US3865740A - Multifunctional lubricating oil additive - Google Patents

Multifunctional lubricating oil additive Download PDF

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US3865740A
US3865740A US332864A US33286473A US3865740A US 3865740 A US3865740 A US 3865740A US 332864 A US332864 A US 332864A US 33286473 A US33286473 A US 33286473A US 3865740 A US3865740 A US 3865740A
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hydrocarbyl
substituted
lubricating oil
lubricating
percent
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Alfred Goldschmidt
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Chevron USA Inc
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Chevron Research and Technology Co
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Priority to FR7317531A priority patent/FR2185673B3/fr
Priority to GB2368273A priority patent/GB1421450A/en
Priority to DE2324923A priority patent/DE2324923A1/de
Priority to JP48056675A priority patent/JPS4950002A/ja
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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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C10M137/105—Thio derivatives not containing metal
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • 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
    • 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
    • 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
    • C10M2205/024—Propene
    • 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
    • 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
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four 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
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
    • C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
    • 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
    • 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
    • C10M2223/047—Thioderivatives not containing metallic elements
    • 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
    • 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
    • C10M2223/08—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-nitrogen bonds
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

Definitions

  • a class of dithiophosphoric acid ester derivatives has been found to possess a surprising lubricating additive trifunctionality, in that they function as effective extreme pressure agents, antioxidants and ashless dispersants when present in 0.5 to 10 percent by weight in lubricating oil compositions.
  • These additives are N- substituted, S-aminomethyl dithiophosphates, wherein said substituent is selected from the group consisting of hydrocarbyl, hydrocarbyl-substituted amine, and hydrocarbyl-substituted succinimide, and said hydrocarbyl-substituents contain at least 40 carbon atoms. They have the additional advantage of being ashless.
  • the dithiophosphates of the present invention are 0,0-diesters of dithiophosphoric acid. These dithiophosphates are alkyl, aryl, alkaryl or aralkyl diesters of dithiophosphoric acid.
  • the N-substituted, S- aminomethyl dithiophosphates of the present invention are derived from the dithiophosphates by concensing the 0,0-diester of dithiophosphoric acid with formaldehyde, or another aldehyde, and a hydrocarbylsubstituted amine, polyamine, or hydrocarbylsubstituted succinimide of a polyamine. The condensation is believed to proceed according to the following reaction:
  • R and R are alkyl, aryl, alkaryl or aralkyl radicals, or heteroatom-substituted hydrocarbyl radicals, of from low to moderate molecular weight and they may be the same or different.
  • the 0,0-diester of dithiophosphoric acid is produced by the reaction of phosphorus pentasulfide with an alcohol, mixture of alcohols, or alkylphenol from which R and R are derived.
  • R and R can be alkyl, aryl, alkaryl or aralkyl groups of from about 1 to about 20 carbon atoms.
  • R and R can also be derived from ether-capped polyloxyalkylene glycols.
  • R and R are hydrocarbyl or substituted hydrocarbyl groups of relatively low molecular weight, such as methyl, ethyl, propyl, butyl, amyl, hexyl, cyclohexyl, tetradecyl, dodecyl, decyl, octadecyl, phenyl, naphthyl, methyl phenyl, butyl phenyl, isooctyl, polypropenyl, polyisobutenyl, etc.
  • the aldehyde which is the preferred condensing agent for the preparation of the products of this invention is formaldehyde, in which case R is hydrogen.
  • formaldehyde may be replaced by other aldehydes, for example, benzaldehyde, isobutyraldehyde, butyraldehyde, propionaldehyde, :acetaldehyde, valeraldehyde, hexaldehyde, etc., in which case R is a hydrocarbyl or substituted hydrocarbyl group.
  • HNXY represents a substituted primary or secondary amine of relatively high molecular weight (SOD-10,000).
  • X and Y are radicals of which one may be hydrogen, but at least one is chosen from the group consisting of hydrocarbyl, hydrocarbyl-substituted amine and hydrocarbyl-substituted succinimide of a polyamine. Consequently, the reactant HNXY is a hydrocarbyl-substituted amine or polyamine, or a hydrocarbyl-substituted succinimide of a polyamine.
  • Hydrocarbyl denotes a monovalent organic radical composed of carbon and hydrogen, except for minor, insubstantial, sometimes adventitious, amounts of other elements such as oxygen, nitrogen, halogen, etc., which may be aliphatic, alicyclic, aromatic, or combinations thereof, e.g., aralkyl.
  • the hydrocarbyl group will be relatively free of aliphatic unsaturation, i.e., ethylenic and acetylenic, particularly acetylenic unsaturation.
  • the hydrocarbyl substituent in HNXY contains an average of at least 40 and preferably less than an average of 300 carbon atoms. It is preferably aliphatic, having preferably from zero to two sites of ethylenic unsaturation and most preferably from zero to one such site. Hydrocarbyl groups derived from a polyolefin, itself derived from olefins (normally l-olefins) of from two to six carbon atoms (ethylene being copolymerized with a higher olefin), or from a higher molecular weight petroleum-derived hydrocarbon, are preferred, and of these, polyisobutene containing from 40 to about 100 carbon atoms is most preferred.
  • Illustrative sources for the high molecular weight hydrocarbyl substituents are petroleum mineral oils such as naphthenic bright stocks, polypropylene, polyisobutylene, poly-l-butene, copolymers of ethylene and propylene, poly-l-pentene, poly-4-methyl-l-pentene, poly-l-hexene, poly-3- methylbutene-l, etc.
  • the hydrocarbyl-substituted amines are derived from lower molecular weight amines (LMW amine), preferably alkylene polyamines and polyalkylene polyamines, by, for example, the reaction of a halogenated hydrocarbon with the LMW amine.
  • LMW amines include ethylenediamine, methylamine, 2- aminoethyl piperazine, decylamine, diethylenetriamine, octadecylamine, di(trimethylene) triamine, ethylene dipiperazine, dipropylenetriamine, piperazine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.
  • the LMW amines encompass substituted and alkylsubstituted amines, e.g., N-methylethylenediamine, hydroxyethyl piperazine, N,N'-dimethylethylenediamine, N,N-dimethylpropylenediamine, N,N-dimethyldiamino propane, N-hydroxyethyl ethylenediamine, etc.
  • Amines having up to about 12 amino nitrogens and up to about 36 carbon atoms are especially preferred LMW amines.
  • the hydrocarbyl-substituted amines are prepared, in general, by the reaction of halogenated hydrocarbon with the LMW amine. Details of such preparations and further description of certain hydrocarbyl amines can be found in Hotten and Anderson US. Pat. No. 3,565,804.
  • the composition is a mixture of materials having various structures and molecular weights. Therefore, in referring to molecular weight, average molecular weights are intended. Furthermore, when speaking of a particular hydrocarbyl group, it is intended that the group include the mixture that is normally contained with materials which are commercially available; that is, polyolefins are known to have a range of molecular weights. Furthermore, depending on the method of preparation, the end group of the polymer may vary and may be terminated, not only with an isobutene group, but also with a 1- or 2-butene group. In addition.
  • alkylene polyamines which are commercially available are frequently mixtures of various alkylene polyamines and branched chain isomers having one or two species dominating.
  • pentaethylene hexamine and triethylene tetramine.
  • hydrocarbyl-substituted tetraethylene pentamine which is the preferred amine, it is intended not only to include the pure compound, but those mixtures which are obtained with commercially available alkylene polyamines.
  • the product will be a mixture of the various possible isomers.
  • hydrocarbyl-substituted succinimides which find use as nitrogen substituents in the N-substituted, S- aminomethyl dithiophosphate are prepared by first making a monohydrocarbyl succinic acid or anhydride derivative and then reacting the resultant anhydride or acid with a polyamine.
  • the mono-hydrocarbyl succinic acids or anhydrides are prepared by forming the adduct of maleic anhydride with a suitable olefin polymer, chlorinated hydrocarbon, etc. This reaction proceeds upon mixing and heating ofthe components at temperatures in the range of from about l00-200C.
  • the preparation of these mono-hydrocarbyl succinimides is then effected by the reaction of, for example, mono-hydrocarbyl succinic anhydride with such LMW primary amines or polyamines containing a primary amino nitrogen atom as ethylamine, propylamine, butylamine, tetraethylene pentamine, triethylene tetramine.
  • the preferred succinimides are polyisobutenyl suc cinimides prepared by reaction of a substituted succinic acid or anhydride derived from a polybutene having at least 40 carbon atoms and tetraethylene pentamine or triethylene tetramine.
  • the succinic acid or anhydride and the polyamine are preferably reacted in approximately equal molar ratio to obtain the succinimide product.
  • Example 1 650 g. of polyisobutenyl ethylene diamine (80 percent concentrate in a 100 SSU at 100F. neutral oil), wherein the number average molecular weight of the polyisobutenyl was 1,400 (average carbon number of 100), was diluted with 300 ml of benzene. 37 g. of a 37 percent aqueous CH O solution was added, whereupon the temperature rose from 75 to 87F. The mixture was stirred one-half hour and 120 g. of di(isooctyl)dithiophosphoric acid was added in 100 ml. of benzene. The temperature rose to 107F, whereupon heat was applied and the mixture was stirred for 5 hours at l70-l80F. 150 g. of a 100 SSU at 100F. neutral petroleum oil was added, and the product stripped of solvent at 220F for 3 minutes. Percent phosphorus, 1.04.
  • Example 2 700 g. of polyisobutenyl succinimide of ethylene diamine (as 50 percent concentrate in 100 SSU at 100F. neutral petroleum oil), wherein the number average molecular weight of the polyisobutenyl was 950, was diluted with 200 ml of benzene. 10.5 g. of paraformaldehyde was added and the mixture was stirred for 1 hour at l20l30F. 120 g. of di(isooctyl)dithiophosphoric acid was added in 50 ml. of benzene. The mixture was heated for four hours at 185F and stripped at 210F for 4 minutes. Percent phosphorus, 1.1 percent.
  • Example 3 830 g. of a 50 percent concentrate of polyisobutenyl succinimide of tetraethylene pentamine, wherein the number average molecular weight of the polyisobutenyl was 950, was diluted with 250 ml. of benzene. 8.5 grams of paraformaldehyde was added and the mixture was stirred for one hour at 130F. 9.6 g. of a di(isooctyl)dithiophosphoric acid in 50 ml. of benzene was then added and the mixture was heated for five hours at 190F. The product was stripped at 210F for 5 minutes. Percent phosphorus, 0.88 percent.
  • Example 4 Analogous to Example 3, using a bis(polypropenyl phenol) dithiophosphoric acid.
  • Lubricant Composition The lubricating oils which comprise the basis for the composition of this invention are those oily or greasy materials employed in lubrication. Examples of these materials are natural and synthetic oils and greases made from these oils, and synthetic oils.
  • Synthetic oils include alkylene polymers, such as polymers of propylene, butylene, etc., and mixtures thereof; alkylene oxide-type polymers, e.g., alkylene oxide polymers prepared by polymerization of alkylene oxide in the presence of water or alcohols, such as propylene oxide polymer, ethylene oxide polymer; carboxylic acid esters, such as those which are prepared by esterifying carboxylic acid, e.g., adipic acid, suberic acid, fumaric acid, etc. with alcohols such as butyl alcohol, hexyl alcohol, pentaerythritol, etc.; polymers of silicon; alkylbiphenyl ethers and other ethers, etc.
  • the base oils can be used individually or in combinations wherever miscible or whenever made so by use of mutual solvents. Oils of lubricating viscosity generally have viscosities of 35-50,000 SUS at F.
  • the lubricating compositions of the present invention contain a major amount of an oil of lubricating viscosity and will also contain a functional amount, from 0.1 to 10 percent by weight, of the N-substituted, S- aminomethyl dithiophosphate of the present invention. In concentrates, the weight percent of this additive will usually range from about 20 to 60 percent by weight.
  • these lubricating compositions can also contain other lubricating oil and grease additives such as oiliness agents, extreme pressure agents, rust inhibitors, other oxidation inhibitors, corrosion inhibitors, viscosity index improving agents, dyes, detergents, dispersants, etc.
  • oiliness agents such as oiliness agents, extreme pressure agents, rust inhibitors, other oxidation inhibitors, corrosion inhibitors, viscosity index improving agents, dyes, detergents, dispersants, etc.
  • oiliness agents such as oiliness agents, extreme pressure agents, rust inhibitors, other oxidation inhibitors, corrosion inhibitors, viscosity index improving agents, dyes, detergents, dispersants, etc.
  • oils to be used in an internal combustion engine the total amount of these additives will range from about 0.1-20 percent by weight, and more usually from about 0.5-10 weight percent.
  • the individual additives may vary in amounts from about 0.01l0 weight percent of the total composition. In concentrates, the weight percent of these additives will usually range from about 20-60 weight percent. Evaluation
  • the Falex test is a test for extreme pressure properties.
  • stationary vee-blocks are pressed on either side of a rotating pin by a nutcracker arrangement of lever arms.
  • Test specimens are immersed in a tank of test lubricant which is at a known temperature. Loading is automatically increased until seizure occurs. This failure point is indicated by shearing of the pin holding the vertical shaft. The load at shear in pounds. is taken as a quantitative measure of the extreme pressure property of the oil composition.
  • Mineral oils may fail at 600-900 pounds. Oils with EP additives will fail at l,000-2,000 pounds. The wear is determined by conducting the test at constant load and measuring the pin weight loss in milligrams.
  • the N-substituted, S-aminomethyl dithiophosphates have also been tested for antiwear properties by means of the well-known 4-Ball Test.
  • 4-Ball Test In this test, three /z-Cliameter steel balls are clamped together and immersed in the test lubricant. A fourth ball is then rotated at about 1,800 rpm in contact with the other three balls. A 2050 kg. load is applied, forcing the rotating ball against the three stationary balls. The test is run for 60-30 minutes and the sizes of the wear scars on the three stationary balls are measured and the average scar size in millimeters reported. The smaller the scar, the greater the anti-wear properties of the test lubricant. These EP properties are reported in Table I and Il.
  • Example 3 O 5' 60% onhe product of Example 3 1300 L9 in a 496 SSU at IOO F neutral petroleum 01] was heated for 48 hours at 300 F.
  • the product was found to have 63% PM!t Example 4 an undiminished oxidator B rating.
  • 4.5 percent "Percent by weight. All test lubricants contain 15 mM/g P in a 496 SSU at 100F. neutral petroleum oil.
  • the Oxidator B test is our laboratory designation for a test measuring resistance to oxidation by means of a Dorntetype oxygen absorption apparatus (R.W.Dornte, Oxidation of While Oils, Industrial and Engineering Chemistry, Vol. 28, p. 26, 1936). Normally, the conditions are 1 atmosphere of pure oxygen at 340F and one reports the hours to absorption of 1,000 ml. of 0 by 100 grams of oil.
  • a catalyst is used and a reference additive package is included in the oil.
  • the catalyst is a mixture of soluble metal-naphthenates simulating the average metal analysis of used crankcase oils.
  • the Oxidator B method measures the response to conventional inhibitors in a simulated application.
  • Table IV illustrates the detergency of the N- substituted, S-aminomethyl dithiophosphates.
  • the data refers to a severe Caterpillar diesel engine test, run for 12 hours at 1,200 rpm, 280 brake means effective pressure in psi, water temperature of the cooling jacket is 190F, the sulfur content of the fuel is 0.4 percent and is input at a rate which provides 6,900 BTU per minute.
  • the base oil was a 496 SSU at F. neutral petroleum oil.
  • the rating of groove deposits is based on a range of 0-100, 100 being completely filled grooves.
  • the rating for land deposits is based on a range of l-800, 800 being completely black.
  • the rating for underhead deposits is based on a range of 0-l0, 10
  • N-substituted, S-aminomethyl dithiophosphates were also found to be noncorrosive towards copper and lead bearings, as well as being antioxidants, dispersants and extreme pressure agents.
  • the unique polyfunctionality of high molecular weight condensation products of the present invention is in sharp contrast with the low molecular weight analogs, which, for example, cannot function as lubricating oil detergents/dispersants. It
  • a lubricating composition comprising an oil of lubricating viscosity and from 0.l to 10 percent by weight of an N-substituted, S-aminomethyl dithiophosphate, wherein said substituent is a hydrocarbyl-subtituted succinimide of a hydrocarbyl polyamine, and wherein said hydrocarbyl substituent contains at least 40 carbon atoms.
  • R and R are alkyl, aryl, alkaryl or aralkyl groups of from about one to 20 carbon atoms
  • X and Y are radicals, one of which may be hydrogen, but at least one of which is a hydrocarbyl-substituted succinimide of a hydrocarbyl polyamine, and wherein said hydrocarbyl substituent contains at least 40 carbon atoms.

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US332864A 1972-05-22 1973-02-14 Multifunctional lubricating oil additive Expired - Lifetime US3865740A (en)

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GB2368273A GB1421450A (en) 1972-05-22 1973-05-17 Multifunctional lubricating oil additive
DE2324923A DE2324923A1 (de) 1972-05-22 1973-05-17 Multifunktionelles schmieroeladditiv
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US4136042A (en) * 1977-10-18 1979-01-23 Gulf Research & Development Company Lubricating oils containing dithiophosphorylated copolymers of aziridineethyl acrylates or methacrylates and alkyl acrylates or methacrylates
US4148981A (en) * 1977-10-18 1979-04-10 Gulf Research & Development Company Dithiophosphorylated copolymers of aziridineethyl acrylates or methacrylates and alkyl acrylates or methacrylates
US4253973A (en) * 1979-11-20 1981-03-03 Mobil Oil Corporation Phosphorus-containing compounds and lubricants containing same
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US5449386A (en) * 1992-10-09 1995-09-12 Institut Francais Du Petrole Amine phosphates having a terminal cyclic imide
US5498809A (en) * 1992-12-17 1996-03-12 Exxon Chemical Patents Inc. Polymers derived from ethylene and 1-butene for use in the preparation of lubricant dispersant additives
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US5643859A (en) * 1992-12-17 1997-07-01 Exxon Chemical Patents Inc. Derivatives of polyamines with one primary amine and secondary of tertiary amines
US5646332A (en) * 1992-12-17 1997-07-08 Exxon Chemical Patents Inc. Batch Koch carbonylation process
US5650536A (en) * 1992-12-17 1997-07-22 Exxon Chemical Patents Inc. Continuous process for production of functionalized olefins
US5652201A (en) * 1991-05-29 1997-07-29 Ethyl Petroleum Additives Inc. Lubricating oil compositions and concentrates and the use thereof
US5767046A (en) * 1994-06-17 1998-06-16 Exxon Chemical Company Functionalized additives useful in two-cycle engines
US20050192185A1 (en) * 2004-02-27 2005-09-01 Saathoff Lee D. Power transmission fluids
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US3960889A (en) * 1973-07-09 1976-06-01 Texaco Inc. Dehydrohalogenated polyalkene-maleic anhydride reaction product
US4136042A (en) * 1977-10-18 1979-01-23 Gulf Research & Development Company Lubricating oils containing dithiophosphorylated copolymers of aziridineethyl acrylates or methacrylates and alkyl acrylates or methacrylates
US4148981A (en) * 1977-10-18 1979-04-10 Gulf Research & Development Company Dithiophosphorylated copolymers of aziridineethyl acrylates or methacrylates and alkyl acrylates or methacrylates
US4253973A (en) * 1979-11-20 1981-03-03 Mobil Oil Corporation Phosphorus-containing compounds and lubricants containing same
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US5449386A (en) * 1992-10-09 1995-09-12 Institut Francais Du Petrole Amine phosphates having a terminal cyclic imide
US5703256A (en) * 1992-12-17 1997-12-30 Exxon Chemical Patents Inc. Functionalization of polymers based on Koch chemistry and derivatives thereof
US6030930A (en) * 1992-12-17 2000-02-29 Exxon Chemical Patents Inc Polymers derived from ethylene and 1-butene for use in the preparation of lubricant disperant additives
US5629434A (en) * 1992-12-17 1997-05-13 Exxon Chemical Patents Inc Functionalization of polymers based on Koch chemistry and derivatives thereof
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US5646332A (en) * 1992-12-17 1997-07-08 Exxon Chemical Patents Inc. Batch Koch carbonylation process
US5650536A (en) * 1992-12-17 1997-07-22 Exxon Chemical Patents Inc. Continuous process for production of functionalized olefins
US5498809A (en) * 1992-12-17 1996-03-12 Exxon Chemical Patents Inc. Polymers derived from ethylene and 1-butene for use in the preparation of lubricant dispersant additives
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Also Published As

Publication number Publication date
FR2185673A1 (it) 1974-01-04
DE2324923A1 (de) 1973-12-13
FR2185673B3 (it) 1976-04-30
JPS4950002A (it) 1974-05-15
GB1421450A (en) 1976-01-21

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