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
  • C10M133/38—Heterocyclic nitrogen compounds
  • C10M133/44—Five-membered ring containing nitrogen and carbon only
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
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  • 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
  • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
  • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
  • C10M129/04—Hydroxy compounds
  • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
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  • 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
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  • 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
  • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
  • C10M133/56—Amides; Imides
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  • 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
  • C10M141/06—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 nitrogen-containing compound
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
  • C10M159/12—Reaction products
  • C10M159/18—Complexes with metals
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  • 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
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  • 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
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
  • C10M2203/102—Aliphatic fractions
  • C10M2203/1025—Aliphatic fractions used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/022—Ethene
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • C10M2219/02—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
  • C10M2219/04—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
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/045—Metal containing thio derivatives
• • 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
  • C10M2227/09—Complexes with metals
• • 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
  • C10N2010/02—Groups 1 or 11
• • 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
  • C10N2030/40—Low content or no 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
  • 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
  • C10N2030/42—Phosphor free or low phosphor 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
  • 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
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines

Definitions

• the invention provides a lubricating composition containing a dispersant treated with cobalt to reduce the formation of high temperature insoluble solids formed during exposure of the composition to heat.
• the invention further relates to the use of the lubricating composition in an internal combustion engine.
• the invention further relates to a method of reducing insoluble deposits in an engine using said dispersant treated with cobalt and said lubricating composition.
• lubricants become less effective during their use due to exposure to the operating conditions of the device they are used in, including exposure to heat, oxygen, and partial combustion by-products generated by the operation of the device.
• engine oil becomes less effective during its use, in part due to exposure of the oil to acidic and pro-oxidant by-products.
• the industry standard high temperature deposit test (Sequence IIIG) is a very severe piston cleanliness test with high sump temperatures and high load.
• Sequence IIIG is a very severe piston cleanliness test with high sump temperatures and high load.
• bench tests that seek to simulate the deposit forming tendencies of lubricating oils in this and other engine tests including the Komatsu hot tube test (KHT).
• KHT Komatsu hot tube test
• the procedure calls for circulating an oil through a hot glass tube (232-320° C. and more typically 270-290° C.) for a specified period of time.
• the tube is rated visually for deposits with a rating of 10 being a perfectly clear tube and 0 being a black tube.
• the test gauges the innate tendency of the lubricant to form deposits in the absence of combustion processes.
• crankcase lubricants such as GF-5 for passenger car motor oils, and PC-10 for heavy duty diesel engines specify increasingly stringent standards or limits to meet government specifications.
• sulfur and phosphorus limits Sulfur and phosphorus from the lubricant can end up in the catalytic converter. It is widely believed that lowering these limits in lubricants may have a serious impact on engine performance, engine wear, and oxidation of engine oils. This is because historically a major contributor to phosphorus content in engine oils has been zinc dialkyldithiophosphate (ZDP), and ZDP has long been used to impart antiwear and antioxidancy performance to engine oils.
• ZDP zinc dialkyldithiophosphate
• Desirable lubricants may be low in one or more of phosphorus and sulfur.
• the present invention relates to cobalt modified dispersants. These cobalt modified dispersants tend to minimize deposits formed as a result of oil insoluble oxidation products on the walls of glass tubes and engine components. These cobalt modified dispersants also increase the oxidation induction times of the formulated lubricant in tests like the SAE CECL85.
• cobalt supplied for instance in the form of a reaction product of aminic (also known as ashless) dispersants and cobalt compounds, such as Co +2 or Co +3 provides a beneficial effect on one or more of the above properties.
• aminic also known as ashless
• cobalt compounds such as Co +2 or Co +3
• KHT Komatsu Hot Tube deposits screen test
• the cobalt can be supplied as a Co-modified dispersant, such as a succinimide dispersant, Mannich base, or hydrocarbyl based polymer dispersants.
• a Co-modified dispersant such as a succinimide dispersant, Mannich base, or hydrocarbyl based polymer dispersants.
• Such materials may be prepared by forming a cobalt mixed anhydride between a cobalt alkoxide, chloride, carbonate, hydroxide, acetate, etc. and a hydrocarbyl-substituted succinic anhydride, such as an alkenyl- or alkyl-succinic anhydride.
• the resulting cobalt-succinate intermediate may be used directly or it may be reacted with any of a number of materials, such as (a) a polyamine-based succinimide/amide dispersant having free, condensable —NH functionality; (b) the components of a polyamine-based succinimide/amide dispersant, i.e., an alkenyl- or alkyl-succinic anhydride and a polyamine, (c) a hydroxy-containing polyester dispersant prepared by the reaction of a substituted succinic anhydride with a polyol, aminoalcohol, polyamine, or mixtures thereof.
• a polyamine-based succinimide/amide dispersant having free, condensable —NH functionality
• the components of a polyamine-based succinimide/amide dispersant i.e., an alkenyl- or alkyl-succinic anhydride and a polyamine
• a hydroxy-containing polyester dispersant prepared by
• the cobalt-succinate intermediate may be reacted with other agents such as alcohols, aminoalcohols, ether alcohols, polyether alcohols or polyols, or fatty acids, and the product thereof either used directly to impart cobalt to a lubricant, or else further reacted with the succinic dispersants as described above.
• a dispersant post treated with metal 1 part (by mole) of cobalt may be reacted with 2 parts (by mole) of a polyisobutene-substituted succinic anhydride at 110-155° C. or 140-150° C. for 5 to 6 hours to provide a cobalt modified dispersant or intermediate.
• the resulting material (30 g) may be further reacted with a succinimide dispersant from polyisobutene-substituted succinic anhydride and a polyethylenepolyamine mixture (127 g +diluent oil) at 155° C. for 1.5 hours, to produce a cobalt-modified succinimide dispersant.
• Dispersants are well known in the field of lubricants and include primarily what is known as ashless-type dispersants and polymeric dispersants. Ashless type dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include nitrogen-containing dispersants such as N-substituted long chain alkenyl succinimide, having a variety of chemical structures including typically
• each R 1 is independently an alkyl group, frequently a polyisobutyl group with a molecular weight of 500-5000, and R 2 are alkylene groups, commonly ethylene (C 2 H 4 ) groups.
• R 2 are alkylene groups, commonly ethylene (C 2 H 4 ) groups.
• Such molecules are commonly derived from reaction of an alkenyl acylating agent with a polyamine, and a wide variety of linkages between the two moieties is possible in addition to the representative imide structure shown above, including a variety of amides and ammonium salts.
• Succinimide dispersants are more fully described in U.S. Pat. Nos. 4,234,435 and 3,172,892.
• the invention further provides a method of lubricating an internal combustion engine comprising the step of supplying to the internal combustion engine the lubricating composition described herein.
• additives present in the lubricating composition disclosed herein are quoted on an oil free basis, i.e., amount of actives, unless otherwise noted.
• the lubricating compositions of the invention comprise an oil of lubricating viscosity.
• Suitable oils include both natural and synthetic oils, oil derived from hydrocracking, hydrogenation, and hydro finishing, unrefined, refined, re-refined oils or mixtures thereof.
• 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.
• Purification techniques include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation and the like.
• Re-refined oils are also known as reclaimed or reprocessed oils, and are obtained by processes similar to those used to obtain refined oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
• Natural oils useful in making the inventive lubricants 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.
• animal 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.
• Synthetic lubricating oils are useful and include hydrocarbon oils such as polymerized, oligomerised, or interpolymerised olefins (e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers); poly(l-hexenes), poly(1-octenes), trimers or oligomers of 1-decene, e.g., poly(l-decenes), such materials being often referred to as poly a-olefins, and mixtures thereof; alkyl-benzenes (e.g.
• dodecylbenzenes tetra-decylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); diphenyl alkanes, alkylated diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulphides and the derivatives, analogs and homologs thereof or mixtures thereof.
• polyphenyls e.g., biphenyls, terphenyls, alkylated polyphenyls
• diphenyl alkanes alkylated diphenyl alkanes, alkylated diphenyl ethers and alkylated diphenyl sulphides and the derivatives, analogs and homologs thereof or mixtures thereof.
• oils include polyol esters (such as Priolube®3970), diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), or polymeric tetrahydrofurans.
• Synthetic oils may be produced by Fischer-Tropsch reactions and typically may be hydroisomerised 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.
• 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 oil of lubricating viscosity may be an API Group II or Group III oil.
• the oil of lubricating viscosity may be an API Group I oil.
• the amount of the oil of lubricating viscosity present is typically the balance remaining after subtracting from 100 wt. % the sum of the amount of the compound of the invention and the other performance additives.
• the lubricating composition may be in the form of a concentrate and/or a fully formulated lubricant. If the lubricating composition of the invention (comprising the additives disclosed herein) is in the form of a concentrate which may be combined with additional oil to form, in whole or in part, a finished lubricant, the ratio of these additives to the oil of lubricating viscosity and/or to diluent oil include the ranges of 1:99 to 99:1 by weight, or 80:20 to 10:90 by weight.
• the present invention provides a lubricating composition containing an oil of lubricating viscosity and an additive comprising a dispersant treated with cobalt.
• the ashless dispersant reacted with cobalt may be present in a lubricating composition in a concentration from about 0.5 to about 10 weight percent, more desirably from about 1 to about 5 weight percent, and preferably from about 1.5 to about 3.5 weight percent based on the total weight of the lubricating compositions.
• the amount of cobalt incorporated into the lubricant from treating the dispersant in the lubricating composition is from about 40 to about 500 parts per million parts by weight (ppm) of lubricating composition, more desirably from about 50, 60 or 70 to about 300 ppm, and in one embodiment from about 80 to 250 ppm.
• Sources of cobalt include CoCl 2 , Co(OH) 2 , Co(CO 3 ), CO(SO 4 ), CoO, Co 4 S 4 , Co(NO 3 ) 2 , CoMoO 4 , Co 2 B, Co 2 P, Co(NO 2 ) 2 , and Co(acac) 2 .
• the ashless dispersant and the cobalt compound will be reacted together at temperatures of at least 100° C., more desirably at least 140° C. for times such as desirably at least 1 hour and more desirably at least 2 or 4 hours so as to form a reaction product where a significant portion of cobalt is physically or chemically associated with the dispersant. While a reaction product is the desired result, it is acknowledged that some cobalt and some ashless dispersant may remain in the form of reactants that haven't been converted to associated materials.
• Suitable dispersants for use in the compositions of the present invention include succinimide dispersants.
• the dispersant may be present as a single dispersant.
• the dispersant may be present as a mixture of two or three different dispersants, wherein at least one may be a succinimide dispersant.
• the succinimide dispersant may be a derivative of an aliphatic polyamine, or mixtures thereof.
• the aliphatic polyamine may be aliphatic polyamine such as an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine, or mixtures thereof.
• the aliphatic polyamine may be ethylenepolyamine.
• the aliphatic polyamine may be selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.
• the dispersant may be a N-substituted long chain alkenyl succinimide.
• N-substituted long chain alkenyl succinimide include polyisobutylene succinimide.
• the polyisobutylene from which polyisobutylene succinic anhydride is derived has a number average molecular weight of 350 to 5000, or 550 to 3000 or 750 to 2500.
• Succinimide dispersants and their preparation are disclosed, for instance in U.S. Pat. Nos.
• Mannich base type Another class of ashless dispersant is Mannich base type. These are materials which are formed by the condensation of a higher molecular weight, alkyl-substituted phenol, an alkylene polyamine, and an aldehyde such as formaldehyde. Such materials may have the general structure
• ashless dispersants is high molecular weight ester type. These materials are similar to the above-described succinimides except that they may be seen as having been prepared by reaction of a hydrocarbyl acylating agent and a polyhydric aliphatic alcohol such as glycerol, pentaerythritol, or sorbitol. Such materials are described in more detail in U.S. Pat. No. 3,381,022.
• dispersants include polymeric dispersant additives, which are generally hydrocarbon-based polymers which contain polar functionality to impart dispersancy characteristics to the polymer.
• Dispersants can also be post-treated by reaction with any of a variety of agents. Among these are urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, and phosphorus compounds. References detailing such treatment are listed in U.S. Pat. Nos. 4,654,403 or 3,306,908.
• compositions of the invention may optionally comprise one or more additional performance additives.
• additional performance additives may include one or more metal deactivators, viscosity modifiers, detergents, friction modifiers, antiwear agents, corrosion inhibitors, dispersants (other than the compound of the present invention), dispersant viscosity modifiers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, pour point depressants, seal swelling agents, and any combination or mixture thereof.
• metal deactivators viscosity modifiers
• viscosity modifiers detergents, friction modifiers, antiwear agents, corrosion inhibitors, dispersants (other than the compound of the present invention), dispersant viscosity modifiers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, pour point depressants, seal swelling agents, and any combination or mixture thereof.
• fully-formulated lubricating oil will contain one or more of these performance additives, and often a package of multiple performance additives.
• the invention provides a lubricating composition further comprising an antiwear agent, a dispersant viscosity modifier, a friction modifier, a viscosity modifier, an antioxidant, an overbased detergent, or a combination thereof, where each of the additives listed may be a mixture of two or more of that type of additive.
• the invention provides a lubricating composition further comprising an antiwear agent, a dispersant viscosity modifier, a friction modifier, a viscosity modifier (typically an olefin copolymer such as an ethylene-propylene copolymer), an antioxidant (including phenolic and/or aminic antioxidants), an overbased detergent (including overbased sulfonates and phenates), or a combination thereof, where each of the additives listed may be a mixture of two or more of that type of additive.
• an antiwear agent typically an olefin copolymer such as an ethylene-propylene copolymer
• an antioxidant including phenolic and/or aminic antioxidants
• an overbased detergent including overbased sulfonates and phenates
• the lubricating composition of the invention further includes an antiwear agent such as a phosphorus- containing antiwear agent such as a dithiophosphate agent such as a metal dihydrocarbyl dithiophosphate (typically zinc dialkyldithiophosphate (ZDDP)), wherein the metal dihydrocarbyl dithiophosphate contributes at least 100 ppm, at least 200 ppm, at least 250 ppm, 200 ppm to 1000 ppm, or 250 or 300 ppm to 800 ppm, or 300 or 400 ppm to 600 ppm of phosphorus to the lubricating composition.
• the lubricating composition is free of or substantially free (meaning less than 100, less than 50 or less than 20 ppm of phosphorus from a metal dialkyldithiophosphate such as zinc dialkyldithiophosphate).
• the lubricating composition of the invention further comprises a dispersant viscosity modifier.
• the dispersant viscosity modifier may be present at 0 wt. % to 5 wt. %, 0 wt. % to 4 wt. %, or 0.05 wt. % to 2 wt. % of the lubricating composition.
• Suitable dispersant viscosity modifiers include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with an acylating agent such as maleic anhydride and an amine; polymethacrylates functionalized with an amine, or esterified styrene-maleic anhydride copolymers reacted with an amine. More detailed description of dispersant viscosity modifiers are disclosed in International Publication WO2006/015130 or U.S. Pat. Nos. 4,863,623; 6,107,257; 6,107,258; and 6,117,825.
• the dispersant viscosity modifier may include those described in U.S. Pat. No. 4,863,623 (see column 2, line 15 to column 3, line 52) or in International Publication WO2006/015130 (see page 2, paragraph [0008] and preparative examples are described paragraphs [0065] to [0073]).
• the lubricant composition has low level or is free of metals selected from the group of molybdenum, titanium, and boron. In one embodiment the lubricant composition has less than 100, less than 50, less than 20, less than 20 or 0 ppm of molybdenum based on the weight of the lubricant composition. Ppm is an abbreviation for parts by weight per million parts by weight of the total composition. In one embodiment the lubricant composition has less than 50, less than 30, less than 10, less than 5 or 0 ppm of titanium based on the weight of the lubricant composition.
• the lubricant composition has less than 100, less than 80, less than 50, less than 25, less than 10, or 0 ppm of boron based on the weight of the lubricant composition. In one embodiment the limitations on molybdenum, titanium, and boron are all together applied to the composition
• the invention provides a lubricating composition further comprising an overbased detergent.
• the overbased detergent may be selected from the group consisting of sulfur-free phenates, sulfur-containing phenates, sulfonates, salixarates, salicylates, and mixtures thereof.
• the overbased 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.
• hybrid detergent would be considered equivalent to amounts of distinct phenate and sulfonate detergents introducing like amounts of phenate and sulfonate soaps, respectively.
• an overbased detergent may be sodium salts, calcium salts, magnesium salts, or mixtures thereof of the phenates, sulfur containing phenates, sulfonates, salixarates and salicylates.
• Overbased phenates and salicylates typically have a total base number of 180 to 450 TBN.
• Overbased sulfonates typically have a total base number of 250 to 600, or 300 to 500.
• Overbased detergents are known in the art.
• the sulfonate detergent may be predominantly a linear alkylbenzene sulfonate detergent having a metal ratio of at least 8 as is described in paragraphs [0026] to [0037] of US Patent Publication 2005065045 (and granted as U.S. Pat. No.
• the linear alkylbenzene sulfonate detergent may be particularly useful for assisting in improving fuel economy.
• the linear alkyl group may be attached to the benzene ring anywhere along the linear chain of the alkyl group, but often in the 2-, 3- or 4- position of the linear chain. In some instances, the linear alkyl group may be attached predominantly in the 2- position, resulting in the linear alkylbenzene sulfonate detergent.
• the overbased detergent may be present at 0 wt. % to 15 wt. %, 0.1 wt. % to 10 wt. %, 0.2 wt. % to 8 wt. %, or 0.2 wt. % to 3 wt.
• the detergent may be present at or 2 wt. % to 3 wt. % of the lubricating composition.
• the detergent may be present at 0.2 wt. % to 1 wt. % of the lubricating composition.
• the lubricating composition includes an antioxidant, or mixtures thereof.
• the antioxidant may be present at 0 wt. % to 15 wt. %, 0.1 wt. % to 10 wt. %, or 0.5 wt. % to 5 wt. % of the lubricating composition.
• Antioxidants include sulfurized olefins, alkylated diarylamines (typically alkylated phenyl naphthyl amines, for example those commercially available as Irganox® L 06 from CIBA, or alkylated diphenylamines such as dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine), hindered phenols, molybdenum compounds (such as molybdenum dithiocarbamates), or mixtures thereof.
• alkylated diarylamines typically alkylated phenyl naphthyl amines, for example those commercially available as Irganox® L 06 from CIBA
• alkylated diphenylamines such as dinonyl diphenylamine, octyl diphenylamine, dioctyl diphenylamine
• hindered phenols such as molybdenum dithioc
• the hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
• the phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and/or a bridging group linking to a second aromatic group.
• hindered phenol antioxidants examples include 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or 4-dodecyl-2,6-di-tert-butylphenol.
• the hindered phenol antioxidant may be an ester and may include e.g., IrganoxTM L-135 from Ciba. A more detailed description of suitable ester-containing hindered phenol antioxidant chemistry is found in U.S. Pat. No. 6,559,105.
• friction modifiers include long chain fatty acid derivatives of amines, fatty esters, or epoxides; fatty imidazolines such as condensation products of carboxylic acids and polyalkylene-polyamines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; or fatty alkyl tartramides.
• fatty as used herein, can mean having a C8-22 linear alkyl group.
• Friction modifiers may also encompass materials such as sulfurised fatty compounds and olefins, molybdenum dialkyldithiophosphates, molybdenum dithiocarbamates, sunflower oil or monoester of a polyol and an aliphatic carboxylic acid.
• the friction modifier may be selected from the group consisting of long chain fatty acid derivatives of amines, long chain fatty esters, or long chain fatty epoxides; fatty imidazolines; amine salts of alkylphosphoric acids; fatty alkyl tartrates; fatty alkyl tartrimides; and fatty alkyl tartramides.
• the friction modifier may be present at 0 wt. % to 6 wt. %, 0.05 wt. % to 4 wt. %, or 0.1 wt. % to 2 wt. % of the lubricating composition.
• the friction modifier may be a long chain fatty acid ester.
• the long chain fatty acid ester may be a monoester or a diester or a mixture thereof, and in another embodiment, the long chain fatty acid ester may be a triglyceride.
• corrosion inhibitors include those described in paragraphs 5 to 8 of US Application US05/038319, published as WO2006/047486, octyl octanamide, condensation products of dodecenyl succinic acid or anhydride and a fatty acid such as oleic acid with a polyamine.
• the corrosion inhibitors include the Synalox® corrosion inhibitor.
• the Synalox® corrosion inhibitor may be a homopolymer or copolymer of propylene oxide.
• the Synalox® corrosion inhibitor is described in more detail in a product brochure with Form No. 118-01453-0702 AMS, published by The Dow Chemical Company.
• the product brochure is entitled “SYNALOX Lubricants, High-Performance Polyglycols for Demanding Applications.”
• Metal deactivators including derivatives of benzotriazoles (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles, or 2-alkyldithiobenzothiazoles; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexyl acrylate and copolymers of ethyl acrylate and 2-ethylhexylacrylate and vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides may be useful.
• benzotriazoles typically tolyltriazole
• dimercaptothiadiazole derivatives 1,2,4-tri
• Pour point depressants that may be useful in the compositions of the invention include poly(alphaolefins), esters of maleic anhydride-styrene, poly(meth)acrylates, polyacrylates or polyacrylamides.
• the lubricating composition may have a composition as described in the following Table 1:
• the present invention provides a surprising ability to reduce high temperature deposit formation on walls of the reactor in the KHT test simply by modifying the dispersant with a few hundred ppm of cobalt.
• the invention provides a method of lubricating an internal combustion engine comprising the step of supplying to the internal combustion engine a lubricating composition as disclosed herein.
• a lubricating composition as disclosed herein.
• the lubricant is added to the lubricating system of the internal combustion engine, which then delivers the lubricating composition to the critical parts of the engine that require lubrication during its operation,.
• the lubricating compositions described above may be utilized in an internal combustion engine.
• the engine components may have a surface of steel or aluminum (typically a surface of steel), and may also be coated for example with a diamond like carbon (DLC) coating.
• DLC diamond like carbon
• An aluminum surface may be comprised of an aluminum alloy that may be a eutectic or hyper-eutectic aluminum alloy (such as those derived from aluminum silicates, aluminum oxides, or other ceramic materials).
• the aluminum surface may be present on a cylinder bore, cylinder block, or piston ring having an aluminum alloy, or aluminum composite.
• the internal combustion engine may or may not have an Exhaust Gas Recirculation (ERG) system.
• EGR Exhaust Gas Recirculation
• the internal combustion engine may be fitted with an emission control system or a turbocharger.
• Examples of the emission control system include diesel particulate filters (DPF), or systems employing selective catalytic reduction (SCR).
• the internal combustion engine may be a diesel fuelled or biofuelled engine (typically a heavy duty diesel engine), a gasoline fuelled engine, a natural gas fuelled engine or a mixed gasoline/alcohol fuelled engine.
• the internal combustion engine may be a diesel fuelled engine and in another embodiment, a gasoline fuelled engine.
• the internal combustion engine may be a 2-stroke or 4-stroke engine.
• Suitable internal combustion engines include marine diesel engines, aviation piston engines, low-load diesel engines, and automobile and truck engines.
• the internal combustion engine of the present invention is distinct from gas turbine.
• individual combustion events which through the rod and crankshaft translate from a linear reciprocating force into a rotational torque.
• a gas turbine may also be referred to as a jet engine
• it is a continuous combustion process that generates a rotational torque continuously without translation and can also develop thrust at the exhaust outlet.
• the lubricant composition for an internal combustion engine may be suitable for any engine lubricant irrespective of the sulfur, phosphorus or sulfated ash (ASTM D-874) content.
• the sulfur content of the engine oil lubricant may be 1 wt. % or less, 0.8 wt. % or less, 0.5 wt. % or less, or 0.3 wt. % or less. In one embodiment, the sulfur content may be in the range of 0.001 wt. % to 0.5 wt. % or 0.01 wt. % to 0.3 wt. %.
• the phosphorus content may be 0.2 wt. % or less, 0.12 wt. % or less, 0.1 wt.
• the phosphorus content may be 100 ppm to 1000 ppm, or 200 ppm to 600 ppm.
• the total sulfated ash content may be 2 wt. % or less, 1.5 wt. % or less, 1.1 wt. % or less, 1 wt. % or less, 0.8 wt. % or less, 0.5 wt. % or less, or 0.4 wt. % or less.
• the sulfated ash content may be 0.05 wt. % to 0.9 wt. %, 0.1 wt. % to 0.2 wt. % or to 0.45 wt. %.
• the amount of sulfur from all the sulfur containing additives is from about 500 or 1000 to about 2500 ppm sulfur, based on the weight of the lubricant compositions, more desirably from about 500 to about 1500 ppm.
• the lubricating composition may be an engine oil, wherein the lubricating composition may be characterized as having at least one of (i) a sulfur content of 0.5 wt. % or less, (ii) a phosphorus content of 0.1 wt. % or less, (iii) a sulfated ash content of 1.5 wt. % or less, or combinations thereof.
• Polyethylene amine still bottoms 25 g, 34 wt. % N were added to the dropping funnel. The mixture was warmed to 110° C. with stirring. The polyamine was added drop-wise to the sub-surface tube over 35 min. The temperature was increased to 155° C. and the preparation was stirred for 5.25 h.
• Polyethylene amine still bottoms 43 g, 34 wt. % N
• the mixture was warmed to 110° C. with stirring.
• the polyamine was added drop-wise to the sub-surface tube over 35 min. The temperature was increased to 155° C. and the preparation was stirred for 5.25 h.
• Examples 1-11 were blended into an API SN capable lubricating oil (5W-30) in group II basestocks as detailed in Table 2. Component descriptions and treat rates are listed on a diluent oil free basis.
• Table 3 shows the KHT performance of the Lubricants from Table 2.
• hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
• hydrocarbyl groups examples include:
• Heteroatoms include sulfur, oxygen, nitrogen, and encompass substituents as pyridyl, furyl, thienyl and imidazolyl.
• substituents as pyridyl, furyl, thienyl and imidazolyl.
• no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, there will be no non-hydrocarbon substituents in the hydrocarbyl group.

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