JPH10510319A - Lubricants and fuel compositions containing organic-substituted diphenyl sulfides - Google Patents

Abstract

  (57) [Summary] The lubricant and fuel composition may be an organic ring-substituted diphenyl sulfide, such as a monoalkyl diphenyl sulfide; a polymer-substituted succinimide, succinamide or succinate; Contains dithiophosphate. This composition has excellent abrasion resistance and extreme pressure resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION         Lubricants and fuel compositions containing organic-substituted diphenyl sulfides   The present invention relates to substituted diimides in combination with succinimide and dithiophosphate additives. The invention relates to fuel and lubricant compositions based on phenyl sulfide. This lubrication Excellent practical performance when combined with specific additives as base material , Especially alkyl-substituted diphenyl sulphides for improved wear resistance and extreme pressure You are using   Alkyldiaryl sulfide high temperature lubricants, dithiophosphates (or Fordithioate) antiwear agent and polymer-substituted succinic acid derivative ashless surfactant Are each known in the art as a component of a lubricant composition.   U.S. Pat. Nos. 3,172,892 and 3,272,746 disclose lubrication. Polymer-substituted succinic acid or succinic anhydride and alkyl Polymer-substituted succinic amide synthesized by reacting polyamine And succinimides are disclosed.   U.S. Pat. No. 3,194,812 discloses a polymer as a dispersant in a lubricant. Teach the use of alkenyl-n-p-aminophenyl succinimide ing.   U.S. Pat. No. 3,216,936 discloses a polymer-substituted succinic acid or Reacting an acid anhydride with an aliphatic hydrocarbon monocarboxylic acid and an alkyleneamine Disclosed are lubricant additives, primarily amides and imides, synthesized by ing. These compounds are suitable for use with metal phosphordithioates I have.   U.S. Pat. No. 3,691,220 discloses that it is used as an additive for lubricating oil. From the corresponding acid and the basic zinc compound in the presence of isopropyl alcohol Synthesized diorganophosphordithioates are described.   U.S. Pat. No. 3,804,763 has at least 30 carbon atoms. Carboxyl-type acylating agents such as polymer-substituted succinic acids, acid anhydrides or Represents an ester with a hydroxy compound, a polyoxyalkylene polyamine and Dispersant compositions useful as additives for lubricating oils synthesized by reacting with kilenamine It has been disclosed.   U.S. Pat. No. 4,153,564 discloses alkenyl succinic anhydrides and aromatics. Emulsifier for lubricant composition, synthesized by reaction with aliphatic amine-aldehyde resin Teach compounds that act as surfactants and antioxidants.   U.S. Pat. No. 4,234,435 discloses that its number average molecular weight (Mn) is one. 300 to 5000, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight is 1 . A dibasic carboxylic acid such as polyalkene and maleic acid, which is 5 to 4 Or the reaction of acylating agents derived from its derivatives with polyethylene polyamines Lubricant additives are described which are more synthetic.   U.S. Pat. No. 4,255,271 teaches friction and friction in addition to lubricants. Nitrogenation of phosphosulfurylated hydrocarbyl oxazoline to reduce wear Phosphorditi synthesized by reacting with olefins containing compounds Oate additives are shown.   U.S. Pat. No. 4,522,736 discloses that when used in lubricants, dispersants and A polyalkenyl succinic acid compound useful as a corrosion inhibitor and / or Hindered phenols containing aromatic secondary amines or hydroxyalkyl groups Reaction with alkanolamine or aminomethane. A synthesized product is disclosed.   U.S. Pat. No. 4,652,387 discloses alkenyl succinic compounds, Borated products of reaction products of aromatic amines and amino alcohols are taught This product is a highly effective dispersant and antioxidant for lubricant compositions / It is described as a corrosion inhibitor additive.   U.S. Pat. No. 4,840,744 discloses useful as a dispersant in lubricating oils. Polyaminoalkenyl or alkyl succinic acids containing carbamate functional groups Imides are described.   U.S. Pat. No. 4,895,579 discloses alkenyl succinic compounds. Lubricant composition synthesized by reaction with aromatic amine and hindered alcohol Dispersant and antioxidant activities.   U.S. Pat. No. 5,171,915 discloses poly-α-O having a large viscosity index. Olefin obtained as a by-product during the production of refin (HVI-PAO) Using a monoolefinic dimer as an alkylating agent, diphenyl sulfide It is taught to alkylate any of a wide variety of aromatic compounds, including You. This alkylation reaction is a Friedel-Crafts compound as an alkylation catalyst. It is carried out in the presence of an object or zeolite. This alkylated aromatic compound is oxidized It is stated that it is useful as an additive for lubricants to provide anti-wear and anti-wear properties I have.   British Patent 1,093,945 discloses high temperature functional fluids such as lubricants. Useful alkyldiaryl sulfides are disclosed.   According to the method of the present invention, 1) an organic ring suitable for use in lubricants and fuels -Substituted diphenyl sulfide; 2) succinic dispersant component; and 3) phosphor A dithiophosphate, also known as a dithioate; Provided. This succinic acid-based dispersant is a polymer-substituted succinic acid derivative: Molecule-substituted succinimides, succinamides or succinates The alcohol or phenol moiety of the ster group may be amide, imide or Or an amine nitrogen functional group) or its amide, imide and / or Or a mixture of esters.   Use alkylated diphenyl sulfide as basic lubricant material if possible Lubricant composition comprising the above three components, unexpectedly good Other desirable properties such as wear resistance and extreme pressure, as well as corrosion resistance and high temperature cleanliness Has the property of   The organic group in the ring-substituted diphenyl sulfide is water bound to a ring carbon atom. An element atom has been substituted. Such organic groups include, for example, alkyl, alkenyl , Arylalkyl, alkylaryl, or aryl, wherein The aliphatic group may be cyclic, linear or branched. In addition One or more hydrogen and / or carbon atoms in such groups may be S, N, O, It may be substituted with P and / or F. This organic-substituted diphenyl sulf The hydride includes an organic group substituted with, for example, 1 to 8, preferably 1 to 2 rings. And each substituted organic group is, for example, 1 to 500, preferably 5 to 50, and And most preferably contains from 10 to 30 carbon atoms. Preferably all The ring-substituted organic group is selected from the hydrocarbon groups listed above, preferably an alkyl group . The most preferred diphenyl sulfides are mono- or dialkylated diphenyls A sulfide in which the alkyl group is straight-chain and contains 5 to 40 carbon atoms You. In certain lubricant and / or fuel applications, the substituted diphenyl sulf Is preferably a monoalkyl whose alkyl contains 10 to 20 carbon atoms. It is a kill-substituted diphenyl sulfide.   This organic-ring-substituted diphenyl sulfide is generally used in the presence of an alkylation catalyst. And it will be attached to the carbon atom of the diphenyl sulfide ring, Organic group to be substituted, preferably except that it contains a terminal double bond Reacting an organic substitution reactant having the same structure with diphenyl sulfide Are synthesized by Thus, to obtain n-alkyldiphenyl sulfide The diphenyl sulfide has the same number of carbon atoms as the n-alkyl substituent. React with α-olefin containing. Different organics containing terminal double bonded carbon atoms Mixtures of substituted reactants as well as reactants containing terminal double bonded carbon atoms and internal double bonds Mixtures with reactants containing combined carbon atoms are also used. Generally speaking, organic substitution anti The molar ratio of the reactant to diphenyl sulfide is from 0.5: 1.0 to 10.0: 1.0 Preferably, it can be changed in the range of 1.0: 1.0 to 4.0: 1.0.   Alkylation catalyst used to synthesize this organic substituted diphenyl sulfide The medium may be a Friedelck such as aluminum trichloride or boron trifluoride. Rafts catalyst. However, substantially mono-substituted diphenyl sulfides were obtained. For this purpose, this reaction is preferably carried out in the presence of a zeolite catalyst. Such a zeo Light catalysts are at least partially acidic in order to provide acidity to the reaction. H) but ammonium (NH_Four ⁺Also includes other cations such as And large holes such as faujasite Olites, such as zeolites X, Y, USY, UHP-Y, ZSM-20 or Is preferably zeolite beta. Another zeolite used is Zeolite M CM-22 (U.S. Pat. Nos. 4,954,325; 5,100,534 and 5, 103,066). The reaction is usually carried out at room temperature to 350 ° C., preferably Temperatures in the range of 00 ° C to 250 ° C, and most preferably 180 ° C to 240 ° C Done in The reaction may be performed, for example, in a batch or catalyst or organic displacement reactant. Is added to diphenyl sulfide continuously or partly by semi-batch method. It is. The catalyst may comprise from 1 g / mole aromatic component to 100 g / mole aromatic component, Or 5 g / mol of aromatic component to 50 g / mol of aromatic component, and most desirable Or 10 to 30 g of catalyst / one mole of aromatic component. . The catalyst may be steamed, calcined or fresh.   This mono-organic substituted diphenyl sulfide, for example obtained with zeolite catalyst Monoalkyl diphenyl sulfide is AlCl_ThreeAnd other protonic acids and Synthesized by reaction with an organic displacement reactant, such as an α-olefin, in the presence of a Lewis acid. It shows superior properties as compared to organic-substituted diphenyl sulfide.   Monosubstituted diphenyl sulfide obtained using zeolite-based alkylation catalyst Is substantially, ie, up to 100%, as evidenced by gas chromatography, and At least 95 to 98% mono-substituted, for example monoalkylated.   This organic-substituted diphenyl sulfide is used as the primary base stock in lubricants. Or as a main component of a fuel composition or with other synthetic and / or mineral oil liquids Used in combination. In each case, it is generally, for example, 2 to 100 ° C. 100 cSt (centistokes), preferably 3 to 100 cSt, and more More preferably, it has a viscosity in the range of 3 to 30 cSt, and in the composition: For example, 0.5 to 95 wt% or more, preferably 2 to 90 wt% Preferably in a range of 2 to 20 wt% for some applications, In other applications, especially another base stock is used with this substituted diphenyl sulfide. If desired, a concentration of 25 to 90 wt% is desirable.   The compounds constituting the dispersant component may be used alone or in combination. For example, 1) succinimide; 2) succinamide; or 3) the ester group The alcohol or phenol moiety may be amide, imide or amine nitrogen Succinic acid esters containing elemental functional groups; the polymer-substituted succinic acids Derivatives are very complex mixtures of the condensation reaction products of the individual reaction components. this Some of the components of the mixture have any of the following structures: In the formula, R is the residue of a homopolymer or copolymer of an ethylenically unsaturated monomer. For example, alkyl groups or alkenes containing, for example, 2 to 20 carbon atoms An alkenyl group that is the residue of a polyalkene of Desirably containing at least 50 and up to 300 or more carbon atoms. And, for example, 300 to 10,000, preferably 500 to 2, Has a number average molecular weight (Mn) of 000; Z is [separately in Formula 2] hydrogen or Aliphatic containing carbon, hydrogen and optionally nitrogen and / or oxygen or Not compatible with aromatic organic groups and / or polymer-substituted succinic acid derivative acylating agents Is the residue of the corresponding amino compound and Y is carbon, hydrogen, nitrogen and optionally Oxygen containing aliphatic or aromatic groups, and / or polymer substitution Amide, imide or amine nitrogen functional groups which are reacted with acyl derivatives of acylate Is the residue of an alcohol containing   The dispersant may be, for example, maleic anhydride or maleic acid and a suitable polymer : Containing, for example, 2 to 20 carbon atoms and double bond or halogen such as chlorine By reacting the polymer of the alkene contained, the polymer substituted succinic acid It is prepared by obtaining an succinic anhydride type acylating agent. Then the latter A suitable hydrocarbyl-substituted amine or, optionally, an amide, imide or React with alcohol or phenol containing amine nitrogen functional group to obtain desired dispersion Get the agent. Some suitable dispersants are listed below: US Pat. No. 3,172,8 Polymer-substituted succinic amides and succinic imis disclosed in US Pat. Where Z is the reactive nitrogen atom of ethylene polyamine having the formula At the residue: Wherein x is, for example, an integer from 1 to 5, and R is hydrogen or a lower alkyl group; Polyisobutenyl-substituted ambers disclosed in U.S. Pat. No. 3,194,812 Acid imide, wherein Z is a p-aminophenyl group; US Pat. No. 3,272 Polymer-substituted succinamides disclosed in U.S. Pat. Such nitrogen-containing and non-nitrogen-containing groups, preferably having the formula The residue attached to the reactive nitrogen atom of lenpolyamine: Wherein n is preferably an integer less than 10, and A is hydrogen or a hydrocarbon group. And alkylene groups have less than 8 carbon atoms; US Pat. No. 936, polymer-substituted succinamides and succinimides , Wherein Z in the imide and at least one Z in the amide are Of alkylene polyamines or mixtures of alkylene polyamines with At the residue attached to the nitrogen atom: Wherein x is preferably an integer less than 6, and the alkylene group is, for example, less than 4 carbon atoms. Lower alkylene containing a hydrogen atom and a cyclic ring of an amine such as piperazine. Group-substituted polymers disclosed in US Pat. No. 3,804,763. Succinamides, succinimides and succinic esters, among which Z in the imide and at least one Z in the amide are various polyalkylenepolyamides. Attached to the reactive nitrogen atom of any of the compounds and alkylene polyamines Y at the residue and in the ester contains various nitrogens and contains nitrogen Hydroxy compounds such as monohydric and polyhydric alcohols and phenols, Polyalkylene glycol, monoester of polyhydric alcohol compound, amino alcohol Residue attached to the hydroxy group of any compound such as phenol, aminophenol, etc. The polymer-substituted amber disclosed in US Pat. No. 4,153,564. Acid imides, wherein Z is an aromatic amine-aldehyde resin or Attached to the reactive nitrogen atom of the reaction products with aromatic triazoles and aldehydes Residue; a polymer-substituted polymer disclosed in US Pat. No. 4,234,435. Succinamides and succinimides, wherein the polymer substituent R is large A group of various ethylenically unsaturated monomers, preferably homopolymers and And a copolymer [having a number average molecular weight (Mn) of 1300 to 5000 and a weight average The ratio of molecular weight (Mw) to Mn is derived from any of 1.5 to 4], and Z in the imides and at least one Z in the amides are referred to in this section. Polyamines such as the alkylene polyamines disclosed in several other patents A residue attached to the reactive nitrogen atom of an amino acid; US Pat. No. 4,522,736. -Substituted succinamides, succinimides or succinimides disclosed in In the case of succinic esters, of which succinamides and succinimides, At least one Z is then reacted with an alkanolamine or aminomethane It is a residue attached to the reactive nitrogen atom of the aromatic secondary amine. In the case of steles, Y is then reacted with alkanolamine or aminomethane. Attached to hydroxy groups of hindered phenols containing hydroxy groups Residue; a polymer-substituted polymer disclosed in US Pat. No. 4,652,387. Borated mixtures of succinamides, succinimides or succinates, Among them, in the case of succinamides and succinimides, Z in the imide And at least one Z in the amide is a diarylamine and / or an aminoalkyl Residue on the reactive nitrogen atom of coal, and of succinates Where Y is the residue attached to the hydroxy group of an amino alcohol; US Pat. No. 4,840,744, polymer-substituted succinimides, Wherein Z contains a carbamate function; and US Pat. No. 4,895. -Substituted succinamides and succinic acid imidates disclosed in U.S. Pat. And wherein Z in the imide and at least one Z in the amide further comprise On the reactive nitrogen atom of the aromatic amine, which is reacted with Residue.   The dispersant derived from the polymer-substituted succinic acid may be present in the composition, for example, 0.1 to 25 wt%, preferably 0.15 to 10 wt%, based on the weight of the composition wt%, and most preferably from 1 to 7 wt%.   The dithiophosphates of the compositions of the present invention will most often have the formula: Derived from ganodithiophosphoric acid: Where R₁And R_TwoIs independently a hydrocarbyl group, or a phosphorus atom and Together with oxygen atoms, they form a monomeric ring structure or a polymer chain structure. Preferably, This dithiophosphate is a metal salt of dihydrocarbyldithiophosphoric acid, The genus is a member of group II of the periodic table, especially zinc and barium, preferably zinc . Ashless dithiophosphates, such as those well known in the art. Reaction product of alkylene oxide, amine or olefin with organic dithiophosphoric acid Are also used. Defining the acid with reference to the above formula, R₁And R_TwoThe group is the same young Different from alkyl, cycloalkyl, aryl having 3 to 30 carbon atoms Alkaryl and aralkyl groups. This R₁And R_TwoThe group is, for example, n- Propyl, iso-propyl, n-butyl, iso-butyl, amyl, hexyl, decyl , Dodecyl, octadecyl, eicosyl, pentacosyl, benzyl, phenethyl , Cyclohexyl, phenyl, naphthyl, tolyl, t-amylphenyl, zide Decylphenyl, a waxphenyl group in which the wax moiety contains 24 carbon atoms, And similar groups. 2,2-dimethyl-1-propyl, 2,2,4-trime Tyl-1-butyl, 2,2-dimethyl-1-decyl and 2,2,4-trimethyl It is also conceivable to use a ru-1-hexadecyl group.   Can be used, R₁And R_TwoExamples of acids wherein are the same are dipropyl, dibutyl , Dihexyl, didodecyl, dioctadecyl, dicyclohexyl, dibenzyl , Diphenethyl, diphenyl, ditolyl, didodecylphenyl, diwaxfe Nil, di (2,2-dimethyl-1-propyl), di (2,2,4-trimethyl- 1-butyl), di (2,2-dimethyl-1-decyl) and di (2,2,4- Trimethyl-1-hexadecyl) dithiophosphoric acid.   R₁And R_TwoIllustrative examples of useful acids differing from: n-propyl amyl, amide Rudecyl, hexyldecyl, decylcyclohexyl, benzylphenyl dithi Oric acid and similar dithiophosphoric acids.   Preferably, R₁And R_TwoIs from 1 to 50 carbon atoms, more preferably 3 to 2 An alkyl group containing zero carbon atoms.   These metal dithiophosphates are described, for example, in US Pat. No. 3,216,936. And as shown in US Pat. No. 3,691,220. R₁When R_TwoTogether form the dithiophosphoric acid that defines the monomeric or macromolecular chain structure Examples are one or more, as shown in U.S. Pat. No. 4,255,271. Are those containing more oxazoline groups.   The dithiophosphate component can be, for example, from 0.05, based on the weight of the composition. 10 wt%, preferably 0.1 to 5 wt%, and most preferably 0.2 to An amount of 3 wt% is present in the composition.   The composition of the present invention may be used with other synthetic and / or mineral oils, especially synthetic poly-α Used in combination with or blended with olefins (PAO). Other synthesis The oil and / or mineral oil and the substituted diphenyl sulfide may be any suitable blend For example, 20 wt% substituted diphenyl sulfide and 80 wt% % PAO base material mixture has been found to be very advantageous. However , Substituted diphenyl sulfides make up the major part of the base stock up to 100% May be.   Generally used as a lubricant or as part of a base stock in a grease vehicle Mineral oils, both paraffinic and naphthenic, and their mixtures, Any suitable lubricating oil viscosity range, for example, from 1.0 cSt at 100 ° C. 1000 cSt at 100 ° C., and preferably 2.0 to 60 cSt at 100 ° C. It is. Recommended oils have a viscosity index ranging up to 150. Average of these oils The molecular weight ranges from 250 to 800.   Suitable synthetic oils are poly-α-olefins such as polyisobutylene, polybutene. Or hydrogenated polydecene, polypropylene glycol, polyethylene glycol Coal, trimethylpropane esters, neopentyl, for example, pentaerythritol Tall esters, di (2-ethylhexyl) sebacate, di (2-ethylhexyl) sebacate Xyl) adipate, dibutyl phthalate, fluorocarbons, silicate ester And esters of acids containing phosphorus and alkyl-substituted diphenyl ethers Kind.   The composition of the present invention may be thickened in grease or with a suitable thickener or gelling agent. It is also used in any of the aforementioned synthetic and / or mineral feedstocks mentioned. This These thickeners are any conventional metal salts or soaps, and in grease yield, Amount to impart the desired viscosity to the resulting grease composition, dispersed in the lubricating oil vehicle It is. Other thickeners used in the formulation of this grease include surface modified clays and silicones. Non-soap types, such as mosquitoes, aryl ureas, calcium complexes and similar materials Is a thickener. Generally, when used at the required temperature in a particular environment Grease thickeners that do not melt and dissolve are used, but all other aspects Usually thickens or gels the liquid hydrocarbons used to prepare the grease. Any of the materials commonly used to prepare greases may be used in the method of the present invention to prepare greases. It is.   The composition of the invention may further comprise, in addition to the substituted diphenyl sulfide, a mineral oil of lubricating oil viscosity. Alternatively, if a synthetic oil base stock is used, it may be based on the total composition, for example, For example, it is present in an amount of 2 to 98 wt%, preferably 5 to 98 wt%.   These three basic components of the composition according to the invention and additional synthetic or mineral base materials In addition to oil, if used, it is commonly used in lubricants and other functional fluids Other components of the various combinations may also be included; for example, additional dispersants, metal salts Surfactant (phenolate, sulfonate and / or salicylate), acid Antioxidants (for example, hindered phenols, aromatic amines, dithiocarbamine , High molecular viscosity index improver (polyisobutylene, styrene-die) Copolymers, polymethacrylates, etc.), antiwear agents or extreme pressure agents B cyclic triazoles, dimercaptothiadiazoles, dithiocarbamates , Phosphites, phosphonates, acid phosphates, thiophosphates , Phosphonothionates, borates, etc.), corrosion inhibitors, emulsifiers, emulsification Breaking agents, seal swelling agents, stain control additives and the like. lubricant When formulated as, the compositions of the present invention provide a particulate soot that inhibits power-properties. For demanding applications, such as diesel oil, which produces large amounts of Oil, circulating oil or fluid power oil, or thickening lubricating oil, such as grease, Used for somewhat less demanding applications.   The recommended use of the composition of the present invention is for lubricating oil applications, but also when used for fuels. Many of the same performance benefits are provided. 1 to 1,000 per 1000 barrels of fuel A component concentration of 0 pounds is recommended. The fuel composition comprises a hydrocarbon fuel, an oxygenated fuel, And a mixture of a hydrocarbon fuel and an oxygen-containing fuel. In fuels, aromatic fluids and dispersion It is particularly convenient to use a mixture of agents.   The following examples further illustrate the present invention.Controls A to G   This example illustrates the use of different amounts of organic-substituted diphenylsulphate in a representative lubricating mineral oil. The effect of mixing the sulfide on lubricity is illustrated.   In a flask with thermocouple and reflux condenser, vigorously stirred, diphenyl Sulfide (186.2 g, 1.0 mol) and 1-hexadecene (224.4 g, 1.0 mol) in a mixture of 19.1 g of FCC octacat^R(Octaca t^R) USY catalyst was added. The mixture is brought to 200 ° C. with stirring for 6 hours. Heated. After cooling to room temperature, the mixture was filtered to remove the catalyst and dried. 0.5-1.5 mmHg to remove corresponding starting materials. Reduced pressure to 170 ° C Distilled.   This diphenyl sulfide, which is substantially monoalkylated as described above ( ADPS) in different amounts at 40 ° C. for 100 Saybolt seconds. It was mixed with a paraffinic neutral lubricating base stock mineral oil having viscosity. This mixture, The lubricity of pure ADPS and mineral oil was determined by the test method of ASTM D2266 and And / or the four-ball wear test described in U.S. Pat. No. 4,761,482. It investigated using.   The results were taken as the wear scar diameter and the "K" factor. [It is a function of the wear volume and the product of the wear volume and the hardness of the metal] Dimensionless numerical value divided by the product). This "K" coefficient is If lubrication is maintained, it is relatively independent of test conditions. This “K” coefficient is Take into account the ruth diameter and extend the life of the machine under various operating and metallurgical conditions. Enables calculation of wear rates that can be associated.   As can be seen from the results in Table 1, other paraffinic neutral lubricating mineral oils 1, 2 and 5% of alkylated diphenyl sulphides without any additional components The wear behavior is hardly improved by mixing the alloy.Examples 1 and 2, and Controls HL   These examples are comparative examples in which the amount of ADPS described in the control example was blended. Effect of Polyisobutylene Succinate Imi on the Lubricity of Mineral Oils Described in Examples AG Dispersant and / or mixed alcohol derived zinc dithiophosphate (ZnDTP) Is illustrated. This polyisobutylene succinimide dispersant is And synthesized as described in U.S. Pat. No. 4,234,435, In formula (I), the group "R" in Formula 1) is a molecular weight as defined in that patent. And the group "Z" in the formula is a residue of polyisobutylene having Is the residue of a polyethylenepolyamine as defined in Zinc is represented by R in formula 4) given above for these compounds.₁And R_TwoBut C_Three~ C₈ Is a zinc salt of dithiophosphoric acid, which is a mixture of alkyl groups. These compositions are: Four ball abrasion tests were performed as described in Controls A to G. The composition of these compositions Table 2 shows the results and the test results.   The results in Table 2 show that the substituted diphenyl sulfide was treated with dispersant and dithiophosphate ( In the presence of Examples 1 and 2) added to mineral oil at a concentration of 10 and 25% This shows that the wear characteristics are improved. In contrast, 0.05% dithio 10 and 25% in the presence of phosphate but no polymeric dispersant When using the dithiophosphate of Examples (Examples K and L), the degree of improvement obtained was The degree is quite small.Examples 3 and 4, and Control Examples M and N   In these examples, a polymer-substituted succinimide-based ashless dispersant and dithiophos Effects of organics on the lubricity of mineral oil-based lubricants used to some extent, including fate The effect of the addition of substituted diphenyl sulfide is illustrated.   A polymer-substituted succinimide ashless dispersant prepared from mineral oil A fully formulated commercial diesel engine oil containing both zinc thiophosphate was added to GM's 6 . Coolant in a 2 liter diesel engine at 1,000 rpm for 50 hours And oil gallery temperature: 12 0 ° C, fuel flow rate: 9 kg / hour, fuel temperature and intake air temperature: 35 ° C And 32 ° C. Absolute intake pressure and back pressure are 97 kPa and 1 respectively. It was 0-3 kPa. During the time of this period, the wear resistance of this oil is partially Significantly reduced by the by-products (soot) produced in the process and by the degradation of the lubricant You. Wear protection of this oil containing (somewhat) worn dispersant and zinc dithiophosphate Was determined using the method of the previous example in two separate measurement experiments (Examples Ma and Mb). Was evaluated. In the previous example, the ADPS used in an amount of 0.5 wt% It was added to the partially worn oil and again tested in two other wear resistance evaluation tests (Examples 3a and 3a). And 3b). The results are shown in Table 3. In addition to the diameter of wear and the K coefficient, the diameter of wear / The values are shown including the value of the wear ratio defined as the Hertz diameter. For a load of 40 kg, The estimated average Hertz diameter = 0.30 (mm).   Based on different commercial mineral oils, polymer-substituted succinimide dispersants and di A diesel engine oil that also contains zinc thiophosphate, which is better for Example 3 and Control Example M The method was repeated. However, no ADPS was contained (Control Example N) and 5 wt% (Example 4) Evaluation of abrasion only once with oil that has been worn to some extent including ADPS Was. Table 4 shows the results.   As is evident from the data in Tables 3 and 4, the ashless dispersant and the dithiophosphate The presence of substituted diphenyl sulfides in oils containing both In the four-ball wear test, as determined by the "K" factor and wear ratio Wear damage is significantly reduced. The wear volume (“K” coefficient) is determined by substituted diphenyl When compared to the same oil without sulfide, it is reduced to 1/6 of their corresponding value Was found.

[Procedural amendment] [Date of submission] March 6, 1998 [Content of amendment] [Claims] 1.1) Organic ring-substituted diphenyl sulfide; 2) Polymer-substituted succinimide, succinamide and / or amber A dispersant component comprising an acid ester; and 3) a lubricant or fuel composition comprising dithiophosphate. 2. The composition of claim 1, wherein said organic substituted diphenyl sulfide is a monoalkyl or dialkyl diphenyl sulfide, wherein each alkyl group contains from 5 to 40 carbon atoms. 3. 3. The composition according to claim 2, wherein said organic substituted diphenyl sulfide is substantially a monoalkyl diphenyl sulfide, wherein said alkyl group contains from 10 to 20 carbon atoms. 4. 2. The composition according to claim 1, wherein the alcohol or phenol moiety of the ester group of the succinic ester contains an imide, amide or amine nitrogen functional group. 5. Wherein the dispersant comprises at least one compound having the formula 1): And / or succinamides comprising at least one compound having the formula 2): Wherein R is an alkyl group or an alkenyl group whose alkene is the residue of a polyalkene containing from 2 to 20 carbon atoms, and R contains at least 20 carbon atoms, and Z is Hydrogen or an aliphatic or aromatic organic group containing carbon, hydrogen and optionally nitrogen and / or oxygen, and / or reactive nitrogen of an amino compound which is reacted with a polymer-substituted succinic acid derivative-based acylating agent 3. The composition according to claim 1, wherein the composition is a residue attached to an atom. 6. Z in formula 1) and / or at least one Z in formula 2) is Wherein n is an integer less than 10, A is a hydrogen or hydrocarbon group, and the alkylene group has less than 8 carbon atoms. The composition according to claim 5, which is: 7. The amino compound has the formula: 7. An alkylene polyamine according to claim 6, wherein n is an integer less than 10, A is a hydrogen or hydrocarbon group, and the alkylene group has less than 8 carbon atoms. Composition. 8. The dithiophosphate has the formula: 8. The zinc salt of dithiophosphoric acid having the formula wherein R ₁ and R ₂ are each independently an alkyl group containing 3 to 30 carbon atoms. A composition according to claim 1. 9. The composition according to claim 1, comprising 0.5-95% by weight of the organic-substituted diphenyl sulfide, 0.1-25% by weight of the dispersant component, and 0.05-10% by weight of dithiophosphate. A composition as described. 10. The composition of claim 9 comprising 10.2 to 95% by weight of the organic-substituted diphenyl sulfide, 0.15 to 10% by weight of the dispersant component, and 0.1 to 5% by weight of dithiophosphate. Composition.

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Claims (1)

Claims: 1.1) an organic ring-substituted diphenyl sulfide; 2) a dispersant component comprising a polymer-substituted succinimide, a succinamide and / or a succinate, and 3) a dithiophosphate. A lubricant or fuel composition comprising. 2. The composition of claim 1, wherein said organic substituted diphenyl sulfide is a monoalkyl or dialkyl diphenyl sulfide, wherein each alkyl group contains from 5 to 40 carbon atoms. 3. 3. The composition according to claim 2, wherein said organic substituted diphenyl sulfide is substantially a monoalkyl diphenyl sulfide, wherein said alkyl group contains from 10 to 20 carbon atoms. 4. 2. The composition according to claim 1, wherein the alcohol or phenol moiety of the ester group of the succinic ester contains an imide, amide or amine nitrogen functional group. 5. The dispersant comprises at least one compound having the formula 1): And / or succinamides comprising at least one compound having the formula 2): Wherein R is an alkyl group or the residue of a polyalkene whose alkene contains from 2 to 20 carbon atoms, and R contains at least 20 carbon atoms, and Z is Reactivity of an amino compound reacted with hydrogen or an aliphatic or aromatic organic group containing carbon, hydrogen, and possibly nitrogen and / or oxygen, and / or a polymer-substituted succinic acid derivative-based acylating agent A residue attached to a nitrogen atom). 6. Z in formula 1) and / or at least one Z in formula 2) is Wherein n is an integer less than 10, A is a hydrogen or hydrocarbon group, and the alkylene group has less than 8 carbon atoms. The composition according to claim 5, which is a group. 7. The amino compound has the formula: Wherein n is an integer less than 10, A is a hydrogen or hydrocarbon group, and the alkylene group has less than 8 carbon atoms. A composition as described. 8. The dithiophosphate has the formula: (Wherein R ₁ and R ₂ are each independently an alkyl group containing 3 to 30 carbon atoms), which is a zinc salt of dithiophosphoric acid. A composition according to claim 1. 9. The composition of claim 1, comprising 0.5 to 95 wt% of the organic-substituted diphenyl sulfide, 0.1 to 25 wt% of the dispersant component, and 0.05 to 10 wt% of dithiophosphate. Composition. 10. The composition according to claim 9, comprising 10.2 to 95 wt% of an organic-substituted diphenyl sulfide, 0.15 to 10 wt% of a dispersant component, and 0.1 to 5 wt% of dithiophosphate. . 11. The composition according to claim 10, comprising 11.1 to 7 wt% of a dispersant component, and 0.2 to 3 wt% of dithiophosphate. 12. The composition of claim 1 further comprising a mineral oil, a synthetic oil, or a mixture of a mineral oil and a synthetic oil of lubricating oil viscosity. 13. 13. The composition according to claim 12, wherein said mineral oil, synthetic oil, or a mixture thereof is present in an amount of 2 to 98 wt%. 14． 14. The composition according to claim 13, wherein said mineral oil, synthetic oil, or mixture thereof is present in an amount of 5 to 90 wt%.