US3432433A - Lubricant compositions - Google Patents

Lubricant compositions Download PDF

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US3432433A
US3432433A US666499A US3432433DA US3432433A US 3432433 A US3432433 A US 3432433A US 666499 A US666499 A US 666499A US 3432433D A US3432433D A US 3432433DA US 3432433 A US3432433 A US 3432433A
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triazine
butylamino
acid
phenyl
oxidation
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Eugene Wittner
Kenneth T Wendler
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Shell USA Inc
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Shell Oil Co
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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
    • C10M3/00—Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
    • 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
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/286—Esters of polymerised unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/302—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monocarboxylic acids, dicarboxylic acids and dihydroxy compounds only and having no free hydroxy or carboxyl 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
    • C10M2207/28—Esters
    • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
    • C10M2207/304—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids derived from the combination of monohydroxy compounds, dihydroxy compounds and dicarboxylic acids only and having no free hydroxy or carboxyl 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
    • C10M2207/28—Esters
    • C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid 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
    • 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
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two 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
    • 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
    • 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
    • C10M2209/109—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C10M2215/065—Phenyl-Naphthyl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • C10M2215/222—Triazines
    • 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
    • C10M2219/085—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/063—Ammonium or amine salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/135—Steam engines or 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
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
    • 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—Form in which the lubricant is applied to the material being lubricated semi-solid; greasy

Definitions

  • This invention relates to synthetic ester lubricating oils having exceptional oxidation stability. More particularly, it relates to synthetic ester oils containing aromatic amines, a salt of a monohaloallcylphosphonic acid and certain s-triazine compounds.
  • Synthetic lubricants have gained recent prominence in the field of lubrication because of stringent requirements of long life under extreme conditions imposed by certain new applications. Synthetic lubricants have low pour points and desirable viscosity characteristics and can generally be used at temperatures considerably above the decomposition temperature of most mineral oils. These oils have found use in jet aircraft, missiles, and the like where Wide temperature ranges and extreme operating conditions are likely to be encountered. Proper lubrication of aircraft gas turbines, for example, requires ability to function at bulk oil temperatures as low as --65 F. to as high as 450 to 500 F. for said applications.
  • a synthetic ester lubricant having excellent oxidation stability comprises a major amount of synthetic ester lubricating oil and minor amounts sufficient to increase the oxidation stability of the oil of an aryl amine, an amine salt of a monohaloalkylphosphonic acid and an s-triazine having the formula 3,432,433 Patented Mar. 11, 1969 where R, R R and R are hydrogen, C to C hydrocarbyl, or pyridyl, and R is C to C hydrocartbyl, C to C hydrocarbylamino, pyridyl, or pyridylamino. R, R R R R and R may all be different, or some or all may be alike.
  • hydrocarbyl is intended to mean a radical formed from a hydrocarbon by removal of a hydrogen atom. All hydrocarbyl groups within the claimed ranges free of aliphatic unsaturation are operable, whether they are alkyl, aryl, alkaryl, aralkyl, cycloalkyl, single or multi-ring, straight chain or branched. Representative groups include methyl, propyl, butyl, phenyl, naphthyl, tridecylphenyl, and the like.
  • the s-triazines to be used in compositions of the invention do not impart any antioxidant activity to the oils by themselves, but show remarkable activity in the presence of an aryl amine and an amine salt of a monohaloalkylphosphonic acid.
  • These triazine compounds are, in general, substituted guanamines and substituted melamines.
  • Preferred hydrocarbyl substituents are phenyl, benzyl and butyl. If desired mixtures of the triazines may also be used. Examples of s-triazines which may be used in accord with the invention are as follows:
  • the aryl amines to be used in combination with the striazines and amine salts of monohaloalkylphosphonic acid described above have from 6 to 30, preferably 12 to 20 carbons, and are preferably diarylamines having the formula where R and R are monoor diaromatic rings, each ring being optionally substituted with one C -C alkyl group.
  • suitable diaryl amines are phenyl-alphanaphthylarnine, phenyl-beta-naphthylamine, beta,betadinaphthylamine, alpha,beta-dinaphthylamine, p,p'-dioctyldiphenylamine, and diphenylamine.
  • Particularly preferred amines are phenyl-alpha-naphthylamine and diphenylarnine.
  • the diarylamines are beneficially present in an amount of from about 0.05 to 5%, preferably 0.1 to 3% by weight of the final lubricating composition. Amounts of about 1% by weight are preferred.
  • the salt to be used in combination with the triazine and arylamine described above is a salt of 0 C alkylamine and a monohaloalkylphosphonic acid, the haloalkyl group containing 1 to 4, preferably 1 to 2 carbon atoms.
  • the haloalkylphosphonic acids used for preparing the salts for use in the invention generally have the formula Ri (OH)1 where R is monohaloalkl containing 1 to 4, preferably 1 to 2 carbon atoms. R preferably contains a chlorine atom substituted on the alpha carbon atom.
  • Preferred halogens are fluorine, chlorine and bromine, especially chlorine.
  • Suitable alpha-monochloroalkylphosphonic acids for preparing the salts include monochloromethylphosphonic acid, 1-monochloroethylphosphonic acid, l-monochloropropylphosphonic acid, l-chloro-l-methyl-ethylphosphonic acid, l-chloro-butylphosphonic acid and l-chlorol-methyl-propylphosphonic acid.
  • Amines which form eifective salts of the phosphonic acids are primary to secondary alkyl amines having at least 8, preferably 8 to 30, and more preferably 12 to 24 carbon atoms per molecule.
  • Branched tertiary-alkyl primary amines are preferred; branched in this context means having at least 2 hydrocarbon substitutents attached to the main carbon chain.
  • the tertiary-alkyl radical the radical of polyisobutylene and polypropylene, and mixtures of these are particularly preferred.
  • Examples of these amines are 1,1,3,3-tetramethylbutylamine, 1,1,3,3,5,5 hexamethylhexylamine, 1,1,3,3,5,5,7,7 octamethyloctylamine and 1,1,3,3,5,5,7,7,9,9-decamethyl-decylamine.
  • Tertiary alkyl methyl primary amines such as 2,2,4,4-tetramethylpentylamine and 2,2,4,6,6-hexamethyl hexylamine are also suitable.
  • C2115 i-C Hn--NH2 as 'well as isoheptyl diethyl carbinylamine, is'ooctylethyl propylcarbinylamine, etc.
  • Primary amines of this type are commercially available from Rohm and Haas Company under the trade name of Primenes.
  • the amine may also be a polyamine, such as a diamine or triamine, and may contain other non-reactive groups, such as amide or ether groups, in the carbon chain.
  • secondary amines for making the phosphonic acid salts are diamylamine, dihexymine, butyl-2-ethylhexylamine, dilaurylamine, methyloleylamine, ethyloctaylamine, isoamylhexylamine, dicyclohexylamine, dicyclopentylamine, cyclohexyloctylamine, cyclohexylbenzylamine, benzyloctylamine, benzyl-Z-ethylhexylamine, allyloctylamine, dodecyI-Z-ethyl-hexylamine, 1 -isobutyl-3-methylbutyl -3,3,3-methylcyclohexylamine, di(1 isobutyl-3-methylbutyl)-amine; N-n-dodecyldiethylenetriamine, N-n-tetradecyldiethylenetriamine,
  • the phosphonic acid-amine salts for use in the invention can be prepared by direct neutralization of haloalkylphosphonic acid with a substantially stoichiometric amount of amine.
  • the reaction occurs at normal or moderately elevated temperatures and may be carried out in the presence of an inert diluent or solvent, such as a hydrocarbon, alcohol, ether, ketone, etc. Preparation of these salts is described in Watson et al., U.S. 2,858,332, issued Oct. 28, 1958.
  • the phosponic acid-amine salts useful in the invention may also be modified with an alkali metal as described in Price et al., U.S. 3,112,267, issued Nov. 26, 1963.
  • the full amine salt of the phosphonic acid is prepared and is then treated in a low-boiling solvent with an alkali metal hydroxide, carbonate, or alcoholate such that one of the amine groups is replaced with an alkali metal.
  • Preferred alkali metals are sodium, potassium, and lithium.
  • the amine-phosphonic acid salts are used in amounts of from about 0.005 to 5% by weight, preferably about 0.01 to 3% by weight of the lubricating composition.
  • Preferred s-triazine constituents have the formula:
  • R and R are hydrogen, C to C hydrocarbyl, or pyridyl, and R is C to C hydrocarbyl or All of the Rs may be the same or different, except that not all of the carbon substituents may be amino since this compound, melamine, is insoluble in the ester base oils.
  • These compounds are particularly and importantly preferred because they substantially inhibit copper corrosion in addition to being good antioxidants. Low copper corrosivity is important because copper parts are generally found in contact with turbine oils in jet engines. Although copper corrosion inhibitors may be added, further additives are expensive and might cause problems of incompatability with other additives.
  • V N Hz N n-C4HHNH -NII 2,4-diamino-6-n-butylaminol striazine. NHz
  • MCMPA chloromethylphosphonic acid and C primary amine
  • PAN phenyl-alpha-naphthylamine
  • DPA diphenylamine
  • the triazine components of lubricants of the invention may be made by any of a variety of methods known to the art. The chemistry of these compounds, along with methods for their preparation, is completely described The following example describes the preparation of 2-amino4-n-butylamino-fi-phenyl-s-triazine, and is included for purposes of illustrating one method of prep aration.
  • Suitable synthetic lubricant base stocks for the practice of the invention are esters of alcohols having 1 to 20, especially 4 to 12 carbons and aliphatic carboxylic acids having from 3 to 20, especially 4 to 12 carbons.
  • the ester base may comprise a simple ester (reaction product of a monohydroxyalcohol and a monocarboxylic acid), a polyester (reaction product of an alcohol and an acid, one of which has more than one functional group), or a complex ester (reaction product of a polyfunctional acid with more than one alcohol, or of a polyfunctional alcohol with more than one acid).
  • excellent synthetic lubricants may be formulated from mixtures of esters, such as major proportions of complex esters and minor amounts of diesters.
  • Monohydric alcohols suitable for making ester base stocks include methyl, butyl, isooctyl, dodecyl and octadecyl alcohols.
  • Oxo alcohols prepared by the reaction of olefins with carbon monoxide and hydrogen are suitable.
  • Neo alcohols, i.e., alcohols having no hydrogens on the beta carbon atom are preferred. Examples of such alcohols are 2,2,4-trimethyl-pentanol-1 and 2,2-dimethyl propanol.
  • Polyalcohols used for the production of base oil esters preferably contain 1 to 12 carbons.
  • dialcohols are 2-ethyl-1,3-hexanediol, 2-propyl-3,3-heptanediol, 2-butyl-1,3-butaneidol, 2,4-dimesityl-1,3-butanediol, and polypropylene glycols having molecular Weights of from about 100 to 300.
  • Alcohols having 3, 4, or more hydroxyl groups per molecule are also suitable and are preferred; examples of these polyols are pentaerythritol, dipentaerythritol, and trimethylolpropane. Mixtures of alcohols may also be used.
  • Suitable carboxylic acids for making the ester base oils include monoand dibasic aliphatic carboxylic acids.
  • appropriate acids are butyric, valeric, sebacic, azelaic, suberic, succinic, caproic, adipic, ethyl suberic, diethyl adipic, oxalic, malonic, 'glutaric, pentadecanedicarboxylic, diglycolic, thiodiglycolic, acetic, propionic, caprylic, lauric, palmitic, pimelic, and mixtures thereof.
  • Preferred acids are sebacic, azelaic, glutaric, adipic, and their mixtures.
  • ester base oils examples include ethyl almitate, ethyl laurate, butyl stearate, di-(Z-ethylhexyl)sebacate, di- (2-ethylhexyl)azelate, ethyl glycol dilaureate, di-(Z-ethylhexyl) phthalate, di-(l,3-methylbutyl) adipate, di-(lethylpropyl) azelate, diisopropyloxylate, dicyclohexyl sebacate, glycerol tri-n-heptoate, di(undecyl) azelate, and tetraethylene :glycol di-(Z-ethylene caproate), and mixtures thereof.
  • An especially preferred mixture of esters consists of about 5080% wt. bis(2,2,4-trimethylpentyl) azelate and 20 to 50% 1,1,1-trimethylyl propane tri
  • esters for use as base stocks in the present invention are esters of monocarboxylic acids having 3 to 12 carbons and polyalcohols such as pentaerythritol, dipentaerythritol, and trimethylol-propane.
  • esters examples include pentaerythrityl tetr-abutyrate, pentaerythrityl tetravalerate, pentaerythrityl tetracaproate, pentaerythrityl dibutyratedicaproate, pentaeryth-rityl butyratecaproate divalerate, pentaerythrityl butyrate trivalerate pentaerythrityl butyrate tricaproate, pentaerythrityl tributyratecaproate, mixed C saturated fatty acid esters of pentaerythritol, dipentaerythrityl hexavalerate, dipentaerythrityl hexacaproate, dipentaerythrityl hexaheptoate, dipentaerythrityl hexacaprylate, dipentaerythrityl tributyratetricaproate, dipentaerythrityl trival
  • Pentaerythrityl mixed hexaesters of C fatty acids and trimethylolpropane heptylate are excellent base oils, and are commercially available from Hercules Chemical Company.
  • Ester oils may be prepared by simple reaction of the alcoholic and acidic reactants in proportions suitable for producing the desired product; preparation preferably takes place in a solvent such as an aromatic hydrocarbon, and in the presence of a catalyst, such as HCl, HF, HBr, H 80 H PO S001 BF etc.
  • a catalyst such as HCl, HF, HBr, H 80 H PO S001 BF etc.
  • Preparation of suitable esters is described in Eickemeyer, US. 3,038,859, issued June 12, 1962, and Young, US. 3,121,109, issued Feb. 11, 1964.
  • Compositions of the invention may also contain other additives to further improve properties of the oil.
  • additives include extreme-pressure agents, viscosity index improvers, anti-corrosion agents, detergents, antifoamants, etc.
  • a lubricant composition comprising a major amount of a synthetic ester lubricating oil and an oxidation inhibitor consisting of (a) 0.05 to 5.0% wt. of an arylamine selected from the group consisting of diphenylamine and 10 phenyl-alpha-naphthylamine, (b) 0.1 to 5% by weight of an s-triazine having the formula R3 R2 where R, R R and R are hydrogen, C to C hydrocarbyl, or pyridyl, and R is C to C hydrocarbyl, C to C hydrocarbylamino, pyridyl, or pyridylamino and (c) 0.005 to 5% by weight of the salt of a C alkyl amine and a monohaloalkylphosphonic acid, wherein the haloalkyl radical contains from 1 to 4 carbon atoms.
  • composition of claim 1 wherein the arylamine is present in an amount of 0.1 to 3% by weight, the salt is present in the amount of 0.01 to 3% by weight and the s-triazine is present in an amount of 0.5 to 3% by weight.
  • An antioxidant containing lubricant composition comprising a major amount of synthetic ester lubricating oil, from .05 to 5% by weight of an arylamine selected from the group consisting of diphenylamine and phenylalpha-naphthylamine, from 0.005 to 5% by weight of the salt of a C primary or secondary alkyl amine or mixtures thereof and monochloromethylphosphonic acid, and from 0.1 to 5% by weight of an s-triazine having the formula where R and R are hydrogen, 0 -0 hydrocarbyl, or pyridyl, and R is C to C hydrocarbyl or 4.
  • composition of claim 3 wherein the arylamine is phenyl-alpha-naphthylamine.
  • composition of claim 3 wherein R is NH 7.
  • composition of claim 3 wherein the s-triazine is 2-n-butylamino-4,6-diamino-s-triazine.
  • composition of claim 3 wherein the s-triazine is 2-amino-4-anilino-6-benzylamino-s-triazine.
  • composition of claim 3 wherein the s-triazine is 2,4-diamino-6-di-nbutylamino-s-triazine.
  • composition of claim 3 wherein the s-triazine is 2,4-diamino-6- (4-tert-butylphenyl) -s-triazine.

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  • Organic Chemistry (AREA)
  • Lubricants (AREA)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3793199A (en) * 1970-06-08 1974-02-19 Texaco Inc Friction reducing agent for lubricants
US20100305011A1 (en) * 2007-11-28 2010-12-02 Nyco Sa Anti-oxidation and/or anti-corrosion agent, lubricating composition containing said agent and method for preparing the same
WO2023209038A1 (fr) 2022-04-27 2023-11-02 Nyco Utilisation d'un antioxydant pour réduire et/ou prévenir la toxicité d'une composition lubrifiante

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT7829957A0 (it) * 1977-12-02 1978-11-20 Goodrich Co B F Composizione antiossidante perl'uso in lubrificanti sintetici.

Citations (7)

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US2714057A (en) * 1951-07-21 1955-07-26 Universal Oil Prod Co Stabilization of organic compounds
US2847383A (en) * 1952-11-19 1958-08-12 Shell Dev Synthetic diester lubricating oils
US3093585A (en) * 1960-06-06 1963-06-11 Shell Oil Co Ester base lubricant compositions
US3197408A (en) * 1960-12-16 1965-07-27 Union Carbide Corp Synthetic functional fluids
US3247111A (en) * 1963-04-08 1966-04-19 Socony Mobil Oil Co High temperature jet lubricant
US3309314A (en) * 1964-05-29 1967-03-14 Shell Oil Co Lubricant compositions
US3330762A (en) * 1964-12-11 1967-07-11 Shell Oil Co Lubricant compositions

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2714057A (en) * 1951-07-21 1955-07-26 Universal Oil Prod Co Stabilization of organic compounds
US2847383A (en) * 1952-11-19 1958-08-12 Shell Dev Synthetic diester lubricating oils
US3093585A (en) * 1960-06-06 1963-06-11 Shell Oil Co Ester base lubricant compositions
US3197408A (en) * 1960-12-16 1965-07-27 Union Carbide Corp Synthetic functional fluids
US3247111A (en) * 1963-04-08 1966-04-19 Socony Mobil Oil Co High temperature jet lubricant
US3309314A (en) * 1964-05-29 1967-03-14 Shell Oil Co Lubricant compositions
US3330762A (en) * 1964-12-11 1967-07-11 Shell Oil Co Lubricant compositions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3793199A (en) * 1970-06-08 1974-02-19 Texaco Inc Friction reducing agent for lubricants
US20100305011A1 (en) * 2007-11-28 2010-12-02 Nyco Sa Anti-oxidation and/or anti-corrosion agent, lubricating composition containing said agent and method for preparing the same
WO2023209038A1 (fr) 2022-04-27 2023-11-02 Nyco Utilisation d'un antioxydant pour réduire et/ou prévenir la toxicité d'une composition lubrifiante
FR3135091A1 (fr) 2022-04-27 2023-11-03 Nyco Utilisation d’un antioxydant pour réduire et/ou prévenir la toxicité d’une composition lubrifiante

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