JPH11508288A - Lubricants using molybdenum-containing compositions and methods of using them - Google Patents

Abstract

  (57) [Summary] The present invention relates to a lubricating composition comprising a major amount of an oil of lubricating viscosity and the following (A) and (B): (A) a wear-improving amount of at least one molybdenum-containing composition; and B) at least one component selected from the group consisting of the following (i), (ii) and (iii): (i) at least one borated overbased metal salt of an acidic organic compound, (A) and (Bi) are not the same; (ii) (a) at least one organic polysulfide or at least one ashless dithiocarbamate-containing composition and (b) metal thiophosphate, phosphoric acid Ester or its salt, phosphorus-containing carboxylic acid, its ester, its ether or its amide, borated dispersant, alkali metal borate, borated fatty amine, borated phospholipid, borate ester, and the like From a mixture of Combinations of and (iii) (i) and (ii); at least one combination of components selected from that group.

Description

DETAILED DESCRIPTION OF THE INVENTION       Lubricants using molybdenum-containing compositions and methods of using them                                Field of the invention   The present invention relates to a lubricating composition containing a molybdenum composition for improving the wear resistance of a lubricant. About things. The invention also relates to a method of lubricating a transmission or a differential gear. These lubricating compositions are particularly useful as manual transmission oils.                                Background of the Invention   The design of engines, transmissions and gears requires a variety of metallurgy during their design. use. Transmissions often use brass synchronizer rings. this The brass synchronizer meshes with the steel cone and changes the gear of this transmission. One problem associated with this design is brass ring wear. Therefore, on steel A lubricant that reduces the wear of brass is desired.   Often, lubricants protect this engine, transmission and gears from wear and oxidation. It contains an additive mixture which is intended to be protected. Lots of such mixtures Is known to those skilled in the art. However, certain protections also protect the wear of brass on steel. Additive mixtures are desired.   U.S. Pat.Nos. 3,541,014 (LeSuer) and 5,143,633 (Gallo et al.) Molybdenum-containing overbased metal salts are described.   U.S. Pat.Nos. 3,446,735 (Wiese), 4,289,635 (Schroeck), 4,456,538 No. 4,692,256 (Umemura et al.), No. 4,704,215 (Hata et al.) No. 4,846,983 (Ward, Jr.) describes various molybdenum compounds, alone or It describes compositions used either in combination with other additives.                                Summary of the Invention   The present invention contains a major amount of oil having lubricating viscosity and the following (A) and (B): (A) at least one molybdenum in an amount that improves wear resistance And (B) selected from the group consisting of the following (i), (ii) and (iii): At least one component: (i) boration of at least one acidic organic compound Overbased metal salts, except that (A) and (Bi) are not the same; (ii (a) at least one organic polysulfide or at least one ashless dithioca -Bamate-containing composition and (b) metal thiophosphate, phosphate ester or a salt thereof, -Containing carboxylic acid, its ester, its ether or amide, borate Dispersants, alkali metal borates, borated fatty amines, borated phospholipids, At least one selected from the group consisting of borate esters, and mixtures thereof. Combinations with species components; and (iii) combinations of (i) and (ii). This lubricating composition is modified Has good abrasion resistance. When using this lubricating composition in a manual transmission, steel The wear of the upper brass is reduced.                             Detailed description of the invention   The term “hydrocarbyl” includes not only hydrocarbon groups but also substantial hydrocarbon groups. I will. Substantial hydrocarbons are heterologous that do not primarily alter the hydrocarbon character of the group. Shows a group containing an atom substituent. Examples of hydrocarbyl groups include: :   (1) hydrocarbon substituents, ie, aliphatic substituents (eg, alkyl or Kenyl), alicyclic substituents (eg, cycloalkyl, cycloalkenyl), aromatic Aromatic-substituted aromatic substituent, aliphatic-substituted aromatic substituent and alicyclic-substituted Aromatic substituents as well as cyclic substituents. Where this ring is the other Part completes (ie, for example, any two designated positions) The substituents can together form an alicyclic group);   (2) A substituted hydrocarbon substituent, that is, a substituent containing a non-hydrocarbon group. This non-hydrocarbon group, within the context of the present invention, is primarily the hydrocarbon nature of the substituents. Do not alter the quality; such groups (eg, halo (especially chloro and fluoro), (Droxy, mercapto, nitro, nitroso, sulfoxy, etc.) are known to those skilled in the art. Has been   (3) heteroatom substituents, i.e., mainly within the context of the present invention, While having properties, it has atoms other than carbon present in the ring or chain, Others are groups composed of carbon atoms (e.g., alkoxy or alkylthio). You. Suitable heteroatoms will be apparent to those skilled in the art, for example, sulfur, oxygen, nitrogen Include. Such substituents include, for example, pyridyl, furyl, thienyl, imid Dazoril and the like.   Generally, the hydrocarbyl group will have no more than about 2 for each 10 carbon atoms. There are heteroatom substituents, preferably no more than one hetero substituent. Typically Has no such heteroatom substituents in the hydrocarbyl group. Obedience Thus, the hydrocarbyl group is a pure hydrocarbon.   As used herein and in the claims, the term "lubricating composition" refers to It means a combination of certain oils and additives. The weight percentage is based on this additive and And the total amount of oil with lubricating viscosity.   As described herein, in combination with certain additives, molybdenum-containing The wear resistance of lubricants, especially of brass on steel, Is improved. The molybdenum composition generally contains about 125 ppm of the lubricating composition. To about 900 ppm, preferably from about 200 ppm to about 800 ppm, more preferably At a level sufficient to provide from about 250 ppm to about 700 ppm of molybdenum metal; used. Here, and elsewhere in this specification, ratios and ranges are May be combined. The molybdenum metal is in an oil-soluble or dispersible shape. These molybdenum compositions include molybdenum-containing overbaked acidic organic compositions. Salts, molybdenum thiocarbamate, and molybdenum thiophosphate You. In one embodiment, the molybdenum composition comprises a molybdenum-containing dispersant (e.g., , Succinimide containing molybdenum).Molybdenum overbased composition   In one embodiment, the molybdenum composition comprises the acidic organic compound molybdenum oxide. It is in the form of a bar-based salt. This molybdenum overbased metal salt is Particularly useful in lubricants that require qualification. This molybdenum-containing overbase The salt forms according to the stoichiometry of the metal and the particular organic compound that reacts with the metal. And is characterized by a metal content in excess of what would be present. Excess gold The genus is usually represented by the metal ratio. The term "metal ratio" refers to this acidic organic It is the ratio of the total equivalents of the metal to the equivalents of the compound. 4.5 times that of metal in normal salt Of a metal having an excess of 3.5 equivalents of metal per equivalent of organic acid, Having a metal ratio of The molybdenum-containing overbased salt is preferably about It has a metal ratio from 1.5, or from about 3. This molybdenum-containing overbake Sulphate salts generally have a metal ratio of up to about 40, or up to about 30, or up to about 25 You. In one embodiment, the metal salt is from about 10, preferably from about 12, to about 40. Or with a metal ratio of up to about 30.   The molybdenum-containing overbased salt may further comprise an alkali metal or an alkali metal. Potassium earth metals may be included. Examples of such metals include sodium, potassium, Lithium, magnesium, calcium, barium, titanium, manganese, cobalt , Nickel, copper and zinc, preferably sodium, potassium, potassium. Lucium and magnesium. This alkali metal or alkaline earth metal Typically comprises from about 2% to about 20% by weight of the molybdenum-containing overbased salt. % By weight, or from about 4% to about 18% by weight, or about 6% by weight To about 14% by weight.   Acidic organics used to prepare this molybdenum-containing overbased metal salt The compounds are generally sulfonic acids, carboxylic acids, phosphorus-containing acids, phenols and their compounds. It is selected from the group consisting of these derivatives. Preferably, this overbased material The quality may be sulfonic acid, carboxylic acid, or derivatives of these acids (e.g., esters , Anhydrides, etc.). These sulfonic acids are preferably mono-, Di- and trialiphatic hydrocarbon substituted aromatic sulfonic acids. This hydrocarbon substitution The groups can be derived from polyalkenes. These polyalkenes include from two to about Up to 16 carbon atoms, preferably 2 to about 8 carbon atoms, more preferably Or a polymerizable olefinic monomer having 2 to about 4 carbon atoms -Homopolymers and interpolymers. These olefins , Monoolefins (e.g., ethylene, propylene, 1-butene, isobutene and And 1-octene) or polyolefinic monomers (e.g., 1,3-butadiene and And isoprene). In one embodiment, the interpolymer is a homopolymer It is a limer. Examples of preferred homopolymers include polybutene, preferably polybutene. There is polybutene in which about 50% of the mer is derived from isobutylene. These polia The alkene is prepared by a usual method.   The polyalkene generally has at least about 8 carbon atoms, or at least Also contain about 15 carbon atoms, or at least about 20 carbon atoms , Characterized. The polyalkene generally has up to about 40 carbon atoms, and Contains up to about 30 carbon atoms. In one embodiment, these polyalkenes From about 250, or from about 300, to about 600, or to about 500, or to about 400 With Mn. The abbreviation Mn is an ordinary symbol representing the number average molecular weight. Gel par Maturation chromatography (GPC) is the weight average molecular weight and number of polymers. It is a method that provides both the average molecular weight as well as the total molecular weight of this polymer. It is also a way to provide cloth. For the purposes of the present invention, isobutene, polyisobutene A series of fractionated polymers are used as calibration standards for GPC.   Examples of sulfonic acids include mahogany sulfonic acid, bright stock sulfonic acid, Petroleum sulfonic acid, mono- and polywax substituted naphthalene sulfonic acids, saturated Hydroxy-substituted sulfonic acids and unsaturated paraffin wax sulfonic acids, waxes Substituted benzene or naphthalenesulfonic acid, tetraisobutylenesulfonic acid , Tetraamylenesulfonic acid, dodecylbenzenesulfonic acid, didodecylbenze Sulfonic acid, dinonylbenzene sulfonic acid, at least one of the above-mentioned polyalkenes (Preferably polybutene) with chlorosulfonic acid. Sulfonic acid and the like.   These sulfonic acids include dodecylbenzene "bottoms" sulfone Acids. Dodecylbenzene bottoms (primarily mono- and didodecyl Mixture of benzenes) is available as a by-product of the manufacture of household detergents . Alkylated bottoms formed during the production of linear alkyl sulfonates (LAS) Similar products obtained from are also used in producing the sulfonate used in the present invention. Useful. The preparation of sulfonic acids is well known to those skilled in the art. For example, John Wiley &  Kirk-Othmer's `` Encyclopedia of Chemic '' published by Sons, N.Y. (1969) al Technology "(2nd edition, volume 19, p. 291 et seq.), chapter" Sulfonates ".   In one embodiment, the acidic organic compound is a carboxylic acid or a derivative thereof. possible. Suitable carboxylic acids include aliphatic, cycloaliphatic and aromatic monobasic or Is a polybasic carboxylic acid. In one embodiment, the carboxylic acid or These derivatives are aliphatic acids containing from about 8 or from about 12 carbon atoms. Or their derivatives. The carboxylic acids or their derivatives are generally , Containing up to about 50, or up to about 25 carbon atoms. Exemplary carboxylic acids and And their derivatives include 2-ethylhexanoic acid, palmitic acid, stearic acid, Oleic acid, linoleic acid, behenic acid, octadecyl-substituted adipic acid, stearyl ammonium Benzoic acid, polybutene (Mn is about 200 to 1500, preferably about 300 to 1500, more preferably Preferably from about 800 to 1200) or a polybutenyl-substituted succinic acid or Its anhydride, polypropene (Mn is 200-2000, preferably about 300-1500, And preferably about 800 to 1200). Or formed by oxidation of their anhydrides, petrolatum or hydrocarbon waxes Acids, two or more carboxylic acids (eg, tall oil and rosin) Acid), and mixtures of the above acids and / or their derivatives. Included.   In one embodiment, the carboxylic acid or derivative thereof is a hydrocarbyl moiety. It is a substituted carboxylic acylating agent. These acylating agents include halides, And an acid, an ester or an anhydride, More preferably, it is an anhydride. Preferably, the carboxylic acylating agent is It is a succinic acylating agent. The acylating agent may be a monocarboxylic acid acylating agent or Is a polycarboxylic acid acylating agent, and one or more of the above polyalkenes Can be derived from In one embodiment, the polyalkene has at least about 400, or even less. Or at least about 500 Mn. Generally, this polyalkene About 500 to about 5000, or about 700 to about 2500, or about 800 to about 2000 Or about 900 to about 1500 Mn. In one embodiment, The carboxylate acylating agent preferably has a hydrocarbyl group of about 400 to about 1200 Mn, preferably Preferably, it has a Mn of about 400 to about 800.   In another embodiment, the hydrocarbyl group has a Mn from about 1300 to about 5000, and And from about 1.5 to about 4, or from about 1.8 to about 3.6, or from about 2.5 to about 3.2. Derived from polyalkenes with Mw / Mn at This hydrocarbyl substituted cal The boronic acid acylating agent is prepared by a known method.   In another embodiment, these acylating agents are combined with the polyalkene and an excess of anhydrous By reacting with maleic acid, the number of succinic groups for each equivalent of substituent is Provided about 1.3 to about 4.5 succinic acid-substituted substituted succinic acylating agents per equivalent To be prepared. A suitable range is about 1.3 per equivalent of substituent. Up to 3.5, or from about 1.5 to about 2.5 succinic groups. This implementation In embodiments, the polyalkene has a Mn value from about 1300 to about 5000. Mn even better A preferred range is from about 1500 to about 2800, and the most preferred range of Mn values is from about 1500 to about 2800. 2400.   Carboxylic acids or their derivatives (e.g., acylating agents) and their preparation are U.S. Patent Nos. 3,215,707 (Rense); 3,219,666 (Norman et al.); 3,231,587. No. 3,912,764 (Palmer); No. 4,110,349 (Cohen); and No. 4, 234,435 (Meinhardt et al.); And GB 1,440,219. This The disclosures of these patents are incorporated herein by reference.   In another embodiment, the acidic organic compound is an alkyloxyalkylene acetic acid. Or alkylphenoxyacetic acid, more preferably alkylpolyoxyalkylene. Acetic acid or a derivative thereof. Certain examples of these compounds include: There is: isostearyl pentaethylene glycol acetic acid; isostearyl-O- (CH<sub>Two</sub> CH<sub>Two</sub>O)<sub>Five</sub>CH<sub>Two</sub>CO<sub>Two</sub>Na; Lauryl-O- (CH<sub>Two</sub>CH<sub>Two</sub>O)<sub>Two</sub>.<sub>Five</sub>CH<sub>Two</sub>CO<sub>Two</sub>H; Lauryl-O- (CH<sub>Two</sub>CH<sub>Two</sub>O)<sub>Three</sub>.<sub>Three</sub> CH<sub>Two</sub>CO<sub>Two</sub>H; Oleyl-O- (CH<sub>Two</sub>CH<sub>Two</sub>O)<sub>Four</sub>-CH<sub>Two</sub>CO<sub>Two</sub>H; Lauryl-O- (CH<sub>Two</sub>CH<sub>Two</sub>O)<sub>Four</sub>.<sub>Five</sub>CH<sub>Two</sub>CO<sub>Two</sub>H; Lauryl-O- (CH<sub>Two</sub>CH<sub>Two</sub>O)<sub>Ten</sub>CH<sub>Two</sub>CO<sub>Two</sub>H; Lauryl-O- (CH<sub>Two</sub>CH<sub>Two</sub>O)<sub>16</sub>CH<sub>Two</sub>CO<sub>Two</sub>H; Octylph Enyl-O- (CH<sub>Two</sub>CH<sub>Two</sub>O)<sub>8</sub>CH<sub>Two</sub>CO<sub>Two</sub>H; octylphenyl-O- (CH<sub>Two</sub>CH<sub>Two</sub>O)<sub>19</sub>CH<sub>Two</sub>CO<sub>Two</sub>H; 2-o Cutyldecanyl-O- (CH<sub>Two</sub>CH<sub>Two</sub>O)<sub>6</sub>CH<sub>Two</sub>CO<sub>Two</sub>H. These acids are available from Sandoz Chemical as S It is marketed under the trade name of andopan acid.   In another embodiment, the acidic organic compound is an aromatic carboxylic acid. helpful A group of aromatic carboxylic acids is of the formula:   Where R<sub>1</sub>Is an aliphatic arsenic derived from the above olefins or polyalkenes. A drocarbyl group, wherein a is a number ranging from 1 to about 4, usually 1 or 2; Ar is an aromatic group and each X is independently sulfur or oxygen, preferably oxygen B is a number ranging from 1 to about 4, usually 1 or 2, c is from 0 to about 4 , Usually 1 or 2, provided that the sum of a, b and c is Does not exceed valence number. Examples of aromatic acids are substituted or unsubstituted benzoic acids, Includes phthalic and salicylic acids. This R<sub>1</sub>Group is directly attached to the aromatic group Ar A hydrocarbyl group. R<sub>1</sub>Examples of groups include those derived from the above polyalkenes. Substituents are included.   Ar can be mononuclear or polynuclear. Mononuclear groups include phenyl and pyridyl Or thienyl. This polynuclear group is one in which one aromatic nucleus is Condensed types condensed at points (e.g., as found in naphthyl, anthranil, etc.) To). The polynuclear group can also be of the bond type, which (E.g., alkylene bond, ether bond, keto bond, sulfide bond, Sulfide and polysulfide bonds (containing 3 to about 6 sulfur atoms) ). Examples of aromatic groups include phenyl, phenylene and Naphthylene groups are included.   In one embodiment, the carboxylic acid or derivative thereof is salicylic acid or Derivatives thereof. Preferably, the salicylic acid or derivative thereof is It is an aliphatic hydrocarbon-substituted salicylic acid or a derivative thereof. This hydrocarbon substitution The groups are generally derived from one or more of the above polyalkenes.   The above aromatic carboxylic acids are known in the art or Can be prepared by a known method. Carbo of the type exemplified by these equations The methods for preparing acids and their neutral and basic metal salts are well known. For example, U.S. Pat. Nos. 2,197,832; 2,197,835; 2,252,662; Nos. 2,714,092; 3,410,798; and 3,595,791 It is shown. These patents cover aromatic carboxylic acids, their salts and their salts. The disclosure of the method of preparing is incorporated herein by reference.   In another embodiment, the acidic organic compound is a phosphorus acid or a derivative thereof. You. The phosphorus-containing acid or a derivative thereof includes a phosphorus-containing acid (for example, phosphoric acid or Thiophosphorus acid or its ester (mono and dithiolyl) Including acid-containing acids or esters thereof). In one embodiment, this resource The sulfur-containing acid is the reaction product of one or more of the above polyalkenes with phosphorus sulfide. It is. Useful phosphorus sulfides include phosphorus pentasulfide, phosphorus sesquisulfide, and phosphorus heptasulfide. No. In general, the reaction between the polyalkene and phosphorus sulfide is carried out at 80 ° C. Higher temperature, usually between 100 ° C and 300 ° C. obtain. Generally, these products have a phosphorus content of about 0.05% to about 10%, preferably It has a phosphorus content of about 0.1% to about 5%. Phosphorating agent for this olefin polymer The relative proportion of the polyalkene is generally 0.1 parts of the phosphorus sulfide per 100 parts of the polyalkene. ~ 50 parts. These phosphorus-containing acids are described in US Pat. No. 3,232,8 issued to Le Suer. No. 83. The content of this document describes the development of phosphorus-containing acids and their preparation. The indications are incorporated herein by reference.   In another embodiment, the acidic organic compound is phenol. This phenol Is the formula (R<sub>1</sub>)<sub>a</sub>-Ar- (OH)<sub>b</sub>Where R<sub>1</sub>Is above for aromatic carboxylic acids Ar is an aromatic group as defined above; a and b are independently The sum of a and b is from 2 to the aromatic nucleus of Ar (one or more) )) Up to the total number of replaceable hydrogens. Preferably, a and b are independent And a number ranging from one to about four, or about two. In one embodiment, R<sub>1</sub> And a represent R for each phenolic compound<sub>1</sub>On average at least about The value is such that eight aliphatic carbon atoms are provided.   In another embodiment, the molybdenum-containing overbased metal salt is a borate It is a molybdenum fluoride-containing overbased metal salt. This molybdenum-containing borate The overbased metal salt is a borated overbased metal salt described below. Is reacted with a molybdenum-containing anion. is there Alternatively, the molybdenum-containing borated overbased metal salt may be The boron-containing compound is added to the initial reaction mixture used to produce the boron-containing metal salt. It can be prepared by containing.Preparation of overbased composition containing molybdenum   In one embodiment, the molybdenum-containing overbased composition comprises molybdenum Alkali metal or alkaline earth metal over anions and acidic organic compounds It is prepared by reacting with a base salt. This alkali metal compound Or an alkaline earth metal salt is an acid (typically carbon dioxide) as described below. An acidic organic compound (e.g., as described above), at least inert to this organic material. Also a reaction medium containing one organic solvent, stoichiometric excess of basic alkali metal Compound or alkaline earth metal compound (typically a metal hydroxide or metal oxide) Prepared by reacting a mixture containing Agents include alcoholic and phenolic accelerators, for example, about Alcohols having 1 to about 12 carbon atoms (e.g., methanol, ethanol , Amyl alcohol, octanol, isopropanol, and mixtures thereof And alkylated phenols (e.g., heptylphenol, octylph Enol and nonylphenol).   Examples of the basic alkali metal compound or alkaline earth metal compound include Potassium or alkaline earth metal hydroxides, oxides, alkoxides (typically Means that the alkoxy group has up to 10 carbon atoms, preferably up to 7 carbon atoms. Hydrides and amides. Useful basic metallization Compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium oxide And calcium hydroxide, calcium oxide and barium hydroxide. These alkali metal salts and alkaline earth metal salts and their preparation method, It is described in U.S. Pat. No. 4,627,928. The content of this patent is not Is incorporated herein by reference. Extensive range of suitable accelerators No. 2,777,874; U.S. Pat. No. 2,695,910; U.S. Pat. No. 2,616,904; Nos. 3,384,586; and 3,492,231. The contents of these patents , The disclosure of accelerators is incorporated herein by reference.   The temperature at which this acidic substance is contacted with the rest of the reaction mass is mostly used Depends on accelerator. With phenolic accelerators, the temperature is usually from about 80 ° C to about 80 ° C. 300 ° C., preferably in the range of about 100 ° C. to about 200 ° C. As this accelerator, Al When using coal or mercaptan, this temperature is the reflux temperature of the reaction mixture. Do not exceed.   Acidic reacting with a mixture of acidic organic compounds, promoters, metal compounds and reaction media The materials are also disclosed in the above cited patents, e.g., U.S. Patent No. 2,616,904. I have. Known groups of useful acidic substances include formic acid, acetic acid, nitric acid, boric acid, sulfuric acid, hydrochloric acid , Hydrobromic acid, carbamic acid, substituted carbamic acids and the like. Acetic acid is non- It is always a useful acidic substance. Inorganic acidic compounds (e.g., HCl, SO<sub>Two</sub>, SO<sub>Three</sub>, CO<sub>Two</sub>, H<sub>Two</sub>S , N<sub>Two</sub>O<sub>Three</sub>Etc.) can also be used as this acidic substance. Preferred acidic substances are S O<sub>Two</sub>, SO<sub>Three</sub>, Carbon dioxide and acetic acid, more preferably carbon dioxide .   Methods for preparing these overbased materials are well known in the prior art, and For example, it is disclosed in the following U.S. Patents: U.S. Pat. No. 2,616,904; No. 2,616,906; No. 3,242,080; No. 3,250,710; No. 3,256,186; Nos. 3,274,135; 3,492,231; and 4,230,586. These patents Methods, materials that can be overbased, suitable metal bases, promoters, and acidic materials Disclose the quality. The contents of these patents are hereby incorporated by reference for such disclosure. Incorporated as a reference. Other descriptions of basic sulfonates and their Can be found in the following U.S. Patents: U.S. Pat. No. 2,174,110; No. 2,202,781; No. 2,239,974; No. 2,319,121; No. 2,337,552; No. 3, Nos. 488,284; 3,595,790; and 3,798,012. These contents are This disclosure is hereby incorporated by reference.   As described above, the alkali or alkaline earth overbased composition comprises: Reacts with molybdenum-containing anions, resulting in molybdenum-containing excess A base metal salt may be formed. This molybdenum anion is Or an ammonium or alkali metal salt of molybdic acid (this includes (NH<sub>Four</sub> )<sub>6</sub>Mo<sub>7</sub>O<sub>twenty four</sub>, (NH<sub>Four</sub>)<sub>Two</sub>Mo<sub>Two</sub>O<sub>7</sub>And various hydrates (e.g., (NH<sub>Four</sub>)<sub>6</sub>Mo<sub>7</sub>O<sub>twenty four</sub>・ 4H<sub>Two</sub>O) ). In one embodiment, the reaction is carried out using a mastication accelerator. Is promoted by The mastication accelerator may include one or more of the ingredients described herein. The above dispersants are mentioned. This method and the molybdenum-containing overbased The composition is described in U.S. Patent No. 3,541,014 (LeSuer). The contents of this patent Is hereby incorporated by reference for this disclosure.   In another embodiment, the molybdenum-containing overbased composition comprises at least Can also be used in this overbased method in the presence of one organomolybdenum complex. It is prepared by reacting various components. This molybdenum-containing organic complex is Preferably, it is an amine-molybdenum complex, which is typically an acidic organic It is prepared by reacting a molybdenum compound with an amine. This molybdenum Molybdate, alkali metal molybdate, hydrogen molybdate Sodium, ammonium molybdate, MoOCl<sub>Four</sub>And molybdenum trioxide I can do it. Sodium molybdate and ammonium molybdate are preferred No. The amine-molybdenum complex is generally prepared in an aqueous medium. This The min is added to the aqueous solution of the inorganic molybdenum compound. The reaction mixture is After addition of the amine, a temperature between about 20 ° C. and about 100 ° C., preferably between about 50 ° C. and about 90 ° C. At a temperature between about 0.5 hours to about 3 hours. To neutralize this reaction mixture The required amount of acid is added before or after the introduction of the amine. Strong mineral acids (good Preferably, sulfuric acid) is used. The amine-molybdenum complex precipitates. So It is recovered by filtration, washing with water and, if appropriate, drying. . This complex can be solid or pasty, depending on the type of amine used. Has the appearance. Its color changes from white to blue. It is, in effect, a hydrocarbon Insoluble or poorly soluble in   The atomic ratio of nitrogen to molybdenum in the complex is generally from about 0.25 to about 4, preferably More preferably, it is about 0.5 to about 2. The molybdenum content of this complex depends on the amine used. Depends on the nature of the It is between about 10% and about 45%. This organic moly Among the butene complexes, complexes using an oxygen-containing compound can also be used. 1,2-, 1, 3- and 1,4-glycols are particularly suitable. Ethylene glycol and propylene Len glycol is preferably used. These polyols include glycerol And trimethylolpropane.   Certain amines or, preferably, ethylene oxide or propylene oxide Polyamines alkoxylated with sides are also suitable. Diethanolamine Or mention may be made of derivatives of triethanolamine.   The preparation of this molybdenum-containing overbased composition is based on a molybdenum compound (e.g., (E.g., ammonium molybdate) in the presence of this oxygen-containing compound at about 90 ° C. It can be performed by heating at 100 ° C. Water generated by this reaction Is removed using a stream of nitrogen. The molybdenum content of the resulting complex is Varies between about 7% and about 50% by weight, depending on the extent to which the silicon-containing compound is removed .   The organomolybdenum complex can be, for example, aromatic at a temperature between about 40 ° C. and about 100 ° C. Hydrogen sulfide in suspension of this complex in a solvent (e.g. xylene or toluene) (H<sub>Two</sub>By the action of S), it can be sulfurized. From the introduction of hydrogen sulfide, the color of this suspension is blue It changes from green to orange and then red. The amount of hydrogen sulfide introduced The amount is such that the atomic ratio of sulfur to butene is between about 1 and about 3.   The molybdenum-containing overbased product obtained according to the invention is transparent. Is stable, and in the case of sulfonate, it is colored brown, In the case of salicylate, it is colored black. This color generally indicates the presence of this overbased detergent in the presence of the sulfide complex. Is red. The proportion of molybdenum in this additive is 100% Close, higher than the ratio obtained during the inclusion of the inorganic molybdenum derivative. This additive is About 0.1% to about 10% by weight, preferably about 1% to about 4% by weight of molybdenum. Contains The overbased additive according to the present invention is soluble or soluble in hydrocarbons. Is dispersive. Molybdenum-containing Au prepared using a molybdenum-amine complex Bar-based salts are described in U.S. Patent No. 5,143,633. The contents of this patent Describes the molybdenum-containing overbased salts and methods for their production. And is incorporated herein by reference.   The following examples illustrate molybdenum-containing overbased compositions and their preparation. About the method. Throughout the specification and the appended claims as well as this example Unless otherwise indicated, parts and percentages are by weight and temperatures are in degrees Celsius. And the pressure is atmospheric. In this example, these overbased additions The basicity of the agents is determined by their neutralization number or AV (alkali number) (this is 1 gram of product) (Expressed in mg of KOH per). It is a standard ASTM  It is determined by titration with a strong acid according to D-2896.                                 Example M-1   (a) sodium molybdate (Na<sub>Two</sub>MoO<sub>Four</sub>・ 2H<sub>Two</sub>O) A solution of 41.17 g of water (100 ml) It is prepared in a reactor equipped with a degree control and stirring device. 30% of this mixture H<sub>Two</sub>SO<sub>Four</sub>(55.6 g), and then heated to 60 ° C. Following this, Dinoram C (21 g) from CECA SA is added. Dinoram C has the formula R-N-H − (CH<sub>Two</sub>)<sub>Three</sub>−NH<sub>Two</sub>Where R is 60% C<sub>12</sub>, 20% C<sub>14</sub>, 10% C<sub>16</sub>And And 5% C<sub>18</sub>Is a mixture of straight-chain saturated alkyl groups containing Filtered, then Before drying, the blue precipitate is recovered by washing with water and methanol. You. Finally, a blue solid containing 32.6% molybdenum and 4.4% nitrogen 47.1% Collect g.   (b) In a reaction vessel, 520 ml of xylene and 30 g of the above Dinoram C / molybdenum complex were placed. Fill. This mixture is stirred. The mixture was then added to C<sub>16-18</sub>Straight chain alkyl Alkyl xylene sulfonic acid 1 having a chain and molecular weight of 430 and containing 96% of active substance 31.8 g, 168 g of 100 Neutral solvent as diluent oil, 113.24 g of slaked lime with 96% purity and 48 ml of methanol are added. After neutralizing the sulfonic acid with the lime (this is If appropriate, this can be done by heating the reaction mixture at 60 ° C. for 30 minutes. Then, 55.2 g of carbon dioxide gas was introduced into the mixture, and the mixture was maintained at a temperature of 42 ° C. Carry.   After carbonation and removal of water and methanol under partial vacuum, this solid residue Objects are removed by centrifugation. After evaporating this solvent, it contains molybdenum. 448 g of superbasic sulfonic acid salt are recovered. Neutralization value is 300 Its content is 11.7% and its molybdenum content is 2.17%. that is It is stable even when diluted with lubricating oil.                                 Example M-2   (a) 20 g of a xylene (200 ml) dispersion of the complex prepared in Example M-1 was subjected to temperature control, Prepare in a 250 ml reactor equipped with a stirrer and aeration system. Kept at 80 ° C To this dispersion, add H<sub>Two</sub>Inject S (6.7 g). Deep red solid collected after removal of this solvent The product contains 28.4% molybdenum, 3.8% nitrogen and 23.7% sulfur.   (b) The same operation as in Example M-1 is performed, except that the sulfide Dinoram C / molybdenum complex (Example M-1) -2 (a)) 28 g are suspended in 520 ml of xylene, which is carried out before the introduction of the other reactants. Operation The order of cropping is the same as in Example M-1, except that the residue is removed by centrifugation. is there. The molybdenum-containing superbasic sulfonate is collected. AV is 304 and its The molybdenum, sulfur and calcium contents were 1.63% and 3.4%, respectively. % And 11.7%. The resulting product is reddish brown, and diluted with lubricating oil Even so, it is stable.                                 Example M-3   (a) Prepare a 2-ethylhexylamine / molybdenum complex as follows: Perform the same operation as in Example M-1, but before heating and acidification, at 60 ° C, 98% of 2-E Add 9.9 g of tylhexylamine and add sodium molybdate over 20 minutes. The solution is introduced into an aqueous solution containing 15.44 g and kept at 60 ° C. 45 minutes at 60 ° C After heating, the mixture is acidified with 23.1 g of 30% sulfuric acid before washing and drying the product. Become The latter is a white solid containing 36.8% molybdenum and 4.38% nitrogen. Shape.   (b) The same operation as in Example M-1 is performed, except that the 2-ethylhexyl prepared in Example M-3 (a) is used. 28 g of the ruamine complex are suspended in 520 ml of xylene before the introduction of the other reactants. Operation The procedure is the same as in Example M-1, except that the residue is removed by centrifugation. A The brown product with V of 353 is collected. Its calcium content and molybdenum content are They are 12.2% and 1.97%, respectively. The stability when diluted with lubricating oil is perfect is there.                                 Example M-4   Perform the same operation as in Example M-1 (b), except that the active substance has a molecular weight of 520 and xylene of 600 ml. 132 g of didodecylbenzenesulfonic acid containing 70% of the substance, prepared in Example M-1 (a) Complex 30 g, slaked lime 104 g, methanol 52 ml, ammonia 4.4 ml and diluent oil 90 g Is continuously introduced into the reactor. The collected product is brown and transparent. And is stable in oil. Its calcium content and molybdenum content They are 10% and 2.35%, respectively.   The same operation as in Example M-1 is performed, except that 30 g of the complex prepared in Example M-1 (a) is added to another compound. Before the addition of the reactants, it is introduced into 520 ml of toluene. The order of operation is during this carbonation To CO<sub>Two</sub>(52.7 g), except that (52.7 g) was introduced. After centrifugation, 448 g of molybdenum-containing superbasic sulphonate are recovered. AV is 298. That Calcium content and molybdenum content are 11.7% and 2.1%, respectively .                                 Example M-5   Perform the same operation as in Example M-4, except that after filtration through diatomaceous earth, a molybdenum having an AV of 292 is used. 440 g of a den-containing overbased sulfonate are recovered.                                 Example M-6   (a) Preparation of barium overbased amine-formaldehyde condensate: reaction In a container, 1000 parts of N-octadecylpropylenediamine, 490 parts of mineral oil, calcium oxide And about 143 parts of water at about 44 ° C., and refluxed for one hour. Heat slowly to 102 ° C. While maintaining the mixture at 100 ° C to 105 ° C, 303 parts of paraformaldehyde are added to the reaction mixture over 3 hours. Maintain this temperature for one hour, then raise the temperature to 150 ° C over two and a half hours You. The distillate (278 parts) is removed and the residue is filtered.   A separate reaction vessel is charged with 197 parts mineral oil and 119 parts heptylphenol. this The mixture was heated to 93-99 ° C, whereupon barium hydroxide monohydrate (465 parts) was added for 1 hour. Add over time. The reaction temperature was then raised to 150 ° C, where Add 149 parts of the amine-formaldehyde product (Example M-6 (a)) over half an hour I do. To this mixture at 150 ° C. for 7 hours at a rate of 15 parts per hour, Blow carbon dioxide below the surface. Add additional mineral oil (100 parts) to the mixture. And blow nitrogen subsurface at 150 ° C. for 2 hours. This mixture To reduce the water content to 0.3%. The residue was filtered through diatomaceous earth, The filtrate is the desired product. This product contains 36% mineral oil and 30.8% barium. Have.   (b) Mix 411 g of ammonium paramolybdate with 300 g of water, and mix By maintaining the temperature of the compound at about 60 ° C, ammonium paramolybdate quaternary water Japanese ((NH<sub>Four</sub>)<sub>6</sub>Mo<sub>7</sub>O<sub>twenty four</sub>・ 4H<sub>Two</sub>An aqueous mixture of O) is prepared. 4 100g portions of this mixture Over 3.5 hours with the barium overbased amine-aldehyde condensation Of the reaction mass (Example M-6 (a)) while maintaining the temperature of the reaction mass at about 95 ° C. Carry. As a result, a molar ratio of barium to molybdenum of 3: 1 is obtained. This water During the addition of the neutral mixture, ammonia and carbon dioxide are evolved. Then nitrogen The volatiles are removed from the reaction mass by heating to 150 ° C while spraying. Leave. The residue is filtered to give an oil solution 550 of the desired molybdenum-containing complex. g is obtained. The product analysis shows that the molybdenum-containing complex Confirms that about 65% of the molybdenum used in this reaction is retained.                                 Example M-7   (A) 44 parts of the product of Example M-6 (b) (all parts represent parts by weight), 10 parts mineral oil, And polyisobutene (Mn = 750) substituted succinic anhydride and tetraethylenepentamine Reaction product with a commercial mixture of polyethylene polyamines having an average composition corresponding to (This is according to the method of U.S. Pat. No. 3,172,892 (e.g., Example 12 thereof): 24 parts of a mixture (reacted in an equivalent ratio of 1) were prepared and over 1.5 hours Heat to 75 ° C. The weight ratio of mastication accelerator to overbased material is 5:95 It is. Into this solution was added an aqueous solution of ammonium molybdate (which is 265 parts by weight of water). Commercially available ammonium molybdate (which has the formula (NH<sub>Four</sub>)<sub>Two</sub>Mo<sub>Two</sub>O<sub>7</sub>Has a composition equivalent to Ammonium dimolybdate containing about 56.5% by weight molybdenum; 265 parts by weight (sold by the Climax Molybdenum Company) (Prepared by mixing for 1.5 hours while maintaining at about 70-80 ° C.) Add 0 parts to obtain a molar ratio of barium to molybdenum of 1: 1.53. The reaction obtained The mass is heated under reflux conditions at about 150 ° C. for about 8.8 hours. Then, in this mixture, Nitrogen is blown at a rate of about 5 parts per hour. Hold for another 1.3 hours. Thereafter, the nitrogen blowing was stopped and the mixture was Maintain at about 150 ° C. for another hour and filter the entire reaction mass. The filtrate is the desired Molybdenum-containing complex containing 19.67% by weight of molybdenum and 21.81% by weight of barium It is characterized by having an amount%.   (B) 2.285 g of the overbased product of Example M-6 (b) and the mastication aids listed above A mixture of 125 g of the promoter (Example M-7 (A)) was added to the mixture of paramolybdate for 3 hours. Ammonium (this involves mixing 1300 g of this molybdate with 1300 g of water) 2600 g of an aqueous solution of Maintain high temperature. The weight ratio of the mastication accelerator to the overbased product is 5: The molar ratio of barium to molybdenum is 1: 1.47. Incidental During the reaction, ammonia, carbon dioxide and water are evolved. Then, to this reaction mass Nitrogen was bubbled to remove water and gas while the product was allowed to flow for 4 hours And heat to 170 ° C. Then, a commercial filter aid is added and the mass is filtered. . The filtrate weighed 2.710 g and contained 20.2% by weight of molybdenum and 21.6% by weight of barium. % Oil and 25.3% oil by weight.Molybdenum-containing thiocarbamates and thiophosphates   As described above, the molybdenum composition comprises a molybdenum-containing thiocarbamate Or it may be a thiophosphate. These molybdenum compositions contain thiocarbamido Molybdenum oxysulfide and molybdenum oxysulfide thiophosphate Is mentioned. The thiocarbamates and their preparation are described below. Mo Ribden-containing thiocarbamates (including dithiocarbamates) are known in the art. Known in the art. These materials are disclosed in U.S. Pat.Nos. 4,098,705 and 4,259,194. No. 4,259,195, No. 4,265,773, No. 4,272,387, No. 4,282,822, No. Nos. 4,283,295, 4,369,119, 4,395,423 and 4,402,840 Has been described. The contents of these patents are directed to molybdenum-containing carbamates and their patents. The disclosure of these manufacturing methods is incorporated herein by reference. Commercially available Examples of molybdenum-containing thiocarbamates include Sakura Lube 500 (Sakura Chemi cal 20% molybdenum dithiocarbamate), and Molyvan 807 (Vanderbilt Che mical 5% molybdenum dithiocarbamate). The present inventor has proposed this Lithium-containing dithiocarbamates are useful in lubricating compositions that require thermal stability. I discovered that. Preferred molybdenum for molybdenum-containing dithiocarbamates Is about 200 ppm to about 800 ppm, preferably about 250 ppm to about 600 ppm, more preferably Preferably, it is from about 300 ppm to about 500 ppm.   In another embodiment, the molybdenum-containing composition is molybdenum thiophosphate. You. Molybdenum salts of thiophosphoric acids are known in the art. This thiophosphoric acid (Including dithiophosphoric acid) are described below. This molybdenum salt and their The method of preparation is described in U.S. Pat.Nos. 3,223,625, 3,256,184, 3,400,140, 3,494. Nos., 866, 3,840,463 and 4,156,099. Of these patents The contents are hereby incorporated by reference for such disclosure.Borated overbased salt   In one embodiment, the molybdenum-containing composition is borated overbased Used in combination with metal salts. This borated overbased metal salt Reacting the boron-containing compound with one or more of the above overbased metal salts Or overbased acidic organic compounds with boric acid Is prepared by The borated overbased metal salt is generally From about 0.1% to about 5% by weight of the lubricating composition, or from about 0.5% to about 3%; %, Or from about 0.5% to about 2% by weight.   Boron-containing compounds include boron oxide, boron oxide hydrate, boron trioxide, Boron iodide, boron tribromide, boron trichloride, boron-containing acids (e.g., boric acid, (Traboric acid and metaboric acid), borohydride, boron amide, and boron Various esters of acids are mentioned. The boron-containing ester is preferably It is a lower alkyl (1 to 7 carbon atoms) ester of boric acid. Preferred boron The containing compound is boric acid. Generally, the overbased metal salt is about 50 ° C. At about 250 ° C, preferably about 100 ° C to about 200 ° C, it is reacted with the boron-containing compound. The overbased metal salt generally comprises at least about 0.5 weight percent of the composition. %, Or at least about 1 wt. Responded. The overbased metal salt generally comprises about 5% by weight of the composition. Up to about 4% by weight, or up to about 3% by weight boron. Reacted with a urine-containing compound.   Borated overbased composition, lubricating composition containing same, and borate A method for preparing an acidified overbased composition is disclosed in U.S. Pat. No. 4,744,920; US Pat. No. 4,792,410 issued to Schwind et al., And PCT It is found in publication WO 88/03144. The disclosure content regarding the above matters is It has been incorporated as a reference.   In another embodiment, the borated overbased metal salt comprises a boronated By reacting the acidic organic compound with a basic metal salt in the presence of the compound. Prepared. This metal includes transition metals (e.g., zinc, copper and cadmium) Is mentioned. These borated overbased compositions and their preparation The method is described in US Pat. No. 5,064,545 (Steckel). The content of this patent is Such disclosure is incorporated herein by reference.   The following examples relate to borated overbased metal salts.                                 Example B-1   (a) 853 g of methyl alcohol, 410 g of mixed oil, 54 g of sodium hydroxide A mixture of water and a neutralizing amount of additional sodium hydroxide is prepared. Sodium hydroxide The latter addition amount depends on the acid number of the subsequently added sulfonic acid. This mix Adjust the temperature of the mixture to 49 ° C. While maintaining this temperature at 49-57 ° C, the linear dial Mixture (1070) of benzylbenzenesulfonic acid (MW430) and a mixed oil (active content 42% by weight) G). Into this reaction vessel, polyisobutenyl (Mn = 950) -substituted anhydrous succinic Add the acid (145 grams). Then 838 grams of sodium hydroxide was added and Is adjusted to 71 ° C. 460 grams of carbon dioxide are blown into the reaction mixture. this The mixture is flash stripped to 149 ° C and filtered until clear To give the desired product. The product has a base number of 440 (bromophenol blue). ), A metal content of 19.45% by weight, a metal ratio of 20, a sulfated ash content of 58% by weight, and 1. Overbased sodium sulfonate with a sulfur content of 3% by weight.   (b) The reaction vessel was charged with 1000 g of the overbased sodium salt (Example B-1 (a)). 0.13 g of antifoam (Dow Corning 200 Fluid with a viscosity of 1000 cSt at 25 ° C) Kerosene solution), and a mixture of 133 grams of mixed oil, 74-79 ° C with stirring Heat until Then 486 grams of boric acid are added to the reaction mixture. This anti The reaction mixture was heated to 121 ° C. and the reaction water and the overbased sodium CO contained in salt<sub>Two</sub>To release 40-50% by weight of The reaction mixture is added to 154 Heat to ℃ 160 ° C. and bring the free and total water content to 0.3 Maintain at this temperature until reduced to less than or equal to about 1% to about 2% by weight. this The reaction product is cooled to room temperature and filtered.                                 Example B-2   (a) 1000 g of mainly branched monoalkylbenzenesulfonic acid (Mw = 500), o -771 grams of xylene and 75.2 grams of polyisobutenyl (Mn = 950) succinic anhydride A mixture is prepared and the temperature is adjusted to 46 ° C. To this reaction mixture, add Nesium (87.3 grams), acetic acid (35.8 grams), methyl alcohol (31.4 grams), And water (59 grams) are added continuously. At a temperature of 49-54 ° C., the reaction mixture Blow in 77.3 grams of carbon dioxide. Then 87.3 grams of magnesium oxide, methyl 31.4 grams of alcohol and 59 grams of water are added and to the reaction mixture at 49-54 ° C. Inhale, 77.3 grams of carbon dioxide. Magnesium oxide, methyl alcohol The step of blowing carbon dioxide following the step of adding water and water is repeated once. Atmospheric pressure The reaction mixture is stripped using stripping and vacuum flash stripping. From which o-xylene, methyl alcohol and water are removed. Cool the reaction mixture And filter until clear. This product has a base number of 400 (bromophen Nord Blue), 9.3% by weight metal, 14.7 metal ratio, 46.0% by weight sulfate ash and And 1.6% by weight of sulfur. You.   (b) In a reaction vessel, 1000 g of the overbased magnesium salt (Example B-2 (a)) Fill ram and heat 181 grams of diluent oil to 79 ° C. Then the reaction mixture , 300 grams of boric acid are added and the mixture is heated to 124 ° C. for 8 hours. You. The reaction mixture is stirred until the magnesium content is constant at 6.8% by weight. Maintain at 21-127 ° C for 2-3 hours. Begin sparging with nitrogen and allow the reaction mixture to cool to 149 ° C. To remove water until the water content is below 3% by weight. This reaction mixture To obtain the desired product.   The molybdenum-containing composition comprises (i) an organic polysulfide or ashless dithiocar Used in combination with a bamate composition and (ii) an extreme pressure agent containing phosphorus or boron. Can be used. The organic polysulfide or ashless dithiocarbamate composition comprises Generally, an amount from about 0.5% to about 5% by weight of the lubricating composition, or about 1% by weight. % To about 4% by weight, or about 2% to about 3.5% by weight Is done.Organic polysulfide or ashless dithiocarbamate-containing composition   The organic polysulfide has at least 2 to about 10 sulfur atoms, preferably Is from 2 to about 6 sulfur atoms, more preferably from 2 to about 4 sulfur atoms Is characterized by a sulfide bond having This organic polysulfide is Generally, a di-, tri- or tetrasulfide composition, comprising a trisulfide group Compositions are preferred.   The organic polysulfides of the present invention provide from about 1% to about 3% sulfur of the lubricating composition. provide. Generally, this organic polysulfide will contain from about 10% to about 60% sulfur, preferably Or about 20% to about 50% sulfur, more preferably about 35% to about 45% sulfur. It contains. Materials that can be sulfurized to form this organic polysulfide include oils. , Fatty acids or esters, or olefins or polyolefins You. These substances may be used as sulfurizing agents (e.g., elemental sulfur, halogenated sulfur, sulfur And combinations of hydrogen sulfide).   Oils that can be sulfurized are natural or synthetic oils, including mineral oil, lard Carbohydrates derived from oils, fatty alcohols and fatty acids or aliphatic carboxylic acids Acid esters (e.g., myristyl oleate and oleyl oleate), Whale oil and synthetic black whale oil substitutes, and synthetic unsaturated esters or Glycerides are included.   Fatty acids generally comprise from about 4 to about 30 or from about 8 to about 24 charcoal. Containing elemental atoms such as palmito oleic acid, oleic acid, ricinoleic acid, There are nol acid and oleostearic acid. Sulfurized fatty acid esters are mixed Saturated fatty acid esters (e.g., animal fats and vegetable oils (tall oil, linseed oil, It is prepared from rapeseed oil, fish oil, black whale oil, etc.)).   The olefinic compound which can be sulfurized has at least one olefinic double bond. including. These double bonds are defined as non-aromatic double bonds; In addition, it contains one linking two aliphatic carbon atoms. In a broad sense, this orifice Is the formula                               R<sup>* 1</sup>R<sup>* 2</sup>C = CR<sup>* 3</sup>R<sup>*Four</sup> Can be defined by: where each R<sup>* 1</sup>, R<sup>* 2</sup>, R<sup>* 3</sup>And R<sup>*Four</sup>Is hydrogen or an organic group is there. Generally, in the above formula, the non-hydrogen R group is --C (R<sup>*Five</sup>)<sub>Three</sub>, -COOR<sup>*Five</sup>, −CON (R<sup>*Five</sup>)<sub>Two</sub> , −COON (R<sup>*Five</sup>)<sub>Four</sub>, -COOM, -CN, -X, -YR<sup>*Five</sup>Or filled with a group such as -Ar Where each R<sup>*Five</sup>Is independently hydrogen, alkyl, alkenyl, aryl, Substituted alkyl, substituted alkenyl or substituted aryl. But any two R<sup>*Five</sup>The group is alkylene or substituted alkylene Thereby forming a ring having up to about 12 carbon atoms; M is 1 equivalent Metal cations (preferably, Group I or Group II, for example, sodium, potassium X is halogen (eg, chlorine, bromine or iodine) Y is oxygen or divalent sulfur; Ar is aryl having up to about 12 carbon atoms Or a substituted aryl group. R<sup>* 1</sup>, R<sup>* 2</sup>, R<sup>* 3</sup>And R<sup>*Four</sup>Any two of Can also together form an alkylene group or a substituted alkylene group You. That is, the olefinic compound can be alicyclic.   The olefinic compound typically has each R<sup>*</sup>The group is independently alkyl Group, alkenyl group or aryl group. Monoolefinic compound And diolefinic compounds, especially the former are preferred, especially terminal monoolefins Hydrocarbon; that is, R<sup>* 3</sup>And R<sup>*Four</sup>Is hydrogen, and R<sup>* 1</sup>And R<sup>* 2</sup>But 1 1 to about 30 carbon atoms, preferably 1 to about 16 carbon atoms, more preferably Has 1 to about 8 carbon atoms, more preferably 1 to about 4 carbon atoms. Alkyl or aryl, especially alkyl (i.e., this olefin is a fatty Is preferred. About 3 to about 30 carbon atoms, especially about 3 Olefinic compounds having from about 16 (in most cases, less than about 9) carbon atoms are Especially desirable.   Isobutene, propylene and their dimers, trimers and tetramers , And mixtures are particularly preferred olefinic compounds. Of these compounds Of these, isobutylene and diisobutylene are particularly useful because of their usefulness and It is particularly desirable because compositions with high sulfur content can be prepared.   In one preferred embodiment, the organic polysulfide contains a sulfurized olefin. And wherein the olefin is described above. For example, organic polysulf According to U.S. Pat. No. 2,708,199, oxides containing four or more carbon atoms The fins can be sulfochloridized and further treated with high-grade inorganic polysulfides. And can be prepared.   In one embodiment, the sulfurized olefin is (1) in stoichiometric excess with sulfur monochloride. (2) reacting the resulting product with free low carbon atom olefins. Alkali in an alcohol-water solvent in a molar ratio of 2: 1 or more in the presence of au Treating with a metal sulfide, and (3) reacting the product with an inorganic base Is generated. This method is described in U.S. Pat. No. 3,471,404 discloses a process for preparing this sulfurized olefin and its disclosure. The discussion of the sulfurized olefins produced by is incorporated herein by reference. Have been. Generally, the olefin reactant will contain from about 2 to about 5 carbon atoms. Examples include ethylene, propylene, butylene, isobutylene, amylene, etc. No.   The sulfurized olefins useful in the compositions of the present invention also include The fin compound is reacted with a mixture of sulfur and hydrogen sulfide in the presence of a catalyst. And subsequently removing low boiling materials. Useful in the present invention A method of preparing a sulfurized composition is described in U.S. Pat.No. 4,191,659, the disclosure of which is hereby incorporated by reference. The contents are incorporated herein by reference for a description of the preparation of useful sulfurized compositions. Have been.   In one embodiment, the organic polysulfide is a catalyst (eg, magnesium oxide). Prepared by the reaction of mercaptan and sulfur in the presence of it can. The mercaptan used to produce this polysulfide is Ruville mercaptan (e.g., of the formula RSH, wherein R is , Which is a hydrocarbyl group as defined above). In one embodiment, R is A kill group, an alkenyl group, a cycloalkyl group or a cycloalkenyl group. R Is also a haloalkyl, hydroxyalkyl, or hydroxyalkyl group. Can be a substituted (e.g., hydroxymethyl, hydroxyethyl, etc.) aliphatic group. You. R is generally from about 2 to about 30 carbon atoms, or from about 2 to about 24 carbon atoms. Containing from about 3 to about 18 carbon atoms. Examples include butyl mercaptan , Amyl mercaptan, hexyl mercaptan, octyl mercaptan, 6-hydr Roxymethyloctanethiol, nonylmercaptan, decylmercaptan, 10 -Aminododecanethiol, dodecylmercaptan, 10-hydroxymethyltetra Includes decanethiol, and tetradecyl mercaptan. These organic Polysulfides and their method of manufacture are described in U.S. Pat. 56 No. 4,709 and U.S. Pat. No. 5,146,000 issued to Ozbalik. The contents of these patents are hereby incorporated by reference for such disclosure. Have been.   The following examples relate to organic polysulfides.                                 Example S-1   Add sulfur to the jacketed high pressure reactor with stirrer and internal cooling coil. (526 parts, 16.4 mol). Before introducing gaseous reactants, cool The line is circulated to cool the reactor. The reactor is sealed and kept at about 2 torr. After degassing and cooling, 920 parts (16.4 mol) of isobutene and And 279 parts (8.2 mol) of hydrogen sulfide. Steam the reactor to the outer jacket And heat to a temperature of about 182 ° C. for about 1.5 hours. During this heating, about 168 At C, a maximum pressure of 1350 psig is reached. Before the maximum reaction temperature is reached, this pressure Begins to drop and continues to drop at a constant rate as this gaseous reactant is consumed . After about 10 hours, at a reaction temperature of about 182 ° C., the pressure will be 310-340 psig and The rate of force change is about 5-10 psig per hour. Unreacted hydrogen sulfide and The isobutene is evacuated to a recovery system. After the pressure in this reactor drops to atmospheric pressure, The sulfide mixture is recovered as a liquid.                                 Example S-2   Heat sulfur monochloride (2025 grams, 15.0 moles) to 45 ° C. Subsurface gas sparging 1468 grams (26.2 moles) of isobutylene gas for 5 hours Supply to vessel. Maintain the temperature between 45 ° C and 50 ° C. At the end of spraying, this reaction The weight of the mixture increases to 1352 grams. In another reaction vessel, 60% flaky sulfidation 2150 grams (16.5 moles) of sodium, 240 grams (7.5 moles) of sulfur, and 4000 ml of water Of isopropanol is added. Heat the contents to 40 ° C. First The prepared adduct of sulfur monochloride and isobutylene is added while increasing the temperature to 75 ° C. Add over 3/4 hours. The reaction mixture is heated and refluxed for 6 hours. This mixture forms a separation layer. Discard the lower aqueous layer. Top organic layer, 10 Mix with 2 liters of aqueous sodium hydroxide solution and reflux the mixture for 6 hours. Remove the organic layer again and wash with 1 liter of water. Wash the washed product at 90 ° C and Dry by heating at a pressure of 30 mmHg. For 30 minutes. Remove the residue Filtration with an adiatomaceous earth filter aid yields 2070 grams of a clear, yellowish-orange liquid. Can be   This ashless dithiocarbamate composition contains dithiocarbamic acid or a salt thereof. Unsaturated amide, carboxylic acid, anhydride, or ester or ether thereof Reaction products with alkylene-coupled dithiocarbamates, (S-alkyldithiocarbamoyl) disulfide. This dithiocar Bamate compound (A) reacts dithiocarbamic acid or a salt thereof with an unsaturated compound. Can be prepared. The dithiocarbamate composition also comprises an amine Can be prepared by simultaneously reacting carbon dioxide, carbon disulfide and an unsaturated compound. . Generally, the reaction is carried out at a temperature of about 25 ° C to about 125 ° C, or at a temperature of about 50 ° C to about 100 ° C. Happens in. U.S. Patent Nos. 4,758,362 and 4,997,969 describe dithiocarbamates Describes compositions and methods of making them. The contents of these patents are For disclosure of carbamate compositions and methods of making them, see References herein. It has been adopted as.   Dithiocarbamic acid used to prepare this dithiocarbamate composition Alternatively, a salt thereof is prepared by reacting an amine with carbon disulfide. The amine can be a primary amine (s) or a secondary amine (s). Can be a plurality), with secondary amines being most preferred. This amine is generally Contains a locarbyl group. Each hydrocarbyl group is independently one to about forty carbon atoms. An elemental atom, or about 2 to about 30 carbon atoms, or 3 to about 24 carbon atoms, or Or may contain up to about 12 carbon atoms. Examples of groups that can be present on this amine include , Ethyl, propyl, butyl, hexyl, octyl and dodecyl groups Is included.   In one embodiment, the amine is a primary amine. First class useful in the present invention Examples of amines include ethylamine, propylamine, butylamine, 2-ethyl Hexylamine, octylamine and dodecylamine are included.   In one embodiment, the primary amine is a fatty (C<sub>8-30</sub>) Amines Is n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine Min, n-hexadecylamine, n-octadecylamine, oleylamine, etc. I can do it. Also useful fatty amines include commercially available fatty amines, such as "Armeen" Amines (products available from Akzo Chemicals (Chicago, Illinois)) You. These amines include, for example, Armeen C, Armeen O, Armeen OL, Armeen T, A rmeen HL, Armeen S, and Armeen SD, where the alphabet The name refers to an aliphatic group (e.g., cocoa, oleyl, taro, or stearyl). Related.   Other useful primary amines include primary ether amines, such as those of the formula R "(OR ')<sub>x</sub>NH<sub>Two</sub> Wherein R 'is from about 2 to about 6 carbon atoms X is a number from 1 to about 150, or from about 1 to about 5 And R "is a hydride having about 5 to about 150 carbon atoms. chemical company (manufactured and sold by Atlanta, Georgia). I can do it. A preferred ether amine is SURFAMP P14B (decyloxypropyl alcohol). Min), SURFAM P16A (Linear C<sub>16</sub>), SURFAM P17B (tridecyloxypropylamine) Illustrated by those identified as SU described above and used later The chain length of RFAMs (ie, C<sub>14</sub>Carbon chain length) is an approximate value, -Contains an ether linkage.   In one embodiment, the amine is a tertiary aliphatic primary amine. In general, The aliphatic group (preferably an alkyl group) has from about 4 to about 30 carbon atoms, or It contains from about 6 to about 24 carbon atoms, or from about 8 to about 22 carbon atoms. Normal This tertiary alkyl primary amine has the formula R<sub>1</sub>−C (R<sub>1</sub>')<sub>Two</sub>−NH<sub>Two</sub>The model represented by Noamine, where R<sub>1</sub>Is a hydrocarb containing 1 to about 27 carbon atoms Building group, and R<sub>1</sub>'Is a hydrocarbyl containing 1 to about 12 carbon atoms Group. Such amines are tertiary butylamine, tertiary hexylamine , 1-methyl-1-aminocyclohexane, tertiary octylamine, tertiary decylua Min, tertiary dodecylamine, tertiary tetradecylamine, tertiary hexadecyl Amines, tertiary octadecylamine, tertiary tetracosanylamine, and tertiary Exemplified by grade octacosanylamine.   Mixtures of amines are also useful for the purposes of the present invention. This type of amine blend Examples of compounds include "Primene 81R" (this is C<sub>11</sub>~ C<sub>14</sub>Tertiary alkyl primary amine ) And `` Primene JMT '' (this is₁₈~ C_{twenty two}Tertiary alk A similar mixture of primary amines), both from Rohm and Haas Company. Available. These tertiary alkyl primary amines and their preparation Is known to those skilled in the art. These tertiary alkyl primary useful for the purposes of the present invention Amines and their methods of preparation are described in U.S. Pat.No. 2,945,749, The contents of which are incorporated herein by reference for their teachings in this regard. ing.   In another embodiment, the amine is a secondary amine. Identification of secondary amine Examples of dimethylamine, diethylamine, dipropylamine, dibutylamine , Diamylamine, dihexylamine, diheptylamine, methylethylamine , Ethylbutylamine, ethylamylamine and the like. In one embodiment Means that the secondary amine is a cyclic amine (e.g., piperidine, piperazine, Holin, etc.).   In one embodiment, the dithiocarbamate compound (A) comprises one or more By reacting a dithiocarbamic acid or a salt thereof with an unsaturated amide, Prepared. Examples of unsaturated amides include acrylamide, N, N'-methylenebis (A Acrylamide), methacrylamide, crotonamide and the like. 1 implementation In embodiments, the dithiocarbamate-containing composition comprises diamylamine or dibutyamine. Derived from the reaction product of thiolamine and carbon disulfide, which To form dithiocarbamic acid or a salt thereof which is reacted with acrylamide. This Is a reaction product of dithiocarbamic acid or a salt thereof and an unsaturated amide, If it has another reactive NH group, the reaction product may further comprise a binding compound or With a coupling compound (e.g., formaldehyde or paraformaldehyde) Can be reacted. Reaction products of dithiocarbamic acid and its salts with unsaturated amides. Are disclosed in U.S. Pat.Nos. 4,758,362 (Butke) and 4,997,969 (Luciani). , These contents include dithiocarbamic acid and its salts, unsaturated amides, and Regarding the disclosure of those reaction products (including coupling products), Ginseng It is used as an idea.   In one embodiment, the ashless dithiocarbamate composition (A) comprises a dithiocarbamate. The reaction product of a mymic acid or its salt with an unsaturated acid, its anhydride or ester is there. Examples of unsaturated carboxylic acids and anhydrides include acrylic acid, methacrylic acid , Itaconic acid, maleic acid, fumaric acid and maleic anhydride. Insatiable If the sum carboxylic acid or its anhydride is used, the ester is dithiocarbamate Acid-unsaturated carboxylic acid or its anhydride adduct and an alcohol (e.g., Subsequent reaction with alcohols mentioned herein) can be formed. 1 implementation In embodiments, the alcohol has 1 to about 12 carbon atoms.   In one embodiment, the unsaturated carboxylic acid or anhydride or ester thereof includes , Maleic acid, fumaric acid, acrylic acid, methacrylic acid, itaconic acid, citracone Acids and their esters. This ester is of one of the following formulas: Can be expressed as: (R₁)_TwoC = C (R₁) C (O) OR_TwoOr R_TwoO- (O) C-HC = CH-C (O) OR_TwoThis Where each R₁And R_TwoIs independently hydrogen, or from 1 to about 18, or about A hydrocarbyl group having up to 12 or up to about 8 carbon atoms, wherein R₁Is , Hydrogen, or an alkyl group having 1 to about 6 carbon atoms. One embodiment Then, R₁Is preferably hydrogen or a methyl group.   Examples of unsaturated carboxylic acid esters include methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, methacrylic acid Chill, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, ethyl maleate, butyl maleate and 2-ethylhexyl maleate is included. The above list includes maleic acid and fuma Diesters as well as monoesters of luic and itaconic acids and their anhydrides Included. In one embodiment, the dithiocarbamic acid or salt thereof is Formed from ruamine or dibutylamine and carbon disulfide. Jichi obtained Ocarbamic acid is then reacted with methyl acrylate.   In another embodiment, the unsaturated carboxylic acid ester is a vinyl ester . This vinyl ester has the formula R₁CH = CH-O (O) CR_TwoWhere R₁Is A hydrocarbyl group having 1 to about 30 or up to about 12 carbon atoms , Preferably hydrogen and R_TwoIs from 1 to about 30, or up to about 12, Or a hydrocarbyl group having up to about 8 carbon atoms. Vinyl ester Examples include vinyl acetate, vinyl 2-ethylhexanoate, vinyl butanoate, etc. Is done.   In one embodiment, the dithiocarbamate compound (A) is dithiocarbamic acid Or a reaction product of a salt thereof and vinyl ether. This vinyl ether , Formula R₁-CH = CH-OR_TwoWhere R₁Is independently hydrogen, or 1 Having up to about 30, or up to about 24, or up to about 12 carbon atoms. Drocarbyl group. R_TwoIs R₁Is a hydrocarbyl group defined similarly to Examples of vinyl ethers include methyl vinyl ether, propyl vinyl ether, Ethylhexyl vinyl ether and the like are included.   In one embodiment, the dithiocarbamate compound (A) is It is a ringed dithiocarbamate. Alkylene useful in the present invention is coupled The dithiocarbamate can then be combined with the dithiocarbamic acid salt described above with the appropriate dihalogen Prepared by reaction with hydrocarbon containing hydrocarbons. The reaction is generally performed at about 25 ° C. Performed at a temperature in the range of from about 150 ° C to about 150 ° C, or up to about 100 ° C. Departs for Holubec Issued U.S. Pat.No. 3,876,550 describes alkylenedithiocarbamate compounds. U.S. Patent Nos. 1,726,647 and 1,731, issued to Cadwell, Inc. No. 6,429 describes phenylmethylene bis (dithiocarbamate) and its production method. Has been described. These patents disclose dithiocarbamate compounds and their preparation. The teachings relating to the manufacturing method are incorporated herein by reference. 1 implementation In an embodiment, the alkylene-coupled dithiocarbamate is di-carbamate.n-B Derived from tylamine, carbon disulfide and methylene dichloride.   In another embodiment, the dithiocarbamate compound is a bis (S-alkyldithi Ocarbamoyl) disulfide. These substances were previously sulfur It was called a pulled dithiocarbamate. This disulfide is (A) A substantially stoichiometric equivalent of (i) at least one olefinic Hydrocarbon or (ii) aldehyde or ketone is converted to di (halohydrocarbyl) io Temperature sufficient to produce the intermediate or dialdehyde or diketosulfur intermediate. And for (B) both halo groups Replace with bamate group or carbonyl of both dialdehyde or diketone The intermediate and dithiocarbamate are generally present in an amount sufficient to react with It is prepared by reacting with a salt. Halogen used in the first step (A) Sulfur chloride is sulfur monochloride (i.e., S_TwoCl_Two), Sulfur dichloride, sulfur monobromide, Various types of sulfur dibromide or any of the above sulfur halides and elemental sulfur It can be a mixture in quantity.   Various olefins and olefin mixtures are used as starting materials in step (A). Can be used. These olefins are disclosed below for organic polysulfides. Have been. Specific examples of aldehydes that can be reacted with sulfur halides include, for example, For example, acetaldehyde, propionaldehyde, butyraldehyde, isobutyl Aldehydes, 2-ethylhexanal, and cyclohexanecarboxyaldehyde C. Examples of ketones include dimethyl ketone, methyl ethyl ketone, die Includes tyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, etc. It is.   The reaction between this sulfur intermediate and the dithiocarbamate is generally carried out from room temperature. The reaction is carried out up to the reflux temperature of the mixture. This reaction takes place until the reaction is complete (general About 5 hours to about 24 hours). In the final stage of the reaction, the aqueous phase is separated The product is recovered from the organic phase.   This bis (S-alkyldithiocarbamoyl) disulfide also provides (A) Reacting a halogenated hydrocarbon with a halogen to produce a halogen-containing intermediate; and And (B) an existing halogen group with a dithiocarbamate group and / or sulfide The intermediate and the dithiocardimate alkane in an amount sufficient to partially replace Prepared by a method comprising reacting a metal sulfide and a salt. obtain. This bis (S-alkyldithiocarbamoyl) disulfide was published by Rudel et al. No. 2,599,350 issued. The content of this patent is For the disclosure of (alkyldithiocarbamoyl) disulfide, refer to It has been adopted as.Phosphorus or boron reagent :   As described above, the molybdenum-containing composition salt comprises (i) an organic sulfide or Is an ashless dithiocarbamate-containing composition, and (ii) a metal thiophosphate, Ter or its salt, phosphorus-containing carboxylic acid, its ester, its ether or its Amides, borated dispersants, alkali metal borates, borated fatty amines, At least one selected from the group consisting of borated phospholipids and borate esters Also used in combination with one phosphorus- or boron-containing antiwear / extreme pressure agent . The phosphorus-containing or boron-containing reagent is typically used in lubricants and functional fluids. At about 20% by weight based on the total weight of this lubricant, functional fluid or grease Up to levels, preferably up to about 10% by weight. Typical This phosphorus- or boron-containing antiwear / extreme pressure agent is a lubricant and functional fluid From about 0.1% by weight, or from about 0.5% by weight, or from about 0.8% by weight At the level, exist. This phosphorus- or boron-containing antiwear or extreme pressure The agent may be present in an amount up to about 10%, or up to about 3%, or up to about 2% by weight, Existing. In one embodiment, the lubricating composition, functional fluid and grease comprise: Contains more than 0.01% phosphorus, or more than 0.05% phosphorus.   Examples of phosphorus-containing or boron-containing antiwear / extreme pressure agents include metal thiophosphates; phosphoric acid Esters or salts thereof; phosphorus-containing carboxylic acids, esters, ethers or salts thereof Amides; borate dispersants; alkali metal borates; borated fatty amines; boric acid Chlorinated phospholipids; and borate esters. These phosphorus-containing acids include: Phosphoric, phosphonic, phosphinic and thiophosphoric acids (including dithiophosphoric acid And monothiophosphoric acid), thiophosphinic acid and thiophosphonic acid No.   In one embodiment, the phosphorus or boron containing antiwear / extreme pressure agent is one or more. More than one phosphorus-containing acid or anhydride and one or about three carbon sources The phosphorus-containing acid ester prepared by reacting It is. The alcohol is generally up to about 30, or up to about 24, or Contains up to about 12 carbon atoms. The phosphorus-containing acid or anhydride is generally An inorganic phosphorus-containing reagent (e.g., phosphorus pentoxide, phosphorus trioxide, phosphorus tetroxide, phosphoric acid, Phosphorous acid, phosphorus halide, lower phosphorus-containing ester, or phosphorus sulfide (Li pentasulfide) N ) Etc.). Preferred phosphorus-containing acids or anhydrides are phosphorus pentoxide, Phosphorus pentasulfide and phosphorus trichloride. The lower phosphorus acid esters are generally The stell group contains from 1 to about 7 carbon atoms. This phosphorus-containing acid ester Can be a monophosphate, diphosphate or triphosphate . The alcohol used to prepare this phosphorus acid ester includes butyl alcohol. Alcohol, amyl alcohol, 2-ethylhexyl alcohol, hexyl alcohol Octyl alcohol, oleyl alcohol, and phenol (e.g., Cresol). Examples of commercially available alcohols include Alfol 810 (8 to 1 A mixture of mainly linear primary alcohols having 0 carbon atoms); Alfol 12 18 (mixture of synthetic primary linear alcohols containing 12 to 18 carbon atoms); Alfol 20 + alcohol (mostly determined by GLC (gas liquid chromatography) Throat C₂₀C with alcohol₁₈~ C₂₈A mixture of primary alcohols); and Alfol 22+ alcohol (mainly C_{twenty two}C containing alcohol₁₈~ C₂₈Primary alcohol) Included. Alfol alcohol is commercially available from Continental Oil Company .   Other examples of commercially available alcohol mixtures include Adol 60 (which comprises about 75% by weight of linear C_{Two Two} Primary alcohol, about 15% by weight C₂₀Primary alcohol, and about 8% by weight C_{1 8} And C_{twenty four}Alcohol) and Adol 320 (oleyl alcohol) ). These Adol alcohols are sold by Ashland Chemical.   Derived from naturally occurring triglycerides and C₈~ C₁₈Fats in the chain length range of Various mixtures of alcohols are available from Procter & Gamble Company. this These mixtures are predominantly oils containing 12, 14, 16 or 18 carbon atoms. Fat alcohols are included in various amounts. For example, CO-1214 is 0.5% C_TenArco , 66.0% C₁₂Alcohol, 26.0% C₁₄Alcohol and 6.5% C₁₆Arco A mixture of fatty alcohols containing alcohol.   Another group of commercially available mixtures includes "Neodol" raw material available from Shell Chemical Co. Products are included. For example, Neodol 23 is C₁₂And C₁₃A mixture of alcohols; N eodol 25 is C₁₂And C_FifteenA mixture of alcohols; and Neodol 45 is C₁₄~ C_Fifteen It is a mixture of linear alcohols. Neodol 91 is C₉, C_TenAnd C₁₁Alcow Is a mixture of   Fat flank diols may also be useful. Fat adjacent diols include Adol 114 and And Adol 158 under the generic trade name available from Ashland Oil. Previous Is C₁₁~ C₁₄Derived from the linear α-olefin fraction of_Fifteen~ C₁₈α -Derived from the olefin fraction.   Examples of useful phosphorus acid esters include phosphoric acid or its anhydride and cresol Phosphate esters prepared by reacting with alcohols are included. This An example of these phosphorus acid esters is tricresyl phosphate.   In another embodiment, the phosphorus- or boron-containing antiwear / extreme pressure agent is thiolyzed. Or a salt thereof. This thiophosphorus acid ester is Reacting phosphorus hydride (e.g., as described above) with an alcohol (e.g., as described above) Can be prepared. This thiophosphorus acid ester contains monothiophosphoric acid. It can be an acid ester or a dithiophosphorus acid ester. Thioline-containing acid S Ter is also commonly referred to as thiophosphoric acid.   In one embodiment, the phosphorus acid ester is a monothiophosphate, That is, it is monothiophosphate. Monothiophosphate esters are compatible with sulfur sources. It can be prepared by reaction with dihydrocarbyl phosphate. This sulfur source, for example, If so, it can be elemental sulfur. This sulfur source can also be a monosulfide (e.g., Ole-coupled olefins or sulfur-coupled dithiolines Acid ester). Elemental sulfur is a preferred sulfur source. Monothioli Preparation of acid esters is described in U.S. Pat.No. 4,755,311 and PCT Publication WO 87/07638. Disclosed are monothiophosphates, sulfur sources, and monothiophosphates. Regarding the disclosure of the method for producing phosphoric acid ester, it is incorporated herein by reference. ing. Monothiophosphates can be used in a lubricant blend in a sulfur source (e.g., Dihydrocarbyl phosphite to lubricating compositions containing And can be formed. The phosphite is blended under blending conditions (i.e., (About 30 ° C. to about 100 ° C. or higher), and It is possible to form a notthiophosphate ester.   In another embodiment, the phosphorus or boron containing antiwear or extreme pressure agent is , Dithiophosphoric acid or phosphorodithioic acid. This dithiophosphoric acid has the formula (RO)_TwoPSS H, where each R is independently from about 3 to about 30 carbon atoms A hydrocarbyl group containing an offspring. R is generally up to about 18, or about 12 Or up to about 8 carbon atoms. Examples of R include an isopropyl group, Isobutyl group, n-butyl group, sec-butyl group, various amyl groups, n-hexyl group, Tyl isobutyl carbyl group, heptyl group, 2-ethylhexyl group, isooctyl Group, nonyl group, behenyl group, decyl group, dodecyl group and tridecyl group. It is. Exemplary lower alkylphenyl groups R include butylphenyl, amylphenyl , Heptylphenyl and the like. Examples of mixtures of R groups include: 1-butyl and 1-octyl; 1-pentyl and 2-ethyl-1-hexyl; iso Butyl and n-hexyl; isobutyl and isoamyl; 2-propyl and 2-methyl Tyl-4-pentyl; isopropyl and sec-butyl; And isooctyl.   In one embodiment, the dithiophosphoric acid is reacted with an epoxide or glycol. Can be This reaction product can be used alone or It can be further reacted with hydrates or lower esters. This epoxide is generally Aliphatic epoxide or styrene oxide. Examples of useful epoxides include Tylene oxide, propylene oxide, butene oxide, octene oxide, Decene oxide, styrene oxide and the like are included. Propylene oxide is preferred Good. The glycol has from 1 to about 12 carbon atoms, or from about 2 to about 6 carbon atoms. An aliphatic glycol having carbon atoms, or 2 or 3 carbon atoms, or It can be an aromatic glycol. Glycols include ethylene glycol and propylene Glycol, catechol, resorcinol and the like. These dithio Phosphoric acid, glycol, epoxide, inorganic phosphorus-containing reagents and their reaction methods Are described in U.S. Patent Nos. 3,197,405 and 3,544,465, the contents of which are The disclosures of which are incorporated herein by reference.   Examples P-1 and P-2 below illustrate the preparation of useful phosphorus acid esters.                                 Example P-1   Phosphorus pentoxide (64 grams) was treated with 0,0-di (4-methyl-2-pentene) at 58 ° C for 45 minutes. 514 grams of hydroxypropyl phosphorodithioate (this is (Tyl-2-pentyl) phosphorodithioic acid and 1.3 moles of propylene oxide And prepared). The mixture was heated at 75 ° C. for 2.5 hours, Mix with diatomaceous earth and filter at 70 ° C. The filtrate contains 11.8% by weight of phosphorus, Contains 15.2% by weight sulfur and an acid number of 87 (bromophenol blue).                                 Example P-2   With 667 grams of phosphorus pentoxide and 3514 grams of diisopropyl phosphorodithioic acid Mix the reaction product at 50 ° C. with 986 grams of propylene oxide at 85 ° C. for 3 hours Heat for a while and filter. The filtrate contains 15.3% by weight of phosphorus and 19.6% by weight of And an acid value of 126 (bromophenol blue).   Acidic phosphate esters react with amine compounds or metal bases to form amines or amines. Can form metal salts. These salts are formed separately and then the phosphorus-containing Acid ester salts may be added to the lubricating composition. On the other hand, acidic phosphorus-containing acid When the lubricant is blended with other ingredients to form a fully formulated lubricating composition, These salts may also be formed in situ.   The amine salt of the phosphorus acid ester may be ammonia or an amine (monoamine And polyamines). These amines are primary amines Can be a secondary, secondary or tertiary amine. In one embodiment, the amine Is one or more of the above amines for preparing dithiocarbamates. helpful Amines include those disclosed in U.S. Pat.No. 4,234,435 at column 21, line 4 to column 27, line 50. And the contents of these sections are incorporated herein by reference.   These monoamines generally contain from 1 to about 24 carbon atoms, or about 12 carbon atoms. It contains up to, or up to, about 6 carbon atoms. Examples of monoamines Is methylamine, ethylamine, propylamine, butylamine, octylua Min, and dodecylamine, dimethylamine, diethylamine, dipropylamine Min, dibutylamine, methylbutylamine, ethylhexylamine, trimethyl Ruamine, tributylamine, methyldiethylamine, ethyldibutylamine, etc. And so on.   In one embodiment, the amine is a fat (C_4-30) Amines, which include n -Hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n- Tetradecylamine, n-hexadecylamine, n-octadecylamine, oleyl Amines and the like. Also useful fatty amines include commercially available fatty amines, e.g., For example, the "Armeen" amine (available from Armak Chemicals (Chicago, Illinois) Products), for example, Armaken-C, Armen-O, Armen-OL. Armeen- T, Armeen-HT, Armeen S, and Armeen SD, where the alphabet The name refers to an aliphatic group (e.g., a cocoa group, an oleyl group, a taro group, or a soya group). .   Other useful amines include primary ether amines, such as those of the formula R "(OR ')_xNH_TwoBy Wherein R ′ has about 2 to about 6 carbon atoms X is a number from 1 to about 150 (preferably 1); and R "is Hydrocarbyl groups having 5 to about 150 carbon atoms. Ether amine (Manufactured and sold by the Company). Preferred ether amine Are SURFAM P14B (decyloxypropylamine), SURFAM P16A (linear C₁₆), SURFA Illustrated by what is identified as MP17B (tridecyloxypropylamine) It is. The carbon chain length of SURFAMs described above and used hereinafter (i.e., C₁₄Such Is an approximate value and includes an oxygen-ether bond.   In one embodiment, the amine can be a hydroxyamine. Typically, this Is a primary, secondary or tertiary alkanolamine or Is a mixture thereof. Such an amine is represented by the formula: H_Two−N -R'-OH, H (R '₁) N-R'-OH, and (R '₁)_Two-N-R'-OH. Where each R '₁Is independent And a hydrocarbyl group having 1 to about 8 carbon atoms, or 1 to about 8 Or a hydroxyhydrocarbyl having 1 to about 4 carbon atoms And R ′ is from about 2 to about 18 carbon atoms, or from 2 to about 4 carbon atoms. A divalent hydrocarbyl group having an atom. The -R'-OH group in these formulas is Represents a xyhydrocarbyl group. R ′ is an acyclic group, an alicyclic group or an aromatic group. Can get. Typically, R ′ is an acyclic straight or branched chain alkylene group (e.g., Ethylene group, propylene group, 1,2-butene group, 1,2-octadecene group, etc.). Two R's in the same molecule₁When groups are present, they are attached to a direct carbon-carbon bond. Or through a heteroatom (e.g., oxygen, nitrogen or sulfur) It may form a six-, six-, seven- or eight-membered ring structure. like this Examples of heterocyclic amines include N- (hydroxyl lower alkyl) -morpholine, -thiomo Ruphorin, -piperidine, -oxazolidine, -thiazolidine and the like. . However, typically, each R '₁Is independently a methyl group, an ethyl group, A pill, butyl, pentyl or hexyl group. These alkanols Examples of amines include mono-, di- and triethanolamine, diethyl ethanol Lamine, ethylethanolamine, butyldiethanolamine, etc. You.   The hydroxyamine is also an ether-N- (hydroxyhydrocarbyl) amide Can be These are the above-mentioned hydroxyamine hydroxypoly (hydrocarbyl) (Vyloxy) analogs (these analogs include hydroxyl-substituted oxyalkyl Len analogs are also included). Such N- (hydroxyhydrocarbyl) Mines are conveniently prepared by the reaction of one or more of the epoxides with the amines. Can be conveniently prepared and represented by the formula: H_TwoN- (R'O)_x−H, H (R '₁) −N− ( R'O)_x−H, and (R ′₁)_TwoN- (R'O)_x-H. Where x is a number from about 2 to about 15, And R₁And R 'are the same as described above. R '₁Is also It may be a tri (hydrocarbyloxy) group.   These amines are hydroxyamines (e.g., represented by the following formula): Can:   Where R₁Is generally a hydrocarbyl containing from about 6 to about 30 carbon atoms Is a group; R_TwoAnd each R_ThreeIs independently an alkyl containing up to about 5 carbon atoms A is a ren group, preferably an ethylene or propylene group; a is 0 or 1 And each z is independently a number from 0 to about 10, provided that at least one of z is Is at least 1. These hydroxyamines are known to those of skill in the art. And many such hydroxyamines are commercially available. These hydroxyamines include fatty oils (e.g., tallow oil, black whale oil, coco And amine mixtures obtained by hydrolysis of nut oils and the like. About 6 ~ Specific examples of fatty amines containing about 30 carbon atoms include saturated aliphatic amines and And unsaturated aliphatic amines (e.g., octylamine, decylamine, laurylamine). , Stearylamine, oleylamine, dodecylamine and octadecylamine Min) are included.   Useful hydroxyamines of the above formula wherein a is 0 include 2-hydroxyethylhexyl Lamine, 2-hydroxyethyloctylamine, 2-hydroxyethylpentadecyl Luamine, 2-hydroxyethyl oleylamine, 2-hydroxyethyl soyamine , Bis (2-hydroxyethyl) hexylamine, bis (2-hydroxyethyl) oley Luamine, and mixtures thereof. In the above formula, at least one of z is At least two similar elements, for example, 2-hydroxyethoxyethylhexyl Amines are also included.   Many hydroxyamines where a is 0 in the above formula are described in Akzona, Inc. (Chicago, Il. linois) from the Armak Chemical Division, "Ethomeen" and "Propomeen" It is available under a common product name. Specific examples of such products include: Ethomeen C / 15 (this is the ethylene oxide condensate of cocoalkylamine And contains about 5 moles of ethylene oxide); Ethomeen C / 20 and C / 25 (this These are also ethylene oxide condensation products of cocoalkylamines, Containing about 10 and 15 moles of ethylene oxide); Ethomeen O / 12 (this It is the ethylene oxide condensation product of oleylamine, one mole of amine Ethomeen S / 15 and S / 20 (containing about 2 moles of ethylene oxide); These are the ethylene oxide condensation products of stearylamine, Containing about 5 and 10 moles of ethylene oxide per mole of amine); E thomeen T / 12, T / 15 and T / 25 (these are ethylene oxide condensations of tallow amine Products, each containing about 2 moles, 5 moles and 15 moles per mole of amine. Propomeen O / 12 (which contains 1 mole of ethylene oxide); A condensation product of railamine with 2 moles of propylene oxide).   Commercially available examples of alkoxylated amines wherein a in the above formula is 1 include Ethoduomeen T / 13 and T / 20, which are the ethylene of N-taro trimethylenediamine. Oxide condensation products, 3 moles and 1 mole per mole of diamine, respectively. Contains 10 moles of ethylene oxide.   The amine can also be a polyamine. The polyamine includes alkoxy Diamine, fatty diamine, alkylene polyamine, hydroxy-containing polyamide , Fused polyamines, and heterocyclic polyamines. Alkoxylated di Commercial examples of amines include those where a in the above formula is 1. These Examples of mins include Ethoduomeen T / 13 and T / 20, which are N-tarots. Ethylene oxide condensation products of rimethylenediamine, each of Contains 3 and 10 moles of ethylene oxide per diamine.   In another embodiment, the polyamine is a fatty diamine. This fatty diamine Include mono- or di-alkyl symmetric or asymmetric ethylene diamines, Lopanenediamine (1,2 or 1,3), and the above polyamine analogs. Suitable Distinct commercially available fatty polyamines include Duomeen C (N-coco-1,3-diaminopropane), Du omeen S (N-soya-1,3-diaminopropane), Duomeen T (N-taro-1,3-diaminopropane) Bread), and Duomeen O (N-oleyl-1,3-diaminopropane). "Duomeen Are commercially available from Armak Chemical Co. (Chicago, Illinois).   In another embodiment, the amine is an alkylene polyamine. Alkylene Polyamines have the formula H (R₁) N- (Alkylene-N)_n-(R₁)_TwoWhere each R₁Is Independently hydrogen, or an aliphatic group having up to about 30 carbon atoms or a hydro Is a xy-substituted aliphatic group; n is a number from 1 to about 10, or a number from about 2 to about 7, or A number from about 2 to about 5 and wherein the "Alkylene" group has 1 to about 10 carbon atoms Or having about 2 to about 6 carbon atoms, or about 2 to about 4 carbon atoms . In other embodiments, R₁Is R '₁Is defined similarly. Such an archi Methylene polyamine, ethylene polyamine, butylene polyamine Examples include amines, propylene polyamines, pentylene polyamines, and the like. this Higher homologs and related heterocyclic amines (e.g., piperazine) and N- Minoalkyl-substituted piperazines are also included. Such a polyamine Specific examples of ethylenediamine, triethylenetetramine, tris (2- (Minoethyl) amine, propylenediamine, trimethylenediamine, Lentetramine, triethylenetetramine, tetraethylenepentamine, hexa Examples include ethylene heptamine and pentaethylene hexamine. 2 or more The higher homologues obtained by condensation of the above alkyleneamines are two or Are useful, as are mixtures of more of the above polyamines.   In one embodiment, the polyamine is an ethylene polyamine. Such a port Liamine is Kirk Othmer's "Encyclopedia of Chemical Technology" (2d version, 7, pages 22-37, Interscience Publishers, New York (1965)) Lene Amines ". Ethylene polyamine is often For example, it is a polyalkylene polyamine complex mixture including a cyclic condensation product. other Useful types of polyamine mixtures include stripping of the above polyamine mixtures. Can leave a residue often called "polyamine bottoms" There is something. Generally, alkylene polyamine bottoms boil below about 200 ° C. Containing less than 2% by weight, usually less than 1% by weight As can be characterized. Obtained from Dow Chemical Company (Freeport, Texas) A representative sample of such ethylene polyamine bottoms (this is `` E-100 '' Has a specific gravity of 1.0168 at 15.6 ° C., a nitrogen percentage of 33.15% by weight, and It has a viscosity of 121 centistokes at 40 ° C. Gas chromatography of such samples According to Raffy analysis, this was approximately 0.93% by weight of "Light Ends" (probably Ethylene triamine), 0.72% by weight triethylene tetramine, 21.74% by weight % Tetraethylenepentamine, and 76.61% by weight pentaethylenehexamine And higher analogues. These alkylene polyamine bots Muss contains cyclic condensation products (e.g., piperazine), and diethylenetriamine. And higher analogs such as triethylenetetramine. These The alkylene polyamine bottoms react only with the acylating agent or , Polyamines or mixtures thereof.   Other useful polyamines include at least one hydroxy compound and at least one At least one polymer containing one primary or secondary amino group; It is a condensation reactant with a min reactant. The hydroxy compound is preferably Polyhydric alcohols and polyamines. These polyhydric alcohols are described below. Has been described. In one embodiment, the hydroxy compound is a polyamine. Polyamines have from 2 to about 20 carbon atoms, or from 2 to about 4 carbon atoms. Alkylene oxides (e.g., ethylene oxide, propylene oxide, Any of the above monoamines that have been reacted with ethylene oxide (such as tylene oxide). Polyvalent Examples of amines include tri- (hydroxypropyl) amine, tris- (hydroxymethine). Tyl) aminomethane, 2-amino-2-methyl-1,3-propanediol, N, N, N ', N'-te Thrakis (2-hydroxypropyl) ethylenediamine and N, N, N ', N'-tetraki Tris (2-hydroxyethyl) ethylenediamine, preferably tris (hydroxymethyl Tyl) aminomethane (THAM).   Reacts with this polyhydric alcohol or amine to form a condensation product or condensed amine. The polyamines that can be formed are described above. Preferred polyamines include trie Tylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylene Oxamine (PEHA), and polyamine mixtures (e.g., "amine bottoms" above) Is included. The condensation reaction between the polyamine reactant and the hydroxy compound High temperature (usually about 60 ° C to about 265 ° C, or about 220 ° C to about 250 ° C) in the presence of an acid catalyst Done in   This amine condensate and a method for producing the same are described in PCT Publication WO86 / 05501 and U.S. Pat. No. 5,230,714 (Steckel), which describes this condensate and its method of manufacture. The disclosure of the Act is incorporated herein by reference. Particularly useful amines The condensate is an amine bottle commercially available from HPA Taft Amines (Union Carbide Co.). And typically has 34.1% by weight of nitrogen, 12.3% by weight of a primary amine, With 14.4% by weight secondary amine and 7.4% by weight tertiary amine), and Tris ( Prepared from (hydroxymethyl) aminomethane (THAM).   In another embodiment, the polyamine is a polyoxyalkylene polyamine, e.g., For example, polyoxy having an average molecular weight in the range of about 200 to about 4000 or about 400 to about 2000. These are silalkylenediamines and polyoxyalkylenetriamines. preferable Polyoxyalkylene polyamines include polyoxyethylene and polyoxypropylene. Ropylenediamine, and polyoxypropylenetriamine. this Polyoxyalkylene polyamines are commercially available, for example, Jefferson Chemic al Company, "Jeffamines D-230, D-400, D-1000, D-2000, T-403 etc." Obtained by trade name. The contents of U.S. Patent Nos. 3,804,763 and 3,948,800 Polyoxyalkylene polyamines and acylated products produced therefrom Is incorporated herein by reference.   In another embodiment, these polyamines are hydroxy-containing polyamines . Hydroxy-containing polyamine analogs of hydroxy monoamines, especially alkoxy Alkylated polyamines (e.g., N, N (diethanol) ethylenediamine) Can be used. Such polyamines may be used alone or in combination Can be produced by reacting with the above alkylene oxide. Similar alkylene oxide-alkanolamine reaction products (e.g., Primary, secondary or tertiary alkanolamines, ethylene oxide, propylene Oxides or higher epoxides in a molar ratio of 1.1 to 1.2. The products prepared by the above) can also be used. The reaction to perform such a reaction Reaction ratios and temperatures are known to those skilled in the art. Specific of hydroxy-containing polyamines Examples include N- (2-hydroxyethyl) ethylenediamine, N.N'-bis (2-hydroxy Ethyl) ethylenediamine, 1- (2-hydroxyethyl) piperazine, mono (hydroxy (Cipropyl) -substituted tetraethylenepentamine, N- (3-hydroxybutyl) tetrame Tylenediamine and the like are included. Amines of the hydroxy-containing polyamines exemplified above Higher homologues obtained by condensation via a hydroxyl or hydroxyl group are likewise useful. is there. Condensation via amino groups, with removal of ammonia, higher amines Is obtained, but by condensation through a hydroxyl group, A product is obtained which contains a thiol bond. Any two or more of the above polyamines The above mixtures are also useful.   In another embodiment, the amine is a heterocyclic polyamine. This heterocyclic poly Amines include aziridine, azetidine, azolidine, tetra- and dihydropyridines. Lysine, pyrrole, indole, piperidine, imidazole, di- and tetra Hydroimidazole, piperazine, isoindole, purine, morpholine, thio Morpholine, N-aminoalkyl morpholine, N-aminoalkyl thiomorpholine, N-aminoalkylpiperazine, N, N'-diaminoalkylpiperazine, azepine, Azocin, azonine, azecine and the respective tetra-, di- and And perhydro derivatives, and mixtures of two or more of these heterocyclic amines Is mentioned. Preferred heterocyclic amines include nitrogen, oxygen and / or Saturated 5- and 6-membered heterocyclic amines containing only sulfur, especially Peridine, piperazine, thiomorpholine, morpholine, pyrrolidine and the like. Piperidine, aminoalkyl-substituted piperidine, piperazine, aminoalkyl-substituted Piperazine, morpholine, aminoalkyl-substituted morpholine, pyrrolidine, and Aminoalkyl-substituted pyrrolidines are particularly preferred. Usually this aminoalkyl The substituents are substituted on the nitrogen-forming part of the heterocycle. Such a heterocyclic amine Specific examples of N-aminopropylmorpholine, N-aminoethylpiperazine, And N, N'-diaminoethylpiperazine. Hydroxy heterocyclic polya Min is also useful. Examples include N- (2-hydroxyethyl) cyclohexylamido , 3-hydroxycyclopentylamine, parahydroxyaniline, N-hydroxy And siethylpiperazine.   This metal salt of a phosphorus-containing acid ester is obtained by reacting a metal base with a phosphorus-containing acid ester. Is prepared by The metal base can be any metal compound capable of forming a metal salt. Things. Examples of metal bases include metal oxides, hydroxides, carbonates, sulfates, Borate and the like. The metals of this metal base include Group IA, IIA, and IB To Group VIIB and Group VIII (CAS type of Periodic Table of Elements) metals. this These metals include alkali metals, alkaline earth metals and transition metals. In one embodiment, the metal is a Group IIA metal (eg, calcium or magnesium). A Group IIB metal (e.g., zinc) or a Group VIIB metal (e.g., manganese). You. Preferably, the metal is magnesium, calcium, manganese or zinc It is. Examples of metal compounds that can react with this phosphorus-containing acid include zinc hydroxide, zinc oxide, Lead, copper hydroxide, copper oxide and the like are included.   In one embodiment, the phosphorus or boron containing antiwear / extreme pressure agent is a gold thiophosphate. Genus, preferably metal dithiophosphate. This metal thiophosphate is known to those skilled in the art. It can be prepared by known methods. Examples of metal dithiophosphates include isopropylmethyl Zinc amyl dithiophosphate, zinc isopropylisooctyldithiophosphate, Nil) barium dithiophosphate, zinc di (cyclohexyl) dithiophosphate, (Tyl) zinc dithiophosphate, calcium di (hexyl) dithiophosphate, Zinc soamyl dithiophosphate and zinc isopropyl secondary butyl dithiophosphate Is included.   Examples P-3 to P-6 below illustrate the preparation of useful phosphorus acid ester salts.                                 Example P-3   A reaction vessel is charged with 217 grams of the filtrate of Example P-1. Commercially available aliphatic primary amine (66 grams) (which has an average molecular weight of 191 where 11 aliphatic groups A mixture of tertiary alkyl groups containing 1414 carbon atoms) at 25-60 ° C. Add over 0 minutes. The product obtained has a phosphorus content of 10.2% by weight, 1.5% by weight. % Nitrogen content and an acid number of 26.3.                                 Example P-4   According to the methods of Examples P-1 and P-3, 1320 parts of the product described in P-1 were And 584 parts. This final product has 8.4% phosphorus and 10% sulfur .                                 Example P-5   The filtrate of Example P-2 (1752 grams) was treated at 25-82 ° C with the aliphatic primary used in Example P-3. Mix with 764 grams of secondary amine. The resulting product is 9.9% phosphorus, 2.7% nitrogen , And 12.6% sulfur.                                 Example P-6   Phosphorous pentoxide (852 grams) was added over 3 hours to isooctyl alcohol 2340 Add to grams. Raise temperature from room temperature but keep it below 65 ° C. This addition is complete When complete, heat the reaction mixture to 90 ° C. and maintain this temperature for 3 hours . Diatomaceous earth is added to the mixture and the mixture is filtered. The filtrate is 12.4% Phosphorus, 192 acid neutralization number (bromophenol blue) and 290 acid neutralization number Olephthalein).   200 g of toluene, 130 g of mineral oil, 1 g of acetic acid, 10 g of water , And mix with 45 grams of zinc oxide. This mixture is subjected to a pressure of 30 mm Hg, Heat to 60-70 ° C. The resulting product mixture is filtered using diatomaceous earth You. The filtrate has 8.6% zinc and 7.0% phosphorus.                                 Example P-7   Heat Alfol 8-10 (2628 parts, 18 moles) to a temperature of about 45 ° C, where Over time, 852 parts (6 moles) of phosphorus pentoxide were added while the reaction temperature was raised to about 45 ° C. And maintain between 65 ° C. The mixture is stirred at this temperature for a further 0.5 h, Thereafter, the mixture is stirred at 70 ° C. for about 2 to 3 hours. While maintaining this temperature between about 30 ° C and 50 ° C, Primene 81-R (2362 parts, 12.6 mol) is added dropwise to the reaction mixture. All amines Was added, the reaction mixture was filtered through a filter aid and the filtrate was phosphorus 7. Desired amine salt containing 4% (theoretical, 7.1%).                                 Example P-8   280 grams of propylene oxide and 1184 grams of 0,0'-diisobutyl phosphorodithioic acid The product prepared by reacting the product at 30-60 ° C with phosphorus pentoxide (208 ). This addition is carried out at a temperature of 50-60 ° C. and the resulting mixture is then Heat to 80 ° C. and hold at this temperature for 2 hours. Keep the temperature in the range of 30-60 ° C Meanwhile, the mixture was added to the commercially available aliphatic primary amine identified in Example P-3 (384 grams). ). The reaction mixture is filtered over diatomaceous earth. The filtrate contains 9.3% 11.4% sulfur, 2.5% nitrogen, and a base number of 6.9 (bromophenol blue). -Indicator).   In another embodiment, the phosphorus- or boron-containing antiwear / extreme pressure agent comprises (a) less At least one dithiophosphoric acid, and (b) at least one aliphatic or cycloaliphatic It is a metal salt of rubonic acid. The dithiophosphoric acid has been described above. This cal Bonic acid usually contains one to about three carboxylic acid groups, or exactly one carboxylic acid group. It may be a monocarboxylic or polycarboxylic acid containing an acid group. Preferred cal Bonic acid is of the formula RCOOH, where R is preferably acetylene An aliphatic or alicyclic hydrocarbyl group containing no carboxylic unsaturation. R is one Generally, it contains from about 2 or from about 4 carbon atoms. R is generally about 4 It contains up to 0, or up to about 24, or up to about 12 carbon atoms. 1 implementation In embodiments, R is from 4, or from about 6, up to about 12, or up to about 8 Containing carbon atoms. In one embodiment, R is an alkyl group. Suitable acids include , Butanoic acid, pentanoic acid, hexanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodeca Acid, octadecanoic acid and arachinic acid, but also olefinic acids (e.g. Oleic acid, linoleic acid, and linolenic acid and linoleic acid dimer). It is. A preferred carboxylic acid is 2-ethylhexanoic acid.   This metal salt is obtained by mixing a metal salt of dithiophosphoric acid and a metal salt of carboxylic acid in a desired ratio. Can be prepared by simply mixing. Of dithiophosphoric acid to carboxylic acid The equivalent ratio is from about 0.5 to about 400: 1. This ratio can range from 0.5 to about 200 or about 100 or It can be about 50 or about 20: 1. In one embodiment, the ratio is between 0.5 and about 4.5: 1. Or about 2.5 to about 4.25: 1. For this purpose, the equivalent of dithiophosphoric acid Is the molecular weight of the carboxylic acid divided by the number of -PSSH groups therein, and Is the value obtained by dividing the molecular weight by the number of carboxy groups therein.   A second preferred method of preparing metal salts useful in the present invention involves the desired proportion of acid (e.g., For example, a mixture of the individual metal salts described above) is prepared and the acid The mixture may be reacted with one of the above metal compounds. Use this preparation method Sometimes, a salt is prepared containing an excess of metal with respect to the number of equivalents of acid present. It is possible to Therefore, about 2 equivalents of metal per equivalent of acid, especially about Metal salts containing up to 1.5 equivalents of metal can be prepared. The metal equivalent for this purpose is , Its atomic weight divided by its valence. The temperature at which this metal salt is prepared is Generally, it is between about 30 ° C and about 150 ° C, preferably up to about 125 ° C. US special Nos. 4,308,154 and 4,417,990 describe methods for preparing these metal salts, And many examples of such metal salts are disclosed. The contents of these patents are These disclosures are incorporated herein by reference.   In one embodiment, the phosphorus-containing or boron-containing antiwear / extreme pressure agent comprises a phosphorus-containing Amides. The phosphorus-containing amide is one of the above-mentioned phosphorus-containing acids (preferably (Thiophosphoric acid) and one of the above unsaturated amides. This phosphorus The reaction product of the acid and the unsaturated amide is a bound compound or a coupling compound. (E.g., formaldehyde or paraformaldehyde). You. This phosphorus containing amide is known in the art and is disclosed in U.S. Pat.No. 4,670,169. Nos. 4,770,807 and 4,876,374, the contents of which are incorporated herein by reference. Including The disclosures of amides and their preparation are incorporated herein by reference. ing.   In one embodiment, the phosphorus-containing or boron-containing antiwear / extreme pressure agent comprises a phosphorus-containing It is a carboxylic acid ester. This phosphorus-containing carboxylic acid ester is An acid (preferably, dithiophosphoric acid) and the unsaturated carboxylic acid or an ester thereof. Prepared by reaction with one of the ters. If you use this carboxylic acid, Esters are obtained by adding the phosphoric acid-unsaturated carboxylic acid adduct and an alcohol (for example, the present invention). Subsequent reaction with those described in the text).   In one embodiment, the phosphorus-containing or boron-containing antiwear / extreme pressure agent comprises a phosphorus-containing A reaction product of an acid (preferably dithiophosphoric acid) and one of the above vinyl ethers. You.   In another embodiment, the phosphorus or boron containing antiwear / extreme pressure agent is an alkali Limetal borate. Alkali metal borates are generally known in the art. Is a hydrated particulate alkali metal borate. For alkali metal borates Mixed alkali and alkaline earth borates are included. These Lucali metal borates are commercially available. A suitable alkali metal borate, and Representative patents disclosing methods of making them include US Pat. No. 3,997,454; No. 3,819,521; No. 3,853,772; No. 3,907,601; No. 3,997,454; and No. 4,08. No. 9,790. These patents cover alkali metal borates, and The disclosure of their production methods is incorporated herein by reference.   In another embodiment, the phosphorus or boron containing antiwear / extreme pressure agent is boric acid. A chlorinated overbased compound, provided that this borated overbased The compound is different from (Bi) above. This borated overbased compound is Is described.   In another embodiment, the phosphorus or boron containing antiwear / extreme pressure agent is boric acid. It is a chlorinated fatty amine. The borated amine may include one or more of the above borated amines. A urine-containing compound and one or more of the above fatty amines (e.g., from about 4 to about 18 Prepared by reacting an amine having two carbon atoms). This e The urated fatty amine is present at about 50 ° C to about 300 ° C, preferably at about 100 ° C to about 250 ° C. , When the equivalent of the amine to the equivalent of the boron-containing compound is in the ratio of 3: 1 to 1: 3, And a boron-containing compound.   In another embodiment, the phosphorus or boron containing antiwear / extreme pressure agent is boric acid. Epoxide chloride. The borated fatty epoxide generally comprises one or more Reaction formation between the further boron-containing compound and at least one epoxide Things. The epoxide will generally have at least 8 and preferably about 10 , More preferably from about 12 to about 24, preferably up to 20 It is an aliphatic epoxide having a carbon atom. Examples of useful aliphatic epoxides include: Heptyl oxide, octyl oxide, stearyl oxide, oleyl oxide Etc. are included. Mixtures of epoxides, e.g. having 14 to about 16 carbon atoms Mixtures of epoxides and epoxides having 14 to about 18 carbon atoms Can also be used. The borated fatty epoxide is generally known No. 4,584,115. The content of this patent is borated fat The disclosure of fatty epoxides and their preparation methods is referred to herein. Has been used.   In another embodiment, the phosphorus or boron containing antiwear / extreme pressure agent is boric acid. It is a chloride phospholipid. This borated phospholipid contains phospholipid and boron-containing It is prepared by reacting the compound formulation. If necessary, this formulation Are amines, acylated nitrogen compounds (eg, carboxylic acylating agents and polyamines) With carboxylic acid esters (for example, a carboxylic acylating agent and Reaction product with coal and optionally amine), Mannich reaction product, Alternatively, it may contain a basic metal salt or a neutral metal salt of an organic acid compound. Phospholipids , Sometimes called phosphatides and phospholipins, which can be natural or synthetic You. Naturally derived phospholipids include fish, fish oil, shellfish, bovine brain, chicken eggs, sunflowers, And those derived from soy, corn and cottonseed. Phospholipids are fine It can be derived from organisms, including blue-green algae, green algae and bacteria.   The reaction of the phospholipid, boron-containing compound, and optional components is usually about It occurs at a temperature from 60 ° C to about 200 ° C, or from about 90 ° C to about 150 ° C. This reaction Typically completes in about 0.5 hours, or about 2 hours, to about 10 hours You. The boron-containing compound and the phospholipid have an atomic ratio of boron to phosphorus. About 1 to about 6: 1, preferably about 2 to about 4: 1, more preferably about 3: 1. Reacted in proportion. When this formulation contains additional components, The compound has an atomic ratio of boron to the equivalent of the mixture of the phospholipid and the optional components. From about (1: 1) to about (6: 1), or from about (2: 1) to about (4: 1). Reacting with a mixture of a phospholipid and one or more optional ingredients in an amount It is. The equivalents of this mixture depend on the equivalents of the phosphorus-based phospholipids and any components. Based on the equivalent of a combination of minute equivalents. This borated phospholipid is -European Patent Publication 540,700. The contents of this publication are It has been incorporated as a reference.   In another embodiment, the molybdenum-containing composition comprises (i) a borated overlayer. And (ii) containing organic polysulfide or ashless dithiocarbamate Use in combination with the composition and phosphorus or boron containing antiwear / extreme pressure agent Wear. These components have been described above.lubricant   As indicated above, the above combinations are useful in lubricants, where Primarily antiwear, welding, extreme pressure, corrosion inhibitors, antioxidants and / or Can function as a friction modifier. These are a variety of oils with lubricating viscosity Include natural and synthetic lubricating oils and mixtures thereof). Can be used in various lubricants. These lubricants include spark ignition and pressure Spark ignition internal combustion engines (this includes automotive and truck engines, two-cycle Engines, piston engines for aircraft, diesel engines for ships and railways, etc. Is included). These are also gas engines, It can be used in stationary power engines and turbines and the like. Automatic or manual transmission oil , Transaxle lubricants, gear lubricants (including open and closed gear lubricants), Tractor lubricants, metalworking lubricants, hydraulic fluids and other lubricants and grease The compositions also benefit from mixing the compositions of the present invention. These are also Wire ropes, walking cams, moving surfaces, rock drills, chains and conveyors Lubricants for belt, worm gear, bearing, and rail and flange applications To Can be used.   This combination can be used in lubricants or concentrates. This concentrate is made of metal Salt alone or with other ingredients used in preparing a fully formulated lubricant Combine and contain. The concentrate also contains a substantially inert organic diluent (such as These include kerosene, mineral distillates, or one or more of the lubricating viscosities described below. Oils that have sexual potential). This combination is the final product, Or in concentrates as antiwear, welding and / or extreme pressure agents for lubricating compositions. Present in an amount effective to act.   In one embodiment, the lubricating composition comprises up to 1.5% by weight, or up to 1.0% by weight, Or up to about 0.5% by weight of a polyisobutene-substituted succinic anhydride and polyamine The reaction product of In other embodiments, the lubricating compositions (e.g., gear lubricants) Lubricants) may contain up to 2%, or up to 1.5%, or up to 1% by weight of dispersant (eg, For example, those described herein). In another embodiment, the lubricating composition The product may contain added lead compounds (e.g., lead naphthenate, lead dithiophosphate and dithiophosphate). Does not contain lead carbamate).   The lubricating compositions and methods of the present invention include oils of lubricating viscosity, including natural lubricating oils. Lubricating or synthetic lubricating oils and mixtures thereof). To natural oil Are animal oils, vegetable oils, mineral lubricating oils, and solvent-treated or acid-treated Mineral oil. Synthetic lubricating oils include hydrocarbon oils (polyalphaolefin), B-substituted hydrocarbon oils, alkylene oxide polymers, dicarboxylic acids and polyols Esters, esters of phosphorus-containing acids, polymeric tetrahydrofurans and silicones Base oil. Unrefined, refined and re-refined oils are both natural or synthetic. Any of the oils may be used in the compositions of the present invention. Oil of lubricating viscosity The description is from U.S. Pat. No. 4,582,618 (column 2, line 37 to column 3, line 63). Including the disclosure of oils with lubricating viscosity. , Incorporated herein by reference.   In one embodiment, the oil of lubricating viscosity is a polyalphaolefin (PAO) ). Typically, the polyalphaolefin has from about 3 to about 30 carbon atoms. Atoms, or about 4 to about 20 carbon atoms, or about 6 to about 16 carbon atoms. Derived from the monomer. Examples of useful PAOs include those derived from decene Included. These PAOs can be obtained at 100 ° C. from about 3 to about 150 cSt, or from about 4 to about 100 cSt.  It may have a viscosity of cSt, or about 4 to about 8 cSt. Examples of PAOs include 4 cSt polio Refin, 6 cSt polyolefin, 40 cSt polyolefin, and 100 cSt Of polyolefins are included.   In one embodiment, the lubricating oil or a mixture of lubricating oils is used. The compound has a kinematic viscosity at 100 ° C of at least about 3.5 cSt or at least about 4.0 cSt. The lubricating composition is selected to provide In one embodiment, the lubricating composition Has a SAE gear ratio of at least about SAE 65, more preferably at least about SAE 75. It has an il viscosity number. The lubricating composition also has a so-called multi-grade rating ( For example, SAE 75W-80, 75W-90, 80W-90, 75W-140, 80W-90, 80W-140, 85W-90 or May have 85W-140). Multi-grade lubricant to get the above lubricant grade It may contain a viscosity improver formulated with an oil of lubricating viscosity. Useful viscosity improver Are polyolefins (e.g., ethylene-propylene copolymer or polybutene). Tylene rubber (e.g., styrene-butadiene rubber or styrene-isoprenego Or polyacrylate (including polymethacrylate) Including). In one embodiment, the viscosity improver is a polyolefin Or polymethacrylate. Commercially available viscosity improvers include Acryloid<sup>TM</sup>Viscosity modification Good agent (available from Rohm &Haas); Shellvis<sup>TM</sup>Rubber (this is Shell Ch available from emical); Trilene<sup>TM</sup>Polymers, such as Trilene<sup>TM</sup>CP-40 (this is U niroyal Chimcal Co.), and Lubrizol 3100 series and And 8400 series polymers, for example, Lubrizol 3174 (this is the Lubrizol Corpora available from).   In one embodiment, the oil of lubricating viscosity comprises at least one dicarboxylic acid. Contains species esters. Typically, the ester has about 4 From about 30 to about 30 carbon atoms, preferably from about 6 to about 24 carbon atoms, or about 7 Contains up to about 18 carbon atoms. Examples of dicarboxylic acids are glutaric acid, adipine Acids, pimelic acid, suberic acid, azelaic acid and sebacic acid are included. D Examples of stele groups include hexyl ester, octyl ester, and decyl ester And dodecyl ester groups. These ester groups have a linear Examples include steer groups and branched ester groups (e.g., the iso sequence of the ester group). It is. A particularly useful ester of a dicarboxylic acid is diisodecyl azelate .   In other embodiments, the oil of lubricating viscosity is used for crankcase (e.g., (For soline and diesel engines) Is done. Typically, the lubricating composition is a 10W, 20W or 30W SAE crankcase viscosity. Selected to obtain degree number lubricant. The lubricating composition also has a so-called Can have multi-grade grades (e.g., SAE 5W-30, 10W-30, 10W-40, 20W-50, etc.) You. As described above, multi-grade grade lubricants get the above lubricant grades For this purpose, it contains a viscosity improver which is formulated with an oil of lubricating viscosity.Other additives   The present invention also contemplates the use of other additives with the above combinations. these Additives include, for example, ash-generating or ash-free detergents and dispersants Agents, corrosion inhibitors and antioxidants, pour point depressants, extreme pressure agents, antiwear agents, color stabilization And defoamers.   This detergent contains alkali metal or alkaline earth metal, sulfonic acid, Oil-soluble with acids, phenols or organic phosphorus-containing acids (e.g., those described above) Exemplified by neutral and basic salts (ie, overbased salts). This Oil-soluble neutral or basic salts of the alkali metal or alkaline earth metal salts of It can also be reacted with a boron-containing compound. Boron-containing compounds have been described above I have. The overbased metal salt and borated overbased metal salt , Described above. Useful overbased metal salts and borated over -Examples of base metal salts include sodium, calcium and magnesium -Base salts and borated sulfonates and carboxylate salts (as described above (Including carbyl-substituted carboxylic acylating agents).   Detergents and dispersants are known in the art. Examples are given below.   (1) "Carboxylic acid dispersants" include at least about 34 carbon atoms, preferably A carboxylic acid containing at least about 54 carbon atoms (or their derivatives); Compounds (e.g., amines), organic hydroxy compounds (e.g., phenol and And alcohols) and / or basic inorganic substances. these Reaction products include imide, amide and ester reaction products of carboxylic acylating agents. Products. These carboxylic dispersants generally comprise one or more A hydrocarbyl (as described above) substituted carboxylic acylating agent and an amine (as described above) (Preferably polyalkylene polyamine or condensed amine) or hydroxy The reaction between the compound (e.g., alcohol) and amine And is prepared by Examples of these materials include succinimide dispersants and Rubonic acid ester dispersants are included. Examples of these "carboxylic dispersants" include: It is described in British Patent No. 1,306,529 and a number of U.S. Patents, including: , 219,666, 3,316,177, 3,340,281, 3,351,552, 3,381,022, No. 3,433,744, No. 3,444,170, No. 3,467,668, No. 3,501,405, No. 3,542,680 No. 3,576,743, No. 3,632,511, No. 4,234,435, and Reissue Patent No. 26,43 No. 3.   (2) "Amine dispersant" is a relatively high molecular weight aliphatic or alicyclic halide And a reaction product of an amine (preferably, a polyalkylene polyamine). this These dispersants are described above as polyalkene-substituted amines. Them Examples are described, for example, in the following U.S. Patents: 3,275,554, 3,438,757. Nos. 3,454,555 and 3,565,804.   (3) `` Mannich dispersants '' are alkylphenols and aldehydes (particularly Aldehydes) and amines (especially amine condensates and polyalkylenepolyamides). ). The materials described in the following U.S. patents are exemplary: No. 36,003, No. 3,236,770, No. 3,414,347, No. 3,448,047, No. 3,461,172, No. No. 3,539,633, No. 3,586,629, No. 3,591,598, No. 3,634,515, No. 3,725,480 Nos. 3,726,882 and 3,980,569.   (4) "Post-treatment dispersant" refers to carboxylic acid dispersant, amine dispersant or Mannich A product obtained by working up a dispersant with the following reagents: urine Elemental, thiourea, carbon disulfide, aldehyde, ketone, carboxylic acid, no hydrocarbon substitution Water succinic acid, nitrile, epoxide, boron-containing compound, phosphorus-containing compound, etc. Exemplary materials of this type are described in the following U.S. Patents: 3,200,107, 3,2 No. 82,955, No. 3,367,943, No. 3,513,093, No. 3,639,242, No. 3,649,659, No. 3,442,808, 3,455,832, 3,579,450, 3,600,372, 3,702,757 And 3,708,422.   (5) The `` polymer dispersant '' is an oil-soluble monomer (decyl methacrylate, vinyl decyl Ethers and high molecular weight olefins) and polar substituent-containing monomers (e.g., Noalkyl acrylate or acrylamide and poly (oxyethylene) substitution Acrylate). Styrene-free polymer dispersants Esters of a maleic copolymer of water. Examples of polymer dispersants include the following rice Disclosed in national patents: 3,329,658, 3,449,250, 3,519,656, 3rd Nos. 3,666,730, 3,687,849, and 3,702,300.   The contents of the above patents are incorporated herein by reference for their disclosure of ashless dispersants. Have been used.   Auxiliary extreme pressure and corrosion inhibitors and antioxidants that may be included in the lubricants of the present invention. Inhibitors may be exemplified by: chlorinated aliphatic hydrocarbons (eg, chlorinated waxes). G), sulfurized alkylphenols, including diphosphite or trihydrocarbyl. Phosphites such as dibutyl phosphite, trioleyl phosphite and Triphenyl phosphite); Phosphorus sulfide hydrocarbons (eg, phosphorus sulfide and terpentine) Or a reaction product with methyl oleate); metal thiocarbamate (eg, Zinc octyldithiocarbamate, and diheptylphenyldithiocarbamate barium). Many of the extreme pressure and corrosion inhibitors and antioxidants listed above also Also useful as a wear agent.   Pour point depressants are additives often included in the lubricating oils described herein. Yes Examples of pour point depressants for use include polymethacrylates; Polyacrylamide; Condensation formation between haloparaffin wax and aromatic compound Products; vinyl carboxylate polymers; and dialkyl fumarate, fatty acid vinyl And polymers of alkyl vinyl ethers. For the purposes of the present invention Pour point depressants, their preparation methods and their uses are described in U.S. Pat. No. 501; No. 2,015,748; No. 2,655,479; No. 1,815,022; No. 2,191,498; No. 2,6 No. 66,746; 2,721,877; 2,721,878; and 3,250,715; The contents of which are incorporated herein by reference for relevant disclosures.   Antifoams are used to reduce or prevent the formation of stable foam. Representative defoamers include silicone or organic polymers. Yet another The foam composition was obtained from "Foam Control Agents" (Henry T. Kerner, Noyes Data Corporat ion, 1976), pages 125-162.   The following example illustrates the combination of a dithiocarbamate compound and an organic polysulfide. The present invention relates to a lubricating composition containing burrs.                                 Example 1   1.5% by weight of the product of Example M-1 and the crude product of Example B-2 in 80W-90 gear oil base oil A lubricant is prepared by incorporating 1% by weight of the composition.                                 Example 2   Explained in Example 1 except that 10W-30 oil was used instead of 80W-90 oil A lubricating composition is prepared as described above.                                 Example 3   1.5% by weight of the product of Example M-1 and 2.5% by weight of the product of Example S-1 in 80W-90 gear oil %, And 1.2% by weight of the product of Example P-3 to prepare a lubricating oil. To make.                                 Example 4   Described in Example 3, except that 10W-30 oil is used instead of 80W-90 oil A lubricating composition is prepared as described above.                                 Example 5   1.5% by weight of the product of Example M-1 and 1% by weight of the product of Example B-2 in 80W-90 oil 2.5% by weight of the product of Example S-1, isooctyldithiophosphoric acid and 2-ethylhexyl 1.2% by weight of mixed salt of sanic acid, 0.7% by weight of dibutyl hydrogen phosphite, alkylbenzene Calcium overbased salt of sulfonic acid (this is a metal ratio of 12, 100 new 53% diluent, including Lal mineral oil and unreacted alkylbenzene acrylate, total 30 Base number, having a molecular weight of 385 for this sulfonic acid) 1.8% by weight, oleylamide Lubrication by containing 0.25% by weight of silicon and 0.07% by weight of silicone defoamer Oil Prepare.                                 Example 6   Sakura Lube 500 (0.2% by weight) in 80W-90 oil, 3.8% by weight of the product of Example S-1 And preparing a lubricating composition by incorporating 1.3% by weight of the product of Example P-3 I do.                                 Example 7   Sakura Lube 500 (0.2% by weight) in 80W-90 oil, 3.8% by weight of the product of Example S-1 1.3% by weight of product of Example P-4, 0.35% by weight of oleoamine, 0.1% by weight of oleamide %, And dimercaptothiadiazole, heptylamine and paraforma A lubricating composition is prepared by including 0.1% by weight of the reaction product of aldehyde. You.                               Examples 8 to 12   The table below shows lubrication prepared by incorporating multiple components into 80W-90 oil. Includes examples of compositions.   1 Isobutyl amyl dithiophosphoric acid, methyl acrylate and propylene oxide Reaction product of Cid.   2 Reaction product of diethylamine, carbon disulfide and methyl acrylate.   Although the invention is described in connection with preferred embodiments thereof, It should be understood that various modifications will be apparent to those skilled in the art upon reading this specification. . Therefore, the invention disclosed herein should include these modifications that fall within the scope of the appended claims. It should be understood that this is intended.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C10N 10:12 30:06 40:04 (72) Inventor Schwind, James Jay. UK Dee6 5N. Dover Ridge, Church Lane, Charnwood (no address) (72) Inventor Constance, Bernard, France E-69360 Serezin, Are de Rameau 4 (72) Inventor Borgonon, Henri France E-69160 Tassan- La Demirune, Avenue de 8-My-1945, bis 49

Claims (1)

[Claims] 1. A lubricating composition comprising a major amount of oil of lubricating viscosity and the following (A) and (B): (A) a wear improving amount of at least one molybdenum-containing composition; and (B) at least one component selected from the group consisting of: (i), (ii) and (iii): (i) at least one borated overbased metal salt of an acidic organic compound, provided that (A) ) And (Bi) are not the same; (ii) (a) at least one organic polysulfide or at least one ashless dithiocarbamate-containing composition and (b) a metal thiophosphate, phosphate ester or salt thereof, The group consisting of phosphorus-containing carboxylic acids, their esters, their ethers or amides, borated dispersants, alkali metal borates, borated fatty amines, borated phospholipids, borate esters, and mixtures thereof. Choose from Combination with at least one component; and a combination of (iii) (i) and (ii). 2. The composition of claim 1, wherein (A) is present in an amount that provides about 125 ppm to about 900 ppm of molybdenum to the lubricating composition. 3. The composition of claim 1, wherein (A) is a molybdenum-containing alkali metal or alkaline earth metal overbased sulfonate, carboxylate or phenate. 4. The composition according to claim 1, wherein (A) is a molybdenum-containing alkali metal or alkaline earth metal sulfonate. 5. The composition according to claim 4, wherein the alkali metal or alkaline earth metal is calcium or magnesium. 6. 2. The composition of claim 1, wherein (A) is prepared by carbonation of a mixture containing at least one alkali metal or alkaline earth metal compound, an acidic organic compound, and at least one hydrocarbon insoluble organomolybdenum complex. Composition. 7. The composition according to claim 6, wherein the organic molybdenum complex is an amine-molybdenum complex. 8. The composition of claim 1, wherein (A) is at least one molybdenum thiophosphate or at least one molybdenum thiocarbamate. 9. The composition according to claim 1, wherein (A) is at least one molybdenum oxysulfide thiophosphate or at least one molybdenum oxysulfide dithiocarbamate. Ten. (B) is (i), and the borated overbased salt of the acidic organic compound is a borated overbased alkali metal or alkaline earth metal sulfonate, carboxylate or phenate. The composition of claim 1. 11． 2. The composition of claim 1, wherein (B) is (i) and the borated overbased salt of the acidic organic compound is a borated overbased sulfonic acid or sodium, calcium or magnesium carboxylate. A composition as described. 12． (B) is (i) and the lubricating composition further comprises (C) at least one sulfurized organic compound or at least one ashless dithiocarbamate-containing compound, or (D) at least one The composition according to claim 1, comprising a phosphorus-containing or boron-containing extreme pressure agent. 13. The composition according to claim 1, wherein (B) is (ii) and the organic polysulfide is a sulfurized oil, a fatty acid or an ester thereof, an olefin, a polyolefin or a mixture thereof. 14. 2. The composition of claim 1, wherein (B) is (ii), and said ashless dithiocarbamate-containing composition (a) is prepared by reacting dithiocarbamic acid or a salt thereof with an unsaturated compound. Composition. 15． The unsaturated compound is of the formula R ¹ R ² C = C (R ³ ) COOR ⁴ acrylate, wherein R ¹ , R ² and R ³ are each independently hydrogen or a hydrocarbyl group and R ⁴ is a hydrocarbyl group containing from 1 to about 24 carbon atoms the composition of claim 14. 16． 15. The composition according to claim 14, wherein the unsaturated compound is methyl acrylate or methyl, ethyl, butyl, pentyl or hexyl. 17． The phosphoric acid ester or a salt thereof (b) is reacted with dithiophosphoric acid and an epoxide to form an intermediate, and the intermediate is further reacted with a phosphorus-containing acid or an anhydride thereof to prepare a phosphoric acid. 2. The composition according to claim 1, which is an ester or a salt of said phosphate ester. 18． 18. The composition of claim 17, wherein the dithiophosphoric acid is a dihydrocarbyl dithiophosphoric acid having from 1 to about 24 carbon atoms independently in each hydrocarbyl group. 19. 19. The composition according to claim 18, wherein the phosphate ester or a salt thereof is prepared by reacting the phosphate ester with ammonia or an amine. 20. 20. The composition of claim 19, wherein said amine is a tertiary aliphatic primary amine. twenty one. The phosphate ester or a salt thereof (b) is a phosphate ester or a salt of the phosphate ester prepared by reacting a phosphorus-containing acid or an anhydride thereof with at least one alcohol, wherein The composition of claim 1, wherein the alcohol independently contains from about 1 to about 30 carbon atoms. twenty two. The composition according to claim 1, wherein the phosphate ester or a salt thereof is a triaryl phosphate. twenty three. 23. The composition of claim 22, wherein said triaryl phosphate is tricresyl phosphate. twenty four. 13. The composition according to claim 12, wherein (C) is a sulfurized olefin. twenty five. A lubricating composition comprising a major amount of an oil of lubricating viscosity and the following (A) and (B): (A) a wear improving amount of at least one molybdenum-containing composition; and (B) an acidic organic compound. At least one borated overbased metal salt, with the proviso that (A) and (B) are not the same. 26. 26. The composition of claim 25, wherein (A) is present in an amount that provides about 125 ppm to about 900 ppm of molybdenum to the lubricating composition. 27. 26. The composition of claim 25, wherein (A) is a molybdenum-containing alkali metal or alkaline earth metal overbased sulfonate, carboxylate or phenate. 28. 26. The composition of claim 25, wherein (A) is a molybdenum-containing alkali metal or alkaline earth metal overbased sulfonate. 29. 26. The method of claim 25, wherein (A) is prepared by carbonation of a mixture containing at least one alkali metal or alkaline earth metal compound, an acidic organic compound, and at least one hydrocarbon insoluble organomolybdenum complex. Composition. 30. 30. The composition of claim 29, wherein said organic molybdenum complex is an amine-molybdenum complex. 31. 26. The composition according to claim 25, wherein (A) is molybdenum thiophosphate or molybdenum thiocarbamate. 32. 26. The composition according to claim 25, wherein (A) is molybdenum oxysulfide thiophosphate or molybdenum oxysulfide dithiocarbamate. 33. (B) The composition according to claim 25, wherein the borated overbased salt of the acidic organic compound is a borated overbased alkali metal or alkaline earth metal sulfonate, carboxylate or phenate. . 34. 26. The composition of claim 25, wherein (B) is a borated overbased sulfonic acid- or carboxylate sodium, calcium or magnesium. 35. Further, (C) at least one organic polysulfide or at least one dithiocarbamate-containing compound, or (D) at least one phosphorus-containing or boron-containing antiwear / extreme pressure agent, wherein (B) 26. The composition of claim 25, wherein and (D) are not the same. 36. 36. The composition according to claim 35, wherein (C) is a sulfurized olefin. 37. 36. The composition according to claim 35, wherein (C) is a dithiocarbamic acid ester prepared by reacting dithiocarbamic acid or a salt thereof with an unsaturated compound. 38. A lubricating composition comprising a major amount of oil of lubricating viscosity and the following (A) and (B): (A) at least one molybdenum-containing composition; and (B) (a) at least one organic polysulfide Or at least one ashless dithiocarbamate-containing composition and (b) a metal thiophosphate, a phosphate ester or a salt thereof, a phosphorus-containing carboxylic acid, an ester thereof, an ether thereof or an amide thereof, a borated dispersant, an alkali metal borate At least one combination with at least one component selected from the group consisting of acid salts, borated fatty amines, borated phospholipids, borate esters, and mixtures thereof. 39. 39. The composition according to claim 38, wherein (A) is a molybdenum-containing alkali metal or alkaline earth metal sulfonate. 40. 39. The composition of claim 38, wherein (A) is molybdenum thiophosphate or molybdenum thiocarbamate. 41. 39. The composition of claim 38, wherein (A) is molybdenum oxysulfide thiophosphate or molybdenum oxysulfide dithiocarbamate. 42. A method of lubricating a transmission or a differential gear comprising: a lubricating composition comprising the transmission or the differential gear comprising a major amount of an oil having lubricating viscosity and the following (A) and (B): And (D) driving the differential gear or transmission: (A) a wear improving amount of at least one molybdenum-containing composition; and (B) the following (i): at least one component selected from the group consisting of (ii) and (iii): (i) at least one borated overbased metal salt of an acidic organic compound, provided that (A) and ( (Ii) are not the same; (ii) (a) at least one organic polysulfide or at least one ashless dithiocarbamate-containing composition and (b) a metal thiophosphate, a phosphate ester or a salt thereof, a phosphorus-containing carboxylic acid. Acid, its ester, its ether or its A combination with at least one component selected from the group consisting of amides, borated dispersants, alkali metal borates, borated fatty amines, borated phospholipids, borate esters, and mixtures thereof; And (iii) a combination of (i) and (ii).