EP0535191B1 - Procedes de fabrication des sels surbasiques de metaux alcalins - Google Patents

Procedes de fabrication des sels surbasiques de metaux alcalins Download PDF

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Publication number
EP0535191B1
EP0535191B1 EP92907871A EP92907871A EP0535191B1 EP 0535191 B1 EP0535191 B1 EP 0535191B1 EP 92907871 A EP92907871 A EP 92907871A EP 92907871 A EP92907871 A EP 92907871A EP 0535191 B1 EP0535191 B1 EP 0535191B1
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EP
European Patent Office
Prior art keywords
reaction mixture
alkali metal
basic
salt
polyalkene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP92907871A
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German (de)
English (en)
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EP0535191A1 (fr
Inventor
John M. Cahoon
Jack L. Karn
Mary F. Salomon
Craig D. Tipton
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Lubrizol Corp
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Lubrizol Corp
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    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased 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
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/02—Unspecified siloxanes; Silicones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12

Definitions

  • This invention relates to novel overbased alkali metal salts of sulfonic acids, carboxylic acids, phenols or mixtures thereof.
  • Alkali metal overbased metal salts of many organic acids are known compounds and are useful in numerous applications including lubricating compositions.
  • the compounds are prepared by reacting an acidic material with a reaction mixture comprising basic metal compounds, an acidic organic compound or salt and a promoter.
  • the acidic material is carbon dioxide and the promoters are usually lower alkyl alcohols, usually methanol, ethanol or butanol or lower alkyl acids.
  • the promoter improves contact between the acidic material and the basic metal compound.
  • the result is an oil-soluble or dispersible form of the basic metal-acidic material salt, usually a metal carbonate. Procedures for making these overbased compounds are generally known.
  • Canadian Patent 1,055,700 relates to basic alkali sulfonate dispersions and processes.
  • U.S. Patent 4,326,972 relates to concentrates, lubricant compositions and methods for improving fuel economy of internal combustion engines. These compositions have as an essential ingredient a specific sulfurized composition and a basic alkali metal sulfonate.
  • U.S. Patent 4,904,401 relates to lubricating oil compositions. These compositions may contain a basic alkali metal salt of at least one sulfonic or carboxylic acid.
  • U.S. Patent 4,938,881 relates to lubricating oil compositions and concentrates. These compositions and concentrates include at least one basic alkali metal salt of sulfonic or carboxylic acid.
  • U.S. Patent 4,952,328 relates to lubricating oil compositions. These compositions contain from about 0.01% to about 2% by weight of at least one basic alkali metal salt of sulfonic or carboxylic acid.
  • overbased alkali metal salts of high molecular weight acidic organic compounds may be prepared.
  • One of the problems associated with working with high molecular weight material is effectively providing contact between the acidic material overbasing and the alkali metal compounds.
  • previously used low molecular weight, i.e. highly volatile, material are ineffective as promoters for high molecular weight acidic organic compounds in providing the contact necessary to produce useful overbased compounds.
  • the temperature used to overbase high molecular weight acidic organic compounds generally exceeds the boiling point of highly volatile promoters.
  • the high molecular weight alkali metal salts are useful in many applications including lubricating applications. These compounds provide strongly basic components (alkali metal-acidic material, usually alkali metal carbonate) along with high molecular weight, solubilizing substituents.
  • composition comprising at least one borated alkali metal overbased salt of at least one hydrocarbyl-substituted acidic organic compound wherein the hydrocarbyl group is derived from a polyalkene having a number average molecular weight of at least 600 and wherein the alkali metal overbased salt is prepared by the above process.
  • composition comprising at least one borated alkali metal overbased salt of at least one acid selected from the group consisting of hydrocarbyl-substituted carboxylic acid or anhydride thereof, or phosphorus acid or anhydride thereof wherein the hydrocarbyl group is derived from a polyalkene having a number average molecular weight of at least 900.
  • composition comprising at least one borated alkali metal overbased salt of at least one hydrocarbyl-substituted acidic organic compound wherein the hydrocarbyl group is derived from a polyalkene having a number average molecular weight of at least 600 and wherein the alkali metal overbased salt is obtainable by the above process.
  • hydrocarbyl includes hydrocarbon, as well as substantially hydrocarbon, groups.
  • substantially hydrocarbon describes groups which contain non-hydrocarbon substituents which do not alter the predominately hydrocarbon nature of the group.
  • hydrocarbyl groups include the following:
  • the present lubricating compositions contain an alkali metal basic salt of a carboxylic acid, sulfonic acid, phosphorus acid or a phenol. These basic salts are often referred to as overbased salts.
  • the overbased salts are single phase, homogeneous Newtonian systems characterized by a metal content in excess of that which would be present according to the stoichiometry of the metal and the particular organic compound reacted with the metal. The amount of excess metal is commonly expressed in metal ratio.
  • the term "metal ratio" is the ratio of the total equivalents of the metal to the equivalents of the acidic organic compound.
  • a neutral metal salt has a metal ratio of one.
  • a salt having 4.5 times as much metal as present in a normal salt will have metal excess of 3.5 equivalents, or a ratio of 4.5.
  • these salts preferably have a metal ratio from about 1.5 to about 40, preferably about 3 to about 30, more preferably about 3 to about 25.
  • the overbased materials are prepared by reacting an acidic material, typically carbon dioxide, with a mixture comprising a carboxylic acid, a sulfonic acid, phosphorus acid or a phenol, a reaction medium comprising at least one inert, organic solvent for said organic material, a stoichiometric excess of the above-described metal compound, and a promoter.
  • the overbased materials are prepared with carboxylic acids or sulfonic acids.
  • the carboxylic and sulfonic acids may have substituent groups derived from the polyalkenes.
  • the polyalkene is characterized as containing from at least about 45, preferably at least about 50, more preferably about 60, up to about 300 carbon atoms, generally about 200, preferably about 100, more preferably about 80.
  • the polyalkene is characterized by an M ⁇ n (number average molecular weight) value of at least about 600.
  • the polyalkene is characterized by an M ⁇ n value of about 600, preferably about 700, more preferably about 800, still more preferably about 900 up to about 5000, preferably 2500, more preferably 2000, still more preferably about 1500.
  • M ⁇ n varies between about 600, preferably about 700, more preferably about 800 to about 1200 or 1300.
  • M ⁇ n is the conventional symbol representing number average molecular weight.
  • Gel permeation chromatography is a method which provides both weight average and number average molecular weights as well as the entire molecular weight distribution of the polymers.
  • GPC Gel permeation chromatography
  • a series of fractionated polymers of isobutene, polyisobutene, is used as the calibration standard in the GPC.
  • M ⁇ n and M ⁇ w values of polymers are well known and are described in numerous books and articles. For example, methods for the determination of M ⁇ n and molecular weight distribution of polymers is described in W.W. Yan, J.J. Kirkland and D.D. Bly, "Modern Size Exclusion Liquid Chromatographs", J. Wiley & Sons, Inc., 1979.
  • the polyalkenes include homopolymers and interpolymers of polymerizable olefin monomers of 2 to about 16 carbon atoms; usually 2 to about 6, preferably 2 to about 4, more preferably 4.
  • the olefins may be monoolefins such as ethylene, propylene, 1-butene, isobutene, and 1-octene; or a polyolefinic monomer, preferably diolefinic monomer, such as 1,3-butadiene and isoprene.
  • the polyalkenes are prepared by conventional procedures.
  • Suitable carboxylic acids from which useful alkali metal salts can be prepared include aliphatic, cycloaliphatic and aromatic mono- and polybasic carboxylic acids free from acetylenic unsaturation, including naphthenic acids, alkyl- or alkenyl-substituted cyclopentanoic acids, alkyl- or alkenyl-substituted succinic acids or anhydrides, alkyl- or alkenyl-substituted cyclohexanoic acids, and alkyl- or alkenyl-substituted aromatic carboxylic acids.
  • the acids are generally prepared by reacting an unsaturated acid or derivative thereof with one of the above-described polyalkenes or derivative thereof.
  • the unsaturated acid is an alpha, beta unsaturated carboxylic acid.
  • these acids include maleic, itaconic, citraconic, glutaric, crotonic, acrylic, and methacrylic acids or derivatives thereof.
  • the derivatives of the unsaturated carboxylic acid include acids, anhydrides, metal or amine salts, lower alkyl esters (C 1-7 alkyl esters), and the like.
  • Illustrative carboxylic acids include propylenyl-substituted glutaric acid, polybutenyl-substituted succinic acids derived from a polybutene ( M ⁇ n equals about 200-1,500, preferably about 300-1500), propenyl-substituted succinic acids derived from polypropylenes ( M ⁇ n equal 200-1000), acids, acids formed by oxidation of petrolatum or of hydrocarbon waxes, available mixtures of two or more carboxylic acids and mixtures of these acids, their metal salts, and/or their anhydrides.
  • the carboxylic acids are aromatic carboxylic acids.
  • a group of useful aromatic carboxylic acids are those of the formula wherein R 1 is an aliphatic hydrocarbyl group preferably derived from the above-described polyalkenes, a is a number in the range of 1 to about 4, usually 1 or 2, Ar is an aromatic group, each X is independently sulfur or oxygen, preferably oxygen, b is a number in the range of from 1 to about 4, usually 1 or 2, c is a number in the range of zero to about 4, usually 1 to 2, with the proviso that the sum of a, b and c does not exceed the number of valences of Ar.
  • aromatic carboxylic acids include substituted benzoic, phthalic and salicylic acids.
  • the R 1 group is a hydrocarbyl group that is directly bonded to the aromatic group Ar.
  • R 1 groups include substituents derived from polymerized olefins such as polyethylenes, polypropylenes, polybutylenes, ethylene-propylene copolymers, chlorinated olefin polymers and oxidized ethylene-propylene copolymers.
  • the aromatic group Ar may have the same structure as any of the aromatic groups Ar discussed below.
  • the aromatic groups that are useful herein include the polyvalent aromatic groups derived from benzene, naphthalene, anthracene, etc., preferably benzene.
  • Specific examples of Ar groups include phenylenes and naphthylene, e.g., methylphenylenes, ethoxyphenylenes, isopropylphenylenes, hydroxyphenylenes, dipropoxynaphthylenes, etc.
  • a useful class of carboxylic acids are those of the formula wherein R 1 is defined above, a is a number in the range of from 1 to about 4, preferably 1 to about 3; b is a number in the range of 1 to about 4, preferably 1 to about 2, c is a number in the range of zero to about 4, preferably 1 to about 2, and more preferably 1; with the proviso that the sum of a, b and c does not exceed 6.
  • b and c are each one and the carboxylic acid is a salicylic acid.
  • the sulfonic acids useful in making the overbased salts (A) of the invention include the sulfonic and thio-sulfonic acids. Generally they are salts of sulfonic acids.
  • the sulfonic acids include the mono- or polynuclear aromatic or cycloaliphatic compounds.
  • the oil-soluble sulfonic acids can be represented for the most part by one of the following formulae: R 2 -T-(SO 3 ) a H and R 3 -(SO 3 ) b H, wherein T is a cyclic nucleus such as, for example, benzene, naphthalene, anthracene, diphenylene oxide, diphenylene sulfide, petroleum naphthenes, etc.
  • R 2 and R 3 are groups derived from petrolatum, saturated and unsaturated paraffin wax, and the above-described polyalkenes.
  • the groups T, R 2 , and R 3 in the above Formulae can also contain other inorganic or organic substituents in addition to those enumerated above such as, for example, hydroxy, mercapto, halogen, nitro, amino, nitroso, sulfide, disulfide, etc.
  • a and b are at least 1.
  • sulfonic acids include polybutene or polypropylene substituted naphthalene sulfonic acids, sulfonic acids derived by the treatment of polybutenes having a number average molecular weight ( M ⁇ n) in the range of 700 to 5000, preferably 700 to 1200, more preferably about 1500 with chlorosulfonic acids, paraffin wax sulfonic acids, polyethylene ( M ⁇ n equals about 900-2000, preferably about 900-1500, more preferably 900-1200 or 1300) sulfonic acids, etc.
  • Preferred sulfonic acids are mono-, di-, and tri-alkylated benzene (including hydrogenated forms thereof) sulfonic acids.
  • the hydrocarbyl-substituted acidic organic compound is a phenol.
  • the phenol may be a coupled or uncoupled phenol, preferably a substituted phenol.
  • the phenols may be alkylene coupled, wherein the alkylene group contains from 1 to about 8 carbon atoms, preferably 1 to about 4 carbon atoms, more preferably 1 carbon atom.
  • Alkylene coupled phenols are prepared by procedures known to those in the art. Generally, the phenol is reacted with an aldehyde, usually formaldehyde or a formaldehyde precursor such as paraformaldehyde, at a temperature from about 50°C to about 175°C.
  • a diluent may be used such as mineral oil, naphtha, kerosene, toluene or xylene.
  • the phenol may be a sulfur-coupled phenol which is prepared by reacting a sulfurizing agent with the phenol.
  • the sulfurizing agent generally is elemental sulfur or a sulfur halide, such as sulfur monochloride or sulfur dichloride, preferably sulfur dichloride.
  • Sulfur coupled phenols also referred to as polyphenol sulfides, are generally prepared by reacting a sulfur halide with a phenol at a temperature from about 50°C to about 75°C. The diluent as described above may also be used.
  • the phenol is substituted with one of the polyalkene groups described above.
  • the phenol has a polybutene or polypropylene substituent having a number average molecular weight of about 700 to about 1200 or 1300.
  • the phenols useful in making the overbased salts of the invention can be represented by the formula (R 1 ) a -Ar-(OH) b , wherein R 1 is defined above; Ar is an aromatic group; a and b are independently numbers of at least one, the sum of a and b being in the range of two up to the number of displaceable hydrogens on the aromatic nucleus or nuclei of Ar. Preferably, a and b are independently numbers in the range of 1 to about 4, more preferably 1 to about 2. R 1 and a are preferably such that there is an average of at least about 8 aliphatic carbon atoms provided by the R 1 groups for each phenol compound.
  • phenol is used herein, it is to be understood that this term is not intended to limit the aromatic group of the phenol to benzene. Accordingly, it is to be understood that the aromatic group as represented by “Ar”, as well as elsewhere in other formulae in this specification and in the appended claims, can be mononuclear such as a phenyl, a pyridyl, or a thienyl, or polynuclear.
  • the polynuclear groups can be of the fused type wherein an aromatic nucleus is fused at two points to another nucleus such as found in naphthyl, anthranyl, etc.
  • the polynuclear group can also be of the linked type wherein at least two nuclei (either mononuclear or polynuclear) are linked through bridging linkages to each other.
  • bridging linkages can be chosen from the group consisting of alkylene linkages, ether linkages, keto linkages, sulfide linkages, polysulfide linkages of 2 to about 6 sulfur atoms, etc.
  • the number of aromatic nuclei, fused, linked or both, in Ar can play a role in determining the integer values of a and b.
  • the sum of a and b is from 2 to 6.
  • Ar contains two aromatic nuclei the sum of a and b is from 2 to 10.
  • the sum of a and b is from 2 to 15.
  • the value for the sum of a and b is limited by the fact that it cannot exceed the total number of displaceable hydrogens on the aromatic nucleus or nuclei of Ar.
  • the promoters that is, these materials which facilitate the incorporation of excess metal into the overbased material act to improve contact between the acidic material and the acidic organic compound (overbasing substrate).
  • the promoter is a material which is slightly acidic and able to form a salt with the basic metal compound.
  • the promoter must also be an acid weak enough to be displaced by the acidic material, usually carbon dioxide.
  • the promoter has a pKa in the range from about 7 to about 10. A particularly comprehensive discussion of suitable promoters is found in U.S. Patents 2,777,874, 2,695,910, 2,616,904, 3,384,586 and 3,492,231.
  • promoters include the phenolic promoters.
  • Phenolic promoters include a variety of hydroxy-substituted benzenes and naphthalenes.
  • a particularly useful class of phenols are the alkylated phenols of the type listed in U.S. Patent 2,777,874, e.g., heptylphenols, octylphenols, and nonylphenols. Mixtures of various promoters are sometimes used.
  • the inorganic or lower carboxylic acidic materials which are reacted with the mixture of promoter, basic metal compound, reaction medium and acidic organic compound, are disclosed in the above cited patents, for example, U.S. Patent 2,616,904. Included within the known group of useful acidic materials are lower carboxylic acids, having from 1 to about 8, preferably 1 to about 4 carbon atoms. Examples of these acids include formic acid, acetic acid, propanoic acid, etc., preferably acetic acid.
  • Useful inorganic acidic compounds include HCl, SO 2 , SO 3 , CO 2 , H 2 S, N 2 O 3 , etc., are ordinarily employed as the acidic materials.
  • Preferred acidic materials are carbon dioxide and acetic acid, more preferably carbon dioxide.
  • the alkali metals present in the overbased alkali metal salts include principally lithium, sodium and potassium, with sodium being preferred.
  • the overbased metal salts are prepared using a basic alkali metal compound.
  • basic alkali metal compounds are hydroxides, oxides, alkoxides (typically those in which the alkoxy group contains up to 10 and preferably up to 7 carbon atoms), hydrides and amides of alkali metals.
  • useful basic alkali metal compounds include sodium oxide, potassium oxide, lithium oxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium propoxide, lithium methoxide, potassium ethoxide, sodium butoxide, lithium hydride, sodium hydride, potassium hydride, lithium amide, sodium amide and potassium amide.
  • sodium hydroxide and the sodium lower alkoxides i.e., those containing up to 7 carbon atoms).
  • the overbased materials of the present invention may be prepared by methods known to those in the art.
  • the methods generally involve adding acidic material to a reaction mixture comprising the hydrocarbyl-substituted acidic organic compound, the promoter and a basic alkali metal compound. These processes are described in the following U.S. Patent Nos.: 2,616,904; 2,616,905; 2,616,906; 3,242,080; 3,250,710; 3,256,186; 3,274,135; 3,492,231; and 4,230,586.
  • the hydrocarbyl-substituted acidic organic materials have relatively high molecular weights.
  • Higher temperatures are generally used to promote contact between the acidic material, the acidic organic compound and the basic alkali metal compound.
  • the higher temperatures also promote formation of the salt of the weakly acidic promoter by removal of water.
  • water must be removed from the reaction.
  • the reaction generally proceeds at temperatures from about 100°C up to the decomposition temperature of the reaction mixture or the individual components of the reaction.
  • the reaction may proceed at temperatures lower than 100°C, such as 60°C or above, if a vacuum is applied.
  • the reaction occurs at a temperature from about 110°C to about 200°C, preferably 120°C to about 175°C and more preferably about 130°C to about 150°C.
  • the reaction is performed in the presence of a reaction medium which includes naphtha, mineral oil, xylenes, toluenes and the like.
  • water may be removed by applying a vacuum, by blowing the reaction mixture with a gas such as nitrogen or by removing water as an azeotrope, such as a xylene-water azeotrope.
  • a gas such as nitrogen
  • an azeotrope such as a xylene-water azeotrope.
  • the acidic material is provided as a gas, usually carbon dioxide.
  • the carbon dioxide while participating in the overbasing process, also acts to remove water if the carbon dioxide is added at a rate which exceeds the rate carbon dioxide is consumed in the reaction.
  • Overbased metal salts may be prepared incrementally (batch) or by continuous process.
  • the incremental process involves the following steps: (A) adding a basic alkali metal compound to a reaction mixture comprising an acidic organic compound and removing free water from the reaction mixture to form an alkali metal salt of the acidic organic compound; (B) adding the basic alkali metal compound to the reaction mixture and removing free water from from the reaction mixture; and (C) introducing the acidic material to the reaction mixture while removing water. Steps (B) and (C) are repeated until a product of the desired metal ratio is obtained.
  • a novel aspect of the present invention is the semi-continuous process for preparing alkali metal overbased salts.
  • the process involves (A) adding at least one basic alkali metal compound to a reaction mixture comprising an alkali metal salt of an acidic organic compound and removing free water from the reaction mixture; and (B) concurrently thereafter, (1) adding basic alkali metal compound to the reaction mixture; (2) adding an inorganic or lower carboxylic acidic material to the reaction mixture; and (3) removing water from the reaction mixture.
  • the inventors have discovered that the addition of basic alkali metal compounds together with the inorganic or lower carboxylic acidic material may be accomplished by a process where the addition is done continuously along with the removal of water. This process shortens processing time of the reaction.
  • free water refers to the amount of water readily removed from the reaction mixture. This water is typically removed by azeotropic distillation. The water which remains in the reaction mixture is believed to be coordinated, associated, or solvated. The water may be in the form of water of hydration. Some basic alkali metal compounds may be delivered to the reaction mixture as aqueous solutions. The excess water added, or free water, with the basic alkali metal compound is usually then removed by azeotropic distillation, or vacuum stripping.
  • Water is generated during the overbasing process and is desirably removed as it is formed to minimize or eliminate formation of oil-insoluble metal carbonates.
  • the amount of water present prior to addition of the inorganic or lower carboxylic acidic material is less than about 30% by weight of the reaction mixture, preferably 20%, more preferably 10%.
  • the amount of water present after addition of the inorganic or lower carboxylic acidic material is up to about 4% by weight of the reaction mixture, preferably about 3%, more preferably about 2%.
  • the hydrocarbyl group of the acidic organic compound is derived from the above-described polyalkenes.
  • the provisos related to the polyalkene of the sulfonic acid and mixture of acidic organic compound are only preferred embodiments.
  • the alkali metal overbased salts are borated alkali metal overbased salts.
  • Borated overbased metal salts are prepared by reacting a boron compound with the basic alkali metal salt.
  • Boron compounds include boron oxide, boron oxide hydrate, boron trioxide, boron trifluoride, boron tribromide, boron trichloride, boron acid such as boronic acid, boric acid, tetraboric acid and metaboric acid, boron hydrides, boron amides and various esters of boron acids.
  • the boron esters are preferably lower alkyl (1-7 carbon atoms) esters of boric acid.
  • the boron compounds are boric acid.
  • the overbased metal salt is reacted with a boron compound at about 50°C to about 250°C, preferably 100°C to about 200°C.
  • the reaction may be accomplished in the presence of a solvent such as mineral oil, naphtha, kerosene, toluene or xylene.
  • the overbased metal salt is reacted with a boron compound in amounts to provide at least about 0.5%, preferably about 1% up to about 5%, preferably about 4%, more preferably about 3% by weight boron to the composition.
  • reaction mixture is cooled to 80°C where 540 parts of a 50% aqueous solution of sodium hydroxide is added to the vessel.
  • the reaction mixture is heated to 140°C over 1.7 hours and water is removed at reflux conditions.
  • the reaction mixture is carbonated at 1 standard cubic foot per hour (scfh) while removing water for 5 hours.
  • Steps (1)-(3) are repeated using 560 parts of an aqueous sodium hydroxide solution.
  • Steps (1)-(3) are repeated using 640 parts of an aqueous sodium hydroxide solution.
  • Steps (1)-(3) are then repeated with another 640 parts of a 50% aqueous sodium hydroxide solution.
  • the reaction mixture is cooled and 1000 parts of 100 neutral mineral oil are added to the reaction mixture.
  • the reaction mixture is vacuum stripped to 115°C, about 30 millimeters of mercury.
  • the residue is filtered through diatomaceous earth.
  • the filtrate has a total base number of 361 (theoretical 398), 43.4% sulfated ash (theoretical 50.3), 39.4% oil and a specific gravity of 1.11.
  • a reaction vessel is charged with 700 parts of a 100 neutral mineral oil, 700 parts (1.25 equivalents) of the succinic anhydride of Example 1 and 200 parts (2.5 equivalents) of a 50% aqueous solution of sodium hydroxide.
  • the reaction mixture is stirred and heated to 80°C where 66 parts (0.25 equivalent) of tetrapropenyl phenol are added to the reaction vessel.
  • the reaction mixture is heated from 80°C to 140°C over 2.5 hours with blowing of nitrogen and removal of 40 parts of water.
  • Carbon dioxide (28 parts, 1.25 equivalents) is added over 2.25 hours at a temperature from 140-165°C.
  • the reaction mixture is blown with nitrogen at 2 standard cubic foot per hour (scfh) and a total of 112 parts of water is removed.
  • the reaction temperature is decreased to 115°C and the reaction mixture is filtered through diatomaceous earth.
  • the filtrate has 4.06% sodium (theoretical 3.66), a total base number of 89, a specific gravity of
  • a reaction vessel is charged with 281 parts (0.5 equivalent) of the succinic anhydride of Example 1, 281 parts of xylene, 26 parts of tetrapropenyl substituted phenol and 250 parts of 100 neutral mineral oil.
  • the mixture is heated to 80°C and 272 parts (3.4 equivalents) of an aqueous sodium hydroxide solution are added to the reaction mixture.
  • the mixture is blown with nitrogen at 1 scfh and the reaction temperature is increased to 148°C.
  • the reaction mixture is then blown with carbon dioxide at 1 scfh for one hour and 25 minutes while 150 parts of water is collected.
  • the reaction mixture is cooled to 80°C where 272 parts (3.4 equivalents) of the above sodium hydroxide solution is added to the reaction mixture and the mixture is blown with nitrogen at 1 scfh.
  • the reaction temperature is increased to 140°C where the reaction mixture is blown with carbon dioxide at 1 scfh for 1 hour and 25 minutes while 150 parts of water is collected.
  • the reaction temperature is decreased to 100°C and 272 parts (3.4 equivalents) of the above sodium hydroxide solution is added while blowing the mixture with nitrogen at 1 scfh.
  • the reaction temperature is increased to 148°C and the reaction mixture is blown with carbon dioxide at 1 scfh for 1 hour and 40 minutes while 160 parts of water is collected.
  • the reaction mixture is cooled to 90°C and where 250 parts of 100 neutral mineral oil are added to the reaction mixture.
  • the reaction mixture is vacuum stripped at 70°C and the residue is filtered through diatomaceous earth.
  • the filtrate contains 50.0% sodium sulfate ash (theoretical 53.8%) by ASTM D-874, total base number of 408, a specific gravity of 1.18 and 37.1% oil.
  • a reaction vessel is charged with 700 parts of the product of Example 3.
  • the reaction mixture is heated to 75°C where 340 parts (5.5 equivalents) of boric acid is added over 30 minutes.
  • the reaction mixture is heated to 110°C over 45 minutes and the reaction temperature is maintained for 2 hours.
  • a 100 neutral mineral oil 80 parts is added to the reaction mixture.
  • the reaction mixture is blown with nitrogen at 1 scfh at 160°C for 30 minutes while 95 parts of water is collected.
  • Xylene (200 parts) is added to the reaction mixture and the reaction temperature is maintained at 130-140°C for 3 hours.
  • the reaction mixture is vacuum stripped at 150°C and 20 millimeters of mercury.
  • the residue is filtered through diatomaceous earth.
  • the filtrate contains 5.84% boron (theoretical 6.43) and 33.1% oil.
  • the residue has a total base number of 309.
  • a reaction vessel is charged with 224 parts (0.4 equivalents) of the succinic anhydride of Example 1, 21 parts (0.08 equivalent) of a tetrapropenyl phenol, 224 parts of xylene and 224 parts of 100 neutral mineral oil.
  • the mixture is heated and 212 parts (2.65 equivalents) of a 50% aqueous sodium hydroxide solution are added to the reaction vessel.
  • the reaction temperature increases to 130°C and 41 parts of water is removed by nitrogen blowing at 1 scfh.
  • the reaction mixture is then blown with carbon dioxide at 1 scfh for 1.25 hours.
  • the sodium hydroxide solution (432 parts, 5.4 equivalents) is added over four hours with carbon dioxide blowing at 0.5 scfh at 130°C.
  • the reaction temperature is increased to 150°C and the rate of carbon dioxide blowing is increased to 1.5 scfh and maintained for 1 hour and 15 minutes.
  • the reaction mixture is cooled to 150°C and blown with nitrogen at 1 scfh while 176 parts of oil is added to the reaction mixture.
  • the reaction mixture is blown with nitrogen at 1.8 scfh for 2.5 hours and the mixture is then filtered through diatomaceous earth.
  • the filtrate contains 15.7% sodium and 39% oil.
  • the filtrate has a total base number of 380.
  • a reaction vessel is charged with 561 parts (1 equivalent) of the succinic anhydride of Example 1, 52.5 parts (0.2 equivalent) of a tetrapropenylphenol, 561 parts xylene and 500 parts of a 100 neutral mineral oil.
  • the mixture is heated to 50°C under nitrogen and 373.8 parts (6.8 equivalents) of potassium hydroxide and 299 parts of water are added to the mixture.
  • the reaction mixture is heated to 135°C while 145 parts of water is removed.
  • the azeotropic distillate is clear. Carbon dioxide is added to the reaction mixture at 1 scfh for two hours while 195 parts of water is removed azeotropically.
  • the reaction is cooled to 75°C where a second portion of 373.8 parts of potassium hydroxide and 150 parts of water are added to the reaction vessel.
  • the reaction mixture is heated to 150°C with azeotropic removal of 70 parts of water. Carbon dioxide (1 scfh) is added for 2.5 hours while 115 parts of water is removed azeotropically.
  • the reaction is cooled to 100°C where a third portion of 373.8 parts of potassium hydroxide and 150 parts of water is added to the vessel.
  • the reaction mixture is heated to 150°C while 70 parts of water is removed.
  • the reaction mixture is blown with carbon dioxide at 1 scfh for one hour while 30 parts of water is removed.
  • the reaction temperature is decreased to 70°C.
  • the reaction mixture is reheated to 150°C under nitrogen.
  • reaction mixture is blown with carbon dioxide at 1 scfh for two hours while 80 parts of water is removed.
  • the carbon dioxide is replaced with a nitrogen purge and 60 parts of water is removed.
  • the reaction is then blown with carbon dioxide at 1 scfh for three hours with removal of 64 parts of water.
  • the reaction mixture is cooled to 75°C where 500 parts of 100 neutral mineral is added to the reaction mixture.
  • the reaction is vacuum stripped to 115°C and 25 millimeters of mercury.
  • the residue is filtered through diatomaceous earth. The filtrate contains 35% oil and has a base number of 322.
  • the alkali metal overbased salts of the present invention may be used, in lubricants or in concentrates, by themselves or in combination with any other known additive which includes, but is not limited to dispersants, detergents, antioxidants, anti-wear agents, extreme pressure agents, emulsifiers, demulsifiers, foam inhibitors, friction modifiers, anti-rust agents, corrosion inhibitors, viscosity improvers, pour point depressants, dyes, and solvents to improve handleability which may include alkyl and/or aryl hydrocarbons. These additives may be present in various amounts depending on the needs of the final product.
  • Dispersants include, but are not limited to, hydrocarbon substituted succinimides, succinamides, carboxylic esters, Mannich dispersants and mixtures thereof as well as materials functioning both as dispersants and viscosity improvers.
  • the dispersants include nitrogen-containing carboxylic dispersants, ester dispersants, Mannich dispersants or mixtures thereof.
  • Nitrogen-containing carboxylic dispersants are prepared by reacting a hydrocarbyl carboxylic acylating agent (usually a hydrocarbyl substituted succinic anhydride) with an amine (usually a polyamine).
  • Ester dispersants are prepared by reacting a polyhydroxy compound with a hydrocarbyl carboxylic acylating agent.
  • the ester dispersant may be further treated with an amine.
  • Mannich dispersants are prepared by reacting a hydroxy aromatic compound with an amine and aldehyde.
  • the dispersants listed above may be post-treated with reagents such as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon substituted succinic anhydride, nitriles, epoxides, boron compounds, phosphorus compounds and the like.
  • Detergents include, but are not limited to, Newtonian or non-Newtonian, neutral or basic salts of alkaline earth or transition metals with one or more hydrocarbyl sulfonic acid, carboxylic acid, phosphoric acid, thiophosphoric acid, dithiophosphoric acid, phosphinic acid, thiophosphinic acid, sulfur coupled phenol or phenol.
  • Basic salts are salts that contain a stoichiometric excess of metal present per acid function.
  • chlorinated aliphatic hydrocarbons such as chlorinated wax
  • organic sulfides and polysulfides such as benzyl disulfide, bis(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized terpene
  • phosphosulfurized hydrocarbons such as the reaction product of a phosphorus sulfide with turpentine or methyl oleate, phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite,
  • Viscosity improvers include, but are not limited to, polyisobutenes, polymethacrylate acid esters, polyacrylate acid esters, diene polymers, polyalkyl styrenes, alkenyl aryl conjugated diene copolymers, polyolefins and multifunctional viscosity improvers.
  • Pour point depressants are a particularly useful type of additive often included in the lubricating oils described herein. See for example, page 8 of "Lubricant Additives” by C. V. Smalheer and R. Kennedy Smith (Lesius-Hiles Company Publishers, Cleveland, Ohio, 1967).
  • Anti-foam agents used to reduce or prevent the formation of stable foam include silicones or organic polymers. Examples of these and additional anti-foam compositions are described in "Foam Control Agents", by Henry T. Kerner (Noyes Data Corporation, 1976), pages 125-162.
  • the concentrate might contain 0.01 to 90% by weight of the alkali metal overbased salts.
  • the alkali metal overbased salts may be present in a final product, blend or concentrate in (in a minor amount, i.e., up to 50% by weight) any amount effective to act as a detergent, but is preferably present in oil of lubricating viscosity, hydraulic oils, fuel oils, gear oils or automatic transmission fluids in an amount of from about 0.1 to about 10%, preferably 0.25 to about 2% by weight, most preferably about 0.50 to about 1.25%.
  • 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, vegetable oils, mineral lubricating oils, solvent or acid treated mineral oils, and oils derived from coal or shale.
  • Synthetic lubricating oils include hydrocarbon oils, halo-substituted hydrocarbon oils, alkylene oxide polymers, esters of carboxylic acids and polyols, esters of polycarboxylic acids and alcohols, esters of phosphorus-containing acids, polymeric tetrahydrofurans, silicon-based oils and mixtures thereof.
  • oils of lubricating viscosity are described in U.S. Patent 4,326,972 and European Patent Publication 107,282.
  • Example 1 The amount of each component in Examples A-C reflects the amount of oil containing product of the indicated additives.
  • Component Lubricant (% weight)
  • Lubricating oil compositions of the present invention exhibit a reduced tendency to deteriorate under conditions of use and thereby reduce rust and corrosive wear and the formation of such undesirable deposits as varnish, sludge, carbonaceous materials and resinous materials which tend to adhere to the various engine parts and reduce the efficiency of the engines.
  • Lubricating oils also can be formulated in accordance with this invention which result in improved fuel economy when used in the crankcase of a passenger automobile.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Steroid Compounds (AREA)
  • Detergent Compositions (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Claims (50)

  1. Un procédé pour la préparation de sels basiques de métaux alcalins de composés acides organiques comportant les étapes de:
    (A) ajouter une portion d'un composé basique de métal alcalin à un mélange de réaction, comportant un composé acide organique à substitution hydrocarbyle, le groupe hydrocarbyle étant dérivé d'un polyalcène présentant un poids moléculaire moyen en nombre d'au moins 600 afin de former un sel de métal alcalin du composé acide, après quoi on élimine l'eau libre du mélange de réaction, et, par la suite,
    (B) conjointement
    (B-1) ajouter une autre partie d'un composé basique de métal alcalin au mélange de réaction;
    (B-2) ajouter au moins un produit de type acide inorganique ou acide carboxylique inférieur au mélange de réaction; et
    (B-3) éliminer l'eau du mélange de réaction, au moins les étapes (B-1), (B-2) et (B-3) étant mises en oeuvre en présence d'un promoteur.
  2. Le procédé de la revendication 1, dans lequel le promoteur présente un pKa de 7 à 10.
  3. Le procédé de la revendication 1 ou de la revendication 2, dans lequel la température de réaction est de 110°C à 200°C.
  4. Le procédé de la revendication 1 ou de la revendication 2, dans lequel la température de réaction est de 130°C à 150°C.
  5. Le procédé de l'une quelconque des revendications 1 à 4, dans lequel le promoteur est un alkyl-phénol ou un alcényl-phénol ou bien un nitroalcane.
  6. Le procédé de l'une quelconque des revendications 1 à 5, dans lequel le sel basique présente un rapport métallique de 1,5 à 40.
  7. Le procédé de l'une quelconque des revendications 1 à 6, dans lequel le composé organique acide est un acide sulfonique ou carboxylique.
  8. Le procédé de l'une quelconque des revendications 1 à 7, dans lequel le sel métallique est un sel de sodium ou un sel de potassium.
  9. Le procédé de l'une quelconque des revendications 1 à 8, dans lequel le sel surbasique est un succinate surbasique.
  10. Le procédé de l'une quelconque des revendications 1 à 9, dans lequel le sel surbasique est un sel de sodium surbasique.
  11. Le procédé de l'une quelconque des revendications 1 à 10, dans lequel le polyalcène présente un Mn de 800 à 5000.
  12. Le procédé de la revendication 11, dans lequel le groupe hydroxyle est dérivé d'un polyalcène ayant un Mn d'au moins 900.
  13. Le procédé de l'une quelconque des revendications 1 à 12, dans lequel le polyalcène est le polybutène.
  14. Un procédé pour préparer des sels basiques de métaux alcalins de composés acides organiques comprenant les étapes de:
    (A) ajouter une partie du composé basique de métal alcalin à un mélange réactionnel comportant un composé acide organique à substitution hydroxyle, dans lequel le groupe hydroxyle est un dérivé d'un polyalcène ayant un poids moléculaire moyen en nombre d'au moins 600 afin de former un sel de métal alcalin du composé acide, après quoi on élimine l'eau libre du mélange de réaction, et, par la suite,
    (B) ajouter une autre partie du composé basique de métal alcalin au mélange de réaction; et
    (C) ajouter au moins un produit acide inorganique ou carboxylique inférieur au mélange de réaction, tout en éliminant l'eau du mélange de réaction, au moins les étapes (B) et (C) étant mises en oeuvre en présence d'un promoteur.
  15. Le procédé de la revendication 14, dans lequel les étapes (B) et (C) sont répétées au moins une fois.
  16. Le procédé de la revendication 14 ou de la revendication 15, dans lequel le promoteur présente un pKa de 7 à 10.
  17. Le procédé de l'une quelconque des revendications 14 à 16, dans lequel le promoteur est un alkyl-phénol ou un alcényl-phénol ou bien un nitroalcane.
  18. Le procédé de l'une quelconque des revendications 14 à 17, dans lequel la température de réaction est de 110°C à 200°C.
  19. Le procédé de l'une quelconque des revendications 14 à 17, dans lequel la température de réaction est de 130°C à 150°C.
  20. Le procédé de l'une quelconque des revendications 14 à 19, dans lequel le composé basique de métal alcalin est un composé basique de sodium.
  21. Le procédé de l'une quelconque des revendications 14 à 20, dans lequel la composition acide organique renferme au moins un acide carboxylique.
  22. Le procédé de l'une quelconque des revendications 14 à 21, dans lequel le groupe hydrocabyle est dérivé d'un polyalcène ayant un Mn de 900 à 5000.
  23. Une composition comportant au moins un sel surbasique de métal alcalin boraté d'au moins un composé acide organique à substitution hydrocarbyle, dans lequel le groupe hydrocarbyle est dérivé d'un polyalcène ayant un poids moléculaire moyen en nombre d'au moins 600 et dans lequel le sel de métal alcalin surbasique est préparé par le procédé selon l'une quelconque des revendications 14 à 22.
  24. La composition de la revendication 23, dans laquelle le sel basique présente un rapport métallique de 1,5 à 40.
  25. La composition de la revendication 23, dans laquelle le sel basique présente un rapport métallique de 9 à 25.
  26. La composition de l'une quelconque des revendications 23 à 25, dans laquelle le polyalcène présente un Mn de 800 à 5000.
  27. La composition de l'une quelconque des revendications 23 à 25, dans laquelle le polyalcène présente un Mn de 900 à 1500.
  28. La composition de l'une quelconque des revendications 23 à 27, dans laquelle le polyalcène est un polybutène.
  29. La composition de l'une quelconque des revendications 23 à 28, dans laquelle le sel basique est un succinate surbasique.
  30. La composition de l'une quelconque des revendications 23 à 28, dans laquelle le sel basique est un succinate de sodium surbasique.
  31. Un procédé pour préparer des sels surbasés de métaux alcalins de composés acides organiques comportant les étapes de:
    (A) ajouter une partie d'un composé basique de métal alcalin qui constitue au moins un excès stoechiométrique par rapport à un mélange de réaction comportant un composé acide organique à substitution hydrocarbyle, le groupe hydrocarbyle étant dérivé d'un polyalcène ayant un poids moléculaire moyen en nombre d'au moins 600 et un promoteur, après quoi on élimine l'eau libre du mélange de réaction;
    (B) ajouter au moins un produit acide inorganique ou carboxylique inférieur au mélange de réaction tout en éliminant l'eau libre du mélange de réaction;
    (C) ajouter une autre partie de composé basique de métal alcalin au mélange de réaction; et
    (D) ajouter au moins un produit acide inorganique ou carboxylique inférieur au mélange de réaction tout en éliminant l'eau du mélange de réaction.
  32. Le procédé de la revendication 34, dans lequel les étapes (C) et (D) sont répétées au moins une fois.
  33. Le procédé de la revendication 34 ou de la revendication 35, dans lequel le promoteur présente un pKa d'environ 7 à environ 10.
  34. Le procédé de l'une quelconque des revendications 31 à 33, dans lequel le promoteur est un alkyl-phénol ou un alcényl-phénol ou bien un nitroalcane.
  35. Le procédé de l'une quelconque des revendications 31 à 34, dans lequel le composé basique de métal alcalin est un composé basique de sodium.
  36. Le procédé de l'une quelconque des revendications 31 à 35, dans lequel la composition acide organique renferme au moins un acide carboxylique.
  37. Un procédé pour la préparation d'une composition comportant au moins un sel surbasique de métal alcalin boraté d'au moins un composé acide organique à substitution hydrocarbyle, le groupe hydrocarbyle étant dérivé d'un polyalcène ayant un poids moléculaire moyen en nombre d'au moins 600, tandis que le sel surbasique de métal alcalin est préparé par le procédé comportant les étapes de:
    (A) ajouter une partie d'un composé basique de métal alcalin qui constitue au moins un excès stoechiométrique par rapport à un mélange de réaction comportant un composé acide organique à substitution hydrocarbyle, le groupe hydrocarbyle étant dérivé d'un polyalcène ayant un poids moléculaire moyen en nombre d'au moins 600 et un promoteur, après quoi on élimine l'eau libre du mélange de réaction;
    (B) ajouter au moins un produit acide inorganique ou carboxylique inférieur au mélange de réaction tout en éliminant l'eau libre du mélange de réaction;
    (C) ajouter une autre partie de composé basique de métal alcalin au mélange de réaction; et
    (D) ajouter au moins un produit acide inorganique ou carboxylique inférieur au mélange de réaction tout en éliminant l'eau du mélange de réaction.
  38. Le procédé de la revendication 37, dans lequel le sel basique présente un rapport métallique de 1,5 à 40.
  39. Le procédé de la revendication 37 ou de la revendication 38, dans lequel le polyalcène présente un Mn de 800 à 5000.
  40. Le procédé de l'une quelconque des revendications 37 à 39, dans lequel le sel basique est un succinate surbasique.
  41. Le procédé de l'une quelconque des revendications 37 à 39, dans lequel le sel basique est un succinate de sodium surbasique.
  42. Un procédé pour la préparation d'une composition lubrifiante, comportant le mélange d'une quantité prépondérante d'une huile de viscosité lubrifiante et d'une composition préparée par un procédé selon l'une quelconque des revendications 1 à 13, 14 à 22 et 31 à 36 ainsi que 37 à 41.
  43. Un procédé pour la préparation d'une composition lubrifiante, comportant le mélange d'une quantité prépondérante d'une huile de viscosité lubrifiante et de la composition de l'une quelconque des revendications 23 à 30.
EP92907871A 1991-04-19 1992-02-27 Procedes de fabrication des sels surbasiques de metaux alcalins Expired - Lifetime EP0535191B1 (fr)

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US68819291A 1991-04-19 1991-04-19
US688192 1991-04-19
PCT/US1992/001476 WO1992018587A1 (fr) 1991-04-19 1992-02-27 Sels surbasiques de metaux alcalins et procedes de fabrication

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US5202036A (en) * 1990-06-28 1993-04-13 The Lubrizol Corporation Diesel lubricants and methods
US5614480A (en) * 1991-04-19 1997-03-25 The Lubrizol Corporation Lubricating compositions and concentrates
US5562864A (en) * 1991-04-19 1996-10-08 The Lubrizol Corporation Lubricating compositions and concentrates
JPH07500375A (ja) * 1992-05-15 1995-01-12 ザ ルブリゾル コーポレイション 潤滑組成物および濃縮物
EP0596048A1 (fr) * 1992-05-15 1994-05-11 The Lubrizol Corporation Compositions lubrifiantes et concentres
CN1037113C (zh) * 1993-10-12 1998-01-21 中国石油化工总公司石油化工科学研究院 录音机芯润滑脂及其制备方法
GB9324208D0 (en) * 1993-11-25 1994-01-12 Bp Chemicals Additives Lubricating oil additives
US6235688B1 (en) 1996-05-14 2001-05-22 Chevron Chemical Company Llc Detergent containing lithium metal having improved dispersancy and deposit control
US5688751A (en) * 1996-08-14 1997-11-18 The Lubrizol Corporation Salicylate salts as lubricant additives for two-cycle engines
TW452793B (en) 1997-03-27 2001-09-01 Matsushita Electric Ind Co Ltd Recording and reproducing method for optical information recording medium, and optical information recording medium
JP3698905B2 (ja) 1999-01-11 2005-09-21 日本電気株式会社 光学的情報記録媒体、その情報記録方法、その情報消去方法
US8969273B2 (en) * 2009-02-18 2015-03-03 Chevron Oronite Company Llc Lubricating oil compositions
FR2980799B1 (fr) * 2011-09-29 2013-10-04 Total Raffinage Marketing Composition lubrifiante pour moteur marin
JP5656939B2 (ja) * 2012-08-24 2015-01-21 興研株式会社 防護服
JP2015196695A (ja) 2014-03-31 2015-11-09 出光興産株式会社 ガスエンジン用潤滑油組成物

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US3422013A (en) * 1967-07-07 1969-01-14 Lubrizol Corp Process for the preparation of non-newtonian colloidal disperse systems
ZA738848B (en) * 1973-10-05 1975-06-25 Lubrizol Corp Basic alkali sulfonate dispersions and processes
DE3676384D1 (de) * 1985-08-13 1991-02-07 Exxon Chemical Patents Inc Ueberbasische zusaetze.
GB8601990D0 (en) * 1986-01-28 1986-03-05 Exxon Chemical Patents Inc Overbased additives
US4952328A (en) * 1988-05-27 1990-08-28 The Lubrizol Corporation Lubricating oil compositions

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FI925776A (fi) 1992-12-18
AU659450B2 (en) 1995-05-18
ES2094351T3 (es) 1997-01-16
EP0535191A1 (fr) 1993-04-07
DE69213376D1 (de) 1996-10-10
ATE142249T1 (de) 1996-09-15
FI925776A0 (fi) 1992-12-18
JPH05508181A (ja) 1993-11-18
AU1533992A (en) 1992-11-17
BR9205242A (pt) 1993-07-27
WO1992018587A1 (fr) 1992-10-29
CA2085372A1 (fr) 1992-10-20
NO924683D0 (no) 1992-12-04
MX9201752A (es) 1993-08-01
NO924683L (no) 1992-12-04
JP3157830B2 (ja) 2001-04-16
DE69213376T2 (de) 1997-03-20

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