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
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound 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
  • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
  • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-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
  • 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
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
  • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/028—Overbased salts thereof
  • C10M2207/0285—Overbased salts thereof used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/283—Esters of polyhydroxy compounds
  • C10M2207/2835—Esters of polyhydroxy compounds used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
  • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
  • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
  • C10M2219/066—Thiocarbamic type compounds
  • C10M2219/068—Thiocarbamate metal salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
  • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
  • C10M2219/106—Thiadiazoles
• • 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
  • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2221/043—Polyoxyalkylene ethers with a thioether 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
  • 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
  • C10N2010/12—Groups 6 or 16
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • 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
  • C10N2040/12—Gas-turbines
• • 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
  • C10N2040/12—Gas-turbines
  • C10N2040/13—Aircraft turbines
• • 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
  • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
  • C10N2050/10—Semi-solids; greasy
• • 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
  • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
  • C10N2060/10—Chemical after-treatment of the constituents of the lubricating composition by sulfur or a compound containing sulfur
• • 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

• an object of the invention is to provide an additive for lubricating compositions, as well as the lubricating oil compositions themselves, which will provide excellent anti-wear performance with respect to corrosion resistant materials.
• Another object of the invention is directed toward a method for imparting anti- wear properties to a corrosion resistant material, comprising using the above lubricating compositions described below.
• an oil composition providing excellent anti-wear protection for corrosion-resistant materials, which comprises a major amount of a synthetic ester lubricating base oils, and a minor amount of a molybdenum compound and an anti-wear additive selected from the group consisting of 1 ,3,4-thiadiazole derivative as an anti-wear additive, particularly 2,5- dimercapto-1 ,3,4-thiadiazole dimers (hereinafter "thiadiazole dimers”), the reaction products of such thiadiazole dimers and poly(ether)glycols, and 2,5-dimercapto-1 ,3,4- thiadiazole monomer, excluding derivatives of such monomer and mixtures thereof.
• thiadiazole dimers 2,5- dimercapto-1 ,3,4-thiadiazole dimers
• the lubricating composition of the invention which provide excellent anti-wear protection are lubricating composition comprising a major amount of a synthetic ester base oil and a minor amount of: (a) a molybdenum compound selected from the group consisting of molybdenum dithiocarbamate, molybdenum dithiophosphate and a mixture thereof; and
• R 1 being hydrogen, a branched or straight chain Ci to C 7 alkyl radical, or combinations thereof
• R 2 being hydrogen, a branched or straight chain Ci to C- 7 alkyl radical, or combinations thereof, with n being 1 to 2 and t being 0 or 1 ;
• F is a hydroxyl radical, a branched or straight chain Ci to C 20 alkoxyl radical, a branched or straight chain C-i to C 20 alkylcarboxyl radical, a mono-substituted, disubstituted, or tri-substituted glycerol residue, hydrogen, or combinations thereof;
• R 3 is hydrogen, a methyl radical, or combinations thereof;
• R 4 is hydrogen, a branched or straight chain Ci to C 20 alkyl radical, a phenyl radical, a C 1 to C 8 branched or straight chain alkyl-substituted-phenyl radical, a Ci to C 20 branched or straight chain acyl radical, or combinations thereof; and with q being 1 to 300;
• R 1 being hydrogen, a branched or straight chain Ci to C 7 alkyl radical, or combinations thereof and R 2 being hydrogen, a branched or straight chain Ci to C 7 alkyl radical, or combinations thereof, wherein t is 0 or 1; and (B) a poly(ether)glycol having formula (III):
• F is a hydroxyl radical, a branched or straight chain Ci to C 2 o alkoxyl radical, a branched or straight chain Ci to C 2 o alkylcarboxyl radical, a mono-substituted, disubstituted, or tri-substituted glycerol residue, hydrogen, or combinations thereof;
• R 3 is hydrogen, a methyl radical, or combinations thereof;
• R 4 is hydrogen, a branched or straight chain Ci to C 2 o alkyl radical, a phenyl radical, a Ci to C 8 branched or straight chain alkyl-substituted-phenyl radical, a Ci to C 2 n branched or straight chain acyl radical, or combinations thereof; and with q being 1 to 300; and
• lubricating compositions are especially useful as gas turbine oils and in providing anti-wear protection for corrosion resistant material.
• the compositions are particularly effective when used, for example, with 440C stainless steel.
• the examples given show effectiveness for the inventive additives in a synthetic ester lubricating oil, when used with a corrosion resistant material. With regard to the applicability of using the above additives in other lubricating compositions, it is believed that similar effectiveness could only be extended to greases as problems with solubility may render the use of other base oils unsuitable for combination with the anti-wear additives.
• thiadiazole dimer/poly(ether)glycol reaction products of the invention include those described in US 6,365,557, and preferably prepared according to the method set forth therein, which patent is incorporated herein by reference, as well as US 6,620,771 , also incorporated herein by reference.
• an additive comprising: (a) a molybdenum compound selected from the group consisting of molybdenum dithiocarbamate, molybdenum dithiophosphate or a mixture thereof; and
• R 1 being hydrogen, a branched or straight chain Ci to C 7 alkyl radical, or combinations thereof and R 2 being hydrogen, a branched or straight chain Ci to C 7 alkyl radical, or combinations thereof, with n being 1 to 2 and t being 0 or 1 ; and (B) a poly(ether)glycol having formula (III):
• an additive which comprises:
• molybdenum compound selected from the group consisting of molybdenum dithiocarbamate, molybdenum dithiophosphate or a mixture thereof;
• R 1 , R 3 and R 4 are independently selected from the above-described group of substituents for the reaction products and n is 1 to 2.
• the number of repeating ether units "m" in the glycol moiety is 1 to 50.
• an additive which comprises:
• molybdenum compound selected from the group consisting of molybdenum dithiocarbamate, molybdenum dithiophosphate or a mixture thereof;
• R 1 being hydrogen, a branched or straight chain Ci to C 7 alkyl radical, or combinations thereof and R 2 being hydrogen, a branched or straight chain Ci to C 7 alkyl radical, or combinations thereof, wherein t is 0 or 1 ; and (B) a poly(ether)glycol having formula (III):
• F is a hydroxyl radical, a branched or straight chain Ci to C 20 alkoxyl radical, a branched or straight chain Ci to C 20 alkylcarboxyl radical, a mono-substituted, disubstituted, or tri-substituted glycerol residue, hydrogen, or combinations thereof;
• R 3 is hydrogen, a methyl radical, or combinations thereof;
• R 4 is hydrogen, a branched or straight chain Ci to C 20 alkyl radical, a phenyl radical, a Ci to C 8 branched or straight chain alkyl-substituted- phenyl radical, a Ci to C 20 branched or straight chain acyl radical, or combinations thereof; and with q being 1 to 300.
• an additive which comprises:
• molybdenum compound selected from the group consisting of molybdenum dithiocarbamate, molybdenum dithiophosphate or a mixture thereof;
• an additive which comprises:
• molybdenum compound selected from the group consisting of molybdenum dithiocarbamate, molybdenum dithiophosphate or a mixture thereof;
• R 1 being hydrogen, a branched or straight chain Ci to C 7 alkyl radical, or combinations thereof and R 2 being hydrogen, a branched or straight chain Ci to C 7 alkyl radical, or combinations thereof, where n is 1 to 2 and t is 0 or 1 ; and (B) a poly(ether)g!ycol having formula (III):
• F is a hydroxyl radical, a branched or straight chain Ci to C o alkoxyl radical, a branched or straight chain Ci to C 20 alkylcarboxyl radical, a mono-substituted, disubstituted, or th-substituted glycerol residue, hydrogen, or combinations thereof;
• R 3 is hydrogen, a methyl radical, or combinations thereof;
• R 4 is hydrogen, a branched or straight chain Ci to C 20 alkyl radical, a phenyl radical, a Ci to C 8 branched or straight chain alkyl-substituted-phenyl radical, a Ci to C 20 branched or straight chain acyl radical, or combinations thereof; and where q is 1 to 300.
• Particular thiadiazole dimer reaction products which correspond to the compounds described by (b)(i) above, tested herein include 1 ,3,4-thiadiazole derivatized by a triethylene glycol monobutyl ether available as Vanlube® 972 additive from R.T. Vanderbilt Company, Inc. (1 ,3,4-thiadiazole derivative 40% and triethylene glycol monobutyl ether 60%).
• Vanlube® 972 additive may be prepared according to the method set forth in US 6,365,557, Example 9 as follows: A thiadiazole dimer-glycol reaction product was synthesized by converting 2, 5-dimercapto-1 ,3,4-thiadiazole ("DMTD”) in situ to DMTD dimer.
• DMTD 2, 5-dimercapto-1 ,3,4-thiadiazole
• Vanchem® DMTD additive which corresponds to the compound of (iii) or formula (VII) and is available from R.T. Vanderbilt Company, Inc. (2,5-dimercapto-1 ,3,4- thiadiazole), was tested by itself and with molydenum dithiophosphate.
• the molybdenum dithiocarbamate is molybdenum dialkylthiocarbamate (available as Molyvan® 822 additive from R.T. Vanderbilt Company, Inc. as molybdenum dialkylthiocarbamate 50% in petroleum process oil 50%) and the molybdenum dithiophosphate is molybdenum di(2- ethylhexyl)phosphorodithioate (available as Molyvan® L additive from R.T. Vanderbilt Company, Inc).
• the weight ratio of the molybdenum compound to the thiadiazole compound may be from about 1 :10 to about 10:1. In a more preferred embodiment of the invention, the weight ratio of the molybdenum compound to the thiadiazole compound may be from about 1 :4 to about 4:1. In a still further preferred embodiment of the invention, the weight ratio of the molybdenum compound to the thiadiazole compound may be from about 1 :2 to about 1 :1. In another embodiment of the invention, the amount of molybdenum compound is about 0.5% by weight based on the total weight of the oil composition.
• the major amount of synthetic ester base oil or grease is at least about 90% by weight based on the total weight of the lubricating composition. In another embodiment of the invention, the major amount of base oil is at least 95% by weight. In another embodiment of the invention, the major amount of base oil is at least 99% by weight.
• Preferred synthetic ester base oils are polyolesters.
• Another aspect of the invention is directed toward a method for imparting anti- wear properties to a corrosion resistant material, comprising using the above described lubricating compositions.
• the lubricating compositions may also contain one or more of the following additives: Antioxidant compounds Seal swell compositions Friction modifiers Extreme pressure/anti-wear agents Viscosity modifiers Phosphates Antifoamants Rust inhibitors 9. Copper corrosion inhibitors
• antioxidants include hindered phenolic antioxidants, secondary aromatic amine antioxidants, sulfuhzed phenolic antioxidants, oil-soluble copper compounds, phosphorus-containing antioxidants, organic sulfides, disulfides and polysulfides and the like.
• Illustrative sterically hindered phenolic antioxidants include orthoalkylated phenolic compounds such as 2,6-di-tertbutylphenol, 4-methyl-2,6-di-tertbutylphenol, 2,4,6-tri- tertbutylphenol, 2-tert-butylphenol, 2,6-disopropylphenol, 2-methyl-6-tertbutylphenol, 2,4-dimethyl-6-tertbutylphenol, 4-(N,N-dimethylaminomethyl)-2,8-di-tertbutylphenol, 4- ethyl-2,6-di-tertbutylphenol, 2-methyl-6-styrylphenol, 2,6-distyryl-4-nonytphenol, and their analogs and homologs. Mixtures of two or more such mononuclear phenolic compounds are also suitable.
• phenol antioxidants for use in the compositions of this invention are methylene-bridged alkylphenols, and these can be used singly or in combinations with each other, or in combinations with sterically-hindered unbridged phenolic compounds.
• Illustrative methylene-bridged compounds include 4,4'-methylenebis(6-tert-butyl o- cresol), 4,4'-methylenebis(2-tert-amyl-o-cresol), 2,2'-methytenebis(4-methyl-6-tert- butylphenol), 4,4'-methylenehis (2, 6-di-tertbutylphenol), and similar compounds.
• Particularly preferred are mixtures of methylene-bridged alkylphenols such as are described in U.S. Pat. No. 3,211 ,652, which is incorporated herein by reference.
• Amine antioxidants especially oil-soluble aromatic secondary amines may also be used in the compositions of this invention.
• aromatic secondary monoamines are preferred, aromatic secondary polyamines are also suitable.
• Illustrative aromatic secondary monoamines include diphenylamine, alkyl diphenylamines containing 1 or 2 alkyl substituents each having up to about 16 carbon atoms, phenyl-.beta.- naphthylamine, phenyl-P-napthylamine, alkyl- or aralkylsubstituted phenyl-.beta.- naphthylamine containing one or two alkyl or aralkyl groups each having up to about 16 carbon atoms, alkyl- or aralkylsubstituted phenyl-p-naphthylamine containing one or two alkyl or aralkyl groups each having up to about 16 carbon atoms, and similar compounds.
• a preferred type of aromatic amine antioxidant is an alkylated diphenylamine of the general formula:
• Ri is an alkyl group (preferably a branched alkyl group) having 8 to 12 carbon atoms, (more preferably 8 or 9 carbon atoms) and R 2 is a hydrogen atom or an alkyl group (preferably a branched alkyl group) having 8 to 12 carbon atoms, (more preferably 8 or 9 carbon atoms). Most preferably, Ri and R 2 are the same.
• One such preferred compound is available commercially as Naugalube ® 438L, a material which is understood to be predominately a 4,4'-dinonytdiphenylamine (i.e., bis(4- nonyiphenyl)(amine)) in which the nonyl groups are branched.
• antioxidants for preferred inclusion in the compositions of the invention are one or more liquid, partially sulfurized phenolic compounds such as are prepared by reacting sulfur monochloride with a liquid mixture of phenols-at least about 50 weight percent of which mixture of phenols is composed of one or more reactive, hindered phenols-in proportions to provide from about 0.3 to about 0.7 gram atoms of sulfur monochloride per mole of reactive, hindered phenol so as to produce a liquid product.
• Typical phenol mixtures useful in making such liquid product compositions include a mixture containing by weight about 75% of 2,6-di-tert-butylphenol, about 10% of 2-tert-butylphenol, about 13% of 2,4.6-tri-tertbutylphenol, and about 2% of 2,4-di- tertbutylphenol.
• the reaction is exothermic and thus is preferably kept within the range of about 15. degree. C. to about 70.degree. C, most preferably between about 40.degree. C. to about 60.degree. C.
• Another useful type of antioxidant are 2,2,4-trimethyl-1 ,2-dihydroquinoline (TMDQ) polymers and homologs containing aromatized terminal units such as those described in U.S. Patent 6,235,686, which is hereby incorporated by reference.
• One suitable mixture is comprised of a combination of: (i) an oil-soluble mixture of at least three different sterically- hindered tertiary butylated monohydric phenols which is in the liquid state at 25.degree.
• compositions which are designed to keep seals pliable are also well known in the art.
• a preferred seal swell composition is isodecyl sulfolane.
• the seal swell agent is preferably incorporated into the composition at about 0.1-3 weight percent.
• Substituted 3- alkoxysulfolanes are disclosed in U.S. Pat. No. 4,029,587 which is incorporated herein by reference.
• Friction modifiers are also well known to those skilled in the art. A useful list of friction modifiers are included in U.S. Pat. No. 4,792,410, which is incorporated herein by reference. U.S. Pat. No. 5,110,488 discloses metal salts of fatty acids and especially zinc salts and is incorporated herein by reference.
• Useful friction modifiers include fatty phosphites, fatty acid amides, fatty epoxides, borated fatty epoxides, fatty amines, glycerol esters, borated glycerol esters alkoxylated fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, sulfurized olefins, fatty imidazolines, molybdenum dithiocarbamates (e.g., U.S. Pat. No. 4,259,254, incorporated herein by reference), molybdate esters (e.g., U.S. Pat. No. 5,137,647 and U.S. Pat. No. 4,889,647, both incorporated herein by reference), molybdate amine with sulfur donors (e.g., U.S. Pat. No. 4,164,473 incorporated herein by reference), and mixtures thereof.
• fatty phosphites fatty acid amides
• the preferred friction modifier is a borated fatty epoxide as previously mentioned as being included for its boron content.
• Friction modifiers are preferably included in the compositions in the amounts of 0.1-10 weight percent and may be a single friction modifier or mixtures of two or more.
• Friction modifiers also include metal salts of fatty acids.
• Preferred cations are zinc, magnesium, calcium, and sodium and any other alkali, or alkaline earth metals may be used.
• the salts may be overbased by including an excess of cations per equivalent of amine. The excess cations are then treated with carbon dioxide to form the carbonate.
• the metal salts are prepared by reacting a suitable salt with the acid to form the salt, and where appropriate adding carbon dioxide to the reaction mixture to form the carbonate of any cation beyond that needed to form the salt.
• a preferred friction modifier is zinc oleate.
• Dialkyl dithiophosphate succinates may be added to provide anti-wear protection.
• Zinc salts are preferably added as zinc salts of phosphorodithioic acids or dithiocarbamic acid.
• the preferred compounds for use are zinc, diisooctyl dithiophosphate and zinc dibenzyl dithiophosphate and amyl dithiocarbamic acid.
• Also included in lubricating compositions in the same weight percent range as the zinc salts to give anti- wear/extreme pressure performance are dibutyl hydrogen phosphite (DBPH) and triphenyl monothiophosphate, and the thiocarbamate ester formed by reacting dibutyl amine-carbon disulfide- and the methyl ester of acrylic acid.
• DBPH dibutyl hydrogen phosphite
• triphenyl monothiophosphate dibutyl hydrogen phosphite
• the thiocarbamate ester formed by reacting dibutyl
• the thiocarbamate is described in U.S. Pat. No. 4,758,362 and the phosphorus-containing metal salts are described in U.S. Pat. No. 4,466,894. Both patents are incorporated herein by reference.
• Antimony or lead salts may also be used for extreme pressure.
• the preferred salts are of dithiocarbamic acid such as antimony diamyldithiocarbamate.
• Viscosity modifiers VM and dispersant viscosity modifiers (DVM) are well known.
• VMs and DVMs are polymethacrylates, polyacrylates, polyolefins, styrene- maleic ester copolymers, and similar polymeric substances including homopolymers, copolymers and graft copolymers.
• Examples of commercially available VMs, DVMs and their chemical types are listed below.
• the DVMs are designated by a (D) after their number.
• Representative viscosity modifers that are commercially available are listed below in Table 1. Table 1
• VMs and/or DVMs preferably are incorporated into the fully-formulated compositions at a level of up to 10% by weight.
• the lubricating compositions can also preferably include at least one phosphorus acid, phosphorus acid salt, phosphorus acid ester or derivative thereof including sulfur- containing analogs preferably in the amount of 0.002-1.0 weight percent.
• the phosphorus acids, salts, esters or derivatives thereof include compounds selected from phosphorus acid esters or salts thereof, phosphites, phosphorus-containing amides, phosphorus-containing carboxylic acids or esters, phosphorus containing ethers and mixtures thereof
• the phosphorus acid, ester or derivative can be a phosphorus acid, phosphorus acid ester, phosphorus acid salt, or derivative thereof.
• the phosphorus acids include the phosphoric, phosphonic, phosphinic, and thiophosphoric acids including dithiophosphoric acid as well as the monothiophosphoric, thiophosphinic and thiophosphonic acids.
• One class of compounds are adducts of O,O-dialkyl-phosphorodithioates and esters of maleic or fumaric acid.
• the compounds can be prepared by known methods as described in U.S. Pat. No. 3,359,203, as for example O,O-di(2-ethylhexyl) S-(1 ,2- dicarbobutoxyethyl) phosphorodithioate.
• dithiophosphoric acid esters of carboxylic acid esters Preferred are alkyl esters having 2 to 8 carbon atoms, as for example 3-[[bis(1-methylethoxy)phosphinothioyl]thio] propionic acid ethyl ester.
• a third class of ashless dithiophosphates for use with the present invention include:
• R and Ri are independently selected from alkyl groups having 3 to 8 carbon atoms (commercially available as VANLUBE 7611 M, from R. T. Vanderbilt Co., Inc.);
• dithiophosphoric acid esters of carboxylic acid such as those commercially available as IRGALUBE ® 63 from Ciba Geigy Corp.;
• triphenylphosphorothionates such as those commercially available as IRGALUBE ® TPPT from Ciba Geigy Corp.;
• methylene bis(dialkyldithiocarbamates) wherein the alkyl group contains 4 to 8 carbon atoms For example, methylenebis(dibutyldithiocarbamate) is commercially available as VANLUBE 7723 ® from R. T. Vanderbilt Co., Inc).
• Zinc salts are preferably added to lubricating compositions in amounts of 0.1-5 triphenylphosphorothionates wherein the phenyl group may be substituted by up to two alkyl groups.
• An example of this group, among others, is triphenyl-phosphorothionate available commercially as IRGALUBE ® TPPT (manufactured by Ciba-Geigy Corp.).
• a preferred group of phosphorus compounds are dialkyphosphoric acid mono alkyl primary amine salts, such as those described in U.S. Pat. No. 5,354,484 which is herein incorporated by reference. Eighty-five percent phosphoric acid is the preferred compound for addition to the fully formulated ATF package and is preferably included at a level of about 0.01-0.3 weight percent based on the weight of the ATF.
• the amine salts of alkyl phosphates are prepared by known methods, e.g., a method disclosed in U.S. Pat. No. 4,130,494, incorporated herein by reference.
• a suitable mono- or diester of phosphoric acid or their mixtures is neutralized with an amine.
• the amount of amine required can be controlled by monitoring the neutral point of the reaction where the total acid number is essentially equal to the total base number.
• a neutralizing agent such as ammonia or ethylenediamine can be added to the reaction.
• the preferred phosphate esters are aliphatic esters, among others, 2-ethylhexyl, n- octyl, and hexyl mono-or diesters.
• the amines can be selected from primary or secondary amines. Particularly preferred are tert-alkyl amines having 10 to 24 carbon atoms. These amines are commercially available as for example Primene ® 81 R manufactured by Rohm and Haas Co.
• the sulfonic acid salts are well known in the art and are available commercially.
• Representative of the aromatic sulfonic acids that can be used in preparing the synergists of the invention are alkylated benzenesulfonic acids and alkylated naphthalenesulfonic acids having 1 to 4 alkyl groups of 8 to 20 carbons each.
• Particularly preferred are naphthalenesulfonates substituted by alkyl groups having 9 to 18 carbons each, as for example dinonylnaphthalenesulfonate.
• Antifoaming agents are well-known in the art as silicone or fluorosilicone compositions. Such antifoam agents are available from Dow Coming Chemical Corporation and Union Carbide Corporation. A preferred fluorosilicone antifoam product is Dow FS-1265. Preferred silicone antifoam products are Dow Coming DC-200 and Union Carbide UC- L45. Other antifoam agents which may be included in the composition either alone or in admixture is a polyacrylate antifoamer available from Monsanto Polymer Products Co. of Nitro, West Virginia known as PC-1244. Also, a siloxane polyether copolymer antifoamer available from OSI Specialties, Inc. of Farmington Hills, Michigan and may also be included. One such material is sold as SILWET-L-7220. The antifoam products are preferably included in the compositions of this invention at a level of 5 to 80 parts per million with the active ingredient being on an oil-free basis.
• Embodiments of rust inhibitors include metal salts of alkylnaphthalenesulfonic acids.
• Embodiments of copper corrosion inhibitors which may optionally be added include include thiazoles, triazoles and thiadiazoles.
• Example embodiments of such compounds include benzothazole, tolylthazole, octyltriazole, decyltriazole, dodecyltriazole, 2- mercapto benzothiazole, 2,5-dimercapto-1 ,3,4-thiadiazole, 2-mercapto-5- hydrocarbylthio-1 ,3,4-thiadiazoles, 2-mercapto-5- hydrocarbyldithio-1 ,3,4-thiadiazoles, 2,5-bis(hydrocarbylthio)-1 ,3,4-thiadiazoles, and 2,5-bis(hydrocarbyldithio)-1 ,3,4- thiadiazoles.
• test 1 a 4-ball wear test was conducted with respect to a polyolester base oil alone (test 1), a comparative test 2 based on the existing bearing lubricant based on TCP (tricresyl phosphate), a well-known anti-wear additive typically used in gas turbine oil compositions), and inventive tests based on thiadiazole dimer derivate (Vanlube® 972 additive) alone and additionally containing molybdenum dithiocarbamate or molybdenum dithiophosphate.
• TCP tricresyl phosphate
• Vanlube® 972 additive thiadiazole dimer derivate
• the base oil used was Hatco® HXL-7597, which is a polyolester with antioxidant and corrosion inhibitors, available from Hatco Corporation.
• the molybdenum dithiocarbamate tested was Molyvan® 822 additive, available from R.T. Vanderbilt Company, Inc. (molybdenum dialklyldithiocarbamate 50% in petroleum process oil 50%).
• the molybdenum dithiophosphate tested was Molyvan® L additive, available from R.T. Vanderbilt Company, Inc. (molybdenum di(2-ethylhexyl)phosphorodithioate 75% in petroleum process oil 25%).
• thiadiazole dimer derivative provides surprisingly superior anti-wear protection in the base oil, compared to the standard TCP formulation; and that the further addition of metal dithiocarbamate or metal dithiophosphate increases the anti-wear protection still further.
• DMTD 2,5- dimercapto-1,3,4 thiadiazole
• HXL-7597 base oil with antioxidant and corrosion inhibitors 1.0% Vanlube® 81 additive (mixture of octylated diphenylamines), 1.0% alkylated PANA (Ciba® L-06) and 0.05% benzotriazole.
• additives include zinc dithiophosphates (ZDDP), amine phosphates (Vanlube® 672, 692, and 9123 additives), ashless dithiophosphates (Vanlube® 727 and 761 1 M additives), borate esters (OD/Vanlube® 289 additive), and tert-butylated phenol phosphates (Durad® 620B additive).
• ZDDP zinc dithiophosphates
• amine phosphates Vanlube® 672, 692, and 9123 additives
• ashless dithiophosphates Vanlube® 727 and 761 1 M additives
• borate esters OD/Vanlube® 289 additive
• Durad® 620B additive tert-butylated phenol phosphates
• Vanlube® 972 (1,3,4-thiadiazole derivative 40% and triethylene glycol monobutyl ether 60%
• Vanlube® 829 - (1 ,3,4-thiadiazole-2(3H)-thione, 5,5-dithiobis)
• Molyvan® 822 (molybdenum dialkylthiocarbamate 50% in petroleum process oil 50%)
• Molyvan® L molybdenum di(2-ethylhexyl)phosphorodithioate 75% in petroleum process oil 25%
• Cuvan® 826 - (2,5-bis(n-octyldithio)-1 ,3,4-thiadiazole 60-80%; dioctyl disulfide 20-40%)
• Vanchem® DMTD (2,5-dimercapto-
• an amount of thiadiazole dimer derivative provides optimal anti-wear performance at about 0.5% by weight, based on the total lubricant composition, in combination with a polyolester base oil. Good results are also obtained at amounts up to about 3.0%. It is expected that about 0.5% to about 5.0% Vanlube® 972 thiadiazole dimer derivative should also give good results. Even better results, in terms of solubility and anti-wear performance, are achieved when the Vanlube® 972 thiadiazole dimer derivative additive is accompanied by an amount of molydenum dithiocarbamate (MoDTC) or molybdenum dithiophosphate (MoDTP).
• MoDTC molydenum dithiocarbamate
• MoDTP molybdenum dithiophosphate
• Vanlube® 829 additive is a DMTD dimer derivative. Excellent anti-wear results are shown for this additive from about 0.1 % to about 0.5% by weight based on the total weight of the composition, with expected good results up to about 5.0% by weight. Addition of a metal DTP or DTC is provides even further increase in performance, with data shown for the combination with MoDTP (Molyvan® L) (compare Formulation 34 in Table 2 with Formulations 33 and 36) .
• Vanchem® DMTD (monomer) is also shown to give excellent results, which results are further improved with the addition of MoDTP. It is expected that other metal DTCs and DTPs will also improve the anti-wear performance. While US 5,422,023 suggests that a copolymer corrosion inhibitor should be used in combination with a DMTD monomer, the present invention provides for a lubricating anti-wear composition for use with corrosion-resistant materials (such as jet turbines manufactured of same) comprising a synthetic base oil and DMTD monomer, without the need for (i.e. being free of) a corrosion inhibitor such as that required by '023 patent.
• corrosion-resistant materials such as jet turbines manufactured of same
• Figure 1 shows a graph of traction coefficient for a wide variety of additive candidates, with the inventive compound of Test 3 above (WA 108 in the figure) having exceptionally good characteristics.
• WA 108 inventive compound of Test 3 above
• formulations that form wear protective coatings on roughness features result in higher traction.
• traction coefficient decreases.
• Most of the formulations in Figure 1 have marginal wear resistance and in most cases poor scuffing performance.
• the low traction formulation WA 108 would be less prone toward surface- initiated fatigue than high traction oils, which limit polishing wear of roughness and cause higher asperity stress.
• Figs. 5-7 are photomicrographs showing surfaces after test runs using the inventive lubricant formulations.

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