JPH07508049A - Lubricating oil composition containing mixed friction modifier - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Lubricating oil composition containing mixed friction modifier Mengogyodan 1 The present invention combines small amounts of alkylated phenol sulfides and alkoxylated hydrocarbons. Contains a friction modifier combination with bilamin and exhibits improved fuel economy The present invention relates to lubricating oil compositions.

m student 11 Provides lubricating oil compositions that show improved fuel efficiency in gasoline and diesel engine vehicles It is the goal of the automotive and petroleum industries to provide To achieve these goals In addition, a brake that significantly reduces friction between moving parts of the engine or transmission. Additives have been developed for rank case oils and transmission applications. This ma The reduction in friction can be expressed in terms of the amount of fuel consumed by an internal combustion engine. Modern lubricant compositions require complex formulations to accommodate the increasing mileage of automobiles. As such, such additives must be compatible with other components present in the oil. and conventional lubricant additives such as dispersibility, viscosity stability, corrosion, oxidation control, etc. should not have a negative impact on numerous other functions.

Representative examples of known oil additives or modifiers include fatty acid esters and amides. No. 3,933,659, Polyisobutenylsuccinic anhydride-aminoal No. 4,176,074 describing Cole's molybten complexes, trimerization. No. 4,105,571 disclosing glycerol esters of fatty acids, alkaline U.S. Pat. No. 3,779,928 discloses phosphine and olea No. 3,778,375 disclosing the reaction product with S-carboxya alkylene hydrocarbyl succinimide, S-carboxyalkylene hydrocarbyl No. 3,852,215, N- disclosing birsuccinic acid and mixtures thereof. Discloses (hydroxyalkyl)alkenylsuccinamic acid or succinimide No. 3,879,306, di(lower alkyl) phosphites and epoxies No. 3,932,290, which discloses reaction products with phosphorus sulfide N- Opening alkylene oxide adducts of droxyalkyl)alkenylsuccinamide No. 4,028,258.

Other known types of friction modifiers include those represented by general formulas 1 and 2 below. Examples include alkoxylated hydrocarbyl mono- or polyamines such as this The amines of U.S. Pat. No. 3,711,406, U.S. Pat. No. 659, No. 4010106, No. 4129508, No. 4170560, No. 4170560, No. N as disclosed in Nos. 4,231,883 and 4,795,583.

Substances such as N-bis(2-hydroalkyl)hydrocarbylamines may be mentioned. .

Additionally, U.S. Pat. No. 4,086,172 discloses that oil-soluble Mixing of hydroxyamines with oil-soluble antioxidant components such as aromatic sulfides Discloses an additive combination for lubricating oils comprising: This mixture is a lubricant It is said that it imparts improved antioxidant properties to.

U.S. Pat. No. 4,938,880 discloses metal salts of phenol sulfides and friction modifiers. Discloses a lubricating oil composition that can contain.

U.S. Pat. No. 4,764,294 discloses metal phosphates, metal carbamates and alkyl hydrides. Lubricating oil additives containing roxyaryl sulfide (nonylphenol sulfide) The combination is disclosed. The combination of these three additives improves wear resistance and It is said to provide synergistic improvements in imparting friction reduction and friction reduction properties.

U.S. Pat. No. 4,587,026 discloses oil additives useful for reducing friction and improving stability. It shows. This additive contains alkylated phenol sulfides and boron-containing compounds and alkoxylated amines, including bis(2-hydroxyethyl)oleamide. amines produced by forming reaction products with It is a sulfide concentrate. Claim 22 of this patent provides a clear structure of the reaction product. It is.

The present invention relates to one or more lubricating oil compositions as defined herein added in a specified proportion to a lubricating oil composition. the above alkoxylated hydrocarbylamine and one or more alkylated phenols The combination with rufido can be used in combination with equivalent amounts of either for such lubricating oil compositions. Based on the discovery that the components provide improved friction modulation properties than either component alone.

Menzudate 11 The present invention provides an improved lubricant assembly for automotive internal combustion engines and transmissions. A compound containing oil of lubricating viscosity that reduces the coefficient of friction between moving mechanical parts. A lubricant blended with a small amount of a friction modifier composition provides improved fuel economy. The present invention provides a lubricating oil composition.

This friction modifier composition comprises an alkoxylated hydrocarbylamine and an alkylated resin. Consists of a combination with phenol sulfide. This combination of ingredients is especially Formed in automotive crankcase lubricants that also contain conventional additive packages. Provides synergistic fuel economy when used in minutes. This action and effect are as follows. It is not observed in oils containing one or the other of these components alone.

Colored mouse Hisataka j Alkoxylated amines suitable as one component in the friction modifier compositions of the present invention include , general formula l and also includes its boronated derivatives. In the above formula, R1 is about 8 to A branched or straight chain hydrocarbyl group containing about 30 carbon atoms, R8 and and R3 are the same or different branched or straight chains each containing 1 to 6 carbon atoms. is an alkylene group, and R4, R, and R6 each contain 2 to 4 carbon atoms are the same or different alkylene groups, X is oxygen or sulfur, and p is O or is an integer within the range of 1 to 20, t is independently O or 1, and a, b and and C are each an integer within the range of 1 to 4. In a more preferred embodiment, R1 is Saturated or ethylenically unsaturated hydrocarbyl groups containing 12 to 24 carbon atoms and 1, R1 and R, each contain 2 to 4 carbon atoms, R4, R, and and R, each contain 2 or 3 carbon atoms, X is oxygen, and a, b and C are each an integer of 1 or 2. In the above formula, p and t are both or both p or t may be 1 when the other of them is 0. may be 1 or p may be from 1 to 20 when t is O.

In a most preferred embodiment, the alkoxylated amine has formula 2 a formula l having the formula: [wherein R', R', R', a and b are as defined above] (where p and t are each 0).

In the most preferred embodiment of the invention, as shown in formula 2, R1 is 12 to 24 carbon atoms. Saturated or ethylenically unsaturated hydrocarbyl groups having elementary atoms, especially tallow amino oleylamine, stearylamine, laurylamine, behenylamine, etc. and a mixture thereof, and R4 and R3 are each 2 or 3 groups. carbon atoms, and a=b=1.

Examples of more preferred alkoxylated amines within the scope of this invention include N, N ’,N’-tri(2-and droxyethyl)-N-octadecylpropylene di Amine, N, N', N'-)su(2-hydroxyethyl)-N-octadecace Nylpropylene diamine, hl, N', N'-tri(2-hydroxyethyl) thyl)-N-hexadecylpropylenediamine, N,N',N'-tri(3 -Hydroxypropyl)-N-ophtade force dienylbrobylenediamine, N,N ’,N’-tri(2-hydroxyethyl)-N-octadecylethylenedia min, N, N', N'-tri(2-hydroxyethyl)-N-octadecenyl Ethylenediamine, N, N', N'-)su(2-hydroxyethyl)-N- Tetradecylpropylene diamine, N,N-di(2-hydroxyethyl)oley N,N-di(2-hydroxyethyl)stearylamine, N,N-di (3-hydroxypropyl)tetradecylamine, N,N-di(2-hydroxy ethyl)octadecylamine, N,N-di(2-hydroxyethyl)eicosyl Amine, N,N-di(2-hydroxyethyl) tallow amine, N,N-di(2-hydroxyethyl) droxypropyl) tallow amine, N-(2-hydroxyethyl)-N-(hydro xyethoxyethyl)-n-dodecylamine, N,N-di(2-hydroxyethyl) )-1-methylundecylamine, N,N-di(2-hydroxyethoxyethoxyethyl)-1-methylundecylamine, xyethyl)-1-ethyloctadecylamine, N,N-di(2-hydroxyethyl)-1-ethyloctadecylamine, ethyl)-n-dodecyloxyethylamine, N,N-di(2-hydroxyethyl ) lauryloxyethylamine, N,N-di(2-hydroxyethyl) stearyl hydroxyethylamine, N,N-di(2-hydroxyethyl)-n-dodecylamine Xyprobylamine, N,N-di(2-hydroxyethyl)stearyloxyp Lopylamine, N,N-di(2-hydroxyethyl)dodecylthioethylamine , N,N-di(2-hydroxyethyl)dodecylthiopropylamine, N,N- di(2-hydroxyethyl)hexadecylthioethylamine, N,N-di(2- hydroxyethyl)hexadecylthiopropylamine, N-2-hydroxyethyl Ru-N-[N',N'-bis(2-hydroxyethyl)ethylamine]octa Decylamine, N-2-hydroxyethyl-N-[N', N'-bis(2-hy- droxyethyl Droxyethyl)ethylamine] stearylamine and analogues thereof; Examples include boronated derivatives.

Examples of the most preferred alkoxylated amines include formula 2 in which R4 and R6 are each is such that it has two carbon atoms, and N,N-bis(2-hydro xyethyl) tallowamine, N,N-bis(2-hydroxyethyl)-n-dodecyl Lamine, N,N-bis(2-hydroxyethyl)-1-methyltridodecyla Min, N.

N-bis(2-hydroxyethyl)hexadecylamine, N,N-bis(2-hydroxyethyl) Droxyethyl)octadecylamine, N,N-bis(2-hydroxyethyl) Octadecenylamine, N,N-bis(2-hydroxyethyl)oleylamine , N,N-bis(2-hydroxyethyl)stearylamine, N,N-bis(2-hydroxyethyl)stearylamine, N,N-bis(2-hydroxyethyl)stearylamine, -hydroxyethyl)undecylamine, and their boronated derivatives. .

Hydroxylamine compounds can be used as is. however , they are boron oxide, boron halide, metaborate, boric acid, or mono-, di- - and triorganoborates such as trialkyl borates. It can also be used in the form of an adduct or reaction product with a boron compound such as

Such adducts or derivatives can be prepared by contacting the above amine with a boronating agent. can be manufactured. Preferred boronating agents include boric acid and boric acid esters. Examples include tributyl borate. reaction to the hydroxyl groups present in the amine. Stoichiometric amounts of the boriding agent can be used, or up to 50-100% or A larger excess of boronating agent can be used, and this is It is often desirable to Typically, the boronation level is between about 0.05 and about 7% by weight boron in the boronated derivative. fluctuate.

Preferably, the boronated derivative is prepared in the presence of an alcohol or hydrocarbon solvent. Ru. However, the presence of a solvent is not essential; if used, it may be reactive or non-reactive, suitable non-reactive solvents include benzene, toluene, , xylene, etc. Suitable reactive solvents include isopropanol, alcohol The reaction temperature is approximately 0°C to approximately 250°C, including tanol, pentanol, etc. 110 to about 170°C is preferred.

The second essential component in the friction modifier composition of the present invention is represented by the following general formula 3: In formula 1, R7 and R8 are hydrogen or the same containing about 5 to 40 carbon atoms. may be different hydrocarbyl groups, but less of R7 or Ra (both 1 is a hydrocarbyl group, X is an integer from 1 to 4, and n is O or 1 to an integer of 4] or is a mixture of them. In a preferred embodiment, R7 is phenol sulfidated. an alkyl group of sufficient chain length to render the compound oil-soluble, and preferably an average and contains about 8 to 20 carbon atoms, n is O, l or 2, preferably 0; X is l or 2 preferably l and R1 is hydrogen. Most preferred of the invention In a new embodiment, R7 is located in the p-position relative to the hydroxyl group and Yellow is attached to the aromatic nucleus in the 0-position relative to the hydroxyl group.

Hydrocarbylphenol sulfides are primarily oxidized in lubricant compositions. It is a known substance used as an inhibitor. These are hydrocarbyl fe or by direct sulfurization of halogens such as sulfur dichloride or sulfur monochloride. It can be easily produced by reaction with sulfur. The reaction product is generally contains mixed phenol sulfide isomers, but the specific isomers mentioned above are Consists of main ingredients.

Preferred phenol sulfides for use in the present invention are primarily 06-C+s Based on phenol monosulfide, with p-nonylphene as the main isomer. Contains phenol monosulfide and p-decylphenol monosulfide.

The lubricating oil base that can be blended with the friction modifier composition of the present invention includes natural diesel and gasoline engines, including synthetic lubricants and mixtures thereof. Automotive crankcase and transmission oils with lubricating viscosity for both It will be done.

Natural oils include animal or vegetable oils such as castor oil or lard oil, liquid petroleum oils and and hydrogenated refined oils, paraffins, naphthenes and mixed paraffin-naphthene type solvents Processed or processed mineral lubricating oils may be mentioned. Also derived from coal or shale Oils of lubricating viscosity are also useful base oils.

Synthetic lubricating oils include polymerized and copolymerized olefins (e.g., polybutylene, polyolefins, propylene, propylene-isobutylene copolymer), chlorinated polybutylene, poly Hydrocarbons such as (1-hexene), poly(1-octene), poly(l-decene) Substituted hydrocarbons, alkylbenzenes (e.g. dodecylbenzene, tetrohydrocarbons, radecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene), as well as polyphenols (e.g. biphenyls, terphenyls, alkylated polyphenyls) phenyl).

Another group of known synthetic lubricating oils are alkylene polymers and copolymers and derivatives thereof. conductor (where the terminal hydroxyl groups are modified by esterification or etherification) These are the polymerization of ethylene oxide or propylene oxide. exemplified by polyoxyalkylene polymers produced by Examples include alkyl or aryl ethers of these polyoxyalkylene polymers. for example, methylpolyisopropylene glycol with an average molecular weight of 1000. polyether, diphthalate of polyethylene glycol with a molecular weight of 500-1000 phenyl ether, polypropylene glycol with a molecular weight of 1000-1500 diethyl ether, and acetate ester of tetraethylene glycol, hybrid Cs “”’ Those such as C fatty acid ester and C oxo acid diester mono- and polycarboxylic acid esters.

Another suitable group of synthetic lubricants include dicarboxylic acids (e.g. phthalic acid, succinic acid, Rukylsuccinic acid, alkenylsuccinic acid, maleic acid, azelaic acid, speric acid , sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid and alkenyl malonic acid) and various alcohols (e.g. butyl alcohol). alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol ethylene glycol, diethylene glycol monoether and propylene including one or more esters with (recall). Specific examples of these esters Examples include dibutyl adipate, di(2-ethylhexyl) sebacate, and fumarate. di-n-hexyl acid, dioctyl sebacate, diisopropyl azelaate, Diisodecyl gelate, dioctyl phthalate, dodecyl phthalate, sebacic acid dieicosyl, 2-ethylhexyl diester of linoleic acid dimer, and 1 mole of sebacic acid to 2 moles of tetraethylene glycol and 2 moles of 2-ethyl Included are complex esters formed by reacting xanoic acids.

In addition, esters useful as synthetic oils include C1-C1 monocarboxylic acids and polyols. alcohols and polyol ethers such as neopentyl glycol, trimethylol, Lopane, pentaerythritol, dipentaerythritol and tripentaerythritol Also mentioned are those made from litol.

Another useful group of synthetic lubricating oils are polyalkyl-, polyaryl-polyalkoxy - or with silicon-based oils such as polyaryloxysiloxane oils and silicate oils. be. Examples of these are tetraethyl silicate, tetraisopropyl silicate, Tetra(2-ethylhexyl), Tetra(4-methyl-2-ethylhexyl silicate) ), tetra(p-t-butylphenyl) silicate, hexa(4-methyl-2-pent) xy)disiloxane, poly(methyl)siloxane and poly(methylphenyl)siloxane Roxane is mentioned. Other synthetic lubricants are liquid esters of phosphorus-containing acids (e.g. Tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphine ) and polymeric tetrahydrofuran.

Unrefined oils, refined oils, and rerefined oils can be used in the lubricating oils of the present invention. . Unrefined oils are those obtained directly from natural or synthetic sources and are subject to further refining treatment. For example, shale oil obtained directly from carbonization operations, or esters obtained directly from an esterification process. Unrefined oil is one that is used without further processing. Refined oil is unrefined oil are similar to , except that they include one or more additives to improve one or more properties. It has been further processed in the purification process. Those skilled in the art will appreciate that distillation, solvent extraction, acid or salt Many such purification techniques are known, such as radical extraction, filtration and percolation. . Rerefined oil is a method similar to that used to obtain refined oil, but used It is obtained by a method applied to refined oils that have already been subjected to. Such re-refining Oil is also known as recycled oil or reprocessed oil, and is a product of spent additives and oil breakdown. May be additionally processed by material removal techniques.

Each of the components in the friction modifier composition of the present invention is Lubricating oil base in an amount that reduces the coefficient of friction between parts and thereby improves fuel economy. mixed into the base material. Generally speaking, alkoxy added to the base oil The amount of amine is about 0.05 to 1.0% by weight and preferably about 0.1 to 0.0% by weight. It is within the range of 5% by weight. Hydrocarbylphenols added to base oil The amount of ruphide is about 0.1-2.5% by weight and preferably about 0.2-1.0% by weight. The amount is within the range of %. Alkoxylated amines vs. hydrocarbylphenolsulfur The preferred weight ratio of It is within the range of 1 to 1.5:1. Most preferably, the phenol sulfide is in excess of the amount of amine, preferably less (both about a 2:1 to 5:1 weight excess) exists in

The lubricating oil of the present invention preferably also includes one or more lubricants to form a fully formulated oil. Additional additives are mixed. Such additives include dispersants, detergents, Inhibitors, viscosity modifiers, corrosion inhibitors, other friction modifiers, antifoaming agents, anti-wear additives, etc. can be mentioned.

Suitable dispersants that can be used are known in the art. Preferred group of dispersants are ashless dispersants, which are usually nitrogen-containing oil-soluble dispersants of mono- or dicarboxylic acids. It is a salt, amide, imide or ester. A particularly preferred dispersant is polyisobutylene Polyolefin-substituted succinic anhydrides and alkylene polyolefins such as nylsuccinic anhydride is a reaction product with lyamine, and this is further treated with a source of boron or copper be able to. Such materials are disclosed in U.S. Pat. No. 4,938,880; , see if necessary, such dispersants generally contain about 0. 1 to approx. It is added to the oil in an amount within the range of 10% by weight.

Metal-containing rust inhibitor additives and/or detergents are often used with ashless dispersants . Such detergents and antiseptic additives include metal salts of sulfonic acids, fatty acid esters, etc. e.g. glycerol mono- and/or distearate (which can be used as a friction modifier) < ), alkylphenol, sulfurized alkylphenol, alkyl salicylate oils, naphthenates, and other oil-soluble mono- and dicarboxylic acids. Qing Highly basic or overbased metal salts often used as detergents include calcium magnesium or magnesium phenates, sulfurized phenates and/or sulfonates. These metal-containing inhibitors and detergents typically weigh less than 0% of the total lubricating oil composition. in a lubricating oil in an amount of about 0.01-10% by weight, preferably about 0.1-5% by weight based on used for. Marine diesel lubricating oils typically contain such reduced metal content. Agents and detergents are used in amounts up to about 20% by weight.

The lubricating oil also contains one or more suitable antioxidants and/or oxidation inhibitors. You can also do that. Suitable antioxidants include phenol and hindered phenol. , bisphenols, sulfurized phenols, catechols, alkylated and sulfurized alkyls alkylated catechol, diphenylamine, alkylated diphenylamine and phenyl- 1-Naphthylamine, alkyl and aryl borates, phosphites and phosphites esters, trialkyl and triaryldithiophosphates, and the like. other Examples of antioxidants include oil-soluble copper compounds. This copper compound is cuprous and copper, which may be in the form of dihydrocarbylthio- or dithiophosphate May be in the form of copper.

Alternatively, copper can be added as a copper salt of a synthetic or natural carboxylic acid. . Examples of these include C3° to C+a, such as stearic acid or valmitic acid. Examples include fatty acids. Unsaturated acids such as oleic acid or those with a molecular weight of 2°O to 500 Branched or synthetic carboxylic acids such as naphthenic acid are preferred because For example, the handleability and solubility of the obtained copper carboxylate are improved.

Also useful are oil-soluble steel dithiocarbamates. Also, copper sulfonate, nates and acetylacetonates can also be used. Copper antioxidants Copper salt of dorocarbyl-substituted 04-C1° monounsaturated dicarboxylic acid forming reaction product It can consist of This reaction product has a molecular weight of 900 to 1400 (for example, 70 A polymer of 02 to C1 monoolefin having a number average molecular weight of 0 to 1200) 04-Coo formed by reacting monounsaturated acid materials. these Examples include hydrocarbyl-substituted 04-C0° monounsaturated dicarboxylic acid-forming reaction products. It is a copper salt. This reaction product has a number average molecular weight of 900-1400 02~C0゜A group consisting of acid, anhydride, and ester groups in monoolefin polymers wherein polymer 1 is formed by reacting succinic acid moieties selected from On average, about 0.8 to 1.6 mole proportions of succinic acid moieties are present per mole.

Copper antioxidants are generally added to oil in an amount of 50 to 500 ppm (by weight) of metal parts. added.

Corrosion inhibitors (also known as corrosion inhibitors) are substances that lubricating oil compositions come into contact with. This reduces deterioration of the metal members of the rollers. Examples of corrosion inhibitors are phosphorus sulfide carbide Preferably hydrogen and phosphorus sulfide hydrocarbons with alkaline earth metal oxides or hydroxides. and also preferably in the presence of alkylated phenols or alkylphenols. It is a product obtained by reacting in the presence of carbon dioxide. phosphorus sulfur Carbonized hydrocarbons include 02-C, olefin polymers such as polyisobutylene, heavy petroleum A suitable hydrocarbon such as a terpene, which is a distillate, is combined with 5-30% by weight of phosphorus sulfide and 15% by weight of phosphorus sulfide. Produced by reacting for 0.5 to 15 hours at a temperature within the range of 0 to 600°C. It will be done. Neutralization of phosphosulfurized hydrocarbons is carried out according to the methods taught in U.S. Pat. No. 1,969,324. It can be done with

Oxidation inhibitors reduce the tendency of mineral oils to deteriorate during use. This deterioration is the formation of oxidation products such as sludge and fest-like deposits on metal surfaces and This can be evidenced by an increase in viscosity. Such oxidation inhibitors are preferably or C1 to C1, alkylphenol thioester having an alkyl side chain. Potassium earth metal salt, calcium nonylphenol sulfide, barium t-octyl Ruphenylsulfide, dioctyl phenylamine, phenyl alpha naphthylamine , phosphorus sulfide or sulfurized hydrocarbon.

Pour point depressants reduce the temperature at which the oil flows or the temperature at which the oil can be poured. It is something that makes you Such depressants are well known. Optimizing the cold flow properties of oil Typical examples of those useful for Cs=C+a dialkyl fumarate/biacetate Nyl copolymers, polymethacrylates and wax naphthalenes.

Control of foaming can be achieved by using antifoaming agents of the polysiloxane type, such as silicone oils and polysiloxanes. It can be provided by tilsiloxane.

Another group of additives that can be included in oils are often used as antiwear additives. dihydrocarbyl dithiophosphate metals that are used and also provide antioxidant activity. It's salt. These compounds generally have the formula [wherein R9 and RIO are each are independently hydrocarbyl groups containing from 3 to about 13 carbon atoms, and M is metal, and n is an integer equal to the valence of M]. I can do it. The hydrocarbyl group in the phosphorodithioate structure is an alkyl group. cycloalkyl, or alkaryl group (which forms an ether or ester bond) and may also contain substituents such as halogen or nitro). It will be done. Examples of alkyl groups include isopropyl, isobutyl, n-butyl, Butyl, amyl, n-hexyl, methylisobutyl, carbinyl, heptyl, 2 -ethylhexyl, diisobutyl, isooctyl, nonyl, behenyl, decyl, Examples include dodecyl and tridecyl. Examples of lower alkylphenyl groups are: xylyl, cresyl, butylphenyl, amyl phenyl, heptylphenyl, etc. Can be mentioned. Cycloalkyl groups are useful as well, and examples of these include Mainly cyclohexyl and lower alkylcyclohexyl groups are mentioned. Also , many substituted hydrocarbon groups, such as chlorbentyl, dichlorophenyl and dichlorphenyl. Roldecyl can also be used.

These compounds first form the appropriate phosphorodithionic acid and then convert this product into Manufactured by reacting appropriate metal-containing compounds.

Phosphorodithionic acid is a mixture of phosphorus pentasulfide, alcohol, phenol, and alcohol. reacting substances, mixtures of phenols, or mixtures of alcohols and phenols. Manufactured by. This reaction involves 4 moles of alcohol per mole of phosphorous pentasulfide. or requires phenol, and from about 50 to about 200°C, preferably from about 50 to about 1 It can be carried out within a temperature range of 50°C. Thus, 0.0-ge n-heki The production of sylphosphorodithionic acid involves adding 4 moles of n-hexyl alcohol to phosphorus pentasulfide. 100° C. for about 2 hours. Hydrogen sulfide is released and its The residue is the specified acid. The production of metal salts of this acid involves reaction with metal oxides. Therefore, it can be done.

Simply mixing and heating these two reactants is sufficient to cause the reaction to occur. and the product obtained has sufficient purity for the purposes of the present invention. .

Metal salts of dihydrocarbyl phosphorodithionate useful in the present invention include: Group 1 metals, Group 1I metals, aluminum, lead, tin, manganese, cobalt and Examples include salts containing nickel and nickel. Preferred metals include Group 1I metals. metals such as tin, iron, cobalt, lead, manganese, nickel and copper. zinc and copper are particularly useful metals. Examples of metal compounds that can be reacted with acids and Lithium oxide, lithium hydroxide, sodium hydroxide, sodium carbonate, Potassium hydroxide, potassium carbonate, silver oxide, magnesium oxide, water, magnesia oxide um, calcium oxide, zinc hydroxide, zinc oxide, copper oxide, strontium hydroxide , cadmium oxide, cadmium hydroxide, barium oxide, iron carbonate, copper hydroxide, hydroxide Examples include lead chloride, butyl tin, cobalt hydroxide, nickel hydroxide, nickel carbonate, etc. It will be done.

In some cases, a small amount of metal acetate or acetic acid may be used in combination with the metal reactant. Addition of seed components accelerates the reaction and provides improved products. For example, using up to about 55% zinc acetate in combination with the required amount of zinc oxide, The production of zinc phosphorodithionate is promoted.

In one preferred embodiment, the alkyl groups R@ and RIG in the above formula are Propyl almal, nibutyl alcohol, 2-pentanol, 4-methyl -2-pentanol, 2-hexanol, 3-hexanol and mixtures thereof derived from secondary alcohols such as

These compounds generally contain from about 0.01 to about 5% by weight, preferably from about 0.1 to about It is blended into the lubricating oil composition within a range of 3% by weight. Preferred compounds are dihydro Zinc carbyl dithiophosphite.

Viscosity modifiers provide high and low temperature operability to lubricating oils. remains relatively viscous at high temperatures, yet has an acceptable viscosity or indicates fluidity, and viscosity modifiers are generally polyesters and polymethacrylates. , a polymer-positioned combination containing polyacrylate and polyolefin. Also, Viscosity modifiers may be used to include other properties or functions, such as to impart dispersibility. It can also be derivatized as These oil-soluble viscosity-adjusting polymers are generally , 101-101 when measured by gel permeation chromatography or osmotic pressure method. 10' preferably io' to 10', e.g. 2.0000 to 250,000 number average It has a molecular weight.

Examples of suitable hydrocarbon polymers include both alpha-olefins and internal olefins. Two or more types of 02-C1° olefin monomers including aliphatic, aromatic, alkyl-aromatic, cycloaliphatic, etc.), e.g. 0 2-C, olefin homopolymers and copolymers. Particularly preferred polymerization The body is made of polyisobutylene, C! and homopolymerization of higher α-olefins polymers and copolymers, active polypropylene, halogenated polymers, styrene and For example copolymers and terpolymers with isoprene and/or butadiene and 0 polymers, which are hydrogenated derivatives of can reduce the molecular weight and can contain oxygen.

These viscosity modifiers are typically added to the oil at levels within the range of about 0.1% to about 10% by weight. added to the product.

It also stabilizes the compatibility of lubricating oil compositions containing relatively high levels of friction modifiers. In some cases, it may be desirable to include additives that act to Examples of such additives and is a hydrocarbyl-substituted succinic acid, more preferably a polyolefin-substituted succinic acid. citric acid anhydride (wherein the polyolefin is about 500 to 10,000, preferably about having a number average molecular weight of 100 to 3000). Preferred polyole Fin substituents include polyisobutylene, polybutene-1, and butene-1 and ethylene and/or propylene. for this purpose A preferred compatibilizer is polyisobutenylsuccinic anhydride. This ingredient is approximately be present in the lubricating oil composition at a level within the range of 0.1-5% by weight (and Preferably, it is present at a level approximately equal to the total weight of the friction modifier.

Compositions containing one or more of these numerous additives typically contain incorporated into the lubricating oil by physical mixing in an amount effective to provide the normal and specific functions of the lubricating oil. will be combined.

The improved lubrication provided by the compositions within the scope of the present invention is 5equence It is called VI Dynaometer Fuel Economy test. things, more specifically A S T M 5equence VI test m Illustrated using ethod RR: Do-2: 1204 can be done. This test is performed at a relatively constant engine temperature of 150°F or 275°F. equipped with cooling means to maintain engine oil temperature, and strictly control engine speed and power. 3.8 liters connected to a power absorption dynamometer for precise control. It is implemented using the vinyl V6 engine.

The lubricant to be evaluated is first flushed into the engine and then heated to 225°F. Aged for 32 hours at oil temperature. Then set the engine to a specific speed and power and tested at two test stage temperatures of 150@F and 275@F. The engine was tested prior to each experiment using industry standard viscosity and friction adjustment reference oils. Set. At each stage, calculate the average consumption of the brakes. After completion of the measurement phase First, flush out the lubricating oil in the engine with cleaning fluid, then apply 5AE30 base rubber. Pour into the oil and repeat the measurements. Then use these measurements to Equivalent Fuel Economy of target oil for line oil Calculate Improvement (EFFI).

The data reported here is a complete A S7 M5 sequence VI tes t cycle or 5eq where the test oil is made into a shortened time Shortened version of ucence VI test (5equence Vl 5cree ner test).

The following examples further illustrate the invention.

Kuko 22 Approximately 94.5 parts by volume of mineral oil with the following additive ingredients in amounts effective to bring the total to 100 parts: , ・Polybutenylsuccinic anhydride polyamine product (boronated), ・Basic petroleum magnesium sulfonate, ・Mixed 2-methylpropertool, penta Zinc salts of ion-1-ol and 3-methylbutanol phosphorodithioate, ・Oil-soluble copper compound, ・Bis-alkarylamine.

・Demulsifier, ・Antifoaming agent, ・Pour point depressant, ・Viscosity modifier, A base control SAEIOM-30 formulation was prepared by mixing.

This base control formulation was taken and the following friction modifier components were added in the following volumes (V).

Example 1: Control formulation + 0.5% V, 0 mixed nonylphenol sulfides Example 2: Control formulation + 0°2% V,N,N-bis(2-hydroxyethyl) beef tallow a min Example 3: Control formulation + 0.5% V, mixed nonylphenol JI/]()” +0 ．． 2% V,N,N-bis(2-hydroxyethyl) tallow amine Example 4: Control formulation + 〇, 2% V,N,N-bis(2-hydroxypropyl) beef tallow amine Example 5: Control formulation +0.5% V, mixed nonylphenol sulfide” +0.2 %V,N,N-bis(2-hydroxypropyl) tallow amine Example 6: Control formulation + 0.2% V, boronated N, N-bis(2-hydroxyethyl) tallow amine Example 7: Control formulation + 0.5% V, mixed nonylphenol sulfide” + 0.2% V, boronated boronated N-bishydroxyethyl) tallow amine 67% active ingredients by weight For the control formulation and each formulation of Examples 1-7, the 5equence VI above dynanometer fuel economy 5cleaner I went to st. The recorded EFEI test results are as follows.

Recorded EFE I test results Control 1.81 Example 1 1.74 Example 2 2.28 Example 3 2.65 Example 4 1.86 Example 5 2.15 Example 6 2.08 Example 7 2.91 Test results show that mixed nonylphenol sulfide (NPS) was included in the control base formulation. When added alone at a level of 0.5% by volume compared to the control, the EFEI test results (1.74 vs. 1.81), e.g. NPS with N,N-bis(2-hydroxyethyl) tallowamine as in 3. When combined at 0.5% by volume and 0.2% by volume respectively, 2,65 EFETs Test results are obtained which indicate that the amine was added at 0.2% by volume as in Example 2. is better than the actual EFET value when used alone. In addition, control base NPS used in conjunction with sterilization formulations results in lower EFEI values and should not be recorded. What are the EFEI test results?

This is higher than expected.

NFS was added to N,N-bis(2-hydroxypropyl) tallow as shown in Example 5. and also boronated N,N-bis(2-hydroxypropylene) as shown in Example 7. Similar unexpected results are obtained when combined with tallow amine.

Thus, the present invention may be incorporated into lubricating oil formulations containing alkoxylated amine friction modifiers. hydrocarbylphenol sulfide (which by itself has friction-enhancing properties) (not shown at all) can significantly and synergistically improve the lubricity of the lubricating oil. Being touched.

international search report 1-115. -1-1+-ρCT/US 9310337B front page continuation (51) Int, C1,' Identification symbol Internal reference number Cl0N 40:04 (72) Inventor Rich, Andrew James Dalgel United States 07928 New Chassis, Chatham, Casitabury Lo Code 83I (72) Inventor Liar, Jack United States 08816 New Chassis, East Brunswick, jensen street 61

Claims (24)

[Claims] 1. The main amount of oil of lubricating viscosity, (i) General formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [wherein R1 is a branched or straight chain hydrocarbon containing about 8 to about 30 carbon atoms] is a rubyl group, R2 and R3 are homologs or R3 each containing 1 to 6 carbon atoms. are different branched or straight chain alkylene groups, and R4, R5 and R6 are each 2 the same or different alkylene groups containing ~4 carbon atoms, and X is oxygen or sulfur, p is 0 or an integer within the range of 1 to 20, and t is independently 0 or 1. and a, b and c are each integers within the range of 1 to 4]. about 0.05 to about 1.0% by weight of an alkoxylated amine, and (ii) the general formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [wherein R7 and R8 are hydrogen or the same species containing about 5 to 40 carbon atoms] may be different hydrocarbyl groups, but at least one of R7 or R8 is a hydrocarbyl group, x is an integer from 1 to 4, and n is 0 or 1 to 4. from about 0.1 to about 2.5% by weight of at least one hydrocarbon having an integer of 4] carbylphenol sulfide, A lubricating oil composition made by mixing. 2. Amine is the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ The composition according to claim 1, comprising: 3. A composition according to claim 1, wherein R1 contains 12 to 24 carbon atoms. 4. The composition according to claim 1, wherein R1 is a tallow group. 5. A composition according to claim 1, wherein R4, R5 and R6 contain 2 carbon atoms. 6. The composition according to claim 2, wherein a and b are each 0. 7. Amine is N,N-bis(2-hydroxyethyl) tallow amine or its boronization The composition according to claim 2, which is a derivative. 8. R7 contains on average about 8 to about 20 carbon atoms and R8 is primarily The composition according to claim 1, which is hydrogen. 9. 9. The composition of claim 8, wherein R7 contains on average 9 carbon atoms. 10. 9. The composition according to claim 8, wherein n is 0. 11. 9. The composition according to claim 8, wherein x is 1. 12. Hydrocarpylphenol sulfide is P-nonylphenol sulfide The composition according to claim 11. 13. the amine includes N,N-bis(2-hydroxyethyl) tallow amine, and 3. The composition of claim 2, wherein the sulfide comprises p-nonylphenol sulfide. 14. 2. The amine is present in the oil at a level of about 0.1% to about 0.5% by weight. composition. 15. Phenol sulfide is present in the oil at a level of about 0.2% to about 1.0% by weight The composition according to claim 14. 16. Dispersants, detergents, oxidation inhibitors, viscosity modifiers, corrosion inhibitors, anti-wear additives , an effective amount of at least one additive selected from the group consisting of antifoaming agents and friction modifiers. The composition according to claim 1, further comprising an additive. 17. Claims where the additive comprises a dihydrocarpyldithiophosphite zinc antiwear additive 16. The composition according to 16. 18. If the additive is a mixture of glycerol monooleate and glycerol dioleate, 17. The composition according to claim 16, comprising a compound. 19. Claim 16 wherein the additive comprises a magnesium or calcium sulfonate detergent. Compositions as described. 20. The additive is a polyolefin-substituted succinic anhydride and alkylene as a dispersant. 17. The reaction product of claim 16, comprising a reaction product with a polyamine or a boronated derivative thereof. Composition. 21. In the lubricating oil composition, (i) the general formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [wherein R1 is a branched or straight chain hydrocarbon containing about 8 to about 30 carbon atoms] is a rubyl group, R2 and R3 are homologs or R3 each containing 1 to 6 carbon atoms. are different branched or straight chain alkylene groups, and R4, R5 and R6 are each 2 the same or different alkylene groups containing ~4 carbon atoms, and X is oxygen or sulfur, p is 0 or an integer within the range of 1 to 20, and t is independently 0 or 1. and a, b and c are each integers within the range of 1 to 4]. about 0.05 to about 1.0% by weight of an alkoxylated amine, and (ii) the general formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [wherein R7 and R8 are hydrogen or the same species containing about 5 to 40 carbon atoms] may be different hydrocarpyl groups, but at least one of R7 or R8 is a hydrocarbyl group, x is an integer from 1 to 4, and n is 0 or 1 to 4. from about 0.1 to about 2.5% by weight of at least one hydrocarbon having an integer of 4] carpylphenol sulfide, A method for improving the frictional properties of a lubricating oil composition comprising mixing. 22. Amine is the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ 22. The method according to claim 21. 23. R1 contains 12 to 24 carbon atoms and R4 and R5 have 2 carbon atoms 23. The method of claim 22, wherein a and b are each 1. 24. 24. wherein R7 is nonyl, x is 1 and n is 0. Method.