnesium with sodium.
• additional detergents may be used.
• the additional detergents include phenates, salicylates, phenolates, phosphonates, thiophosphonates, ionic surfactants, and the like.
• additional detergents include hybrid and/or complex detergents.
• the antioxidant compositions of present disclosure may be used in lubricating oil to impart oxidation stability to the lubricating oil.
• the primary antioxidant, secondary antioxidant, and one or more detergents may be present in any ratio provided that their concentrations fall within the guidelines provided herein.
• the antioxidant compositions are oil soluble meaning that they are, for instance, soluble or stably dispersible in oil to an extent sufficient to exert their intended effect in the environment in which the oil is employed. Moreover, the additional incorporation of other additives may also permit incorporation of higher levels of a particular additive, if desired.
• oil-soluble does not necessarily indicate that the compounds or additives are soluble, dissolvable, miscible, or capable of being suspended in the oil in all proportions. If other antioxidants are present in the lubricating oil composition, a lesser amount of the antioxidant of the present invention may be used.
• Oils used as the base oil will be selected or blended depending on the desired end use and the additives in the finished oil to give the desired grade of engine oil, e.g. a lubricating oil composition having an Society of Automotive Engineers (SAE) Viscosity Grade of 0W, OW-8, OW-16, 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W- 20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, or 15W-40.
• SAE Society of Automotive Engineers
• the oil of lubricating viscosity (sometimes referred to as “base stock” or “base oil”) is the primary liquid constituent of a lubricant, into which additives and possibly other oils are blended, for example to produce a final lubricant (or lubricant composition).
• a base oil which is useful for making concentrates as well as for making lubricating oil compositions therefrom, may be selected from natural (vegetable, animal or mineral) and synthetic lubricating oils and mixtures thereof.
• base stocks and base oils in this disclosure are the same as those found in American Petroleum Institute (API) Publication 1509 Annex E ("API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils," December 2016).
• Group I base stocks contain less than 90% saturates and/or greater than 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table E-1.
• Group II base stocks contain greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table E-1.
• Group III base stocks contain greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 120 using the test methods specified in Table E-1.
• Group IV base stocks are polyalphaolefins (PAO).
• Group V base stocks include all other base stocks not included in Group I, II, III, or IV.
• Natural oils include animal oils, vegetable oils (e.g., castor oil and lard oil), and mineral oils. Animal and vegetable oils possessing favorable thermal oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary widely as to their crude source, for example, as to whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful. Natural oils vary also as to the method used for their production and purification, for example, their distillation range and whether they are straight run or cracked, hydrorefined, or solvent extracted.
• Synthetic oils include hydrocarbon oil.
• Hydrocarbon oils include oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene- alphaolefin copolymers).
• Polyalphaolefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oil.
• PAOs derived from Cs to CM olefins e.g., Cs, Cio, Ci2, CM olefins or mixtures thereof, may be utilized.
• base oils include non-conventional or unconventional base stocks that have been processed, preferably catalytically, or synthesized to provide high performance characteristics.
• Non-conventional or unconventional base stocks/base oils include one or more of a mixture of base stock(s) derived from one or more Gas-to-Liquids (GTL) materials, as well as isomerate/isodewaxate base stock(s) derived from natural wax or waxy feeds, mineral and or non-mineral oil waxy feed stocks such as slack waxes, natural waxes, and waxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxy raffinate, hydrocrackate, thermal crackates, or other mineral, mineral oil, or even non petroleum oil derived waxy materials such as waxy materials received from coal liquefaction or shale oil, and mixtures of such base stocks.
• GTL Gas-to-Liquids
• Base oils for use in the lubricating oil compositions of present disclosure are any of the variety of oils corresponding to API Group I, Group II, Group III, Group IV, and Group V oils, and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils, and mixtures thereof, more preferably the Group III to Group V base oils due to their exceptional volatility, stability, viscometric and cleanliness features.
• the base oil will have a kinematic viscosity at 100°C (ASTM D445) in a range of 2.5 to 20 mm 2 /s (e.g., 3 to 12 mm 2 /s, 4 to 10 mm 2 /s, or 4.5 to 8 mm 2 /s).
• the present lubricating oil compositions may also contain conventional lubricant additives for imparting auxiliary functions to give a finished lubricating oil composition in which these additives are dispersed or dissolved.
• the lubricating oil compositions can be blended with antioxidants, ashless dispersants, anti-wear agents, detergents such as metal detergents, rust inhibitors, dehazing agents, demulsifying agents, friction modifiers, metal deactivating agents, pour point depressants, viscosity modifiers, antifoaming agents, co-solvents, package compatibilizers, corrosion-inhibitors, dyes, extreme pressure agents and the like and mixtures thereof.
• a variety of the additives are known and commercially available. These additives, or their analogous compounds, can be employed for the preparation of the lubricating oil compositions of the invention by the usual blending procedures.
• each of the foregoing additives when used, is used at a functionally effective amount to impart the desired properties to the lubricant.
• a functionally effective amount of this ashless dispersant would be an amount sufficient to impart the desired dispersancy characteristics to the lubricant.
• the concentration of each of these additives, when used may range, unless otherwise specified, from about 0.001 to about 20 wt %, such as about 0.01 to about 10 wt %.
• the fully formulated engine oils include one or more antioxidants and a sulfonate detergent as well as common lubricant additives such as dispersant, and corrosion inhibitor.
• the first engine oil samples (“DPA Only”) includes a sulfonate detergent and an alkylated diphenylamine.
• the alkylated diphenylamine is a nonylated diphenylamine or a diphenylamine alkylated with a propylene tetramer.
• Gas chromatography analysis of the diphenylamine alkylated with propylene tetramer is summarized in Table 1 below. The analysis shows that roughly half of the sample is mono alkylated diphenylamine. Roughly another half of the sample is di alkylated diphenylamine. There is a very small amount of diphenylamine with C3-C8 alkyl group.
• Other engine oil samples include one or more additional antioxidants (i.e., molybdenum succinimide, hindered phenol, dithiocarbamate).
• additional antioxidants i.e., molybdenum succinimide, hindered phenol, dithiocarbamate.
• each antioxidant present is present in equal treat levels / weight percent.
• Test engine oil samples featuring two antioxidants include an alkylated diphenylamine with molybdenum succinimide (“DPA/Mo succinimide”), hindered phenol (“DPA/hindered phenol”) or dithiocarbamate (“DPA/dithiocarbamate”).
• DPA/Mo succinimide alkylated diphenylamine with molybdenum succinimide
• DPA/hindered phenol hindered phenol
• DPA/dithiocarbamate dithiocarbamate
• Test engine oil samples featuring three antioxidants include an alkylated diphenylamine with molybdenum succinimide and hindered phenol (“DPA/Mo succinimide/hindered phenol”), molybdenum succinimide and dithiocarbamate (“DPA/Mo succinimide/dithiocarbamate”), or hindered phenol and dithiocarbamate (“DPA/hindered phenol/dithiocarbamate”).
• Test engine oil samples feature four antioxidants include an alkylated diphenylamine with molybdenum succinimide, hindered phenol, and dithiocarbamate (“DPA/Mo succinimide/hindered phenol/dithiocarbamate”).
• sulfonate detergent low and medium overbased sulfonates
• the total concentration of the antioxidant(s) is 1.5 wt %.
• Oxidation induction times were evaluated using Pressurized Differential Scanning Calorimetry (PDSC) according to ASTM D6186 test protocol. Greater oxidation induction times indicated greater oxidation stability.
• PDSC Pressurized Differential Scanning Calorimetry

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

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• 2021
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