US2977305A - Lubricating oil composition - Google Patents

Lubricating oil composition Download PDF

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US2977305A
US2977305A US724871A US72487158A US2977305A US 2977305 A US2977305 A US 2977305A US 724871 A US724871 A US 724871A US 72487158 A US72487158 A US 72487158A US 2977305 A US2977305 A US 2977305A
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oil
lubricating oil
weight
mineral lubricating
viscosity
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US724871A
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Andrew D Abbott
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California Research LLC
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California Research LLC
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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
    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/02—Moulds or cores; Details thereof or accessories therefor with incorporated heating or cooling means
    • B29C33/04—Moulds or cores; Details thereof or accessories therefor with incorporated heating or cooling means using liquids, gas or steam
    • B29C33/044—Moulds or cores; Details thereof or accessories therefor with incorporated heating or cooling means using liquids, gas or steam in rolls calenders or drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/16—Cooling
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy 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
    • 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
    • C10M2207/027—Neutral 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
    • C10M2207/28—Esters
    • C10M2207/32—Esters of carbonic acid
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/082—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type monocarboxylic
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • C10M2215/08—Amides
    • 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
    • C10M2215/08—Amides
    • C10M2215/082—Amides containing hydroxyl groups; Alkoxylated 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
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
    • C10M2217/023—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group the amino group containing an ester bond
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/028—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a nitrogen-containing hetero 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a 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
    • 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
    • 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
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088—Neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased 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
    • 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

Definitions

  • This invention relates to a lubricating oil composition having improved physical properties. More particularly the invention is concerned with a stable viscosity mineral lubricating oil composition containing metal salt organic detergent additives in combination with polymeric thickening additives.
  • Polymeric additives are extensively used in mineral lubricating oil compositions to impart desirable viscositytemperature characteristics to the compositions. These additives are designed to modify lubricating oils so that changes in viscosity occurring with variations in temperature arekept as small as possible. Lubricating oils containing such polymeric additives are somewhat thickened at the higher temperatures normally encountered in engine operation while at the same time retaining desirable low viscosity fluidity at' cold starting temperatures. The ability of a lubricating oil to accommodate increased temperatures with a minimum decrease in viscosity is indicated by its high viscosity index as derived from commonly accepted viscosity standards. Because of the aforementioned properties, these polymeric additives have been conveniently termed both thickeners and viscosity index improvers.
  • Polymers of alkyl methacrylates are particularly effective additives of the above type. Included are polyalkyl methacrylates. in which the alkyl groups are mixtures of lower alkyl groups of 7 carbon atoms or less and higher alkyl groups of 8 carbon atoms or more. Some of the more important polymeric methacrylates also provide enhanced detergent properties to mineral lubricating oil compositions as Well as desirable viscosity-temperature characteristics.
  • polymeric viscosity index improvers and detergents of this type are the copolymers of the aforementioned alkyl methacrylates with monomers containing polar groups such as the N,N dialkylaminoalkylmethacrylates, the polyglycolmonomethacrylates and the vinyl nitrogen heterocycles.
  • Mineral lubricating oils containing polymeric additives as described above are also commonly compounded with metal salt organic detergent additives.
  • These metal salt additives alleviate the formation of undesirable engine deposits, by giving the oil enhanced ability to maintain deposit-forming materials such as sludge and resins from oxidation in dispersion in the oil.
  • the more important additives of this type are the essentially neutral alkaline earth metal petroleum sulfonates and the alkaline ear metal phenates of their sulfurized derivatives.
  • Another important type of metal salt organic detergent additive, namely the zinc dithiophosphates imparts not only detergent characteristics but also oxidation and corrosion inhibiting properties to mineral lubricating oil compositions.
  • mineral lubricating oil compositions comprising a major" portion of a mineral lubricating oil, a minor portion suificient to improve the viscosity index of the mineral lubricating oil of an alkylmethacrylate polymer, a minor portion sufiicient to enhance the detergent characteristics of the mineral lubricating oil of a metal salt organic detergent additive selected from the class consisting of neutral alkaline earth metal petroleum sulfonate, alkaline earth metal phenate;
  • the mineral lubricating oil compositions of the invention possess unusually stable viscosity-temperature char-v acteristics compared to mineral lubricating oil,composi-'- tions containing polymethacrylate ester viscos'it'yinde'xd improvers in combination with metal salt organic detergent additives without the alkanediol.
  • the outstanding properties of ⁇ the Y compositions according to the invention are mo stappreciated.
  • the alkanediols containing from 4 to 8 carbon'ator'ns pounds include 1,4-butanediol, Z-methyI-ZA- en'tanediQl f It is found that the viscosity as well as the 'viscosity index of the present compositions remains pra' c-r and 2-ethyl-l,3-hexanediol. For present purposes the 2- methyl-2-4-pentanediol is preferred since it provides the most viscosity stable compositions at lowest concentration.
  • the metal salt organic detergent additives of the more important types such as are employed in the mineral lubricating oil compositions according to the present invention include the neutral alkaline earth metal petroleum sulfonates, alkaline earth metal phenates, sulfurized alkaline earth metal phenates and zinc aromatic dithiophosphates as mentioned above. These particular metallo organic additives are generally recognized as effective lubricating oil detergents and inhibitors and should require no particular description here.
  • Illustrative alkaline earth metal petroleum sulfonates include barium petroleum sulfonate, calcium petroleum sulfonate, magnesium petroleum sulfonate and slightly basic calcium petroleum sulfonates having a base ratio not greater than 0.6 (base ratio" being the ratio of basic calcium to total calcium).
  • Suitable alkaline earth metal alkyl phenates and sulfurized alkaline earth metal alkyl phenates include calcium cetylphenate, calcium tetradecylphenate, barium cetylphenate, and sulfurized calcium cetylphenate.
  • the aforementioned phenates preferably contain from to carbon atoms in the alkyl group and may be normal or basic in nature since both types alter the viscosity-temperature characteristics of the thickened oils undesirably.
  • the zinc aromatic dithiophosphates of the compositions of the invention are characterized by the presence of at least one aryl group.
  • Illustrative thiophosphates of this type include zinc dodecyl phenyl thiophosphate, zinc dihexylphenyl dithiophosphate, zinc hexyl naphthyl dithionhosphate and zinc diamylphenyl dithiophosphate.
  • Thiophosphates without aryl groups do not appear to affect the critical viscosity properties of the thickened compositions.
  • the polymeric methacrylate ester lubricating oil thickeners of the compositions according to the invention are also a recognized class of effective lubricating oil additives.
  • they are polymers of higher alkyl esters of a,fl-unsaturated monocarboxylic acids of from 3 to 8 carbon atoms which contain oil-solubilizing alkyl groups of at least 8 carbon atoms.
  • Illustrative esters of these types include dodecyl methacrylate, octadecyl methacrylate, tridecylacrylate and tetradecyl crotonate.
  • the methacrylates are presently preferred since they provide very satisfactory improvement in the viscosity indexes of lubricating oil compositions.
  • the more suitable polar monomers are the N,N-dialkylaminoalkyl methacrylates such as N,N-diethylaminoethyl methacrylate, the vinyl nitrogen heterocylic compounds such as vinyl pyridine and vinyl pyrrolidone and the polyglycol monomethacrylates such as the dodecyl ether of octadecaethyleneglycol monomethacrylate.
  • Polymeric methacrylate viscosity index improvers of the above-mentioned types are generally characterized by molecular weights in the range of 100,000 to 300,000 and higher.
  • the polar monomers are ordinarily present in proportions of from about 0.1 to about 35.0% by weight of the polymer.
  • the mineral lubricating oil of the lubricant composition of the invention may be any of the usual types of mineral lubricating base oils.
  • Parafiinic or naphthenic base stocks are suitable.
  • the mineral lubricating base oils may be refined by any of the conventional methods Only the substantially neutral sulfonates such as solvent refining or sulfuric acid refining. Solvent-refined Mid-Continent parafiinic-type base stocks appear to present the greatest viscosity stability problem and, therefore, have particular application to the compositions of the invention.
  • the oil was thickened with 6% by weight of the copolymer of a mixture of dodecyl methacrylate, octadecyl methacrylate, butylacrylate and N-vinylpyrrolidone in which there are approximately 65 parts by weight of the dodecyl and octadecyl methacrylates, approximately 25 parts by weight of butylacrylate and approximately 10 parts by weight of N-vinylpyrrolidone.
  • the copolymer has an average molecular weight of approximately 150,000 to 200,000.
  • Various metal salt detergent additives are added to the thickened mineral lubricating oil and the etfect on the viscosity of the oil in Saybolt Seconds Universal (SSU) at 210 F. is observed as indicated in the following table. The proportions of the metallic salt detergent additives are given in millimoles per kilogram (mM./kg.).
  • Oil A in the table is the thickened oil described above consisting of a 200 neutral solvent-refined mineral lubricating oil containing 6% by weight of methacrylate and vinylpyrrolidone copolymer.
  • Oil B is the thickened oil plus 25 mM./kg. of calcium petroleum sulfonate (base ratio 0.4) having an average molecular Weight of approximately 500.
  • Oil C is the thickened oil containing 35 rnM./kg of I mM./kg. of calcium petroleum sulfonate (base ratio 0.4), 6.5 mM./kg. sulfurized calcium tetradecyl phenate and mM./kg. zinc butyl hexyl dithiophosphate.
  • Oil F is a thickened oil consisting of a 150 neutral solvent-refined mineral lubricating oil containing 7.1% by weight of the copolymeric thickener described. above.
  • Oil G is the immediately preceding thickened oil containing 28 mM./ kg. of calcium petroleum sulfonate (base ratio 0.4) having an average molecular weight of approximately 500, 6.5 mM./kg. sulfurized calcium tetradecyl phenate and 10 mM./kg.-zinc butyl hexyl dithiophosphate.
  • Oil H is a thickened oil consisting of 50% by weight 100 neutral solvent-refined mineral lubricating oil and 50% by weight 200 neutral solvent-refined mineral lubricating oil containing 5.0% by weight of the copolymer of butyl and dodecyl methacrylates having a molecular weight of approximately 250,000.
  • Oil I is the thickened oil immediately preceding containing 35 mM./kg. of calcium petroleum sulfonate (base ratio 0.4) having an average molecular weight of approximately 500, 30 mM./kg. sulfurized calcium tetradecyl phenate, l0 mM./kg. Zinc butyl hexyl dithiophosphate and 7 ppm. Dow Corning silicone fluid DC 200, a commercial foam inhibitor.
  • alkanediol to the lubricating oil compositions is shown to overcome practically all the adverse effect on the viscosity incurred by the addition of the metal salt to the thickened oil.
  • the alkanediols of from 4 to 8 carbon atoms are surprisingly better than other glycols in their improving ability while 2-methyl-2,4-pentanediol is the best.
  • the metal salt f 10.0% by weight of the composition. will be, expressed in mM./kg., in the range of ,5 to
  • the alkanediol will be present in amountslin the range of from 0.05 to 1.0% by weight of the composition.
  • a mineral lubricating oil composition comprising a major portion of a mineral lubricating oil, from 0.1 to 10.0% by weight of an oil-soluble copolymer of (A) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 4 to 6 carbon atoms each, (B) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 12 to 20 carbon atoms each and (C) vinyl pyrrolidone, said copolymer having a molecular weight in the range of 100,000 to 300,000 and said vinyl pyrrolidone being from about 0.1 to about 35.0% by weight of the copolymer, from 5 to 100 millimoles per kilogram of a metal salt organic detergent additive selected from the class consisting of neutral alkaline earth metal petroleum sulfonate, alkaline earth metal phenate, sulfurized alkaline earth metal phenate andzinc aromatic dithiophosphat
  • a mineral lubricating oil composition comprising a major portion of a mineral lubricating oil, from 0.1 to 10.0% by weight of a copolymer of (A) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 4 to 6 carbon atoms each, (B) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 12 to 20 carbon atoms each and (C) vinyl pyrrolidone, said copolymer having a molecular Weight in the range of 100,000 to 300,000 and said vinyl pyrrolidone being from about 0.1 to about 35.0% by weight of the copolymer, from 5 to 100 millimoles per kilogram each of neutral alkaline earth metal petroleum sulfonate, sulfurized alkaline earth metal phenate and Zinc dialkyl dithiophosphate containing from 4 to 6 carbon atoms in each of the alkyl groups, and from
  • a lubricating oil composition comprising a major portion of a mineral lubricating oil, from 0.1 to 10.0% by weight of oil-soluble copolymer of (A) an ester selected from the group consisting of alkyl acrylates and alkylmethacrylates having alkyl groups in the range of 4 to 6 carbon atoms each (B) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups in the range of 12 to 20 carbon atoms each and (C) vinyl pyrrolidone, said copolymer having a molecular weight in the range of 100,000 to 300,000 and said vinyl pyrrolidone being from about 0.1 to about 35.0% by Weight of the copolymer, from 5 to 100 millimoles per kilogram each of neutral calcium petroleum sulfonate, sulfurized calcium tetradecylphenate and zinc butyl hexyl dithiophosphate and from 0.05 to 1.0% by weight of 2-methyl-2,4-p
  • a lubricating oil composition comprising a major portion of a mineral lubricating oil, from 0.1 to 10.0% by weight of oil-soluble copolymer of (A) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 4 to 6 carbon atoms each, (B) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 12 to 20 carbon atoms each and (C) vinyl pyrrolidone, said copolymer having a molecular weight in the range of 100,000 to 300,000 and said vinyl pyrrolidone being from about 0.1 to about 35.0% by weight of the copolymer, from 5 to millimoles per kilogram each of neutral calcium petroleum sulfonate, sulfurized calcium tetradecylphenate and zinc butyl hexyl dithiophosphate and from 0.05 to 1.0% by weight of 2-ethyl-1,3-he
  • a lubricating oil composition comprising a major portion of a mineral lubricating oil, from 0.1 to 10.0% by weight of oil-soluble copolymer of (A) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 4 to 6 carbon atoms each, (B) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 12 to 20 carbon atoms each and (C) vinyl pyrrolidone, said copolymer having a molecular weight in the range of 100,000 to 300,000 and said vinyl pyrrolidone being from about 0.1 to about 35.0% by weight of the copolymer, from 5 to 100 millimoles per kilogram of neutral calcium petroleum sulfonate and from 0.05 to 1.0% by weight of 2-ethyl-1,3-hexanedio1.
  • a lubricating oil composition comprising a major portion of a mineral lubricating oil, from 0.1 to 10.0% by weight of oil-soluble copolymer of (A) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 4 to 6 carbon atoms each, (B) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 12 to 20 carbon atoms each and (C) vinyl pyrrolidone, said copolymer having a molecular weight in the range of 100,000 to 300,000 and said vinyl pyrrolidone being from about 0.1 to about 35.0% by weight of the copolymer, from 5 to 100 millimoles per kilogram of sulfurized calcium tetradecyl phenate and from 0.05 to 1.0% by weight of 2-ethyl-1,3-hexanediol.

Description

LUBRICATING OIL COMPOSITION Andrew D. Abbott, Ross, Calif., assignor to California Research Corporation, San Francisco, Calif., a corporation of Delaware No Drawing. Filed Mar. 31, 1958, Ser. No. 724,871
6 Claims. (Cl. 252-32.7)
This invention relates to a lubricating oil composition having improved physical properties. More particularly the invention is concerned with a stable viscosity mineral lubricating oil composition containing metal salt organic detergent additives in combination with polymeric thickening additives.
Polymeric additives are extensively used in mineral lubricating oil compositions to impart desirable viscositytemperature characteristics to the compositions. These additives are designed to modify lubricating oils so that changes in viscosity occurring with variations in temperature arekept as small as possible. Lubricating oils containing such polymeric additives are somewhat thickened at the higher temperatures normally encountered in engine operation while at the same time retaining desirable low viscosity fluidity at' cold starting temperatures. The ability of a lubricating oil to accommodate increased temperatures with a minimum decrease in viscosity is indicated by its high viscosity index as derived from commonly accepted viscosity standards. Because of the aforementioned properties, these polymeric additives have been conveniently termed both thickeners and viscosity index improvers.
Polymers of alkyl methacrylates are particularly effective additives of the above type. Included are polyalkyl methacrylates. in which the alkyl groups are mixtures of lower alkyl groups of 7 carbon atoms or less and higher alkyl groups of 8 carbon atoms or more. Some of the more important polymeric methacrylates also provide enhanced detergent properties to mineral lubricating oil compositions as Well as desirable viscosity-temperature characteristics. Among the more important polymeric viscosity index improvers and detergents of this type are the copolymers of the aforementioned alkyl methacrylates with monomers containing polar groups such as the N,N dialkylaminoalkylmethacrylates, the polyglycolmonomethacrylates and the vinyl nitrogen heterocycles.
Mineral lubricating oils containing polymeric additives as described above are also commonly compounded with metal salt organic detergent additives. These metal salt additives alleviate the formation of undesirable engine deposits, by giving the oil enhanced ability to maintain deposit-forming materials such as sludge and resins from oxidation in dispersion in the oil. Among the more important additives of this type are the essentially neutral alkaline earth metal petroleum sulfonates and the alkaline ear metal phenates of their sulfurized derivatives. Another important type of metal salt organic detergent additive, namely the zinc dithiophosphates imparts not only detergent characteristics but also oxidation and corrosion inhibiting properties to mineral lubricating oil compositions.
The two different classes of additives described above have been combined to give mineral lubricating oil com positions having excellent detergent properties along with superior viscosity-temperature characteristics. Unfortu-' nately, it happens that the addition of the important metal salt organic detergents to mineral lubricating oils containing the polymeric thickeners mentioned above has a decidedly adverse effect on the viscosity-temperature characteristics of the mineral lubricating oil compositions.
' ranges commonly encountered in internal combustion en gines. Polymeric thickener-s of the important polymethacrylate ester type are added to these oils to raise the viscosity index radically and thus enable a single oil to meet the specification viscosity ranges of two or three different SAE viscosity grades. The increase in viscosity, particularly at low temperatures where only certain viscosities can be tolerated, and the depreciation of the aforementioned critical viscosity index improvement of the thickened lubricating oil by the addition of the more important metal salt organic detergent additives referred to above may prevent an oil from qualifying as a .multigrade oil. a g I The addition of the metal salt organic detergent additives to the thickened mineral lubricating oils has both an immediate adverse effect as described above, an d also a postponed effect in that further undesirable increases in viscosity and depreciation of the viscosity index are observed over certain periods of time. This effect which has been conveniently termed viscosity drift is extremely critical since an otherwise satisfactory oil may become completely unsatisfactory during the usual storage periods for lubricating oils.
It has now been found that stable viscosity-temperature characteristics are'provided in mineral lubricating oil compositions comprising a major" portion ofa mineral lubricating oil, a minor portion suificient to improve the viscosity index of the mineral lubricating oil of an alkylmethacrylate polymer, a minor portion sufiicient to enhance the detergent characteristics of the mineral lubricating oil of a metal salt organic detergent additive selected from the class consisting of neutral alkaline earth metal petroleum sulfonate, alkaline earth metal phenate;
sulfurized alkaline earth metal phenate and zinc aromatic dithiophosphate and a minor portion sufficient to stabilize I the viscosityof the mineral lubricating oil composition of an alkanediol containing from 4 to 8 c'arbonatoms.
The mineral lubricating oil compositions of the invention possess unusually stable viscosity-temperature char-v acteristics compared to mineral lubricating oil,composi-'- tions containing polymethacrylate ester viscos'it'yinde'xd improvers in combination with metal salt organic detergent additives without the alkanediol. Particularly in the case of the multigrade lubricating oils where certain minimum low temperature'viscosities and minimum variations in viscosty of the oil over broad temperature ranges are critical, the outstanding properties of} the Y compositions according to the invention are mo stappreciated.
tically unchanged, even over extended periods'of time.
The alkanediols containing from 4 to 8 carbon'ator'ns pounds include 1,4-butanediol, Z-methyI-ZA- en'tanediQl f It is found that the viscosity as well as the 'viscosity index of the present compositions remains pra' c-r and 2-ethyl-l,3-hexanediol. For present purposes the 2- methyl-2-4-pentanediol is preferred since it provides the most viscosity stable compositions at lowest concentration. The metal salt organic detergent additives of the more important types such as are employed in the mineral lubricating oil compositions according to the present invention include the neutral alkaline earth metal petroleum sulfonates, alkaline earth metal phenates, sulfurized alkaline earth metal phenates and zinc aromatic dithiophosphates as mentioned above. These particular metallo organic additives are generally recognized as effective lubricating oil detergents and inhibitors and should require no particular description here. Illustrative alkaline earth metal petroleum sulfonates include barium petroleum sulfonate, calcium petroleum sulfonate, magnesium petroleum sulfonate and slightly basic calcium petroleum sulfonates having a base ratio not greater than 0.6 (base ratio" being the ratio of basic calcium to total calcium). seem to have an adverse effect on the thickened mineral lubricating oils. Suitable alkaline earth metal alkyl phenates and sulfurized alkaline earth metal alkyl phenates include calcium cetylphenate, calcium tetradecylphenate, barium cetylphenate, and sulfurized calcium cetylphenate. The aforementioned phenates preferably contain from to carbon atoms in the alkyl group and may be normal or basic in nature since both types alter the viscosity-temperature characteristics of the thickened oils undesirably. The zinc aromatic dithiophosphates of the compositions of the invention are characterized by the presence of at least one aryl group. Illustrative thiophosphates of this type include zinc dodecyl phenyl thiophosphate, zinc dihexylphenyl dithiophosphate, zinc hexyl naphthyl dithionhosphate and zinc diamylphenyl dithiophosphate. Thiophosphates without aryl groups do not appear to affect the critical viscosity properties of the thickened compositions.
The polymeric methacrylate ester lubricating oil thickeners of the compositions according to the invention are also a recognized class of effective lubricating oil additives. In general, they are polymers of higher alkyl esters of a,fl-unsaturated monocarboxylic acids of from 3 to 8 carbon atoms which contain oil-solubilizing alkyl groups of at least 8 carbon atoms. Illustrative esters of these types include dodecyl methacrylate, octadecyl methacrylate, tridecylacrylate and tetradecyl crotonate. The methacrylates are presently preferred since they provide very satisfactory improvement in the viscosity indexes of lubricating oil compositions. Other monomers, including lower alkyl methacrylates such as butyl methacrylate, may also be copolymerized with the aforementioned higher alkyl methacrylates. Polar monomers such as those characteristic of polymeric detergent additives for lubricating oils may also be included. These polymeric additives are also eiiective viscosity index improvers as well as superior detergents. The more suitable polar monomers are the N,N-dialkylaminoalkyl methacrylates such as N,N-diethylaminoethyl methacrylate, the vinyl nitrogen heterocylic compounds such as vinyl pyridine and vinyl pyrrolidone and the polyglycol monomethacrylates such as the dodecyl ether of octadecaethyleneglycol monomethacrylate.
Polymeric methacrylate viscosity index improvers of the above-mentioned types are generally characterized by molecular weights in the range of 100,000 to 300,000 and higher. In the case of the detergent polymeric com pounds, the polar monomers are ordinarily present in proportions of from about 0.1 to about 35.0% by weight of the polymer.
The mineral lubricating oil of the lubricant composition of the invention may be any of the usual types of mineral lubricating base oils. Parafiinic or naphthenic base stocks are suitable. The mineral lubricating base oils may be refined by any of the conventional methods Only the substantially neutral sulfonates such as solvent refining or sulfuric acid refining. Solvent-refined Mid-Continent parafiinic-type base stocks appear to present the greatest viscosity stability problem and, therefore, have particular application to the compositions of the invention.
Further illustrations of the improved mineral lubricating oil compositions according to the present invention are provided by the following examples. Unless otherwise specified, the proportions in the examples are on a weight basis.
Several mineral lubricating oil compositions containing the typical polymethacrylate thickeners referred to above and the metal salt organic detergent additives were prepared to show the effect of the metal salt additives on the thickened mineral lubricating oil compositions. In the compositions the base oil was a Mid-Continent parafiinic 200 neutral solvent refined mineral lubricating oil having a viscosity of 200 SSU at F. The oil was thickened with 6% by weight of the copolymer of a mixture of dodecyl methacrylate, octadecyl methacrylate, butylacrylate and N-vinylpyrrolidone in which there are approximately 65 parts by weight of the dodecyl and octadecyl methacrylates, approximately 25 parts by weight of butylacrylate and approximately 10 parts by weight of N-vinylpyrrolidone. The copolymer has an average molecular weight of approximately 150,000 to 200,000. Various metal salt detergent additives are added to the thickened mineral lubricating oil and the etfect on the viscosity of the oil in Saybolt Seconds Universal (SSU) at 210 F. is observed as indicated in the following table. The proportions of the metallic salt detergent additives are given in millimoles per kilogram (mM./kg.).
TABLE I Viscosity Viscosity Oil at 210 F., Increase,
SSU SSU,210F.
Thic ened Oil 63.0 Thickened Oil plus 25 mMJkg. calcium sulfonate (base ratio 0.4) 76. 0 13.0 Thickened Oil plus 35 miNL/kg. sulfurized 021- v clum tetradecyl phenate 1 80. 0 17.0 Thickened Oil plus 30 mMJkz. zinc di(tetradecylphenyll dithiophosphate 70.0 7.0 Thiclrcned Oil plus 25 mMJkg. zinc butylhexyl dithiophosphate 63.0 0.0
l 'Ietradecyl phenate derived from a. mixture of propylene tetramer and penta'ner alkylated phenols having an average of approximately 1-1 carbon atoms in the alkyl group.
According to the above test results, it will be seen that the important metallic salt detergent additives of the alkaline earth metal petroleum sulfonate, alkaline earth metal phenate and zinc aromatic dithiophosphate types all have an adverse effect on the viscosity of the thickened mineral lubricating oil. The unusual nature of the viscosity stability problem shown by'the above test data is emphasized by the fact that certain other metal salt detergent additives such as the zinc dialkyl dithiophosphates do not have any such adverse effect on the viscosity of the thickened mineral lubricating oil.
The effect of the inclusion of an alkanediol containing from 4 to 8 carbon atoms in the thickened mineral lubricating oil compositions containing metal salt detergent additives in accordance with this invention is shown by a number of examples. Test results illustrating the viscosity-temperature characteristics of these examples are given in the following table.
Oil A in the table is the thickened oil described above consisting of a 200 neutral solvent-refined mineral lubricating oil containing 6% by weight of methacrylate and vinylpyrrolidone copolymer.
Oil B is the thickened oil plus 25 mM./kg. of calcium petroleum sulfonate (base ratio 0.4) having an average molecular Weight of approximately 500.
Oil C is the thickened oil containing 35 rnM./kg of I mM./kg. of calcium petroleum sulfonate (base ratio 0.4), 6.5 mM./kg. sulfurized calcium tetradecyl phenate and mM./kg. zinc butyl hexyl dithiophosphate.
Oil F is a thickened oil consisting of a 150 neutral solvent-refined mineral lubricating oil containing 7.1% by weight of the copolymeric thickener described. above.
Oil G is the immediately preceding thickened oil containing 28 mM./ kg. of calcium petroleum sulfonate (base ratio 0.4) having an average molecular weight of approximately 500, 6.5 mM./kg. sulfurized calcium tetradecyl phenate and 10 mM./kg.-zinc butyl hexyl dithiophosphate.
Oil H is a thickened oil consisting of 50% by weight 100 neutral solvent-refined mineral lubricating oil and 50% by weight 200 neutral solvent-refined mineral lubricating oil containing 5.0% by weight of the copolymer of butyl and dodecyl methacrylates having a molecular weight of approximately 250,000.
Oil I is the thickened oil immediately preceding containing 35 mM./kg. of calcium petroleum sulfonate (base ratio 0.4) having an average molecular weight of approximately 500, 30 mM./kg. sulfurized calcium tetradecyl phenate, l0 mM./kg. Zinc butyl hexyl dithiophosphate and 7 ppm. Dow Corning silicone fluid DC 200, a commercial foam inhibitor.
with varying amounts of Z-methyl-Z,4-p'entanediol. The
results of these tests are given in Table III as follows:
TABLE III Days storage at Per Cent 0 0.1% 0.3 Room Tempera- Alkanediol tnre SSU, 210 F 63. 9 61. 7 60. 4 0 SSU, 0 F 5, 300 VI 150 SSU, 210 F 00. 4; 7 SSU, 0 F 5, 600
VI 149 SSU, 2l0 F 00.3 14; SSU, 0 F 5,700 .I 149 SSU, 210 F 60. 4 a0 SD, 5, 600 I 149 From the above test results it is seen that the mineral lubricating oil compositions containing polymeric thickener and metal salt have unstableviscosity-temperature characteristics during storage. The viscosities at 0v F. are undesirably high to begin with and become drastically worse with time. Furthermore, the viscosity index of such oils deteriorates with time.
By way of contrast, the same mineral lubricating oil compositions with 2-rnethyl-2,4-pentanediol have considerably improved low viscosities at 0 F. Their viscosity indexes are raised substantially. Both low temperature viscosity and the viscosity indexes of such compositions are stable throughout the extended period of 30 days" storage time.
In the foregoing description of the mineral lubricating TABLE II Visco ity Viscosity Viscosity Viscosity Percent Oil at 0 F., at 210 F., Increase, Correction, Improve- SSU SSU 0 F., 210 F., ment SSU SSU' A-(Thickeued Oil) 7, 800 63.0 B('Ihickeuel Oil Metal Salt) 13,000 76.0 13.0 B(Ihickened Oil Metal Salt) 0.3%
z-Ethyl lfi-llexanediol 10, 600 68. 0 8. 0 62 o-(Thic'ze-iei Oil Metal Salt) 14, 500 80.0 17.0 C-(Thickeaed Oil Metal Salt) 3% 2 Ethyl-l,3-Hexanediol 12,000 70. 0 10. 0 D('Ihickenefl Oil) 4, 900 55. 2 E-(Thickeneil Oil Metal Salt) 9, 900 62.3 7. 1 E-(Thickeue'.l Oil Metal Salt) 0.2%
2-Methyl-2,4-Pentanediol 9, 300 59. 2 3. 1 43 E-(Thicke' ei Oil Metal Salt) yl g F-(Thickeaerl 0il) G-(Tbickeued Oil Metal Salt) G(Thickenecl Oil Metal Salt 0.1%
2-MetbyL2A-Pentanediol G(Thie r-ened Oil Metal Salt) 0.3%
2-Methyl-2A-Pe'1tanedlol G-(Thickene'l Oil Meta] Salt) 2-Ethyl-1,3Hexanedl0l G-(Thickenefl Oil Metal Salt) -l- 0.5%
2-Ethyl-l,3-Hexanediol G(Thicke'1e:l Oil Metal Salt) 0.2%
Negative Dlbntylether Diethylcueglycol 10,000 H-(Thiclrenerl Oil) I-(Thicrenei Oil Metal Salt) 10, 700 I-(Thicreuel Oil Metal Salt) 0.3%
2-Methyl-2,4-Pentanediol 8, 700
In the above-described test results addition of alkanediol to the lubricating oil compositions is shown to overcome practically all the adverse effect on the viscosity incurred by the addition of the metal salt to the thickened oil. The alkanediols of from 4 to 8 carbon atoms are surprisingly better than other glycols in their improving ability while 2-methyl-2,4-pentanediol is the best.
Experiments were also carried out with the mineral lubricating oil compositions of the invention to illustrate the stability of their desirable viscosity-temperature characteristics over extended periods of time such as those encountered under normal storage conditions. A number of samples of thickened oils and metal salts, as described in connection with oil G above, were treated be apparent to those skilled in the art. Expressed in numerical ranges, however, the polymeric thickening additives will be in the customary range of from 0.1 to
The metal salt f 10.0% by weight of the composition. will be, expressed in mM./kg., in the range of ,5 to
mM./kg. The alkanediol will be present in amountslin the range of from 0.05 to 1.0% by weight of the composition.
I claim:
1. A mineral lubricating oil composition comprising a major portion of a mineral lubricating oil, from 0.1 to 10.0% by weight of an oil-soluble copolymer of (A) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 4 to 6 carbon atoms each, (B) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 12 to 20 carbon atoms each and (C) vinyl pyrrolidone, said copolymer having a molecular weight in the range of 100,000 to 300,000 and said vinyl pyrrolidone being from about 0.1 to about 35.0% by weight of the copolymer, from 5 to 100 millimoles per kilogram of a metal salt organic detergent additive selected from the class consisting of neutral alkaline earth metal petroleum sulfonate, alkaline earth metal phenate, sulfurized alkaline earth metal phenate andzinc aromatic dithiophosphate in which the aromatic groups are selected from the class consisting of alkyl phenyl and alkyl naphthyl groups and from 0.05 to 1.0% by weight of alkanediol containing from 4 to 8 carbon atoms.
2. A mineral lubricating oil composition comprising a major portion of a mineral lubricating oil, from 0.1 to 10.0% by weight of a copolymer of (A) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 4 to 6 carbon atoms each, (B) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 12 to 20 carbon atoms each and (C) vinyl pyrrolidone, said copolymer having a molecular Weight in the range of 100,000 to 300,000 and said vinyl pyrrolidone being from about 0.1 to about 35.0% by weight of the copolymer, from 5 to 100 millimoles per kilogram each of neutral alkaline earth metal petroleum sulfonate, sulfurized alkaline earth metal phenate and Zinc dialkyl dithiophosphate containing from 4 to 6 carbon atoms in each of the alkyl groups, and from 0.05 to 1.0% by weight of alkanediol containing from 4 to 8 carbon atoms.
3. A lubricating oil composition comprising a major portion of a mineral lubricating oil, from 0.1 to 10.0% by weight of oil-soluble copolymer of (A) an ester selected from the group consisting of alkyl acrylates and alkylmethacrylates having alkyl groups in the range of 4 to 6 carbon atoms each (B) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups in the range of 12 to 20 carbon atoms each and (C) vinyl pyrrolidone, said copolymer having a molecular weight in the range of 100,000 to 300,000 and said vinyl pyrrolidone being from about 0.1 to about 35.0% by Weight of the copolymer, from 5 to 100 millimoles per kilogram each of neutral calcium petroleum sulfonate, sulfurized calcium tetradecylphenate and zinc butyl hexyl dithiophosphate and from 0.05 to 1.0% by weight of 2-methyl-2,4-pentanediol.
4. A lubricating oil composition comprising a major portion of a mineral lubricating oil, from 0.1 to 10.0% by weight of oil-soluble copolymer of (A) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 4 to 6 carbon atoms each, (B) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 12 to 20 carbon atoms each and (C) vinyl pyrrolidone, said copolymer having a molecular weight in the range of 100,000 to 300,000 and said vinyl pyrrolidone being from about 0.1 to about 35.0% by weight of the copolymer, from 5 to millimoles per kilogram each of neutral calcium petroleum sulfonate, sulfurized calcium tetradecylphenate and zinc butyl hexyl dithiophosphate and from 0.05 to 1.0% by weight of 2-ethyl-1,3-hexanediol.
5. A lubricating oil composition comprising a major portion of a mineral lubricating oil, from 0.1 to 10.0% by weight of oil-soluble copolymer of (A) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 4 to 6 carbon atoms each, (B) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 12 to 20 carbon atoms each and (C) vinyl pyrrolidone, said copolymer having a molecular weight in the range of 100,000 to 300,000 and said vinyl pyrrolidone being from about 0.1 to about 35.0% by weight of the copolymer, from 5 to 100 millimoles per kilogram of neutral calcium petroleum sulfonate and from 0.05 to 1.0% by weight of 2-ethyl-1,3-hexanedio1.
6. A lubricating oil composition comprising a major portion of a mineral lubricating oil, from 0.1 to 10.0% by weight of oil-soluble copolymer of (A) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 4 to 6 carbon atoms each, (B) an ester selected from the group consisting of alkylacrylates and alkylmethacrylates having alkyl groups containing from 12 to 20 carbon atoms each and (C) vinyl pyrrolidone, said copolymer having a molecular weight in the range of 100,000 to 300,000 and said vinyl pyrrolidone being from about 0.1 to about 35.0% by weight of the copolymer, from 5 to 100 millimoles per kilogram of sulfurized calcium tetradecyl phenate and from 0.05 to 1.0% by weight of 2-ethyl-1,3-hexanediol.
References Cited in the file of this patent UNITED STATES PATENTS 2,329,474 Lazar et al. Sept. 14, 1943 2,602,048 Michaels et a1. July 1, 1952 2,623,016 Mertes Dec. 23, 1952 2,833,719 Van Horne et al. May 6, 1958 2,850,450 Galindo et al. Sept. 2, 1958 2,850,455 Kern et a1. Sept. 2, 1958 OTHER REFERENCES Hexylene Glycol, Shell Chem. Corp., San Francisco, Calif. 1950, pages 8 and 15. v

Claims (1)

1. A MINERAL LUBRICATING OIL COMPOSITION COMPRISING A MAJOR PORTION OF A MINERAL LUBRICATING OIL, FROM 0.1 TO 10.0% BY WEIGHT OF AN OIL-SOLUBLE COPOLYMER OF (A) AN ESTER SELECTED FROM THE GROUP CONSISTING OF ALKYLACRYLATES AND ALKYLMETHACRYLATES HAVING ALKYL GROUPS CONTAINING FROM 4 TO 6 CARBON ATOMS EACH, (B) AN ESTER SELECTED FROM THE GROUP CONSISTING OF ALKYLACRYLATES AND ALKYLMETHACRYLATES HAVING ALKYL GROUPS CONTAINING FROM 12 TO 20 CARBON ATOMS EACH AND (C) VINYL PYRROLIDONE, SAID COPOLYMER HAVING A MOLECULAR WEIGHT IN THE RANGE OF 100,000 TO 300,000 AND SAID VINYL PYRROLIDONE BEING FROM ABOUT 0.1 TO ABOUT 35.0% BY WEIGHT OF THE COPOLYMER, FROM 5 TO 100 MILLIMOLES PER KILOGRAM OF A METAL SALT ORGANIC DETERGENT ADDITIVE SELECTED FROM THE CLASS CONSISTING OF NEUTRAL ALKALINE EARTH METAL PETROLEUM SULFONATE, ALKALINE EARTH METAL PHENATE, SULFURIZED ALKALINE EARTH METAL PHENATE AND ZINC AROMATIC DITHIOPHOSPHATE IN WHICH THE AROMATIC GROUPS ARE SELECTED FROM THE CLASS CONSISTING OF ALKYL PHENYL AND ALKYL NAPHTHYL GROUPS AND FROM 0.05 TO 1.0% BY WEIGHT OF ALKANEDIOL CONTAINING FROM 4 TO 8 CARBON ATOMS.
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Publication number Priority date Publication date Assignee Title
US3127349A (en) * 1964-03-31 Lubricating oil compositions having a
US4534873A (en) * 1983-09-28 1985-08-13 Clark Gary G Automotive friction reducing composition

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