WO2006066068A2 - Lubrifiants, graisses et fluides aqueux contenant des additifs derives de polymeres de dimercaptothiadiazole - Google Patents

Lubrifiants, graisses et fluides aqueux contenant des additifs derives de polymeres de dimercaptothiadiazole Download PDF

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WO2006066068A2
WO2006066068A2 PCT/US2005/045559 US2005045559W WO2006066068A2 WO 2006066068 A2 WO2006066068 A2 WO 2006066068A2 US 2005045559 W US2005045559 W US 2005045559W WO 2006066068 A2 WO2006066068 A2 WO 2006066068A2
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composition
acid
oil
carboxcylic
acids
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PCT/US2005/045559
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WO2006066068A9 (fr
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Robert J. Brouse
Andrew Sleutjes
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Brouse Robert J
Andrew Sleutjes
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Priority to US11/720,930 priority Critical patent/US20090298728A1/en
Publication of WO2006066068A2 publication Critical patent/WO2006066068A2/fr
Publication of WO2006066068A9 publication Critical patent/WO2006066068A9/fr

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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
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06—Well-defined aromatic compounds
    • C10M2203/065—Well-defined aromatic compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2205/022—Ethene
    • C10M2205/0225—Ethene used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2205/0265—Butene used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2205/0285—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 used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
    • 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
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • 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

Definitions

  • This invention relates to lubricants, greases and aqueous fluids containing additives which are derived from cyclic organic compounds which contain nitrogen and sulfur atoms in the ring structure.
  • Lubrication involves the process of friction reduction, accomplished by maintaining a film of a lubricant between surfaces which are moving with respect to each other.
  • the lubricant prevents contact of the moving surfaces, thus greatly lowering the coefficient of friction.
  • the lubricant also can be called upon to perform heat removal, containment of contaminants, and other important functions.
  • additives Since lubricants for different uses must operate under different conditions, numerous additives have been developed to establish or enhance various properties of lubricants. Representative types of additives which are used include viscosity improvers, detergents, dispersants, antioxidants, extreme pressure additives, corrosion inhibitors and several others. Very frequently, combinations of additive types are required. In addition, certain additives can have more than one function in a lubricant.
  • antiwear agents are antiwear agents, many of which function by a process of interaction with the surfaces, thereby
  • Extreme pressure agents have a very high affinity for surfaces, particularly metal surfaces (with which many of these agents actually chemically react), and are frequently selected from the following chemical types: zinc organodithiophosphates; sulfurized carboxcylic acids; chlorinated waxes; amine salts of phosphate esters; phosphites; and others. Certain of these materials, however, must be used judiciously in certain applications due to their property of accelerating corrosion of metal parts, such as bearings. In addition, some applications require very low concentrations of certain elements, such as phosphorus, which restricts the utility of otherwise quite useful extreme pressure agents.
  • U.S. Pat. No. 2,764,547 to Fields describes compounds which can be added to lubricants for the purpose of inhibiting the corrosion of silver-containing metal parts. These compounds are prepared by reacting 2,5-dimercapto- 1,3,4-thiadiazole with an unsaturated cyclic compound containing at least about 5 carbon atoms. Examples of suitable cyclic compounds are: dipinene; pinene; alpha-methyl styrene; and styrene. The compounds are used to control the corrosion of silver which is normally exhibited by sulfur- containing detergent additives for lubricating oil.
  • Richardson et al in U.S. Pat. No. 2,799,651, teach compounds which are related to those of the foregoing patent, and which are also useful as corrosion inhibitors for silver and similar metals. These inhibitors are prepared by reacting 2-mercapto-4-phenyl-5-thionel,3,4-thiadiazole with an carboxcylic acidic compound, a sulfonyl chloride, or, after chlorinating the thiadiazole, with a mercaptan. As with the compounds of the preceding patent, the reaction products are typically used in conjunction with sulfur- or phosphorus containing detergent additives for lubricating oils.
  • the present invention relates to the composition
  • the composition comprising (A) an oil of lubricating viscosity and (B) a reaction product of (i) at least one dimercaptothiadiazole polymer or derivative thereof; and (ii) at least one carboxcylic acid, or salt of the reaction product.
  • reaction products generally show an ability to improve antiwear, antiweld, extreme pressure, and corrosion inhibiting properties of lubricants, and greases.
  • hydrocarbyl includes hydrocarbon as well as substantially hydrocarbon groups.
  • substantially hydrocarbon describes groups which contain hetero atom substituents which do not alter the predominantly hydrocarbon nature of the group.
  • hydrocarbyl groups include the following:
  • hydrocarbon substituents that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, aromatic-, aliphatic- and alicyclic-substituted aromatic substituents and the like as well as cyclic substituents wherein the ring is completed through another portion of the molecule (that is, for example, any two indicated substituents may together form an alicyclic radical);
  • aliphatic e.g., alkyl or alkenyl
  • alicyclic e.g., cycloalkyl, cycloalkenyl
  • substituted hydrocarbon substituents that is, those substituents containing nonhydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent; those skilled in the art will be aware of such groups (e.g., halo (especially chloro
  • hetero atom substituents that is, substituents which will, while having a predominantly hydrocarbon character within the context of this invention, contain an atom other than carbon present in a ring or chain otherwise
  • heteroatoms e.g. alkoxy or alkylthio
  • Suitable heteroatoms will be apparent to those of ordinary skill in the art and include, for example, sulfur, oxygen, nitrogen and such substituents as, e.g., pyridyl, furyl, thienyl, imidazolyl, etc.
  • substituents e.g., pyridyl, furyl, thienyl, imidazolyl, etc.
  • no more than about 2, preferably no more than one, hetero substituent will be present for every ten carbon
  • hydrocarbyl group 105 atoms in the hydrocarbyl group.
  • hydrocarbyl group is purely hydrocarbon.
  • the present invention is based, in part, upon an additive for lubricants 110 which is (A) the reaction product of (i) a dimercaptothiadiazole polymer and (ii) an carboxcylic acid, or salt thereof.
  • DMTDPP 2,5Dimercapto-l,3,4-thiadiazole polymer
  • DMTDPP 2,5Dimercapto-l,3,4-thiadiazole polymer
  • Carboxcylic acids which are useful in the invention include branched or unbranched hydrocarbons which contain a non-aromatic double bond, that is, 130 a double bond connecting two aliphatic carbon atoms.
  • the carboxcylic acids are monocarboxcylic acidic compounds.
  • the carboxcylic acids are terminal monocarboxcylic acidic compounds (mono-1-carboxcylic acids or alpha carboxcylic acids).
  • Carboxcylic acidic compounds containing up to about 50 carbon atoms are 135 suitable for reaction with DMTDP.
  • the carboxcylic acids contain from about 3, or about 6 to about 30, or to about 16 carbon atoms.
  • these carboxcylic acids are alpha-carboxcylic acids (sometimes referred to as mono-1-carboxcylic acids) or isomerized alpha- 140 carboxcylic acids.
  • alpha-carboxcylic acid fractions that can be used include the C. sub.15-18 alpha-carboxcylic acids, C. sub.12-16 alpha- carboxcylic acids, C. sub.14- 16 alpha-carboxcylic acids, C. sub.1418 alpha- 145 carboxcylic acids, C. sub.16-18 alpha-carboxcylic acids, C. sub.16-20 alpha- carboxcylic acids, C. sub.22-28 alpha-carboxcylic acids, etc.
  • Isomerized alpha-carboxcylic acids are alpha-carboxcylic acids that have been converted to internal carboxcylic acids.
  • carboxcylic acids suitable for use herein are usually in the form of mixtures of internal carboxcylic acids with some alpha-carboxcylic acids present.
  • the procedures for isomerizing alpha-carboxcylic acids are well known to those in the art. Briefly these procedures involve contacting alpha-carboxcylic acid with a cation exchange resin at a temperature in a range of about 8O.degree.
  • DMTDP dimethyl methacrylate
  • mercapto functions in DMTDP can be reacted; thus, depending upon whether a "mono-adduct" or a "bis-adduct” is desired, one mole of DMTDP can be reacted with one or two moles of an carboxcylic acid. Reacting one mole of DMTDP with more than one, but less than two, moles of unsaturated compound will give a mixture of mono- and
  • one mole of DMTDP can be reacted with one mole of an carboxcylic acid, then the reaction product can be further reacted with a different carboxcylic acid to give a final product having mixed functionality.
  • each R.sub. l group is a hydrocarbyl group.
  • each R.sub. l may be independently a hydrocarbyl group containing up to 50 carbon 185 atoms. In one embodiment, each R.sub.l independently contains about 3, or about 6 up to about 30, or to about 16 carbon atoms.
  • Each R.sub. l is generally derived from one or more of the carboxcylic acids listed above.
  • Ammonium salts can be formed by reacting ammonia or amines with the DMTDP reaction products.
  • the amines include ammonia, monoamines or polyamines.
  • the monoamines generally contain from 1 to about 24 carbon atoms, or to 195 about 12, or to about 6.
  • monoamines useful in the present invention include methylamine, ethylamine, propylamine, butylamine, octylamine, and dodecylamine.
  • secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, methylbutylamine, ethylhexylamine, etc.
  • Tertiary amines include 200 trimethylamine, tributylamine, methyldiethylamine, ethyldibutylamine, etc.
  • the amine is a tertiary-aliphatic primary amine.
  • the aliphatic group preferably an alkyl group, contains from about 4, or about 6, or about 8 to about 30, or to about 24 carbon atoms.
  • the tertiary alkyl primary amines are monoamines represented by the formula alkyl 1- 12 ##STR3## wherein R.sub.2 is a hydrocarbyl group containing from one to about 27 carbon atoms and R.sub.2 ' is a hydrocarbyl
  • amines containing from 1 to about 12 carbon atoms.
  • Such amines are illustrated by tertiary-butylamine, tertiaryhexylamine, 1 -methyl-l-amino- cyclohexane, tertiary-octylamine, tertiary-decylamine, tertiary- dodecylamine, tertiary-tetradecylamine, tertiary-hexadecylamine, tertiary-
  • amine mixtures of this type are “Primene 8 IR” which is a mixture of C. sub.11 -C. sub.14 tertiary alkyl primary amines and “Primene JMT” which is a similar mixture of C. sub.18 -C. sub.22 tertiary alkyl primary
  • the amine may be a hydroxylamine.
  • the amine may be a hydroxylamine.
  • 230 hydroxylamines are primary, secondary or tertiary alkanolamines or mixtures thereof.
  • Such amines can be represented by the formulae: ##STR4## wherein each R" is independently a hydrocarbyl group of one to about eight carbon atoms or hydroxyhydrocarbyl group of two to about eight carbon atoms, preferably one to about four, and R' is a divalent hydrocarbyl group of about
  • R 1 can be an acyclic, alicyclic or aromatic group. Typically, R 1 is an acyclic straight or branched group such as an ethylene, 1 ,2-propylene, 1,2-butylene, 1,2- octadecylene, etc. group. Where two R" groups are present in the same
  • each R" is N- (hydroxyl lower alkyl)-morpholines, -thiomorpholines, -piperidines, - oxazolidines, -thiazolidines and the like.
  • each R" is N- (hydroxyl lower alkyl)-morpholines, -thiomorpholines, -piperidines, - oxazolidines, -thiazolidines and the like.
  • each R" is
  • alkanolamines examples include mono-, di-, and triethanolamine, diethylethanolamine, ethylethanolamine, butyldiethanolamine, etc.
  • the hydroxylamines can also be an ether N-(hydroxylhydrocarbyl)amine.
  • Such N-(hydroxylhydrocarbyl) amines can be
  • 255 conveniently prepared by reaction of epoxides with aforedescribed amines and can be represented by the formulae: ##STR5## wherein x is a number from about 2 to about 15 and R" and R' are as described above. R" may also be a hydroxylpoly(hydrocarbyloxy) group.
  • the amine may also be a polyamine.
  • the polyamine may be aliphatic, cycloaliphatic, heterocyclic or aromatic. Examples of the polyamines include polyamines, hydroxyl-containing polyamines, arylpolyamines, and heterocyclic polyamines.
  • Alkylenepolyamines are represented by the formula ##STR6## wherein n has an average value between about 1, or 2 to about 10, or to about 7, or to about 5, and the "Alkylene" group has from 1, or 2 up to about 10, to about 270 6, or to about 4.
  • R. sub.3 is independently preferably hydrogen; or an aliphatic or hydroxy- substituted aliphatic group of up to about 30 carbon atoms. In one embodiment, when R. sub.3 is not hydrogen, then R. sub.3 is defined the same as R" above.
  • alkylenepolyamines include methylenepolyamines, ethylenepolyamines, butylenepolyamines, propylenepolyamines, pentylenepolyamines, etc.
  • the higher homologs and related heterocyclic amines such as piperazines and N-
  • Q amino alkyl-substituted piperazines are also included.
  • Specific examples of such polyamines are ethylenediamine, triethylenetetramine, tris- 280 (2aminoethyl)amine, propylenediamine, trimethylenediamine, tripropylenetetramine, tetraethylenepentamine, hexaethylene- heptamine, pentaethylenehexamine, etc.
  • Ethylenepolyamines such as some of those mentioned above, are useful. Such polyamines are described in detail under the heading Ethylenediamines
  • Such polyamines are most conveniently prepared by the reaction of ethylene dichloride with ammonia or by reaction of an ethyleneimine with a ring opening reagent such as water, ammonia, etc. These reactions result in the production of a
  • alkylenepolyamine bottoms can be characterized as having less than two, usually less than 1% (by weight) material boiling below about 200. degree. C.
  • a typical sample of such ethylene polyamine bottoms obtained from the Dow Chemical Company of 305 Freeport, Texas designated “E-100” has a specific gravity at 15.6. degree. C. of 1.0168, a percent nitrogen by weight of 33.15 and a viscosity at 40. degree. C. of 121 centistokes. Gas chromatography analysis of such a sample contains about 0.93% "Light Ends" (most probably diethylenetriamine (DETA)), 0.72% triethylene tetramine TETA, 21.74%
  • alkylenepolyamine bottoms include cyclic condensation products such as piperazine and higher analogs of diethylenetriamine, triethylenetetramine and the like.
  • Another useful polyamine is obtained by condensing at least one hydroxy compound with at least one polyamine reactant containing at least one primary or secondary amino group.
  • the hydroxy compounds are preferably
  • polyhydric alcohols and amines.
  • the polyhydric alcohols are described below (See carboxylic ester dispersants).
  • the hydroxy compounds are polyhydric amines.
  • Polyhydric amines include any of the above-described monoamines reacted with an alkylene oxide (e.g., ethylene oxide, propylene oxide, butylene oxide, etc.) having 2 to about 20 carbon atoms, or to about 4.
  • alkylene oxide e.g., ethylene oxide, propylene oxide, butylene oxide, etc.
  • polyhydric amines examples include tri-(hydroxypropyl)amine,tris- (hydroxymethyl)aminomethane,2amino-2-methyl - 1 ,3-propanediol, N,N,N',N'-tetrakis(2hydroxypropyl)ethylenediamine, and N,N,N',N'- tetrakis(2hydroxyethyl)ethylenediamine, preferably tris(hydroxymethyl)aminomethane (THAM).
  • THAM tris(hydroxymethyl)aminomethane
  • Polyamine reactants which react with the polyhydric alcohol or amine to form the condensation products or condensed amines, are described above.
  • Preferred polyamine reactants include triethylenetetramine (TETA), tetraethylenepentamine CTEPA), pentaethylenehexamine (PEHA), and
  • the condensation reaction of the polyamine reactant with the hydroxy compound is conducted at an elevated temperature, usually about 60. degree. C. to about 265 degree. C, (preferably about 220 degree. C. to about 340 250. degree. C.) in the presence of an acid catalyst.
  • 355 is then heated to 120. degree. C. over 0.6 hour. With N. sub.2 sweeping, the mixture is then heated to 150. degree. C. over 1.25 hour, then to 235. degree. C. over 1 hour more, then held at 230. degree.235. degree. C. for 5 hours, then heated to 240. degree. C. over 0.75 hour, and then held at 240. degree. - 245. degree. C. for 5 hours.
  • the product is cooled to 150. degree. C. and
  • the polyamines are hydroxyl polyamines.
  • Hydroxyl 365 polyamine analogs of hydroxylmonoamines, particularly alkoxylated alkylenepolyamines (e.g., N,N(diethanol)ethylenediamine) can also be used.
  • Such polyamines can be made by reacting the above-described amines with one or more of the above-described oxides.
  • Similar oxidealkanolamine reaction products can also be used such as the products made by reacting the 370 aforedescribed primary, secondary or tertiary alkanolamines with ethylene, propylene or higher epoxides in a 1.1 to 1.2 molar ratio. Reactant ratios and temperatures for carrying out such reactions are known to those skilled in the art.
  • alkoxylated alkylenepolyamines include N-(2- hydroxyethyl) ethylenediamine, N,N-bis(2-hydroxyethyl)-ethylenediamine, 1 -(2-hydroxyethyl)piperazine, mono(hydroxypropyl)-substituted tetraethylenepentamine, N-(3-hydroxybutyl)-tetramethylene aliamine, etc. Higher homologs obtained by condensation of the above illustrated hydroxy- containing polyamines through amino groups or through hydroxy groups are likewise useful.
  • the amine may be a heterocyclic mono-or polyamine.
  • the heterocyclic amines include aziridines, azetidines, azolidines, tetra- and dihydropyridines, piperidines, imidazoles, diand tetrahydroimidazoles, piperazines, purines, morpholines, thiotnorpholines, N- aminoalkylmorpholines, N-aminoalkylthiomorpholines, N- aminoalkylpiperazines, N,N'-diaminoalkylpiperazines, azepines, azocines, azonines, anovanes and tetra-, di- and perhydro derivatives of each of the above and mixtures of two or more of these heterocyclic amines.
  • Preferred heterocyclic amines are the saturated 5- and ⁇ membered heterocyclic amines containing only nitrogen, oxygen and/or sulfur in the hetero ring, especially the piperidines, piperazines, thiamorpholines, morpholines, pyrrolidines, and the like.
  • Piperidine, aminoalkyl-substituted piperidines, piperazine, aminoalkyl-substituted piperazines, morpholine, aminoalkyl-substituted morpholines, pyrrolidine, and aminoalkyl-substituted pyrrolidines are especially preferred.
  • the aminoalkyl substituents are substituted on a nitrogen atom forming part of the heterocycle.
  • Specific examples of such heterocyclic amines include N-aminopropyl-morpholine, N-
  • the amine is a polyalkene-substituted amine.
  • These polyalkene-substituted amines are well known to those skilled in the art. These amines are disclosed in U.S. Pat. Nos. 3,275,554; 3,438,757; 415 3,454,555; 3,565,804; 3,755,433; and 3,822,289. These patents are hereby incorporated by reference for their disclosure of hydrocarbyl amines and methods of making the same.
  • polyalkene-substituted amines are prepared by reacting 420 carboxcylic acids and carboxcylic acid polymers (polyalkenes) with amines
  • the amines may be any of the amines described above. Examples of these compounds include poly(propylene)amine; N,N- dimethyl-N-poly (ethylene/propylene)amine, (50:50 mole ratio of monomers); polybutene amine; 425 N,N-di(hydroxyethyl)N-polybuteneamine; N-(2-hydroxypropyl)-N- poly(butene)amine;
  • N-poly(butene)aniline N-poly(butene)morpholine
  • N-- poly(butene)ethylenediamine N-poly(butene)aniline; N-poly(butene)morpholine; N-- poly(butene)ethylenediamine;
  • the polyalkene is characterized as containing from at least about 8 carbon atoms, or at least about 30, or at least about 35 up to about 300, or to about 435 200, or to about 100 carbon atoms.
  • the polyalkene is characterized by an Mn (number average molecular weight) value of at least about 500.
  • Mn number average molecular weight
  • Mn varies between about 500 to about 1200 or 1300.
  • the polyalkenes include homopolymers and interpolymers of polymerizable carboxcylic acid monomers of 2 to about 16, or to about 6, or to about 4 carbon atoms.
  • the carboxcylic acids may be monocarboxcylic acids such as ethylene, propylene, 1-butene, isobutene, and 1-octene; or a polycarboxcylic
  • the interpolymer is a homopolymer.
  • An example of a preferred homopolymer is a polybutene, preferably a polybutene in which about 50% of the polymer is derived from isobutylene.
  • the polyalkenes are prepared by conventional procedures.
  • the amine may also be an acylated nitrogen-containing compound.
  • the acylated nitrogen-containing compounds include reaction products of
  • hydrocarbylsubstituted carboxylic acylating agents such as substituted carboxylic acids or derivatives thereof.
  • These compounds include imides, amides, amidic acid or salts, heterocycles (imidazolines, oxazolines, etc.), and mixtures thereof.
  • these compounds are useful as dispersants in lubricating compositions and have been referred to as
  • the amines are described above, typically the amines are polyamines, preferably the amines are ethyleneamines, amine bottoms or amine condensates.
  • the hydrocarbyl-substituted carboxylic acylating agent may be derived from 465 a monocarboxylic or polycarboxylic acylating agent.
  • Polycarboxylic acylating agents generally are preferred.
  • the acylating agents may be a carboxylic acid or derivatives of the carboxylic acid such as the halides, esters, anhydrides, etc., preferably acid, esters or anhydrides, more preferably anhydrides.
  • the carboxylic acylating agent is a succinic
  • the hydrocarbyl-substituted carboxylic acylating agent includes a hydrocarbyl group derived from a polyalkene.
  • the polyalkenes are described above.
  • the hydrocarbyl group is derived from polyalkenes having an Mn of at least about 1300 up to about 5000, and the Mw/Mn value is from about 1.5, or about 1.8, or about 2.5 to about 4, or to about 3.6, or to about 3.2.
  • the hydrocarbyl-substituted carboxylic acylating agents are prepared by a reaction of one or more polyalkenes with one or more unsaturated carboxylic reagent.
  • the unsaturated carboxylic reagent generally contains an alpha-beta carboxcylic acidic unsaturation.
  • the carboxylic reagents may be carboxylic
  • acylating agents may be either monobasic or polybasic in nature. When they are polybasic they are preferably dicarboxylic reagents, although tri- and tetracarboxylic reagents can be used. Specific examples of useful monobasic unsaturated carboxylic reagents are acrylic acylating agents, methacrylic acylating agents, cinnamic acylating
  • crotonic acylating agents include malefic acylating agents, fumaric acylating agents, mesaconic acylating agents, itaconic acylating agents and citraconic acylating agents.
  • unsaturated carboxylic reagents are maleic anhydrides or maleic or fumaric acids or esters, or
  • the polyalkene may be reacted with the carboxylic reagent such that there is at least one mole of reagent for each mole of polyalkene. In one embodiment, an excess of reagent is used. This excess is generally between 500 about 5% to about 25%.
  • the acylating agents are prepared by reacting the above described polyalkene with an excess of maleic anhydride to provide substituted succinic acylating agents wherein the number of succinic groups
  • the polyalkene has an Mn from about 1300 to about 5000 and a Mw/Mn of at least 1.5, as described
  • the Mn is preferably between about 1300 and 5000. A more preferred range for Mn is from about 1500 to about 2800, and a most preferred range of Mn is from about 1500 to about 2400.
  • the preparation and use of substituted succinic acylating agents wherein the substituent is derived from such polycarboxcylic acids are described in U.S. Pat. No. 4,234,435, the
  • reaction products of DMTDP polymers and carboxcylic acids, and the salts of these reaction products are useful as additives for lubricants, particularly for improving the antiwear and corrosion resistance properties of the lubricants.
  • the use of the carboxcylic acid- DMTDPP reaction products is achieved by preferably dissolving or stably dispersing a composition of the present invention in an oil of lubricating
  • That 535 amount is usually from about 0.05, or about 0.1 to about 20, or about 5 parts per 100 parts of the oil.
  • reaction products of DMTDPP and a carboxcylic acid, and salts thereof are useful as additives for lubricants in which they can function primarily as antiwear, antiweld, extreme pressure, anticorrosion, oxidation inhibiting and/or friction modifying agents. They can be employed in a variety of lubricants based on diverse oils of
  • lubricating viscosity including natural and synthetic lubricating oils and mixtures thereof.
  • lubricants include crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad diesel engines, and the like. They can also be
  • reaction products and salts of the reaction products of the present invention may be used in lubricants or in concentrates.
  • the concentrate contains the reaction products and their salts alone or in combination with other components used in preparing fully formulated lubricants.
  • the 560 concentrate may also contains a substantially inert organic diluent, which includes kerosene, mineral distillates, or one or more of the oils of lubricating viscosity discussed below.
  • the concentrates contain from 0.01%, or about 0.10, or about 1 ° to about 70% or about 800, even up to about 90% by weight of the compositions of the present
  • compositions may be present in a final product, blend or
  • oils such as gear oils
  • the lubricating compositions and methods of this invention employ an oil of lubricating viscosity, including natural or synthetic lubricating oils and mixtures thereof.
  • Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as mineral lubricating oils such as liquid petroleum oils and solvent treated or acid treated mineral lubricating oils of
  • paraffinic, naphthenic or mixed paraffinic-naphthenic types are also useful.
  • Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized carboxcylic acids (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers,
  • alkylbenzenes e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2ethylhexyl)-benzenes, etc.
  • polyphenyls e.g., biphenyls, terphenyls, alkylated polyphenyls, etc.
  • alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, etherification, etc. constitute another class of known synthetic lubricating 595 oils that can be used. These are exemplified by the oils prepared through polymerization of ethylene oxide, propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., polyoxypropylene glycol methyl
  • esters of dicarboxylic acids e.g., phthalic acid, succinic acid, alkylsuccinic acids, alkenylsuccinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic
  • esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl
  • Esters useful as synthetic oils also include those made from C. sub.5 to C. sub.22 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
  • Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another useful class of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra- (2ethylhexyl) silicate, tetra-(4methylhexyl) silicate, tetra-(p-tert- butylphenyl) silicate, hexyl-(4methyl-2-pentoxy)di si loxane, poly(methyl)
  • synthetic lubricants e.g., tetraethyl silicate, tetraisopropyl silicate, tetra- (2ethylhexyl) silicate, tetra-(4methylhexyl) silicate, tetra-(p-tert- butylphenyl) silicate, he
  • Suitable synthetic lubricating oils include liquid esters of phosphoruscontaining acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid, etc.), polymeric tetrahydrofurans and the like.
  • Unrefined, refined and rerefined oils either natural or synthetic (as well as mixtures of two or more of any of these) of the type disclosed hereinabove can be used in the concentrates of the present invention.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further
  • a shale oil obtained directly from retorting operations a petroleum oil obtained directly from primary distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or
  • Such rerefined oils are also known as reclaimed, recycled or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives, oil contaminants such as water and fuel, and oil breakdown products.
  • the oil of lubricating viscosity is generally present in a major amount (i.e. an amount greater than 50% by weight).
  • the oil of lubricating viscosity is present in an amount greater than about 60%, preferably 70°-, more preferably 80 9 - by weight.
  • the oil of lubricating viscosity may be present in an amount from about 90% by weight.
  • the oil of lubricating viscosity or a mixture of lubricating oils are selected to provide lubricating compositions with a kinematic viscosity of at least about 3.5, or about 4.0 Cst at 100. degree. C.
  • the lubricating compositions have an SAE gear viscosity number
  • the lubricating composition may also have a socalled multigrade rating such as SAE 75W-80, 75W-90, 75W-90, or 80W-90.
  • Multigrade lubricants may include a viscosity improver which is formulated 680 with the oil of lubricating viscosity to provide the above lubricant grades.
  • Useful viscosity improvers include polycarboxcylic acids, such as ethylene- propylene copolymers, or polybutylene rubbers, including hydrogenated rubbers, such as styrene-butadiene or styreneisoprene rubbers; or polyacrylates, including polymethacrylates.
  • the viscosity 685 improver is a polycarboxcylic acid or polymethacrylate, more preferably polymethacrylate.
  • Viscosity improvers available commercially include Acryloid.TM. viscosity improvers available from Rohm & Haas; Shellvis.TM. rubbers available from Shell Chemical; and Lubrizol 3174 available from The Lubrizol Corporation. 690
  • the oil of lubricating viscosity is selected to provide lubricating compositions for crankcase applications, such as for gasoline
  • the lubricating compositions are selected to provide an SAE crankcase viscosity number of 1OW, 2OW, or 3OW
  • the lubricating composition may also have a so called multi- grade rating such as SAE 5W-30, 10W-30, 10W-40, 20W-50, etc.
  • multi-grade lubricants include a viscosity improver which is formulated with the oil of lubricating viscosity to provide the above lubricant grades.
  • the sulfurized organic compositions include mono- or polysulfide compositions or mixtures thereof.
  • the sulfurized organic compositions are
  • the sulfurized organic compositions are polysulfide compositions generally characterized as di-, tri- or tetrasulfide compositions. Generally, the sulfurized organic compositions are present in
  • Materials which may be sulfurized to form the sulfurized organic compositions include oils, fatty acids or esters, olefins or polycarboxcylic 715 acids made thereof, terpenes, or Diels-Alder adducts.
  • Oils which may be sulfurized are natural or synthetic oils including mineral oils, lard oil, carboxylic acid esters derived from aliphatic alcohols and fatty acids or aliphatic carboxylic acids (e.g., myristyl oleate and oleyl 720 oleate) sperm whale oil and synthetic sperm whale oil substitutes and synthetic unsaturated esters or glycerides.
  • natural or synthetic oils including mineral oils, lard oil, carboxylic acid esters derived from aliphatic alcohols and fatty acids or aliphatic carboxylic acids (e.g., myristyl oleate and oleyl 720 oleate) sperm whale oil and synthetic sperm whale oil substitutes and synthetic unsaturated esters or glycerides.
  • Fatty acids generally contain from about 4, or about 8, or about 12, to about 24, or to about 22, or to about 18 carbon atoms.
  • the unsaturated fatty acids generally contain from about 4, or about 8, or about 12, to about 24, or to about 22, or to about 18 carbon atoms.
  • the unsaturated fatty acids may comprise mixtures of acids such as those obtained from naturally occurring animal and vegetable oils such as lard oil,
  • Tall oil is a mixture of rosin acids, mainly abietic acid, and unsaturated fatty acids, mainly oleic and linoleic acids.
  • Tall oil is a by-product of the sulfate process for the manufacture of wood pulp.
  • the unsaturated fatty acid esters are the fatty oils, that is, naturally occurring esters of glycerol with the fatty acids described above, and synthetic esters of similar structure.
  • naturally occurring fats and oils containing unsaturation include animal fats such as Neat's-foot oil, lard oil, depot fat, beef tallow, etc. Examples of naturally occurring
  • vegetable oils include cottonseed oil, corn oil, poppy-seed oil, safflower oil, sesame oil, soybean oil, sunflower seed oil and wheat germ oil.
  • the fatty acid esters also may be prepared from aliphatic carboxcylic acidic acids of the type described above such as oleic acid, linoleic acid, linolenic
  • alcohols and polyols examples include monohydric alcohols as described above. Examples of these alcohols include methanol, ethanol, propanol, and butanol. Polyhydric alcohols are described above and include ethylene glycol, propylene glycol,
  • trimethylene glycol 750 trimethylene glycol, neopentyl glycol, glycerol, etc.
  • the carboxcylic acidic compounds which may be sulfurized are diverse in nature. They contain at least one carboxcylic acidic double bond, which is defined as a non-aromatic double bond; that is, one connecting two aliphatic 755 carbon atoms.
  • the carboxcylic acid may be defined by the formula R.sup.*l R.sup.*2 C.dbd.CR.sup.*3 R.sup.*4, wherein each of
  • R.sup.*l, R.sup.*2, R.sup.*3 and R.sup.*4 is hydrogen or an organic group.
  • the R* groups in the above formula which are not hydrogen may be represented by --(CH. sub.2). sub. n -A, wherein n is a number from 0-10 760 and A is represented by -C(R. sup. *5). sub.3, — COOR. sup. *5, --
  • each R.sup.*5 is independently hydrogen, alkyl, alkenyl, aryl, substituted 765 alkyl, substituted alkenyl or substituted aryl, with the proviso that any two R.sup.*5 groups can be or substituted whereby a ring of up to about 12 carbon atoms is formed;
  • M is one equivalent of a metal cation (preferably Group I or II, e.g., 770 sodium, potassium, barium, calcium);
  • X is halogen (e.g., chloro, bromo, or iodo);
  • Y is oxygen or rivalent sulfur
  • Ar is an aryl or substituted aryl group of up to about 12 carbon atoms.
  • R. sup. *1, R.sup.*2, R.sup.*3 and R.sup.*4 may also together form an or substituted group; i.e., the carboxcylic acidic compound may be 780 alicyclic.
  • the carboxcylic acidic compound is usually one in which each R group which is not hydrogen is independently alkyl, alkenyl or aryl group.
  • Monocarboxcylic acidic and dicarboxcylic acidic compounds, particularly 785 the former, are preferred, and especially terminal monocarboxcylic acidic hydrocarbons; that is, those compounds in which R.sup.*3 and R.sup.*4 are hydrogen and R.sup.* l and R.sup.*2 are alkyl or aryl, especially alkyl (that is, the carboxcylic acid is aliphatic) having 1 to about
  • Carboxcylic acidic compounds having about 3 to about 30, or to about 16 (most often less than about 9) carbon atoms are particularly desirable.
  • Isobutene, propylene and their dimers, trimers and tetramers, and mixtures thereof are especially preferred carboxcylic acidic compounds.
  • isobutylene and diisobutylene are particularly desirable because of their availability and the particularly high sulfur containing compositions which can be prepared therefrom.
  • the sulfurized organic compound is a sulfurized
  • terpene compound as used in the specification and claims is intended to include the various isomeric terpene hydrocarbons having the empirical formula C. sub.10 H. sub.16, such as contained in turpentine, pine oil and dipentenes, and the various synthetic and naturally occurring oxygen-containing derivatives. Mixtures of these various isomeric terpene hydrocarbons having the empirical formula C. sub.10 H. sub.16, such as contained in turpentine, pine oil and dipentenes, and the various synthetic and naturally occurring oxygen-containing derivatives. Mixtures of these various
  • 805 compounds generally will be utilized, especially when natural products such as pine oil and turpentine are used.
  • a group of pine oil-derived products are available commercially from Hercules Incorporated. It has been found that the pine oil products generally known as terpene alcohols available from Hercules Incorporated are useful in the preparation of the sulfurized organic
  • alpha-Terpineol containing about 95-97° of alpha-terpineol, a high purity tertiary terpene alcohol mixture typically containing 96.3% of tertiary alcohols;
  • Terpineol 318 Prime which is a mixture of isomeric terpineols obtained by dehydration of terpene hydrate and contains about 60-65 weight percent of alpha-terpineol and 15-
  • sulfurized carboxcylic acids are produced by (1)
  • the sulfurized carboxcylic acids which are useful in the compositions of the present invention also may be prepared by the reaction, under superatmospheric pressure, of carboxcylic acidic compounds with a
  • the sulfurized carboxcylic acid is prepared by reacting 16 moles of isobutylene with 16 moles of sulfur and 8 moles of hydrogen sulfide.
  • the sulfurized organic composition is at least one 845 sulfur-containing material which comprises the reaction product of a sulfur source and at least one Diels-Alder adduct in a molar ratio of at least 0.75: 1.
  • the molar ratio of sulfur source to DielsAlder adduct is in a range of from about 0.75, or about 1 , up to about 4.0, or to about 3.0, or to about
  • additives include, for example, detergents and dispersants of the ashproducing or ashless type, corrosion- and oxidation-inhibiting agents, pour point depressing agents, extreme pressure agents, antiwear agents, color stabilizers and anti-foam
  • the ash-producing detergents are exemplified by oil-soluble neutral and basic salts (i.e. overbased salts) of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, phenols or organic phosphorus acids
  • a direct carbon-to-phosphorus linkage such as those prepared by the treatment of an carboxcylic acid polymer (e.g., polyisobutene having a molecular weight of 1000) with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulftde, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a
  • carboxcylic acid polymer e.g., polyisobutene having a molecular weight of 1000
  • a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulftde, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a
  • basic salt is used to designate metal salts wherein the metal is 875 present in stoichiometrically larger amounts than the organic acid radical.
  • the commonly employed methods for preparing the basic salts involve heating a mineral oil solution of an acid with a stoichiometric excess of a metal neutralizing agent such as the metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature of about 50. degree. C. and filtering 880 the resulting mass.
  • a “promoter” in the neutralization step to aid the incorporation of a large excess of metal likewise is known.
  • examples of compounds useful as the promoter include phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation products of formaldehyde with a phenolic substance; alcohols
  • 28 885 such as methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenothiazine, phenyl-beta-naphthylamine, and dodecylamine.
  • a particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal
  • the oil-soluble neutral or basic salts of alkali or alkaline earth metal salts may also be reacted with a boron compound.
  • Boron compounds include
  • Ashless detergents and dispersants may upon combustion yield a non-volatile material such as boric oxide or phosphorus pentaoxide.
  • the ashless detergents and dispersants do not ordinarily contain metal and, therefore, do not yield a metalcontaining ash on combustion.
  • Many types are known in the art. The following are illustrative.
  • Carboxylic dispersants are the reaction products of carboxylic acids (or derivatives thereof) containing at least about 34 and preferably at least about 54 carbon atoms and nitrogen containing compounds (such as amine), organic hydroxy compounds (such as phenols and alcohols), and/or basic
  • reaction products include amide, amide, and ester reaction products of carboxylic acylating agents.
  • acylated nitrogen containing compounds are examples of carboxylic dispersants.
  • these materials include succinimide dispersants and carboxylic ester dispersants.
  • Examples of these "carboxylic dispetsants” are 920 described in British Patent 1 ,306,529 and in many U.S. patents including the following: U.S. Pat. Nos. 3,219,666, 3,316, 177, 3,340,281 , 3,351,552, 3,381 ,022, 3,433,744, 3,444, 170, 3,467,668, 3,501 ,405, 3,542,680, 3,576,743, 3,632,511 ,4,234,435, and Re 26,433.
  • Amine dispersants are the reaction products of relatively high molecular weight aliphatic or alicyclic halides and amines, preferably polyalkylene polyamines. These dispersants are described above as polyalkene-substituted amines. Examples thereof are described for example, in the following U.S. Pat. Nos.: 3,275,554, 3,438,757, 3,454,555, and
  • Mannich dispersants are the reaction products of alkylphenols in which the alkyl group contains at least about 30 carbon atoms and aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines). 935
  • the materials described in the following U.S. patents are illustrative: U.S. Pat Nos. 3,036,003, 3,236,770, 3, 414, 347, 3, 448, 047, 3, 461 , 172, 3, 539, 633, 3, 586, 629, 3, 591, 598, 3,634,515, 3,725,480, 3,726,882, and 3,980,569.
  • Post-treated dispersants are the products obtained by posttreating the carboxylic, amine or Mannich dispersants with reagents such as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or the like.
  • reagents such as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or the like.
  • reagents such as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds
  • Polymeric dispersants are interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight 950 carboxcylic acids with monomers containing polar substituents, e.g., aminoalkyl acrylates or acrylamides and poly(oxyethylene)-substituted acrylates. Examples thereof are disclosed in the following U.S. Pat. Nos.: 3,329,658, 3,449,250, 3,519,656, 3,666,730, 3,687,849, and 3,702,300.
  • pour point depressants are a particularly useful type of additive often included in the lubricating oils described herein.
  • the use of such pour point 960 depressants in oil-based compositions to improve low temperature properties of oil-based compositions is well known in the art. See, for example, page 8 of "Lubricant Additives" by C. V. Smallbeer and R. Kennedy Smith (Lezius- Hiles Co. publishers, Cleveland, Ohio, 1967).
  • pour point depressants are polymethacrylates; polyacrylates; polyacrylamides; condensation products of haloparaffin waxes and aromatic compounds; vinyl carboxylate polymers; and terpolymers of dialkylfumarates, vinyl esters of fatty acids and alkyl vinyl ethers.
  • Antifoam agents are used to reduce or prevent the formation of stable foam.
  • Typical antifoam agents include silicones or organic polymers. Additional antifoam compositions are described in "Foam Control Agents", by Henry T. Kerner (Noyes Data Corporation, 1976), pages 125162.
  • a lubricant is prepared by incorporating 3% by weight of the product of Example 1 into a SAE 10W-40 lubricating oil mixture.
  • a gear lubricant is prepared by incorporating 2.5% by weight of the 990 product of Example 6 into an SAE 90 lubricating oil mixture.
  • a gear lubricant is prepared by incorporating 3% by weight of the product of Example 1, and 4% by weight of a polysulfide prepared from butylene, 995 sulfur and hydrogen sulfide into an SAE 80W-90 lubricating oil mixture.
  • a lubricant is prepared as described in Example III except a SAE IOW-40 lubricating oil mixture is used in place of the SAE 8OW-90 lubricating oil 1000 mixture.
  • a gear lubricant is prepare by incorporating 3% by weight the product of 1005 Example 11 , and 1.9% by weight of a zinc isopropyl, methylamyl dithiophosphate into an SAE 8OW-90 lubricating oil mixture.
  • a lubricant is prepared as described in Example V except an SAE 1 OW-30 1010 lubricating oil mixture is used in place of the SAE 80W-90 lubricating oil mixture.
  • a gear lubricant is prepared by incorporating 3% by weight the product of Example 11 , and 0.5% by weight of a succinic dispersant prepared by reacting a polybutenyl-substituted succinic anhydride, with a polybutenyl group having a number average molecular weight of about 950, with a commercial polyamine having the equivalent structure of tetraethylene
  • a lubricant is prepared as described in Example VII except an SAE 1OW30 lubricating oil mixture is used in place of the SAE 75W-90 lubricant oil 1025 mixture.
  • the lubricating oil 1030 generally is employed in an amount sufficient to balance the total grease composition and, generally, the grease compositions will contain various quantities of thickening agents and other additive components to provide desirable properties.
  • the reaction products or salts thereof are present in an amount from about 0.50, or about 1% to about 10%, or to about 5% by 1035 weight.
  • thickeners can be used in the preparation of the greases of this invention.
  • the thickener is employed in an amount from about 0.5 to about 30 percent, and preferably from 3 to about 15 percent by weight of the 1040 total grease composition.
  • Including among the thickeners are alkali and alkaline earth metal soaps of fatty acids and fatty materials having from about 12 to about 30 carbon atoms.
  • the metals are typified by sodium, lithium, calcium and barium. Examples of fatty materials include stearic
  • thickeners include salt and salt-soap complexes, such as calcium stearate-acetate (U.S. Pat. No. 2, 197,263), barium stearate-acetate (U.S. Pat. No. 2,564,561), calcium stearate-caprylate-acetate complexes (U.S. Pat. No. 1050 2,999,066), calcium salts and soaps of low-intermediate and high-molecular weight acids and of nut oil acids, aluminum stearate, and aluminum complex thickeners.
  • salt and salt-soap complexes such as calcium stearate-acetate (U.S. Pat. No. 2, 197,263), barium stearate-acetate (U.S. Pat. No. 2,564,561), calcium stearate-caprylate-acetate complexes (U.S. Pat. No. 1050 2,999,066), calcium salts and soaps of low-intermediate and high-molecular weight acids and of
  • Particularly useful thickeners employed in the grease compositions are:
  • ammonium compound 1060 ammonium compound.
  • Typical ammonium compounds are tetraalkyl ammonium chlorides, such as dimethyl dioctadecyl ammonium chloride, dimethyl dibenzyl ammonium chloride and mixtures thereof. This method of conversion, being well known to those skill in the art, is believed to require no further discussion. More specifically, the clays which are useful as
  • 1065 starting materials in forming the thickeners to be employed in the grease compositions can comprise the naturally occurring chemically unmodified clays.
  • These clays are crystalline complex silicates, the exact composition of which is not subject to precise description, since they vary widely from one natural source to another.
  • These clays can be described as complex inorganic
  • silicates such as aluminum silicates, magnesium silicates, barium silicates and the like, containing, in addition to the silicate lattice, varying amounts of cation-exchangeable groups such as sodium.
  • Hydrophilic clays which are particularly useful for conversion to desired thickening agents include montmorillonite clays, such as bentonite, attapulgite, hectorite, illite,
  • This invention is applicable to lubricants in many fields, such as the automotive and machinery industries, and all industries in which lubricants are utilized.

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Abstract

L'invention concerne une composition comprenant une huile de viscosité lubrifiante et un mélange d'au moins un polymère de dimercaptothiadiazole ou d'un dérivé de celui-ci, et au moins un acide carboxylique. Ces produits présentent généralement une aptitude à améliorer l'anti-usure (y compris sous des pressions extrêmes) et les propriétés anti-corrosion dans des lubrifiants.
PCT/US2005/045559 2004-12-17 2005-12-15 Lubrifiants, graisses et fluides aqueux contenant des additifs derives de polymeres de dimercaptothiadiazole WO2006066068A2 (fr)

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BR112013028918A2 (pt) 2011-05-09 2017-02-07 Vanderbilt Chemicals Llc aditivos de alcalinos e alcalinos terrosos e composições lubrificantes contendo os mesmos

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EP1172430A3 (fr) * 2000-06-29 2002-04-03 Bridgestone Corporation Composition lubrifiante pour filaments en acier et materiau composite filamentaire en caoutchouc-acier
US6528458B1 (en) * 2002-04-19 2003-03-04 The Lubrizol Corporation Lubricant for dual clutch transmission

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110028363A1 (en) * 2008-02-29 2011-02-03 The Lubrizol Corporation Liquid Extreme Pressure Additive
US8536103B2 (en) * 2008-02-29 2013-09-17 Richard A. Denis Liquid extreme pressure additive
AU2009222194B2 (en) * 2008-02-29 2013-12-19 The Lubrizol Corporation Liquid extreme pressure additive

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