US3625893A - Lubricating compositions having improved oxidation stability and antirust properties - Google Patents

Lubricating compositions having improved oxidation stability and antirust properties Download PDF

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US3625893A
US3625893A US772840A US3625893DA US3625893A US 3625893 A US3625893 A US 3625893A US 772840 A US772840 A US 772840A US 3625893D A US3625893D A US 3625893DA US 3625893 A US3625893 A US 3625893A
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acids
composition
salts
oxidation stability
basic
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James H T Brook
Joyce Williams
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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
    • C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10—Compounds containing silicon
    • C10M2201/102—Silicates
    • 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
    • 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
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/024—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings having at least two phenol groups but no condensed ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/16—Naphthenic 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
    • C10M2207/22—Acids obtained from 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
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—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
    • 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
    • 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
    • C10M2219/083—Dibenzyl sulfide
    • 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
    • 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
    • C10M2223/042—Metal 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
    • 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/02—Unspecified siloxanes; Silicones
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
    • 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
    • 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
    • C10N2060/04—Oxidation, e.g. ozonisation

Definitions

  • Lubricating oil compositions comprising essentially a major amount of lubricating oil and a minor amount of a mixture of basic group II metal salts of aromatic carboxylic acids and naphthenic acids have improved oxidation stability and antirust properties.
  • the composition optionally contains zinc dialkyldithiophosphate.
  • This invention relates to improved lubricating oil compositions particularly suitable for use in large marine diesel propulsion engines and in shipboard auxiliary equipment.
  • a number of other highly basic compounds such as calcium naphthasulfonates, barium versatates, calcium phenates, etc., might improve the oxidation stability and antirust properties but are not suitable for use in main engines because they tend to either emulsify, leach out, or form gells with salt water often found in the crankcases of marine diesel engines.
  • a lubricating composition which would be capable of neutralizing acidic combustion products, and also possessing good oxidation stability and antirust characteristics therefore would be extremely desirable.
  • the compositions of the present invention fulfill these requirements.
  • the excess basicity of the group ll metal salicylates is less than that of the naphthenates used in the prior art; therefore, in order to maintain the basicity of the final composition at a desired level it is necessary to combine the metal salicylates with other basic salts such as metal naphthenates which have a greater inherent basicity. Accordingly, by using a mixture of metal salts as herein defined, a final composition is obtained in which the basicity is held at an acceptable level, while the antirust and oxidation stability properties of the final blends are greatly improved.
  • a lubricant composition according to the present invention consists essentially of a hydrocarbon lubricating oil and a mixture of highly basic oil-soluble group ll metal salts of aromatic carboxylic acids and highly basic oil-soluble group II metal salts of naphthenic acids wherein the group ll metal salts have an atomic number of from 12 to 56.
  • the hydrocarbon lubricating oil employed in the present invention, can be a mineral oil or a synthetic oil.
  • the preferred mineral oils are generally parafiinic and/or naphthenic or character and may contain substantial proportions of hydrocarbons having an aromatic structure.
  • the viscosity can vary within wide limits so that the oils belonging to S.A.E. classes W, lOW, 20, 30, 40, 50, 60, or 70 are acceptable.
  • Suitable oils can also be derived from highly paraffinic crude in which case distillation and/or dewaxing may be necessary to provide a suitable base stock. Chemical or selective solvent treatment can be used if desired. Mixed base crudes and highly aromatic crudes which contain parafi'inic hydrocarbons also provide suitable oil base stocks after refining.
  • the mineral oil bases may be blends of distillate lubricating oils and bright stocks.
  • the mineral oils may be mixed with, or even entirely replaced by, synthetic lubricants or polymerized olefins, for example polyisobutylene.
  • the highly basic oil-soluble group ll metal salts of aromatic carboxylic acids include such compounds as basic calcium, barium, magnesium, strontium and zinc salts of hydrocarbon-substituted benzoic, salicylic resorcylic, anthranilic and naphthoic acids.
  • Such salts are basic calcium, barium, magnesium and/or zinc salts of C -C alkylbenzoic, C -C -alkyl salicylic, C -C -alkylnaphthoic acids and mixtures thereof.
  • the preferred salts are the basic barium, calcium, magnesium and zinc salts of lauryl-salicylic acid, or of stearyl-salicylic acids or a mixture of alkyl-salicylic acids in which the alkyl groups contain from 8 to 22, preferably 14 to 22, carbon atoms.
  • the basic calcium salts of these alkyl salicylic acids have been found to be particularly advantageous.
  • the salts are present in an amount 1 to 6 percent by weight based on the lubricant composition.
  • the excess basicity of the salts is defined by the formula wherein M represents the number of equivalents of metal, and E the number of equivalents of organic acid per 100 grams of basic salt, to give a neutralization number by potentiometric titration determined according to ASTM method No. D 664-58 or IP 177/64, hereafter referred to as the TBNE (Total Base Number Electrometric) per 1 percent in the lubricating oil between 1 and L5 m. KOH/g.
  • the oil-soluble group II metal salts of naphthenic acids comprise the salts of strontium, magnesium, zinc, barium, and calcium, those particularly preferred being barium and calcium.
  • the naphthenic acids may be derived from mixtures of naphthenic acids obtained from various petroleum fractions.
  • the naphthenic acids preferably have average molecular weights in the range from to 750, although lower or higher molecular weight materials may also be used.
  • the basicity of the group ll metal naphthenates may be calculated using the same formula as that employed for the alkyl salicylic acid salts disclosed above, wherein M represents the equivalents of metal and E the equivalents of combined na hthenic acid in 100 grams of the basic salt, and will be probably in excess of 400, preferably in excess of 600 and maybe 800 or more up to the limit which is practically attainable.
  • the salts will be chosen for use in the present invention so that they will give a TBNE per 1 percent in the lubricating oil of between 1.5 and 3.0 m. KOH/g.
  • the salts are present in an amount 0.5 to 3 percent by weight based on the lubricant composition.
  • the two additives as defined above are present in such amounts as to give an overall TBNE in the range 5 to 12, preferably 6 to 10, the preferred value being 8.
  • compositions of the present in vention relatively small amounts (e.g., from 0.01 to 2.0 percent, preferably from 0.05 to 1.0 percent by weight) of other additives.
  • suitable additives is constituted by the metal thiophosphates such as calcium or zinc dialkyldithiophosphates, especially those wherein the alkyl groups are aryl and/or butyl.
  • Alkyl phenols e.g., diand tri-alkyl phenols, or alkyl bisphenols, e.g., bis (3,5-di-tertiary-butyl-4- hydroxyphenyl)methane, constitute a second class.
  • a third class is formed by aryl-amines such as phenyl-alphanaphthylamine or phenyl-beta-naphthylamine. These various classes may be used in admixture if required.
  • additives which may also be incorporated into the lubricating composition for the purposes of the present invention are for example antiscuffing agents, e.g., phosphorus esters; antifoaming agents, e.g., silicone polymers; viscosity index improvers, e.g., polymeric acrylic esters; extreme pressure additives, e.g., dibenzyl disulfide; rust inhibitors, e.g., the condensation product of maleic anhydride and long chain olefins; oiliness agents, e.g., acidless tallow; and surface-active agents, e.g., peroxidized aromatic extracts.
  • antiscuffing agents e.g., phosphorus esters
  • antifoaming agents e.g., silicone polymers
  • viscosity index improvers e.g., polymeric acrylic esters
  • extreme pressure additives e.g., dibenzyl disulfide
  • rust inhibitors e.g
  • Composition A wt. percent:
  • ANTIRUST TEST This was according to the ASTM D665 procedure but using 20 percent of saturated salt solution as corrosive medium.
  • OXIDATION STABILITY TEST The test employed here was the SCOT test at 160 C. using soluble iron catalyst.
  • Composition D wt. percent:
  • compositions of the present invention represented by compositions C, E, and F have greatly improved antirust and oxidation stability properties and also improve engine cleanliness while still maintaining the required basicity.
  • a lubricating composition consisting essentially of a major amount of a mineral lubricating oil and a mixture of from 1 percent to 6 percent basic group II metal salts of aromatic carboxylic acids and from 0.5 percent to 3 percent basic group II metal salts of naphthenic acids wherein:
  • the aromatic carboxylic acids are selected from a group consisting of C -C alkyl benzoic, C -C alkyl salicylic, C,,-C alkyl naphthoic and mixtures thereof;
  • the naphthenic acids have an average molecular weight offrom to 750;
  • the basic group ll metals have an atomic number of from d.
  • the salts are present in an amount necessary to give a TBNE value of from 5 to 12.
  • composition of claim 1 in which the aromatic carboxylic acids are C -C alkyl salicylic acids.
  • composition of claim 2 in which the basic metal salts of the aromatic carboxylic acids are selected from the group consisting of barium, calcium, magnesium, and zinc.
  • composition of claim 4 in which the aromatic carboxylic acids are C -C salicylic acids and the basic salts of these acids are calcium salts.
  • composition of claim 1 which contains from 0.01 percent to 2 percent of zinc dialkyldithiophosphate.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
US772840A 1967-11-06 1968-11-01 Lubricating compositions having improved oxidation stability and antirust properties Expired - Lifetime US3625893A (en)

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GB50317/67A GB1137819A (en) 1967-11-06 1967-11-06 Improvements in or relating to lubricant compositions

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US3625893A true US3625893A (en) 1971-12-07

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US (1) US3625893A (enrdf_load_stackoverflow)
JP (1) JPS4829361B1 (enrdf_load_stackoverflow)
DE (1) DE1806899C3 (enrdf_load_stackoverflow)
FR (1) FR1590499A (enrdf_load_stackoverflow)
GB (1) GB1137819A (enrdf_load_stackoverflow)
NL (1) NL6815667A (enrdf_load_stackoverflow)
NO (1) NO122141B (enrdf_load_stackoverflow)
SE (1) SE347284B (enrdf_load_stackoverflow)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4308154A (en) * 1979-05-31 1981-12-29 The Lubrizol Corporation Mixed metal salts and lubricants and functional fluids containing them
US4417990A (en) * 1979-05-31 1983-11-29 The Lubrizol Corporation Mixed metal salts/sulfurized phenate compositions and lubricants and functional fluids containing them
US4627928A (en) * 1976-08-26 1986-12-09 The Lubrizol Corporation Basic non-carbonated magnesium compositions and fuel, lubricant and additive concentrate compositions containing same
US4784781A (en) * 1987-02-27 1988-11-15 The Lubrizol Corporation Lubricating oil compositions containing multi-functional additive component
US4871473A (en) * 1987-12-17 1989-10-03 Dr. Wolman Gmbh Wood preservative
US4876020A (en) * 1987-06-25 1989-10-24 Shell Oil Company Lubricating oil composition
US5219477A (en) * 1991-04-15 1993-06-15 The Dow Chemical Company Antioxidant-containing cyclophosphazene compositions, antioxidants for use therein, and method therefor
US5250203A (en) * 1987-02-27 1993-10-05 The Lubrizol Corporation Lubricating oil compositions containing a polyoxyalkylene carboxylic acid salt additive
US6784143B2 (en) * 2001-05-11 2004-08-31 Infineum International Ltd. Lubricating oil composition
US20040195825A1 (en) * 2001-07-25 2004-10-07 Toshiro Anraku Threaded joint for steel pipes
US7053027B2 (en) * 2000-05-09 2006-05-30 Infineum International Limited Lubricating oil compositions
US20070191237A1 (en) * 2000-08-25 2007-08-16 Holmes Andrew J Hydraulic fluid
US20110034359A1 (en) * 2009-08-07 2011-02-10 Rabbat Philippe Marc Andre Lubricant composition
US8802606B2 (en) 2010-08-06 2014-08-12 Basf Se Lubricant composition having improved antiwear properties

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2149810B (en) * 1983-11-15 1987-04-08 Shell Int Research Borated basic metal salt and oil composition containing it
BR9304553A (pt) * 1992-12-23 1994-07-26 Lubrizol Corp Fluído funcional, concentrado, fluído funcional de base aquosa e método para melhorar a estabilidade térmica de um fluído funcional

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2839470A (en) * 1957-02-06 1958-06-17 Shell Dev Preparation of basic polyvalent metal salts of organic acids
US2865956A (en) * 1954-09-27 1958-12-23 Shell Dev Preparation of basic polyvalent metal salts of organic acids
US2958662A (en) * 1955-09-26 1960-11-01 Shell Oil Co Detergent and wear inhibiting mineral oil compositions
US3269946A (en) * 1961-08-30 1966-08-30 Lubrizol Corp Stable water-in-oil emulsions
US3372116A (en) * 1965-10-05 1968-03-05 Lubrizol Corp Preparation of basic metal phenates and salicylates
US3471403A (en) * 1967-03-07 1969-10-07 Lubrizol Corp Basic metal carboxylate complex

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2865956A (en) * 1954-09-27 1958-12-23 Shell Dev Preparation of basic polyvalent metal salts of organic acids
US2958662A (en) * 1955-09-26 1960-11-01 Shell Oil Co Detergent and wear inhibiting mineral oil compositions
US2839470A (en) * 1957-02-06 1958-06-17 Shell Dev Preparation of basic polyvalent metal salts of organic acids
US3269946A (en) * 1961-08-30 1966-08-30 Lubrizol Corp Stable water-in-oil emulsions
US3372116A (en) * 1965-10-05 1968-03-05 Lubrizol Corp Preparation of basic metal phenates and salicylates
US3471403A (en) * 1967-03-07 1969-10-07 Lubrizol Corp Basic metal carboxylate complex

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4627928A (en) * 1976-08-26 1986-12-09 The Lubrizol Corporation Basic non-carbonated magnesium compositions and fuel, lubricant and additive concentrate compositions containing same
US4417990A (en) * 1979-05-31 1983-11-29 The Lubrizol Corporation Mixed metal salts/sulfurized phenate compositions and lubricants and functional fluids containing them
US4308154A (en) * 1979-05-31 1981-12-29 The Lubrizol Corporation Mixed metal salts and lubricants and functional fluids containing them
US5250203A (en) * 1987-02-27 1993-10-05 The Lubrizol Corporation Lubricating oil compositions containing a polyoxyalkylene carboxylic acid salt additive
US4784781A (en) * 1987-02-27 1988-11-15 The Lubrizol Corporation Lubricating oil compositions containing multi-functional additive component
US4954273A (en) * 1987-02-27 1990-09-04 The Lubrizol Corporation Oil formulations containing overbased multi-functional additive
US4876020A (en) * 1987-06-25 1989-10-24 Shell Oil Company Lubricating oil composition
US4871473A (en) * 1987-12-17 1989-10-03 Dr. Wolman Gmbh Wood preservative
US5219477A (en) * 1991-04-15 1993-06-15 The Dow Chemical Company Antioxidant-containing cyclophosphazene compositions, antioxidants for use therein, and method therefor
US7053027B2 (en) * 2000-05-09 2006-05-30 Infineum International Limited Lubricating oil compositions
US20070191237A1 (en) * 2000-08-25 2007-08-16 Holmes Andrew J Hydraulic fluid
US6784143B2 (en) * 2001-05-11 2004-08-31 Infineum International Ltd. Lubricating oil composition
US20040235688A1 (en) * 2001-05-11 2004-11-25 Locke Christopher J. Lubricating oil composition
US20040195825A1 (en) * 2001-07-25 2004-10-07 Toshiro Anraku Threaded joint for steel pipes
US20110034359A1 (en) * 2009-08-07 2011-02-10 Rabbat Philippe Marc Andre Lubricant composition
US8802605B2 (en) 2009-08-07 2014-08-12 Basf Se Lubricant composition
US9340745B2 (en) 2009-08-07 2016-05-17 Basf Se Lubricant composition
US8802606B2 (en) 2010-08-06 2014-08-12 Basf Se Lubricant composition having improved antiwear properties

Also Published As

Publication number Publication date
JPS4829361B1 (enrdf_load_stackoverflow) 1973-09-10
DE1806899C3 (de) 1975-08-14
SE347284B (enrdf_load_stackoverflow) 1972-07-31
GB1137819A (en) 1968-12-27
DE1806899B2 (de) 1975-01-09
DE1806899A1 (de) 1969-06-12
NO122141B (enrdf_load_stackoverflow) 1971-05-24
NL6815667A (enrdf_load_stackoverflow) 1969-05-08
FR1590499A (enrdf_load_stackoverflow) 1970-04-13

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