Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/20—Thiols; Sulfides; Polysulfides
  • C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
  • C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives thereof
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
  • C10M159/12—Reaction products
  • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
  • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
  • C10M2201/04—Elements
  • C10M2201/05—Metals; Alloys
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
  • C10M2201/06—Metal compounds
  • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
• • 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
  • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
  • C10M2201/06—Metal compounds
  • C10M2201/063—Peroxides
• • 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
  • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
  • C10M2201/08—Inorganic acids or 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
  • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
  • C10M2201/08—Inorganic acids or salts thereof
  • C10M2201/081—Inorganic acids or salts thereof containing halogen
• • 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
  • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
  • C10M2201/08—Inorganic acids or salts thereof
  • C10M2201/082—Inorganic acids or salts thereof containing nitrogen
• • 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
  • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
  • C10M2201/08—Inorganic acids or salts thereof
  • C10M2201/084—Inorganic acids or salts thereof containing sulfur, selenium or tellurium
• • 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
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/02—Well-defined aliphatic 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
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/02—Well-defined aliphatic compounds
  • C10M2203/022—Well-defined aliphatic compounds saturated
• • 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
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/02—Well-defined aliphatic compounds
  • C10M2203/024—Well-defined aliphatic compounds unsaturated
• • 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
  • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
  • C10M2203/04—Well-defined cycloaliphatic compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty 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
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
• • 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
• • 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
  • C10M2215/26—Amines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • C10M2223/041—Triaryl phosphates
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/02—Groups 1 or 11
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
• • 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
  • C10N2070/00—Specific manufacturing methods for lubricant compositions
  • C10N2070/02—Concentrating of additives

Definitions

• This invention relates to a sulfur-based additive exhibiting improved performance for use in lubricants and functional fluids. More specifically, substantially labile-sulfur free additives for lubricants and functional fluids are obtained by treatment with copper, or copper and another material reactive with labile-sulfur in order to substantially eliminate the detrimental metal corrosivity and the detrimental degradation of elastomer materials which are exhibited by labile-sulfur containing additives.
• Sulfur-based additives have been widely used in various lubricants, e.g., crankcase lubricating oils, gear lubricants, metal-working lubricants and the like, and in various functional fluids, e.g., hydraulic fluids, automatic transmission fluids, heat transfer fluids and the like.
• the most common of such sulfur-based additives are phenolsulfides, disulfides, polysulfides, salts thereof, overbased salts thereof, and mixtures thereof. These additives function as oxidation inhibitors, antiwear additives and load carrying additives for these different categories of fluids.
• sulfur-based additives While these sulfur-based additives have been found to be quite effective for the above-mentioned functions, they have generally been found to be corrosive to metals such as copper and copper alloys which are widely used as bearings and bearing liners and have been found to cause the degradation of elastomer materials which are used as seals or sealant devices.
• US Patent No. 4228022 describes a lubricating oil additive formed from the reaction of (a) an alkylphenol, (b) sulfur, (c) an alkaline earth metal, and (d) an olefin.
• the reaction may be carried out in two steps with a sulfurized alkylphenol being formed in a first step followed by reaction of the sulfurized phenol with the olefin in the second step.
• EP-A-0076376 describes a method for improving the odour of dialkyl polysulfides which contain sulfur-bearing odoriferous impurities wherein the polysulfide is contacted with an inorganic or monocarboxylic acid salt of a metal selected from manganese, iron, cobalt, nickel, copper, zinc, silver, lead, cadmium and mercury.
• British Patent No. 1209500 describes a process for improving the oxidative stability of a polyphenyl thioether functional fluid by treating the thioether with a Group Ib or IIb metal or oxide thereof.
• a sulfur-based additive selected from phenol sulfides, disulfides or polysulfides and salts thereof or overbased salts thereof, which has been treated with a) copper in its elemental state or as a salt, or with b) copper and an optional material reactive with labile-sulfur selected from olefins, unsaturated natural oils, a Diels-Alder reaction product of butadiene and esters of acrylic acid, metallic basic salts, amines, organic phosphites and combinations thereof, at an elevated temperature to remove labile-sulfur from said additive, as an additive for lubricants or functional fluids to substantially eliminate the detrimental degradation of elastomer materials contacted by said lubricant or functional fluid.
• labile-sulfur free additives exhibiting improved performance
• labile-sulfur free additive concentrates containing such additives
• lubricant and functional fluid compositions containing such additives and a method for lubricating copper and copper-alloy bearings by applying lubricant and functional fluid compositions containing such additives thereto are contemplated and within the scope of the present invention.
• the method of the present invention involves contacting certain sulfur-based additives for lubricants and functional fluids with copper or copper and another material reactive with labile-sulfur at an elevated temperature conveniently followed by filtering off copper sulfide and other particulate material from the thus treated additive to give an essentially labile-sulfur free additive.
• essentially all labile-sulfur is removed from these additives where the resulting treated additive contains at most about 0.4% by weight of labile-sulfur.
• Employing thus treated additives in lubricants and functional fluids substantially eliminates the problem of metal corrosion and elastomer degradation previously exhibited by sulfur-based additives.
• the method of the present invention does not have some of the other inherent problems associated with previous approaches to overcome the metal corrosion and elastomer degradation problem such as various formulating problems, inhibition of the properties of these additives and the like.
• sulfur-based additives may be treated with copper or copper and another labile-sulfur reactive material.
• copper includes metallic copper as well as copper salts.
• the physical form of metallic copper used in the method of the invention is not particularly critical and may include turnings, granules and powder.
• copper powder has been found to be particularly useful.
• Copper salts that may be useful within the scope of the present invention there may be mentioned oxides, oleates and halides, preferably chlorides.
• the amount of copper used to treat various sulfur-based additives should be sufficient to essentially remove all labile-sulfur contained by the additive. More specifically, the amount of copper generally utilized in the method of the present invention ranges from about 5% by weight based on the additive to about 0.01% by weight and preferably in the range of about 1.0% to about 0.1% by weight of the additive.
• unsaturated natural oils including vegetable and animal oils such as soybean oil, lard and the like: various olefins, particularly alpha-olefins which preferably have 4 to 30 carbon atoms and most preferably 10 to 20 carbon atoms: the Diels-Alder reaction products of butadiene and esters of acrylic acid, preferably butylacrylate: organic phosphites such as triphenol phosphite: basic metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate and the like: and various amines, including primary and secondary amines.
• vegetable and animal oils such as soybean oil, lard and the like: various olefins, particularly alpha-olefins which preferably have 4 to 30 carbon atoms and most preferably 10 to 20 carbon atoms: the Diels-Alder reaction products of butadiene and esters of acrylic acid, preferably butylacrylate: organic phosphites such as triphenol phosphite: basic metal salt
• the amount of these other reactive materials used with copper in the method of the present invention is not particularly critical wherein the amount of labile-sulfur present in the, particular additive to be treated and economics will be determinative of the actual amount used.
• the amount used within the practice of the present invention may range from about 1 part of other reactive material to about 10 parts copper to 10 parts other reactive material to about 1 part copper.
• the method of the present invention is generally conducted at atmospheric pressure, however, higher pressures may be utilized.
• the contacting of the sulfur-based additives with the treating agents of the present invention is conducted at temperatures sufficient to react essentially all the labile-sulfur present in the particular additive which is usually at an elevated temperature, preferably in the temperature range of from about 100°C to about 250°C and most preferably from about 130°C to about 160°C.
• the temperature range may vary widely depending upon the particular treating agent and/or the presence of a catalyst.
• the additives that may be treated according to the method of the present invention are selected from phenolsulfides, disulfides, polysulfides, salts thereof and overbased salts thereof.
• These "sulfurized" phenols include alkyl and dialkyl phenols wherein the alkyl group may range from about 6 to about 100 carbon atoms.
• Many of these sulfurized phenols are commercially available or may be prepared by initially reacting a phenol or alkylphenol with a sulfur monohalide (e.g., sulfurmonochloride). This reaction may be conducted in the presence of excess base to result in the salts of the mixture of sulfides, disulfides or polysulfides that may be produced depending upon the reaction conditions.
• One particular class of phenates for use in this invention are the basic (i.e., overbased, etc.) Group IIA metal sulfurized phenates made by sulfurizing a phenol as described hereinabove with a sulfurizing agent such as sulfur, a sulfur halide, or sulfide or hydrosulfide salt. Techniques for making these sulfurized phenates are described in U.S. Patents 2,680,096: 3,036,971 and 3,775,321.
• the additives of the present invention which are essentially labile-sulfur free, find use in a wide range of lubricants and functional fluids.
• Such additives may be employed in a variety of lubricants based on diverse oils of lubricating viscosity, including natural and synthetic lubricating oils and mixtures thereof.
• the lubricants include crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, including automobile and truck engines, 2-cycle engines, aviation piston engines, marine and railroad diesel engines and the like. Also contemplated are lubricants for gas engines, stationary power engines and turbines and the like.
• Transaxle lubricants are within the scope of the present invention.
• Various functional fluids to which the additives of the present invention may be added include hydraulic fluids, heat transfer fluids, automatic transmission fluids and the like.
• Natural oils include animal oils and vegetable oils (e.g., castor, lard oil) liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
• animal oils and vegetable oils e.g., castor, lard oil
• mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types.
• Oils of lubricating viscosity derived from coal or shale are also 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(Z-ethylhexyl)benzenes]: polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols): and alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, 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, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of poly-ethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500): and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters and C13 Oxo acid diester of tetraethylene glycol.
• polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide,
• 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, sebacic 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, sebacic acid, fumaric acid, adipic acid, linole
• esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
• Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
• Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils and silicate oils comprise another useful class of synthetic lubricants: they include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-pentoxy)disiloxane, poly(methyl)siloxanes and poly(methylphenyl) siloxanes.
• Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
• Unrefined, refined and rerefined oils can be used in the lubricants of the present invention.
• Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
• a shale oil obtained directly from retorting operations a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil.
• Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art.
• Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
• the lubricants of the present invention contain a performance and lubricating improving amount of one or more of the treated sulfur-based additives of this invention which do not corrode metals or only to a minor, insignificant extent and do not degrade elastomer materials or only to a minor, insignificant extent.
• the amount employed will be about 0.05% to about 20%, preferably about 0.1% to about 10% of the total weight of the lubricating composition. This amount is exclusive of solvent/diluent medium.
• the sulfur based additives of this invention may be present in amounts of up to about 30% by weight, or more, of the total weight of the lubricating composition.
• additives include, for example, detergents and dispersants of the ash-producing or ashless type, and other oxidation-inhibiting agents, pour point depressing agents, extreme pressure agents, antiwear agents, color stabilizers and anti-foam agents.
• the ash-producing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, or organic phosphorus acids characterized by at least one direct carbon-to-phosphorus linkage such as those prepared by the treatment of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride.
• olefin polymer e.g., polyisobutene having a molecular weight of 1000
• a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide,
• basic salt is used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical.
• the commonly employed methods for preparing the basic salts involve heating a mineral oil solution of an acid with a stoichiometric excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature of about 50°C. and filtering the resulting mass.
• a “promoter” in the neutraliziation step to aid the incorporation of a large excess of metal likewise is known.
• compound useful as the promoter examples include phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation products of formaldehyde with a phenolic substance: alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol: and amines such as aniline, phenylenediamine, phenothiazine, phenyl- ⁇ -naphthylamine, and dodecylamine.
• a particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol promoter, and carbonating the mixture at an elevated temperature such as 60-200°C.
• Ashless detergents and dispersants are so called despite the fact that, depending on its constitution, the dispersant may upon combustion yield a non-volatile material such as boric oxide or phosphorus pentoxide: however, it does not ordinarily contain metal and therefore does not yield a metal-containing ash on combustion.
• a non-volatile material such as boric oxide or phosphorus pentoxide
• Many types are known in the art, and any of them are suitable for use in the lubricant compositions of this invention.
• the following are illustrative: (1) Reaction products of carboxylic acids (or derivatives thereof) containing at least about 34 and preferably at least about 54 carbon atoms with nitrogen containing compounds such as amine, organic hydroxy compounds such as phenols and alcohols, and/or basic inorganic materials.
• amine dispersants examples thereof are described for example, in the following U.S. patents: 3,275,554 3,454,555 3,438,757 3,565,804 (3) Reaction products of alkyl phenols in which the alkyl group contains at least about 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines), which may be characterized as "Mannich dispersants".
• aldehydes especially formaldehyde
• amines especially polyalkylene polyamines
• chlorinated aliphatic hydrocarbons such as chlorinated wax
• phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate,phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethyl napthyl phosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecular weight 500)-substituted phenyl phosphite, diisobutyl
• Zinc dialkylphosphorodithioates are a well known example.
• pour point depressants are a particularly useful type of additive often included in the lubricating oils described herein.
• the use of such pour point depressants in oil-based compositions to improve low temperature properties of oil-based compositions is well known in the art. See, for example, page 8 of "Lubricant Additives" by C.V. Smalheer and R. Kennedy Smith (Lezius-Hiles Co. publishers, Cleveland, Ohio, 1967).
• pour point depressants examples include polymethacrylates, polyacrylates; polyacrylamides; condensation products of haloparaffin waxes and aromatic compounds; vinyl carboxylate polymers: and terpolymers of dialkylfumarates, vinylesters of fatty acids and alkylvinylethers.
• Pour point depressants useful for the purposes of this invention techniques for their preparation and their uses are described in U.S. Patents 2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498; 2,666,746; 2,721,877; 2,721,878; and 3,250,715.
• Anti-foam agents are used to reduce or prevent the formation of stable foam.
• Typical anti-foam agents include silicones or organic polymers. Additional anti-foam compositions are described in "Foam Control Agents". by Henry T. Kerner (Noyes Data Corporation, 1976), pages 125-162.
• the labile-sulfur free additive compositions of this invention can be added directly to the lubricant. Preferably, however, they are diluted with a substantially inert, normally liquid organic diluent such as mineral oil, naphtha, benzene, toluene or xylene, to form an additive concentrate. These concentrates usually contain from about 5% to 90% by weight of the additive of this invention and may contain, in addition, one or more other additives known in the art or described hereinabove. The remainder of the concentrate is the substantially inert normally liquid diluent.
• a substantially inert, normally liquid organic diluent such as mineral oil, naphtha, benzene, toluene or xylene
• While maintaining a temperature of 55° 1000 parts phenol and 68 parts sulfonated polystyrene catalyst (marketed as Amberlyst-15 by Rohm and Haas Company) are charged to a reactor equipped with a stirrer, condenser, thermometer and subsurface gas inlet tube. The reactor contents are then heated to 120° while nitrogen blowing for 2 hours. 1232 parts propylene tetramer is charged, and the reaction mixture is stirred at 120° for 4 hours. Agitation is stopped, and the batch is allowed to settle for 0.5 hour. The crude supernatant reaction mixture is filtered and vacuum stripped until a maximum of 0.5 percent residual propylene tetramer remains.
• Benzene (217 parts) is added to phenol (324 parts, 3.45 moles) at 38°C and the mixture is heated to 47°C.
• Boron trifluoride (8.8 parts, 0.13 mole) is blown into the mixture over a one-half hour period at 38-52°C.
• Polyisobutene (1000 parts, 1.0 mole) derived from the polymerization of C4 monomers predominating in isobutylene is added to the mixture at 52-58°C over a 3.5 hour period. The mixture is held at 52°C for one additional hour.
• a 26% solution of aqueous ammonia (15 parts) is added and the mixture heated to 70°C over a two-hour period.
• a commercial mixture of ethylene polyamines (41 parts, 1.0 equivalent) corresponding in empirical formula to penta(ethylene)hexamine is added to a mixture of the substituted phenol (400 parts, 0.38 equivalent) described in Example 2 and diluent oil (181 parts) at 65°C.
• the mixture is heated to 93°C and paraformaldehyde (12 parts, 0.4 equivalent) added.
• the mixture is heated from 93-140°C over a 5-hour period and then held at 140°C for 4 hours under nitrogen.
• the mixture is cooled to 93°C and additional paraformaldehyde (12 parts, 0.4 equivalent) is added.
• the mixture is heated from 93-160°C for a total of 12 hours.
• the total amount of distillate collected is 13.2 parts.
• An additional amount of diluent oil (119 parts) is added to the mixture which is then filtered.
• the filtrate is a 40% oil solution of the desired Mannich condensation product containing 1.87% nitrogen.
• a reactor equipped with a stirrer, condenser, thermometer and subsurface addition tube is charged with 1000 parts of the reaction product of Example 1.
• the temperature is adjusted to 48-49° and 319 parts sulfur dichloride is added while the temperature is kept below 60°.
• the batch is then heated to 88-93° while nitrogen blowing until the acid number (using bromphenol blue indicator) is less than 4.0. 400 parts diluent oil is then added, and the mixture is mixed thoroughly.
• Example 5 1000 parts of the reaction product of Example 1 is reacted with 175 parts of sulfur dichloride. The reaction product is diluted with 400 parts diluent oil.
• Example 5 1000 parts of the reaction product of Example 1 is reacted with 319 parts of sulfur dichloride. 788 parts diluent oil is added to the reaction product, and the materials are mixed thoroughly.
• a reactor equipped with a stirrer, condenser, thermometer and subsurface gas inlet tube is charged with 1000 parts phenol, 38.4 parts SuperFiltrol (a sulfuric acid treated clay supplied by Filtrol Corporation) and 845 parts of a mixture of isomeric heptenes.
• the reactants are heated to 120° while nitrogen blowing.
• the reaction is then continued at 120° for 4 hours.
• the reaction mixture is filtered, and vacuum stripped to remove water, unreacted heptenes, and excess phenol.
• the residue after stripping is the product.
• Example 13 To a reactor equipped as described in Example 13, is charged 406 parts of the reaction product of Example 4. With fast stirring, 2.4 parts cupric oxide and 1.2 parts copper metal powder is charged, followed by heating to 155° with a slight nitrogen purge. The mixture was heated at 155° for 5 hours. The materials were then filtered using a diatomaceous earth filter aid.
• a 1-liter, 4-necked flask equipped with a stirrer, thermowell, and reflux condenser is charged with 600 parts of the reaction product of Example 7. With fast stirring, 3 parts copper metal powder is added, the mixture is heated to 120° and is held at 120° for 5 hours. The reaction mixture is filtered using a diatomaceous earth filter aid.
• a 1-liter, 4-necked flask equipped with a stirrer, thermometer, below surface gas inlet and a Dean-Stark trap is charged with 475 parts of the reaction product of Example 7.
• the material is heated to 80°C, 25 parts copper metal powder is added and the reaction mixture is heated to 155° over 0.5 hour followed by heating at 155-160° for 5 hours.
• the material is filtered at 140° using a diatomaceous earth filter aid.
• the product contains 0.0032 percent copper.
• a 1-liter, 4-necked flask equipped with a stirrer, thermowell, condenser, subsurface tube, nitrogen inlet and Dean-Stark trap was charged with 200 parts of the reaction product of Example 7 and 145 parts of diluent oil.
• the materials are heated to 80° followed by the addition of 1.7 parts copper metal powder.
• the mixture is heated to 155° and held at 155° for 5 hours while maintaining a light nitrogen purge.
• the materials are filtered using a diatomaceous earth filter aid.
• Example 19 The procedure of Example 19 is followed except 885 parts of the reaction product of Example 7, 641 parts diluent oil and 76 parts copper metal powder are used.
• a 1-liter, 4-necked flask equipped with a stirrer, nitrogen inlet, subsurface tube, thermowell Dean-Stark trap and condenser is charged with 386 parts of the reaction product of Example 5.
• the material is heated to 150° and 5.8 parts cupric hydroxide is added.
• the materials are heated to 180° while water is removed.
• a total of approximately 1 gram water was obtained in the Dean-Stark trap.
• the total heating time was 2 hours.
• the product was filtered using a diatomaceous earth filter aid. The filtered product contains 0.36 percent copper.
• Example 6 A reactor as described in Example 6 is charged with 351 parts of the reaction product of Example 5. The material is heated to 50° and 4.5 parts cupric oxide and 1.1 parts copper metal powder is added. The mixture is heated to 150° and held at 150° for 2 hours. The materials were then heated to 180° over 1 hour and heating at 180° is continued for 4 additional hours. The materials are filtered using a diatomaceous earth filter aid. The filtered product contains 0.43 percent copper.
• Example 21 To a reactor as described in Example 21 is charged 351 parts of the reaction product of Example 5. The materials is heated to 50° and 5.3 parts cuprous oxide is charged. The mixture is stirred at fast speed for 0.5 hour followed by the addition of 2.2 parts acetic acid. The mixture is heated to 105° over 0.5 hour, heated to 150° over 0.5 hour and held at 150° for 3.5 hours. The temperature is increased to 180° and held at 180° for 3 additional hours. The reaction mixture is filtered using a diatomaceous earth filter aid. The filtered product contains 0.113 percent copper.
• a 2-liter reactor equipped with a stirrer, thermometer, below surface nitrogen inlet and Dean-Stark trap is charged with 990 parts of the reaction product of Example 5.
• the material is heated to 90° at which time 10 parts of copper metal powder is added.
• the materials are heated with nitrogen blowing to 150° over 0.35 hour and held at 150-154° for 5.5 hours. 285 parts diluent oil is added, the materials are mixed thoroughly and filtered at 105° using a diatomaceous earth filter aid.
• Cupric chloride dihydrate (51 parts) and 125 parts toluene are charged to a 250 milliliter flask equipped with a subsurface nitrogen inlet and a Dean-Stark trap. The materials are azeotroped for 2 hours to dry.
• a 2-liter reactor equipped with a stirrer, thermowell, and Dean-Stark trap is charged with 710 parts of the reaction product of Example 5 and 110 parts xylene. 48 parts of a 50 percent aqueous NaOH solution is added at 80°, and the reaction mixture is refluxed at 105-180° for 4.75 hours. The mixture is cooled and 150 parts isopropynol is added.
• toluene is decanted from the dried cupric chloride and the solid is added to the solution in the 2-liter flask.
• Remaining cupric chloride was washed from the 250 milliliter flask using 175 parts methanol.
• the materials in the 2-liter flask are then held at 55-60° for 0.5 hour then refluxed at 68-70° for 2.5 hours, and stripped to 165 o at 1.1 kPa (8 torr).
• the residue is filtered at 115° using a diatomaceous earth filter aid.
• the filtered product contained no sodium and 1.72 percent copper.
• Example 25 The procedure of Example 25 is repeated employing 312 parts of the reaction product of Example 6, 32 parts of 50 percent aqueous sodium hydroxide, 34 parts of cupric chloride dihydrate, 125 parts toluene, 100 parts xylene, 100 parts methanol, 100 parts of the isobutanol/primary amyl alcohol mixture, and 75 parts isopropanol.
• a 2-liter, 4-necked reactor equipped with a stirrer, addition funnel, subsurface tube, thermowell, and condenser is charged with 800 parts of the reaction product of Example 12.
• the materials are heated to 50° with a light nitrogen purge.
• Sulfur dichloride is added dropwise over 5 hours.
• the materials are heated to 150° and nitrogen blown for 2 hours at 150°.
• 646 parts diluent oil are added and the materials are stirred at 100° for 1 hour.
• 1537 parts of the reaction product are transferred to a 3-liter flask and 7.7 parts copper powder is added.
• the materials are heated to 150° with fast stirring.
• the materials are then held for 5 hours at 150°, then filtered using a diatomaceous earth filter aid.
• the filtered product contains 13 parts per million copper.
• a 3-liter, 4-necked flask equipped with a stirrer, subsurface cube, addition funnel, thermowell and reflux condenser is charged with 787 parts of the reaction product of Example 10.
• the material is heated to 50° and sulfurdichloride is added dropwise over 4.25 hours.
• the materials are heated to 150° with nitrogen blowing and held at 150° with nitrogen blowing for 1.5 hours.
• 638 parts of diluent oil is added and the materials are stirred for 0.25 hour.
• the mixture is reheated to 150° and 7.6 parts of copper metal powder is added.
• the materials are mixed for 5 hours at 150° with a slight nitrogen purge.
• the materials are filtered using a diatomaceous earth filter aid.
• the filtered material contains 20 parts per million copper.
• a 3-liter reactor equipped with a stirrer, thermowell, subsurface gas inlet and reflux condenser is charged with 700 parts of the reaction product as described in Example 17 and 204 parts of diluent oil.
• the mixture is heated to 55° and 85 parts methanol, 11 parts acetic acid, 58 parts calcium hydroxide and 57 parts toluene are added.
• the mixture is blown with CO2 for 0.5 hour at 1.4 x 10 ⁇ 2m3 (0.5 cubic feet) per hour at a temperature of 65-70°C.
• the reaction mixture is stripped to 150° at 4.2 x 10 ⁇ 2m3 (1.5 cubic feet) nitrogen purge.
• the residue is filtered using a diatomaceous earth filter aid.
• Example 30 Following the procedure of Example 30, 3000 parts of the reaction product of Example 9 are reacted with 40 parts of C15 ⁇ 18 alpha-olefin and 10 parts of copper metal powder.
• the additives treated according to the method of the present invention which showed very little or no labile-sulfur, demonstrated greatly improved performance inthat the detrimental metal corrosivity and elastomer degradation originally exhibited by these additives before treatment had essentially been eliminated.
• a lubrication oil composition is prepared by blending 11.64% by weight of the above-described additive concentrate in a 15W-40 oil which contains polymeric viscosity improvers.

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• 1985
  • 1985-04-04 WO PCT/US1985/000572 patent/WO1985004896A1/en active IP Right Grant
  • 1985-04-04 JP JP60501703A patent/JPS61501925A/ja active Pending
  • 1985-04-04 DE DE85901882T patent/DE3587624T2/de not_active Expired - Fee Related
  • 1985-04-04 BR BR8506703A patent/BR8506703A/pt unknown
  • 1985-04-04 EP EP85901882A patent/EP0179814B1/en not_active Expired - Lifetime
  • 1985-04-04 AU AU42120/85A patent/AU577116B2/en not_active Ceased
  • 1985-04-10 IN IN272/CAL/85A patent/IN163735B/en unknown
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