EP1657292B1 - Concentrés d'additifs de lubrifiants - Google Patents

Concentrés d'additifs de lubrifiants Download PDF

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Publication number
EP1657292B1
EP1657292B1 EP05110044.4A EP05110044A EP1657292B1 EP 1657292 B1 EP1657292 B1 EP 1657292B1 EP 05110044 A EP05110044 A EP 05110044A EP 1657292 B1 EP1657292 B1 EP 1657292B1
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mass
concentrate
group
oil
overbased
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EP1657292A1 (fr
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Raymond Fellows
Ian Bell
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Infineum International Ltd
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Infineum International Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-macromolecular 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
    • 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
    • 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
    • C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed 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
    • 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
    • C10M2207/028—Overbased salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • 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
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • 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
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • 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
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • 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 is directed to additive concentrates useful in the preparation of lubricating oil compositions. More specifically, preferred embodiments of the present invention provide lubricating oil additive concentrates exhibiting improved storage stability.
  • Lubricating oil compositions for use in crankcase engine oils comprise a major amount of base stock oil and minor amounts of additives that improve the performance and increase the useful life of the lubricant.
  • Crankcase lubricating oil compositions conventionally contain basic metal complexes, which act as detergents and acid neutralizers, phenolic and/or aminic antioxidants and organic friction modifiers containing at least one hydroxyl or amino group, which function as organic friction modifiers that are effective in improving fuel economy.
  • formulators In the face of increased demands for improved fuel economy, and further demands for reductions in the amounts of metal (ash) contained in the lubricant, formulators have used ever-increasing amounts of organic friction modifiers.
  • Lubricating oil additives are commonly provided to lubricant formulators in the form of 10 to 80 mass %, e.g., 20 to 80 mass % active ingredient (AI) concentrates, which are then dissolved in major amounts of oil of lubricating viscosity to provide a fully formulated lubricant.
  • the concentrates are commonly diluted in 3 to 100, e.g., 5 to 40 parts by weight of oil of lubricating viscosity, per part by weight of the additive concentrate.
  • certain lubricating oil additives are known to interact with others in concentrates. One such known interaction occurs between organic friction modifiers and overbased metal detergents.
  • the organic friction modifiers have been found to adversely affect the complex of the metal detergents, causing the formation of sediment in the concentrate upon storage. Previously, this interaction has been minimized by selecting detergents that did not severely interact with the organic friction modifier. The addition of a polyalkenyl acylating agent has also been found to regulate this unwanted interaction.
  • the detergents less likely to interact with organic friction modifiers have been found to cause gelation problems in additive packages, and the presence of polyalkenyl acylating agents (e.g., polyisobutenyl succinic anhydride (PIBSA)) has been found to negatively impact the fuel economy potential of lubricating oil compositions. Further, with the increased amounts of the organic friction modifier now required, the effect of polyalkenyl acylating agent compatibilizers and detergent selection on additive package stability has become insufficient.
  • PIBSA polyisobutenyl succinic anhydride
  • US5021173 A discloses oleaginous compositions having improved storage stability properties, which comprise a combination of ashless dispersants, friction modifier and oil-soluble copper antioxidants, and are substantially free of boron.
  • US5616816 A discloses tert. alkylphenol(s) used as antioxidants for lubricants and fuels and prepared by reaction of phenol(s) with olefin in the presence of an acidic catalyst, then by reaction with an aldehyde or ketone in the presence of a basic or acidic catalyst.
  • the present invention provides a lubricant additive concentrate comprising an oil of lubricating viscosity, an overbased metal detergent, an oil-soluble hydrocarbyl phenol aldehyde condensate present in an amount of from 2 mass % to 20 mass %, based on the total mass of the concentrate, and at least 3 mass %, based on the total mass of the concentrate, of an organic friction modifier containing at least one hydroxyl or amino group selected from the group consisting of glycerol oleates, ethoxylated amines and mixtures thereof.
  • the oil-soluble hydrocarbyl phenol aldehyde condensate is preferably a methylene bridged alkyl phenol.
  • the presence of the oil-soluble, hydrocarbyl phenol aldehyde condensate improves concentrate stability.
  • the present invention provides the use of an oil-soluble hydrocarbyl phenol aldehyde condensate to stabilise a lubricant additive concentrate comprising an oil of lubricating viscosity and an admixture of an overbased metal detergent and at least 3 mass %, based on the total mass of said concentrate, of an organic friction modifier containing at least one hydroxyl or amino group selected from the group consisting of glycerol oleates, ethoxylated amines and mixtures thereof.
  • Organic friction modifiers useful in the practice of the invention include oil-soluble compounds containing at least one polar group selected from hydroxyl and amine groups selected from glycerol oleates, particularly glycerol monooleate, and ethoxylated amines, particularly ethoxylated tallow amine. Such compounds are capable of reducing friction under hydrodynamic and mixed hydrodynamic/boundary layer conditions. Because adverse interactions are more severe when elevated levels of organic friction modifier are present in the concentrate, the concentrate of the present invention contains at least 3 mass %, and more preferably at least 5 mass %, of organic friction modifier, based on the total weight of the additive concentrate.
  • concentrates that contain the organic friction modifier in an amount sufficient to provide a formulated lubricant with at least 0.15 mass %, preferably, at least 0.25 mass % and more preferably at least 0.5 mass % of organic friction modifier after dilution are preferred.
  • Basic metal complexes useful in the context of the invention function as both detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life.
  • Detergents generally comprise a polar head with a long hydrophobic tail.
  • the polar head comprises a metal salt of an acidic organic compound.
  • the salts may contain a substantially stoichiometric amount of the metal in which case they are usually described as normal or neutral salts, and would typically have a total base number or TBN (as can be measured by ASTM D2896) of from 0 to 80.
  • a large amount of a metal base may be incorporated by reacting excess metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide).
  • the resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base (e.g. carbonate) micelle.
  • Such overbased detergents may have a TBN of 150 or greater, and typically will have a TBN of from 250 to 450 or more.
  • Detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium.
  • a metal particularly the alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium.
  • the most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium.
  • Particularly convenient metal detergents are neutral and overbased calcium sulfonates having TBN of from 20 to 450, neutral and overbased calcium phenates and sulfurized phenates having TBN of from 50 to 450 and neutral and overbased magnesium or calcium salicylates having a TBN of from 20 to 450. Combinations of detergents, whether overbased or neutral or both, may be used.
  • Sulfonates may be prepared from sulfonic acids which are typically obtained by the sulfonation of alkyl substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum or by the alkylation of aromatic hydrocarbons. Examples included those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene.
  • the alkylation may be carried out in the presence of a catalyst with alkylating agents having from about 3 to more than 70 carbon atoms.
  • the alkaryl sulfonates usually contain from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms per alkyl substituted aromatic moiety.
  • the oil soluble sulfonates or alkaryl sulfonic acids may be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylate, sulfides, hydrosulfides, nitrates, borates and ethers of the metal.
  • the amount of metal compound is chosen having regard to the desired TBN of the final product but typically ranges from about 100 to 220 mass % (preferably at least 125 mass %) of that stoichiometrically required.
  • Metal salts of phenols and sulfurized phenols are prepared by reaction with an appropriate metal compound such as an oxide or hydroxide and neutral or overbased products may be obtained by methods well known in the art.
  • Sulfurized phenols may be prepared by reacting a phenol with sulfur or a sulfur containing compound such as hydrogen sulfide, sulfur monohalide or sulfur dihalide, to form products which are generally mixtures of compounds in which 2 or more phenols are bridged by sulfur containing bridges.
  • Carboxylate detergents e.g., salicylates
  • an aromatic carboxylic acid can contain heteroatoms, such as nitrogen and oxygen.
  • the moiety contains only carbon atoms; more preferably the moiety contains six or more carbon atoms; for example benzene is a preferred moiety.
  • the aromatic carboxylic acid may contain one or more aromatic moieties, such as one or more benzene rings, either fused or connected via alkylene bridges.
  • the carboxylic moiety may be attached directly or indirectly to the aromatic moiety.
  • the carboxylic acid group is attached directly to a carbon atom on the aromatic moiety, such as a carbon atom on the benzene ring. More preferably, the aromatic moiety also contains a second functional group, such as a hydroxy group or a sulfonate group, which can be attached directly or indirectly to a carbon atom on the aromatic moiety.
  • a second functional group such as a hydroxy group or a sulfonate group
  • aromatic carboxylic acids are salicylic acids and sulfurized derivatives thereof, such as hydrocarbyl substituted salicylic acid and derivatives thereof.
  • Processes for sulfurizing, for example a hydrocarbyl - substituted salicylic acid are known to those skilled in the art.
  • Salicylic acids are typically prepared by carboxylation, for example, by the Kolbe - Schmitt process, of phenoxides, and in that case, will generally be obtained, normally in a diluent, in admixture with uncarboxylated phenol.
  • Preferred substituents in oil - soluble salicylic acids are alkyl substituents.
  • the alkyl groups advantageously contain 5 to 100, preferably 9 to 30, especially 14 to 20, carbon atoms. Where there is more than one alkyl group, the average number of carbon atoms in all of the alkyl groups is preferably at least 9 to ensure adequate oil solubility.
  • Detergents generally useful in the formulation of lubricating oil compositions also include "hybrid" detergents formed with mixed surfactant systems, e.g., phenate/salicylates, sulfonate/phenates, sulfonate/salicylates, and sulfonate/phenate/salicylates, as described, for example, in pending U.S. Patent Application Nos. 09/180,435 and 09/180,436 and U.S. Patent Nos. 6,153,565 and 6,281,179 .
  • the basic metal complex is calcium overbased detergent or overbased sulfonate or sulfonate-containing complex detergent, more preferably overbased calcium sulfonate or sulfonate-containing complex detergent.
  • Oil-soluble hydrocarbyl phenol aldehyde condensates useful in the practice of the present invention are those having the following structure: wherein n is 0 to 10, preferably 1 to 8, more preferably 2 to 7, and most preferably 3 to 6; Y is a divalent bridging group, and is preferably a hydrocarbyl group, preferably having from 1 to 4 carbon atoms; and R is a hydrocarbyl group having from 4 to 30, preferably 8 to 18, and most preferably 9 to 15 carbon atoms.
  • the hydrocarbyl phenol aldehyde condensate is preferably a hydrocarbyl phenol formaldehyde condensate.
  • the hydrocarbyl group is composed of only hydrogen and carbon atoms.
  • the hydrocarbyl group is an aliphatic group, preferably alkyl or alkylene group, especially alkyl groups, which may be linear or branched.
  • R is preferably an alkyl or alkylene group.
  • R is preferably branched.
  • the hydrocarbyl phenol aldehyde condensate preferably has a weight average molecular weight (Mw) in the range of 600 to 4000, preferably 800 to 3500, more preferably 1000 to 2000, even more preferably 1200 to 1900, and most preferably 1400 to 1750, as measured by MALDI-TOF (Matrix Assisted Laser Desorption Ionization- Time of Flight) Mass Spectrometry.
  • Mw weight average molecular weight
  • the hydrocarbyl phenol aldehyde condensate is preferably one obtained by a condensation reaction between at least one aldehyde or ketone or reactive equivalent thereof and at least one hydrocarbyl phenol, in the presence of an acid catalyst such as, for example, an alkyl benzene sulphonic acid.
  • the product is preferably subjected to stripping to remove any unreacted hydrocarbyl phenol, preferably to less than 5 mass %, more preferably to less than 3 mass %, even more preferably to less than 1 mass %, of unreacted hydrocarbyl phenol.
  • the product includes less than 0.5 mass %, such as, for example, less than 0.1 mass % of unreacted hydrocarbyl phenol.
  • the acid catalyst may be selected from a wide variety of acidic compounds such as, for example, phosphoric acid, sulphuric acid, sulphonic acid, oxalic acid and hydrochloric acid.
  • the acid may also be present as a component of a solid material such as acid treated clay.
  • the amount of catalyst used may vary from 0.05 to 10 mass % or more, such as for example 0.1 to 1 mass % of the total reaction mixture.
  • the hydrocarbyl phenol aldehyde condensate is preferably branched dodecyl phenol formaldehyde condensate, such as, for example, a tetrapropenyl tetramer phenol formaldehyde condensate.
  • the hydrocarbyl phenol aldehyde condensate is present in the additive concentrate in an amount ranging from 2 to 20 mass %, preferably from 5 to 15 mass %, and more preferably from 10 to 12 mass %, based on the mass of the concentrate.
  • the organic friction modifier and hydrocarbyl phenol aldehyde condensate are present in amounts providing a ratio of mass % organic friction modifier to mass % hydrocarbyl phenol aldehyde condensate of from 1:3 to 1:7, more preferably from 1:1.5 to 1:3.5, most preferably from 1:1 to 1:2.5.
  • a concentrate containing at least 3 mass % of the organic friction modifier preferably contains at a minimum of from 9 to 21 mass % of hydrocarbyl phenol aldehyde condensate.
  • hydrocarbyl phenol aldehyde condensates are known to provide antioxidancy, and dispersancy (see, for example, U.S. Patent No. 5,259,967 to Ripple). Therefore, when a hydrocarbyl phenol aldehyde condensate is used to stabilize the additive package, phenolic and/or aminic antioxidants commonly used to provide lubricating oil compositions with oxidation inhibition could possibly be used in reduced amounts, or even eliminated. Some hydrocarbyl phenol aldehyde condensates have also been found to provide inherent detergency and when a hydrocarbyl phenol aldehyde condensate is used to stabilize the additive package, the amount of metal detergent could possibly be reduced.
  • hydrocarbyl phenol aldehyde condensates are free of metal and can also be free of sulfur, any inherent detergency provides the compositions of the present invention with an additional important advantage, particularly when the additive packages are to be used for the formulation of the new generations of "Low SAPS” (Sulphated Ash, Phosphorus and Sulphur) lubricants.
  • Low SAPS Sulphated Ash, Phosphorus and Sulphur
  • the hydrocarbyl phenol aldehyde condensate can be used in an amount providing a ratio of mass % basic metal complex to mass % hydrocarbyl phenol aldehyde condensate of from 1:7 to 23:1, preferably at least 1:3 to 6:1, more preferably from 1:2 5:1.
  • the additives may be in solution in an oleaginous carrier or such a carrier may be provided separately or both.
  • suitable carriers are oils of lubricating viscosity, such as described in detail hereinafter, and aliphatic, naphthenic and aromatic hydrocarbons.
  • the oil of lubricating viscosity useful for making concentrates of the invention, or for making lubricating oil compositions from such concentrates, may be selected from natural (vegetable, animal or mineral) and synthetic lubricating oils and mixtures thereof. It may range in viscosity from light distillate mineral oils to heavy lubricating oils such as gas engine oil, mineral lubricating oil, motor vehicle oil, and heavy duty diesel oil. Generally, the viscosity of the oil ranges from 2 centistokes to 30 centistokes, especially 5 centistokes to 20 centistokes, at 100°C.
  • Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil); liquid petroleum oils and hydro-refined, solvent-treated or acid-treated mineral oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale also serve as useful base oils.
  • Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes)); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-ethylhexyl)benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and derivative, analogs and homologs thereof.
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-polyiso-propylene glycol ether having a molecular weight of 1000 or diphenyl ether of poly-ethylene glycol having a molecular weight of 1000 to 1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3 -C 8 fatty acid esters and C 13 Oxo acid diester of tetraethylene glycol.
  • polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide
  • alkyl and aryl ethers of polyoxyalkylene polymers e.g.
  • Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linole
  • esters examples 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 useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
  • Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils comprise another useful class of synthetic lubricants; such oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butyl-phenyl) silicate, hexa-(4-methyl-2-ethylhexyl)disiloxane, poly(methyl)siloxanes and poly(methylphenyl)siloxanes.
  • oils include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexy
  • Other synthetic lubricating oils include liquid esters of phosphorous-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
  • the oil of lubricating viscosity may comprise a Group I, Group II, Group III, Group IV or Group V oil or blends of the aforementioned oils.
  • the oil of lubricating viscosity may also comprise a blend of a Group I oil and one or more of Group II, Group III, Group IV or Group V oil.
  • oils as used herein are the same as those found in the American Petroleum Institute (API) publication "Engine Oil Licensing and Certification System", Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998 . Said publication categorizes oils as follows:
  • the oil of lubricating viscosity preferably has a saturate content of at least 65%, more preferably at least 75%, such as at least 85%. Most preferably, the oil of lubricating viscosity has a saturate content of greater than 90%. Preferably, the oil of lubricating viscosity has a sulfur content of less than 1%, preferably less than 0.6%, more preferably less than 0.3%, by mass, such as 0 to 0.3% by mass.
  • the volatility of the oil of lubricating viscosity is less than or equal to about 40 mass %, such as less than or equal to about 35 mass %, preferably less than or equal to about 32 mass %, such as less than or equal to about 28 mass %, more preferably less than or equal to about 16 mass %.
  • the viscosity index (VI) of the oil of lubricating viscosity is at least 85, preferably at least 100, most preferably from about 105 to 140.
  • a concentrate of the present invention can contain a number of other performance improving additives selected from ashless dispersants, antiwear agents, oxidation inhibitors or antioxidants, metal-containing friction modifiers and fuel economy agents, antifoamants, corrosion inhibitors, and polyalkenyl acylating agent.
  • the additives when formulating a lubricant, the additives will be provided to the formulator in one or more, preferably a single concentrated additive package, oftentimes referred to as a DI (dispersant-inhibitor) package and a VI improver and/or VI improver and LOFI, will be provided in a second package.
  • DI dispenserant-inhibitor
  • VI improver and/or VI improver and LOFI VI improver and/or VI improver and LOFI
  • Ashless dispersants maintain in suspension oil insolubles resulting from oxidation of the oil during wear or combustion. They are particularly advantageous for preventing the precipitation of sludge and the formation of varnish, particularly in gasoline engines.
  • Dihydrocarbyl dithiophosphate metal salts are frequently used as antiwear and antioxidant agents.
  • the metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper.
  • the zinc salts are most commonly used in lubricating oil and may be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohol or a phenol with P 2 S 5 and then neutralizing the formed DDPA with a zinc compound.
  • DDPA dihydrocarbyl dithiophosphoric acid
  • a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols.
  • multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character.
  • any basic or neutral zinc compound could be used but the oxides, hydroxides and carbonates are most generally employed.
  • Commercial additives frequently contain an excess of zinc due to the use of an excess of the basic zinc compound in the neutralization reaction.
  • Oxidation inhibitors or antioxidants reduce the tendency of mineral oils to deteriorate in service. Oxidative deterioration can be evidenced by sludge in the lubricant, varnish-like deposits on the metal surfaces, and by viscosity growth.
  • Oxidative deterioration can be evidenced by sludge in the lubricant, varnish-like deposits on the metal surfaces, and by viscosity growth.
  • Such oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkylphenolthioesters having preferably C 5 to C 12 alkyl side chains, calcium nonylphenol sulfide, oil soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons, phosphorous esters, metal thiocarbamates, oil soluble copper compounds as described in U.S. Patent No. 4,867,890 , and molybdenum-containing compounds and aromatic amines.
  • Known metal-containing friction modifiers include oil-soluble organo-molybdenum compounds. Such organo-molybdenum friction modifiers also provide antioxidant and antiwear credits to a lubricating oil composition.
  • oil soluble organo-molybdenum compounds there may be mentioned the dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof.
  • Particularly preferred are molybdenum dithiocarbamates, dialkyldithiophosphates, alkyl xanthates and alkylthioxanthates.
  • Foam control can be provided by an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
  • additives can provide a multiplicity of effects; thus for example, a single additive may act as a dispersant-oxidation inhibitor. This approach is well known and need not be further elaborated herein.
  • the concentrates of the invention are preferably prepared at an elevated temperature, i.e. above ambient temperature.
  • Such concentrates may be prepared at a temperature of at least 50°C such as at least 80°C, preferably at least 90°C, more preferably at least 100°C.
  • energy is saved at low temperatures, practical considerations dictate the most convenient temperature that can be used.
  • an additive is used that is solid at ambient temperature it is usually more convenient to raise the temperature to a temperature at which the additive flows, rather than dissolving it in oil prior to addition to the other additives.
  • Temperatures of 100°C or more can be employed if any additive is more conveniently handled at such temperatures. Consideration must be given to the time for which it is held at the mixing temperature and its stability under such temperatures and time conditions.
  • the dispersant and detergent are pre-blended at a relatively high temperature, and the resulting pre-blend is then mixed with the remaining additives at a lower temperature.
  • the blending sequence has not been found to have a significant impact on the effect of the hydrocarbyl phenol aldehyde condensate on concentrate stability. Therefore, the hydrocarbyl phenol aldehyde condensate can be pre-blended with the dispersant and detergent before being mixed with the remaining additives, including the organic friction modifier, may be mixed with other additives, including the organic friction modifier prior to contact with the dispersant/detergent pre-blend, or can be introduced into the concentrate, as a separate component at any stage during concentrate formation.
  • the components of the concentrate are advantageously held at the mixing temperature for a time sufficient to achieve a homogenous mixture thereof. This can usually be accomplished within one half hour, particularly when the temperature of mixing exceeds 80°C.
  • the concentrates of the invention can be incorporated into a lubricating oil composition in any convenient way.
  • they can be added directly to an oil of lubricating viscosity by dispersing or dissolving them in the oil at the desired concentrations of the dispersant and detergent, respectively.
  • Such blending can occur at ambient temperature or elevated temperatures.
  • the composite can be blended with a suitable oil-soluble solvent and base oil to form a further concentrate which is then blended with an oil of lubricating viscosity to obtain the final lubricating oil composition.
  • Such concentrate will typically contain (on an active ingredient (A.I.) basis) from about 1.7 to about 20 mass %, preferably from about, preferably from about 3 to about 10 mass %, of the organic friction modifier containing at least one hydroxyl or amino group, and from about 3 to about 45 mass %, preferably from about 5 to about 30 mass %, more preferably from about 7.5 to about 25 mass % of the basic metal complex, and from about 1 to about 15 mass %, preferably from about 3 to about 13 mass %, more preferably from about 6 to about 8 mass % of the hydrocarbyl phenol aldehyde condensate, based on the total concentrate weight; the remainder of the concentrate comprising diluent (preferably no more than about 90 mass %, such as not more than 80 mass %) oil and, optionally, other additives.
  • diluent preferably no more than about 90 mass %, such as not more than 80 mass %
  • Nonylphenol (10.5 mol) diluted in heptane was reacted with formaldehyde (9.0 mol) in water using a sulphonic acid catalyst.
  • the reagents were charged to a 5 L flask and heated under nitrogen to 100°C. After addition of diluent oil, the water and heptane were distilled off until the temperature reached 150°C. The reaction mixture was then stripped under vacuum to remove residual solvent and yield a final product.
  • the quantities of the reagents used are provided in Table 3.
  • the final product had a number average molecular weight (Mn) of about 840, a weight average molecular weight (Mw) of about 1260 and contained about 0.09 mass % residual nonylphenol, as determined by GPC and HPLC analysis.
  • Additive concentrates of the present invention (I2, I3, I5 and 16), in which the methylene bridged alkyl phenol (MBAP) of Synthesis Example A was substituted for the Irganox L135 hindered phenol antioxidant were then prepared as shown in Table 5 (amounts are expressed in terms of mass %).
  • the blending procedure and order were identical (preblending of dispersant and detergent at higher temperature, followed by mixing of detergent/dispersant preblend with other additives at lower temperature), to those used to form the concentrates of Comparative Example 1.
  • Table 5 Component I1 I2 I3 I4 I5 I6 Ca Sulf Det.
  • compositions comprising, consisting of, or consisting essentially of multiple specified components, as presented herein and in the appended claims, should be construed to also encompass compositions made by admixing said multiple specified components.

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  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (19)

  1. Concentré d'additif pour huile lubrifiante comprenant une huile de viscosité propre à la lubrification, un détergent métallique surbasique, un condensat d'aldéhyde et d'hydrocarbylphénol soluble dans l'huile présent en une quantité de 2 % en masse à 20 % en masse par rapport à la masse totale dudit concentré, et au moins 3 % en masse, par rapport à la masse totale dudit concentré, d'un modificateur de frottement organique contenant au moins un groupe hydroxyle ou amino choisi dans l'ensemble constitué par les oléates de glycérol, les amines éthoxylées et leurs mélanges.
  2. Concentré d'additif pour huile lubrifiante selon la revendication 1, dans lequel ledit condensat d'aldéhyde et d'hydrocarbylphénol soluble dans l'huile est au moins un composé de formule :
    Figure imgb0006
     dans laquelle n vaut de 0 à 10 ; Y est un groupe pontant divalent ; et R est un groupe hydrocarbyle ayant 4 à 30 atomes de carbone.
  3. Concentré selon la revendication 2, dans lequel n vaut de 3 à 6 ; Y est un groupe hydrocarbyle ayant de 1 à 4 atomes de carbone ; et R est un groupe hydrocarbyle ayant de 9 à 15 atomes de carbone.
  4. Concentré selon la revendication 1, 2 ou 3, comprenant 5 % en masse à 15 % en masse dudit condensat d'aldéhyde et d'hydrocarbylphénol soluble dans l'huile, par rapport à la masse totale dudit concentré.
  5. Concentré selon la revendication 4, comprenant 10 % en masse à 12 % en masse dudit condensat d'aldéhyde et d'hydrocarbylphénol soluble dans l'huile, par rapport à la masse totale dudit concentré.
  6. Concentré selon l'une quelconque des revendications précédentes, dans lequel ledit modificateur de frottement organique est choisi dans l'ensemble constitué par le monooléate de glycérol, l'amine de suif éthoxylée, et leurs mélanges.
  7. Concentré selon l'une quelconque des revendications précédentes, comprenant au moins 5 % en masse dudit modificateur de frottement organique, par rapport à la masse totale dudit concentré.
  8. Concentré selon l'une quelconque des revendications précédentes, dans lequel ledit détergent métallique surbasique est choisi dans l'ensemble constitué par les sulfates de calcium surbasiques, les sulfonates de magnésium surbasiques, les phénates de calcium surbasiques, les phénates de magnésium surbasiques, les carboxylates de calcium surbasiques, les carboxylates de magnésium surbasiques, les détergents hybrides de calcium surbasiques contenant des systèmes tensioactifs comprenant au moins deux parmi un tensioactif sulfonate, un tensioactif phénate et un tensioactif carboxylate, les détergents hybrides de magnésium surbasiques contenant des systèmes tensioactifs comprenant au moins deux parmi un tensioactif sulfonate, un tensioactif phénate et un tensioactif carboxylate, et leurs mélanges.
  9. Concentré selon la revendication 8, dans lequel ledit détergent métallique surbasique est un détergent au calcium surbasique.
  10. Concentré selon la revendication 8 ou 9, dans lequel ledit détergent métallique surbasique est un détergent sulfonate métallique surbasique, ou un détergent hybride métallique surbasique contenant un système tensioactif comprenant un tensioactif sulfonate et au moins un autre tensioactif.
  11. Concentré selon la revendication 8, dans lequel ledit détergent métallique surbasique est un détergent sulfonate de calcium surbasique, ou un détergent hybride au calcium surbasique contenant un système tensioactif comprenant un tensioactif sulfonate et au moins un autre tensioactif.
  12. Concentré selon l'une quelconque des revendications précédentes, dans lequel ledit modificateur de frottement organique et ledit condensat d'aldéhyde et d'hydro-carbylphénol sont présents en des quantités réalisant un rapport du pourcentage en masse du modificateur de frottement organique au pourcentage en masse du condensat d'aldéhyde et d'hydrocarbylphénol de 1:3 à 1:7.
  13. Concentré selon l'une quelconque des revendications précédentes, dans lequel ledit détergent métallique surbasique et ledit condensat d'aldéhyde et d'hydrocarbylphénol sont présents en des quantités réalisant un rapport du pourcentage en masse du complexe métallique basique au pourcentage en masse du condensat d'aldéhyde et d'hydro-carbylphénol de 1:7 à 23:1.
  14. Concentré selon l'une quelconque des revendications précédentes, comprenant en outre au moins un autre additif choisi dans l'ensemble constitué par un dispersant, des antioxydants et des agents anti-usure.
  15. Utilisation d'un condensat d'aldéhyde et d'hydro-carbylphénol soluble dans l'huile, tel que défini dans l'une quelconque des revendications précédentes, pour stabiliser un concentré d'additif pour lubrifiant comprenant une huile de viscosité propre à la lubrification et un mélange d'un détergent métallique surbasique, tel que défini dans l'une quelconque des revendications précédentes, et d'au moins 3 % en masse, par rapport à la masse totale dudit concentré, d'un modificateur de frottement organique tel que défini dans l'une quelconque des revendications précédentes, contenant au moins un groupe hydroxyle ou amino, choisi dans l'ensemble constitué par les oléates de glycérol, les amines éthoxylées et leurs mélanges.
  16. Utilisation selon la revendication 15, dans laquelle le condensat d'aldéhyde et d'hydrocarbylphénol est de formule :
    Figure imgb0007
     dans laquelle n vaut de 0 à 10 ; Y est un groupe pontant divalent ; et R est un groupe hydrocarbyle ayant 4 à 30 atomes de carbone.
  17. Utilisation selon la revendication 16, où n vaut de 3 à 6 ; Y est un groupe hydrocarbyle ayant 1 à 4 atomes de carbone ; et R est un groupe hydrocarbyle ayant 9 à 15 atomes de carbone.
  18. Utilisation selon l'une quelconque des revendications 15 à 17, où ledit modificateur de frottement est choisi dans l'ensemble constitué par le monooléate de glycérol, l'amine de suif éthoxylée, et leurs mélanges.
  19. Utilisation selon l'une quelconque des revendications 15 à 18, où le condensat d'aldéhyde et d'hydrocarbylphénol soluble dans l'huile est utilisé en une quantité de 2 % en masse à 20 % en masse par rapport à la masse totale du concentré.
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CA2772542C (fr) 2009-05-01 2015-06-23 Infineum International Limited Lubrification de moteur marin
WO2011066141A2 (fr) * 2009-11-30 2011-06-03 The Lubrizol Corporation Mélanges stabilisés contenant des modificateurs de friction
EP2507351B1 (fr) 2009-11-30 2018-05-16 The Lubrizol Corporation Utilisation de compositions stabilisees contenant de modificateurs de frictions
GB2498635A (en) * 2011-12-21 2013-07-24 Infineum Int Ltd A method of reducing the rate of depletion of basicity of a lubricating oil composition for use in an engine

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EP0389237A2 (fr) * 1989-03-20 1990-09-26 Ethyl Petroleum Additives Limited Agent modifiant la friction

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US5021173A (en) * 1988-02-26 1991-06-04 Exxon Chemical Patents, Inc. Friction modified oleaginous concentrates of improved stability
US5118875A (en) * 1990-10-10 1992-06-02 Exxon Chemical Patents Inc. Method of preparing alkyl phenol-formaldehyde condensates
US5259967A (en) * 1992-06-17 1993-11-09 The Lubrizol Corporation Low ash lubricant composition
US6002051A (en) * 1992-10-16 1999-12-14 The Lubrizol Corporation Tertiary alkyl alkylphenols and organic compositions containing same
ES2169785T3 (es) * 1995-02-01 2002-07-16 Lubrizol Corp Composicion lubricante con bajo contenido en cenizas.
JP4017317B2 (ja) * 2000-06-05 2007-12-05 東燃ゼネラル石油株式会社 自動変速機用潤滑油組成物

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EP0389237A2 (fr) * 1989-03-20 1990-09-26 Ethyl Petroleum Additives Limited Agent modifiant la friction

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