JP2008127563A - Lubricant composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an additive composition which can bring at least one of the reduction of thin film friction and the improvement of fuel economy, and to provide a lubricant composition. <P>SOLUTION: This additive composition comprises a cleanser and an additive selected from a phosphorus-containing compound, a friction-improving agent, and a dispersant, and exhibits at least one of smaller thin film friction and improved fuel efficiency than those of additive compositions not containing the cleanser and the additive. The lubricant composition comprises a major amount of a base oil and a small amount of the additive composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present disclosure provides base oil and additive compositions [which include additives and detergents selected from, for example, phosphorus-containing compounds, friction modifiers and dispersants, and further examples of friction modifiers and dispersants. It is related with the lubricating oil composition containing. Also disclosed are methods of using the additives and lubricating oil compositions.

  In recent years, there has been an increasing need to produce energy efficient lubricated parts. In addition, modern engine oil specifications require lubricants that show fuel efficiency in standardized engine tests. It is known that the thickness and friction characteristics of a thin film of lubricating oil affect fuel efficiency characteristics such as crankcase oil and gear oil. Improved fuel efficiency is achieved by reducing thin film friction. Thin film friction is friction caused by a fluid that pushes between two surfaces where the distance between the two surfaces is very narrow, such as a lubricating oil. It is known that various additives normally present in lubricating oil compositions can form films of various thicknesses that can affect thin film friction. It is known that the addition of certain additives, such as zinc dialkyldithiophosphate (ZDDP), to the base oil increases the thin film friction. Such additives need to be present in the lubricant for the purpose of protecting the engine and gear, however, such high film friction can be detrimental to fuel efficiency.

  In addition, certain additives are also known to be very expensive. Also, the use of additional amounts in the lubricating oil composition that are intended to reduce thin film friction can be very expensive for the manufacturer.

  There is a need for lubricating oil compositions that are inexpensive and can provide at least one of reduced thin film friction and improved fuel economy.

SUMMARY OF THE DISCLOSURE In accordance with the present disclosure, an additive composition is disclosed, comprising an additive selected from a phosphorus-containing compound, a friction modifier and a dispersant and a detergent, wherein the additive composition Indicates at least one of reduced thin film friction and improved fuel efficiency compared to additive compositions without the detergent or additive.

  According to another aspect, an additive composition comprising a friction modifier and a dispersant is disclosed, wherein the additive composition is an additive composition that does not contain the friction modifier or the dispersant. Shows at least one of reduced thin film friction and improved fuel efficiency.

  In accordance with yet another aspect, a method for reducing the thin film friction exhibited by a fluid between surfaces is disclosed, the method comprising adding a base oil and additive composition to the fluid (which includes phosphorus-containing compounds, friction modifiers and dispersants). Providing a lubricating oil composition comprising an additive selected from and a detergent.

  In addition, a method for reducing the thin film friction exhibited by a fluid between surfaces is also disclosed, which includes adding a base oil and additive composition to the fluid (which comprises a friction modifier and a dispersant). Providing a lubricating oil composition comprising.

Further disclosed is a method for improving fuel efficiency in a vehicle, which includes a base oil and additive composition (which includes additives and cleaning selected from phosphorus-containing compounds, friction modifiers and dispersants). Providing a composition comprising an agent).

  In various aspects, a method for improving fuel efficiency in a vehicle is also disclosed, the method including a base oil and additive composition (which comprises a friction modifier and a dispersant) in the vehicle. Providing a composition comprising:

  Additional benefits of this aspect, to some extent, are set forth in the following description and can be learned by practitioners of the present disclosure. Such advantages are realized and attained using elements and combinations particularly pointed out in the appended claims.

  It is to be understood that both the general description provided above and the detailed description provided below are merely exemplary and explanatory and are not restrictive of the disclosure as claimed.

DESCRIPTION OF EMBODIMENTS The present disclosure comprises a minor amount of a base oil and a minor amount of an additive composition, which comprises an additive selected from a phosphorus-containing compound, a friction modifier and a dispersant, and a detergent. For lubricating oil compositions, where the additive composition exhibits at least one of reduced thin film friction and improved fuel efficiency as compared to an additive composition without the detergent or the additive. . The additive composition in one aspect can comprise a friction modifier and a dispersant.

  Any necessary or effective amount of base oil may be present in the lubricating composition. For example, such a base oil may be present in a major amount. “Major amount” is understood to mean equal to or greater than 50% by weight, based on the total weight of the composition. As a further example, such a base oil may be in an amount equal to or greater than 80% by weight, based on the total weight of the composition, and as an additional example, an amount equal to or greater than 90% by weight. May be present.

  Base oils suitable for use in formulating the lubricating oil compositions disclosed herein can be selected from either synthetic or mineral oils or mixtures thereof. Mineral oils include animal and vegetable oils (eg, castor oil, lard oil) as well as other lubricating mineral oils such as liquid petroleum and solvent treated or acid treated paraffinic, naphthenic or paraffinic-naphthenic mixtures Contains a type of lubricating mineral oil. Oils derived from coal or shale are also suitable. Furthermore, oils obtained by a gas-to-liquid process may also be suitable.

  Non-limiting examples of synthetic oils include hydrocarbon oils such as olefin polymers and copolymers (eg polybutylene, polypropylene, propylene and isobutylene copolymers); polyalphaolefins [eg poly (1-hexene), Poly- (1-octene), poly (1-decene) and the like and mixtures thereof]; alkylbenzene [eg, dodecylbenzene, tetradecylbenzene, di-nonylbenzene, di- (2-ethylhexyl) benzene, etc.]; polyphenyl ( For example, biphenyl, terphenyl, alkyl-substituted polyphenyl, etc.); alkyl-substituted diphenyl ethers and alkyl-substituted diphenyl sulfides, and derivatives, analogs and homologues thereof.

  Accordingly, the base oils that can be used in making the compositions as described herein can be selected from any of the base oils belonging to Group I-IV as specified by the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. It is. Such base oil groups are as follows:

  Group I has a saturate content of less than 90% and / or a sulfur content greater than 0.03% and a viscosity index equal to or greater than 80 and less than 120, Group II has a saturate content The amount is equal to or greater than 90% and the sulfur content is equal to or less than 0.03% and the viscosity index is equal to or greater than 80 and less than 120; III has a saturate content equal to or greater than 90% and a sulfur content equal to or less than 0.03% and a viscosity index equal to or greater than 120 And Group IV is polyalphaolefin (PAO).

  The test method used in the group limitation is one of ASTM D2007 for saturates, ASTM D2270 for viscosity index, and ASTM D2622, 4294, 4927 and 3120 for sulfur.

  Group IV base stocks, or polyalphaolefins (PAOs), include hydrogenated oligomers of alpha-olefins, the most important methods of oligomerization being free radical methods, Ziegler catalysis, and cationic, free It is a Del Crafts catalytic reaction.

  The viscosity of such polyalphaolefins at 100 ° C is typically from about 2 to about 100 cSt, for example from about 4 to about 8 cSt at 100 ° C. They may be, for example, branched or linear alpha-olefin oligomers having from about 2 to about 30 carbon atoms, including, but not limited to, polypropene, polyisobutene, poly-1-butene, poly-1- Hexene, poly-1-octene and poly-1-decene are included. Homopolymers, copolymers and mixtures are included.

  Base stocks suitable for use herein can be produced using a wide variety of methods including, but not limited to, distillation, solvent purification, hydroprocessing, oligomerization and Repurification is included.

Such base oils may be oils derived from Fischer-Tropsch synthetic hydrocarbons. Fischer-Tropsch synthesized hydrocarbons can be produced from synthesis gas containing H ₂ and CO using a Fischer-Tropsch catalyst. Such hydrocarbons typically require further processing in order to make it useful as a base oil. For example, such hydrocarbons may be hydroisomerized using the methods disclosed in US Pat. No. 6,103,099 or 6,180,575, or US Pat. It may be hydrocracked and hydroisomerized using the methods disclosed in US Pat. No. 4,943,672 or 6,096,940 or disclosed in US Pat. No. 5,882,505. May be dewaxed using the methods described, or use the methods disclosed in US Pat. Nos. 6,013,171, 6,080,301 or 6,165,949. Hydroisomerization and dewaxing may be performed.

  Unrefined, refined, and rerefined oils of the type of mineral or synthetic oil disclosed above (as well as mixtures of any two or more thereof) can be used as the base oil. Unrefined oils are oils obtained directly from mineral oils or synthetic sources without further purification. For example, shale oil obtained directly from retort harvesting operations, petroleum oil obtained directly from primary distillation, or ester oil obtained directly from the esterification process (used without further treatment) would be unrefined oil. Refined oils are similar to unrefined oils except that they have undergone further processing in one or more purification stages to improve one or more properties. Many such purification techniques are known to those skilled in the art, such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, and the like. The re-refined oil can be obtained by applying the same treatment as that used for obtaining the refined oil to the refined oil that has already been used in practice. Such rerefined oils are also known as reclaimed or reprocessed oils, and often they undergo additional processing using techniques aimed at removing spent additives, contaminants and oil breakdown products. ing.

  Certain oils within such types of base oils may be used because of the specific properties they exhibit, such as biodegradability, high temperature stability, or incombustibility. In other compositions, other types of base oils may be preferred due to availability or low cost. Accordingly, those skilled in the art can use the various types of base oils discussed above in the lubricating oil composition of the present invention, while they do not necessarily correspond to each other in all applications. You will recognize.

  In one aspect, a cleaning agent suitable for use in the additive composition disclosed herein can be a metal-containing cleaning agent. Suitable metal-containing detergents include alkali or alkaline earth metals and the following acidic substances (or mixtures thereof): (1) sulfonic acid, (2) carboxylic acid, (3) salicylic acid, (4) alkylphenol, ( One or more oil-soluble neutral or overbased salts in 5) sulfurized alkylphenols and (6) organophosphoric acids (characterized by having at least one direct carbon-phosphorus bond) may be included. Such organophosphoric acids include olefin polymers (eg, polyisobutylene having a molecular weight of about 1,000), phosphating agents such as phosphorous trichloride, phosphorous pentasulfide, phosphorous pentasulfide, phosphorous trichloride and sulfur, white phosphorous, and the like. Phosphoric acid produced by treatment with sulfur halide, phosphorothioic acid chloride or the like may be included.

  In the context of metal-containing detergents, the term “overbase” is used to indicate metal salts in which the metal is present in a stoichiometrically higher amount than the organic group. Commonly used methods for producing overbased salts include the use of a mineral oil solution of acid in a stoichiometric excess of a metal neutralizing agent such as metal oxides, hydroxides, carbonates, bicarbonates or It involves filtering the resulting product after heating to a temperature of about 50 ° C. with sulfides and the like. It is likewise known to use a “facilitator” in the neutralization stage with the aid of taking up a large excess of metal. Examples of compounds useful for use as a promoter include phenolic materials such as phenol, naphthol, alkylphenols, thiophenols, sulfurized alkylphenols, and condensation products of formaldehyde and phenolic materials, alcohols such as methanol, 2-propanol , Octanol, 2-ethoxyethanol, ethyl ether of diethylene glycol, ethylene glycol, stearyl alcohol and cyclohexyl alcohol, and the like, and amines such as aniline, phenylenediamine, phenothiazine, phenyl-beta-naphthylamine, and dodecylamine. A particularly effective method for forming a basic salt is to mix an acid with an excess of a basic alkaline earth metal as neutralizing agent and at least one facilitating alcohol and into the mixture carbon dioxide. At a high temperature, for example from 60 ° C to 200 ° C.

  Examples of suitable metal-containing detergents include, but are not limited to, neutral sodium sulfonate, overbased sodium sulfonate, sodium carboxylate, sodium salicylate, sodium phenate, sodium sulfide phenate, sulfonic acid Lithium, lithium carboxylate, lithium salicylate, lithium phenate, lithium sulfide phenate, calcium sulfonate, calcium carboxylate, calcium salicylate, calcium phenate, calcium sulfide phenate, magnesium sulfonate, magnesium carboxylate, magnesium salicylate, magnesium Phenate, magnesium sulfide phenate, potassium sulfonate, potassium carboxylate, potassium salicylate, potassium phenate, potassium sulfide phenate, sulfonate , Zinc carboxylic acid, neutral and overbased salts of such substances, such as zinc salicylate, zinc phenates and sulfurized zinc phenates. Further examples include phosphosulfurized hydrolysates of olefins having from about 10 to about 2,000 carbon atoms or alcohol and / or fatty substituted phenol compounds having from about 10 to about 2,000 carbon atoms Calcium, lithium, sodium, potassium and magnesium salts of phosphosulfide hydrolysates. Further examples include calcium, lithium, sodium, potassium and magnesium salts of aliphatic and aliphatic substituted alicyclic carboxylic acids, and similar alkali and alkaline earth metal salts of various other oil-soluble organic acids. It is. It is also possible to use a mixture of neutral or overbased salts of two or more different alkali and / or alkaline earth metals. It is also possible to use neutral and / or overbased salts of mixtures of two or more different acids.

  As is well known, overbased metal detergents are generally considered to contain inorganic bases in an overbased amount and are generally in the form of microdispersions or colloidal dispersions. Thus, when applying the term “oil-soluble” to a metal-containing detergent, the term includes a metal with an inorganic base (which need not be completely or truly oil-soluble in the strict sense of the term) It is intended to include a cleaning agent because when it is mixed with a base oil it behaves in much the same way as if it were completely dissolved in the oil. Because. The various metal-containing detergents indicated above are sometimes collectively referred to as neutral, basic or overbased alkali metal or alkaline earth metal-containing organic acid salts.

  Methods for producing oil-soluble neutral and overbased metal-containing detergents and alkaline earth metal-containing detergents are well known to those skilled in the art and have been extensively reported in the patent literature. U.S. Pat. Nos. 2,001,108; 2,081,075; 2,095,538; 2,144,078; 2,163,622; 2,270,183; 2,292,205; 2,335 2,399,877; 2,451,345; 2,451,346; 2,485,861; 2,501,731; 2,501,732; 2,585,520; 2,671,758; 2,616,904; 2,616,905; 2,616,906; 2,616,911; 2,616,924; 2,616,925; 2,617,049; 2, 695,910; 3,178,368; 3,367,867; 3,496,105; 3,629,109; 3,865,737; 3,907,691; 4,100,085; 4,129 589; 4,137,184; 4,184,740; 4,212,752; 4,617,135; 4,647,387 and references No. 4,880,550.

  The metal-containing detergent used in the present invention may be an oil-soluble neutral boronated and / or overbased alkali or alkaline earth metal-containing detergent, if necessary. For example, US Pat. Nos. 3,480,548; 3,679,584; 3,829,381; 3,909,691; 4,965,003, and 4,965,004 It is described in.

  Such detergents may be present in any necessary or effective amount in the lubricating oil composition. In one aspect, the lubricating oil composition is about 0.01 wt% to about 0.8 wt%, such as about 0.05 wt% to about 0.6 wt%, based on the total weight of the lubricating composition. % By weight, for example from about 0.09% to about 0.4% by weight. In one aspect, the additive composition is added to about 0.06 wt% to about 5 wt%, such as about 0.30 wt% to about 3.6 wt%, based on the total weight of the additive composition. %, For example, from about 0.54 wt% to about 2.38 wt%. However, one of ordinary skill in the art will appreciate that any amount can be used.

  The disclosed additive composition may contain a phosphorus-containing compound. The phosphorus-containing compound in one aspect can be a metal-containing phosphorus-containing compound. Such metal-containing phosphorus-containing compounds may be, for example, metal dihydrocarbyl dithiophosphates. The metal of the metal dihydrocarbyl dithiophosphate may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. A zinc salt that can be used can be, for example, zinc dialkyldithiophosphate.

The preparation of such metal dihydrocarbyl dithiophosphates was first made by reacting dihydrocarbyl dithiophosphate (DDPA), usually with one or more alcohols or phenols, and P ₂ S ₅ according to known techniques. It can be carried out by neutralizing DDPA produced later with a zinc compound. For example, dithiophosphoric acid can be produced by reacting a mixture of a primary alcohol and a secondary alcohol. Alternatively, multiple dithiophosphoric acids can be prepared that contain both hydrocarbyl groups that are secondary in nature and hydrocarbyl groups that are primary in nature. Any basic or neutral zinc compound can be used in the production of the zinc salt, but most commonly oxides, hydroxides and carbonates are used.

Zinc dihydrocarbyl dithiophosphate is an oil-soluble salt of dihydrocarbyl dithiophosphoric acid, which has the following formula: [(RO) (R ¹ O) P (S)] ₂ Z _n , where R and R ¹ Can be the same or different and include hydrocarbyl groups having from about 1 to about 18, such as from about 2 to about 12 carbon atoms (including groups such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and alicyclic groups). ) May be expressed. The R and R ¹ groups on one face may be alkyl groups having from about 2 to about 8 carbon atoms. Thus, this group is for example ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, amyl, n-hexyl, i-hexyl, n-octyl, decyl, dodecyl, octadecyl, 2- It may be ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl and the like. For the purpose of obtaining oil solubility, the total number of carbon atoms (ie R and R ¹ in dithiophosphate) may generally be 5 or more. Thus, the zinc dihydrocarbyl dithiophosphate may include a zinc dialkyldithiophosphate.

  In addition, such phosphorus-containing compounds include oil-soluble amine salts of phosphate esters, such as US Pat. Nos. 5,354,484 and 5,763,372, the disclosures of which are hereby incorporated by reference. And the reaction products of dicyclopentadiene and thiophosphoric acid, and the like taught in

  Such an amine salt of a phosphate ester can be prepared by reacting the phosphate ester with ammonia or a basic nitrogen compound such as an amine. The salt may be formed separately and then the phosphate salt may be added to the lubricating composition.

  Useful phosphate esters for use in preparing the amine salts of the present invention are of the formula

[Wherein R ¹ may be hydrogen or a hydrocarbyl group, R ² may be a hydrocarbyl group, and both X groups may be either O or S]
Can be characterized.

An exemplary method of producing a composition containing (I) is to formulate at least one hydroxy compound of the formula ROH, wherein R may be a hydrocarbyl group, and the formula P ₂ X ₅ [ Wherein X may be O or S]. The phosphorus-containing compound obtained in this manner can be a mixture of phosphorus compounds, generally mono- and dihydrocarbyl substituted phosphoric acid and / or thiophosphoric acid depending on the choice of phosphorus reactant (ie P ₂ O ₅ or P ₂ S ₅ ) It is a mixture of

  The hydroxy compounds used in the preparation of the phosphate esters of the present disclosure can be characterized by the formula ROH, where R can be a hydrocarbyl group. The hydroxy compound to be reacted with the phosphorus compound includes a mixture of hydroxy compounds represented by the formula ROH, wherein the hydrocarbyl group R may contain from about 1 to about 30 carbon atoms. obtain. However, the resulting amine salt of the substituted phosphate ester must be soluble in the lubricating composition of the present disclosure. The number of carbon atoms contained in the R group is generally at least about 2, and the number of carbon atoms is typically from about 3 to about 30.

  The R group may be a fatty or aromatic group such as an alkyl, aryl, alkaryl, aralkyl and alicyclic hydrocarbon group. Non-limiting examples of useful hydroxy compounds represented by the formula ROH include, for example, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, amyl alcohol, hexyl alcohol, 2-ethyl-hexyl alcohol, nonyl alcohol, dodecyl alcohol, stearyl alcohol. , Amylphenol, octylphenol, nonylphenol, methylcyclohexanol and alkyl-substituted naphthol.

  The alcohol in one aspect, ROH, may be an aliphatic alcohol, such as a primary aliphatic alcohol containing at least about 4 carbon atoms. Thus, examples of typical monohydric alcohols ROH that may be useful for use in the present disclosure include amyl alcohol, 1-octanol, 1-decanol, 1-dodecanol, 1-tetradecanol, 1-hexadecanol, 1-octadecanol, oleyl alcohol, linoleyl alcohol, linoleyl alcohol, phytol, myricyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol are included. As used herein, commercial alcohols (including mixtures) are contemplated, and such commercial alcohols may contain minor amounts of alcohols that are not specified herein but do not detract from the main purpose of the present disclosure.

The molar ratio of hydroxy compound ROH to phosphorus reactant P ₂ X ₅ included in the reaction should be in the range of about 1: 1 to about 4: 1, with a typical ratio of 3: 1. This reaction can be carried out simply by mixing the two reactants at an elevated temperature, for example from about 50 ° C. or higher to a composition temperature indicated by either the reactant or the desired product. In one aspect, the temperature may range from about 50 ° C. to about 150 ° C., and most often less than about 100 ° C. This reaction can be performed in the presence of a solvent that facilitates temperature control and mixing of the reactants. Such a solvent may be either an inert flowable material in which one or both reactants are soluble or the product is soluble. Such solvents include benzene, toluene, xylene, n-hexane, cyclohexane, naphtha, diethyl ether carbitol, dibutyl ether dioxane, chlorobenzene, nitrobenzene, carbon tetrachloride and chloroform.

  The product of the reaction is acidic but does not accurately confirm its chemical composition. However, there is evidence to show that the product is a mixture of acidic phosphates mainly containing mono- and di-esters of phosphoric acid (or thio- or dithiophosphoric acid), whose ester groups are derived from the alcohol ROH. Exists.

The preparation of the amine salts of the present disclosure involves the reaction of a phosphate ester as described above, such as the phosphate ester of formula I, and at least one amino compound (which may be primary or secondary). It can be implemented. In one aspect, the amine reacted with the substituted phosphoric acid for the purpose of forming the amine salt has the general formula:
R'NH ₂
[Wherein R ′ may be a hydrocarbyl group having about 150 carbon atoms or less, and more often an aliphatic hydrocarbyl group having about 4 to about 30 carbon atoms]
It is a primary hydrocarbylamine represented by these.

  In one aspect, hydrocarbyl amines useful for use in forming the amine salts of the present disclosure are those wherein the hydrocarbyl group contains from about 4 to about 30 carbon atoms, for example, the hydrocarbyl group contains from about 8 to about 20 carbon atoms. It may be a primary hydrocarbylamine. Such hydrocarbyl groups may be saturated or unsaturated. A representative example of a primary saturated amine is the example known as an aliphatic primary fatty amine. Typical fatty amines include alkylamines such as n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n- Octadecylamine (stearylamine) and the like are included. Such primary amines are available in both distillation quality and industrial quality. Although distillation quality results in a reaction product that is more pure, reaction with industrial grade amines will also produce the desired amides and imides. Mixed fatty amines are also suitable.

In another aspect, the amine salt of the phosphorus-containing compound may be a compound derived from a tertiary aliphatic primary amine in which an alkyl group has at least 4 carbon atoms. They can be derived mostly from alkylamines having less than about 30 carbon atoms that the entire alkyl group contains. Tertiary aliphatic primary amines are usually of the formula
R (CH ₃ ) ₂ CNH ₂
[Wherein R may be a hydrocarbyl group having 1 to about 30 carbon atoms]
It is the monoamine represented by these. Examples of such amines are t-butylamine, t-hexyl primary amine, 1-methyl-1-amino-cyclohexane, t-octyl primary amine, t-decyl primary amine, t-dodecyl primary. It may be a primary amine, t-tetradecyl primary amine, t-hexadecyl primary amine, t-octadecyl primary amine, t-tetracosanyl primary amine, t-octacosanyl primary amine.

Mixtures of amines are also useful for purposes of this disclosure. Examples of this type of amine mixture are mixtures of C ₁₁ -C ₁₄ tertiary alkyl primary amines and similar mixtures of C ₁₈ -C ₂₂ tertiary alkyl primary amines. Tertiary alkyl primary amines and their methods of preparation are well known to those of ordinary skill in the art and therefore no further discussion will be necessary. Tertiary alkyl primary amines useful for the purposes of this disclosure and methods for their preparation are described in US Pat. No. 2,945,749, incorporated herein by reference with respect to teachings thereon. ing.

  Primary amines in which the hydrocarbon chain contains olefinic unsaturation are also very useful. Thus, R ′ and R ″ groups may contain one or more olefinic unsaturations, depending on the length of the chain, but the number of double bonds is generally no more than 1 per 10 carbon atoms. Typical amines are dodecenylamine, myristolamine, palmitoleylamine, oleylamine and linoleylamine.

  Secondary amines include dialkylamines having two alkyl groups as indicated above, including such commercially available fatty secondary amines, and also mixed dialkylamines [where R ′ is It may be a fatty amine and R ″ may be a lower alkyl group (having 1-9 carbon atoms) such as methyl, ethyl, n-propyl, i-propyl, butyl, etc., or R ″ may be Even alkyl groups with other non-reactive or polar substituents (CN, alkyl, carbalkoxy, amide, ether, thioether, halo, sulfoxide, sulfone) that do not destroy the essential hydrocarbon character of the group Good] is also included. Such fatty polyamine diamines include symmetric or asymmetric mono- or dialkylethylene diamines, propane diamines (1, 2 or 1, 3) and the aforementioned polyamine analogs. Suitable polyamines include N-coco-1,3-diaminopropane, N-soya alkyl trimethylene diamine, N-tallow-1,3-diaminopropane or N-oleyl-1, 3-diaminopropane is included.

  The oil-soluble amine salt can be prepared by mixing the above-described phosphate ester and the above-described amine at a temperature of room temperature or higher. Generally, about 1 hour is sufficient for mixing at room temperature. The amount of amine reacted with the phosphate ester for the purpose of forming a salt of the present disclosure is at least about 1 equivalent weight amine (based on nitrogen) per equivalent of phosphoric acid, and the equivalent ratio is generally about 1.

  Suitable methods for generating such amine salts are well known and reported in the literature. For example, U.S. Pat. Nos. 2,063,629; 2,224,695; 2,447,288; 2,616,905; 3,984,448; 4,431,552; 5,354,484, Pesin et al. , Zhurnal Obshchei Kimii, Vol. 31, No. 8, pages 2508-2515 (1961) and PCT International Application Publication No. WO 87/07638, the entire disclosures of which are incorporated herein by reference.

  Alternatively, when an acidic phosphate ester is mixed with the above-described amine, such salts can be generated in situ when generating the gear oil concentrate or the formulated gear oil itself.

  Other phosphorus-containing compounds suitable for use in the lubricating compositions presented herein include the reaction product of dicyclopentadiene and thiophosphoric acid (also referred to herein as dicyclopentadiene dithioate). Thiophosphoric acid has the formula:

[Wherein R may be a hydrocarbyl group having from about 2 to about 30, such as from about 3 to about 18, carbon atoms]
It is represented by In one aspect, R includes a mixture of hydrocarbyl groups having from about 3 to about 18 carbon atoms.

  In one aspect, such phosphorus-containing compounds are at least one of neopentyl glycol phosphite, sulfur-containing neopentyl glycol phosphite and sulfur-containing neopentyl glycol phosphite salts.

Such dicyclopentadiene dithioate can be prepared by mixing dicyclopentadiene and dithiophosphoric acid for a sufficient time at a temperature sufficient to react the thioacid with dicyclopentadiene. Typical reaction times can range from 30 minutes to 6 hours, but one skilled in the art will readily be able to determine appropriate reaction conditions. The reaction product may be subjected to conventional post-reaction treatments, such post-reaction treatments include vacuum stripping and filtration.

  Such phosphorus-containing compounds may be present in the lubricating oil composition in any necessary or effective amount. In one aspect, the lubricating oil composition is added to about 0.05 wt% to about 3 wt%, such as about 0.2 wt% to about 1.5 wt%, based on the total weight of the lubricating composition. As a further example, about 0.3 wt% to about 1 wt% may be included. In one aspect, the additive composition is added to about 0.3 wt% to about 18 wt%, such as about 1.2 wt% to about 8.9 wt%, based on the total weight of the additive composition. %, For example, from about 1.8% to about 6% by weight. However, one of ordinary skill in the art will appreciate that any amount can be used.

  The disclosed additive composition may also contain a friction modifying compound. Friction modifiers suitable for use in the disclosed additive composition can be selected from a number of suitable compounds and materials useful for providing such functionality to the lubricating oil composition. Such friction modifiers can be used as a single compound or as a mixture of various types of compounds. Non-limiting examples of friction modifiers include nitrogen-containing compounds, ash-containing compounds and nitrogen-free compounds. In one aspect, the disclosed lubricating composition may contain a nitrogen-free compound and a molybdenum-containing compound.

  The nitrogen-containing compound may be any compound containing basic nitrogen. The nitrogen-containing compound in one aspect can be a long chain alkylene amine. Long chain alkylene amine compounds for friction improvement include, for example, N-fatty hydrocarbyl substituted trimethylene diamines, wherein the N-fatty hydrocarbyl substituent has at least carbon atoms in the range of from about 14 to about 20 without acetylenic unsaturation. A straight chain fatty hydrocarbyl group). A non-limiting example of such a friction modifier compound is N-oleyl-trimethylenediamine. Other suitable compounds include N-tallow-trimethylene diamine and N-coco-trimethylene diamine.

  One group of friction modifiers includes N-fatty hydrocarbyl substituted diethanolamines, wherein the N-fatty hydrocarbyl substituent has at least one linear chain having no acetylenic unsaturation in the range of about 14 to about 20 carbon atoms. A fatty hydrocarbyl group).

As used herein, the term “hydrocarbyl substituent” or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group in which the carbon atom is directly bonded to the rest of the molecule and has predominantly hydrocarbon character. Examples of hydrocarbyl groups include the following:
(1) Hydrocarbon substituents, ie, fat (eg, alkyl or alkenyl), alicyclic (eg, cycloalkyl, cycloalkenyl) substituents and aromatic substitutions, aliphatic and alicyclic aromatic substituents as well as rings are A cyclic substituent completed through another moiety (eg, two substituents together form an alicyclic group);
(2) Substituted hydrocarbon substituents, ie groups other than hydrocarbons [this is in the context of the present invention a group which does not change the hydrocarbon-dominated substituents such as halo (especially chloro and fluoro), hydroxy, Alkoxy, mercapto, alkylmercapto, nitro, nitroso and sulfoxy];
(3) Hetero substituents, i.e. mainly having hydrocarbon character, but in connection with the present invention, atoms other than carbon in rings or chains composed of carbon atoms (hetero atoms include sulfur, oxygen, nitrogen (Including substituents such as pyridyl, furyl, thienyl and imidazolyl). The number of non-hydrocarbon substituents present per 10 carbon atoms in the hydrocarbyl group is generally 2 or less, such as 1 or less, and typically the number of non-hydrocarbon substituents present in the hydrocarbyl group is zero. is there.

  As discussed above, such friction modifiers include mixtures of various compounds, such as at least one N-fatty hydrocarbyl substituted diethanolamine and at least one N-fatty hydrocarbyl substituted trimethylenediamine (of which N -Fatty hydrocarbyl substituents may include combinations such as those having at least one straight chain fatty hydrocarbyl group having from about 14 to about 20 carbon atoms without acetylenic unsaturation. Further details regarding such friction modifier combinations are provided in US Pat. Nos. 5,372,735 and 5,441,656, the disclosures of which are hereby incorporated by reference.

  Such friction modifiers may be ash-containing compounds. The ash-containing compound in one aspect may be a molybdenum-containing compound. Molybdenum-containing compounds suitable for use in the lubricating compositions disclosed herein may not contain sulfur and / or phosphorus. Preparation of the molybdenum-containing compound containing neither sulfur nor phosphorus can be carried out by reacting a molybdenum source containing neither sulfur nor phosphorus with an organic compound containing amino and / or alcohol groups. Examples of molybdenum sources that do not contain sulfur or phosphorus include molybdenum trioxide, ammonium molybdate, sodium molybdate, and potassium molybdate. The amino group may be a monoamine, diamine or polyamine. The alcohol group may be a monosubstituted alcohol, a diol or bis-alcohol or a polyalcohol. As an example, reacting a diamine with a fatty oil results in a product containing both amino and alcohol groups, which may be reacted with a molybdenum source that contains neither sulfur nor phosphorus.

  Examples of molybdenum-containing compounds that do not contain sulfur or phosphorus as found in patents and patent applications, which are hereby incorporated by reference in their entirety, include: US Pat. No. 4,259,195 And a compound produced by reacting a molybdenum source as defined in US Pat. No. 4,261,843 with certain basic nitrogen compounds, a molybdenum source as defined in US Pat. No. 4,164,473, and A compound formed by reacting a hydrocarbyl-substituted hydroxyalkyl-substituted amine, a molybdenum source as defined in US Pat. No. 4,266,945, a monoalkyl-substituted alkylenediamine and a phenol aldehyde condensation product. The resulting compound, a module as defined in US Pat. No. 4,889,647. Compound formed by reacting buden source, diethanolamine and fatty oil, molybdenum source as defined in US Pat. No. 5,137,647, 2- (2-aminoethyl) aminoethanol and fatty oil or acid A compound formed by reacting a secondary amine with a molybdenum source as defined in US Pat. No. 4,692,256, US Pat. No. 5,412,130 A compound produced by reacting a molybdenum source as defined in No. 1 with a diol, diamino or amino-alcohol compound, a molybdenum source as defined in European Patent Application EP 1 136 496 A1, a fatty oil and a monoalkyl Compound produced by reacting substituted alkylene diamine, published in European patent Compound formed by reacting a molybdenum source as defined in application EP 1 136 497 A1, a fatty acid, a monoalkyl substituted alkylenediamine and a glyceride, molybdenum as defined in US Pat. No. 4,889,647 A compound produced by reacting a source, fatty oil and diethanolamine.

In one aspect, molybdenum-containing compounds containing sulfur can also be used in the lubricating compositions disclosed herein. The preparation of such sulfur-containing molybdenum-containing compounds can be performed using a variety of methods. One method involves reacting a sulfur and / or phosphorus-free molybdenum source with an amino group and one or more sulfur sources. Sulfur sources include, but are not limited to, for example, carbon disulfide, hydrogen sulfide, sodium sulfide, and elemental sulfur. Alternatively, such a sulfur-containing molybdenum-containing compound can be prepared by reacting a sulfur-containing molybdenum source with an amino or thiuram group and optionally a second sulfur source. As an example, molybdenum dioxide, secondary amine, and carbon disulfide are reacted to form molybdenum dithiocarbamate. Alternatively, (NH ₄ ) ₂ Mo ₃ S ₁₃ ^* n (H ₂ O) [where n is in the range of about 0 to 2] and tetraalkylthiuram disulfide are reacted to form trinuclear sulfur. This produces a molybdenum dithiocarbamate.

Non-limiting examples of sulfur-containing molybdenum-containing compounds found in patents and patent applications include: Molybdenum trioxide as defined in US Pat. Nos. 3,509,051 and 3,356,702 A compound formed by reacting a secondary amine with carbon disulfide, a sulfur-free molybdenum source as defined in US Pat. No. 4,098,705, a secondary amine and carbon disulfide; Compounds produced by reacting additional sulfur sources, compounds produced by reacting molybdenum halides, secondary amines and carbon disulfide as defined in US Pat. No. 4,178,258 U.S. Pat. Nos. 4,263,152, 4,265,773, 4,272,387, 4,285,822, 4,369,119, 4,395,343 Compound formed by reacting molybdenum source with basic nitrogen compound and sulfur source as defined, ammonium tetrathiomolybdate and basic nitrogen compound as defined in US Pat. No. 4,283,295 A compound formed by reacting an olefin, sulfur, an amine and a molybdenum source as defined in US Pat. No. 4,362,633, US Pat. No. 4,402,633, Compound formed by reacting ammonium tetrathiomolybdate, a basic nitrogen compound and an organic sulfur source as defined in US Pat. No. 840, a phenolic compound as defined in US Pat. No. 4,466,901 , A compound produced by reacting an amine, a molybdenum source and a sulfur source, US Pat. No. 4,765,918 A compound formed by reacting a triglyceride, a basic nitrogen compound, a molybdenum source and a sulfur source as defined in US Pat. No. 4,966,719, an alkali metal alkylthioxanthate as defined in US Pat. No. 4,966,719 A compound formed by reacting a salt with molybdenum halide, a compound formed by reacting tetraalkylthiuram disulfide with molybdenum hexacarbonyl as defined in US Pat. No. 4,978,464, Compounds formed by reacting an alkyl dicanthogen and molybdenum hexacarbonyl as defined in US Pat. No. 4,990,271; alkyls of alkali metals as defined in US Pat. No. 4,995,996 Generated by reacting xanthate salt with dimolybdenum tetraacetate Compound was reacted U.S. Patent No. 6,232,276 No. such as defined in ^{_{(NH 4) 2 Mo 3 S}} 13 * 2 H 2 O with an alkali metal dialkyl dithiocarbamate or tetraalkylthiuram disulfides of A compound formed by reacting an ester or acid, a diamine, a molybdenum source and carbon disulfide as defined in US Pat. No. 6,103,674, US Pat. No. 6,117 , 826, a compound formed by reacting an alkali metal dialkyldithiocarbamate with 3-chloropropionic acid followed by molybdenum trioxide.

  Non-limiting examples of molybdenum-containing compounds include molybdenum carboxylates, molybdenum amides, molybdenum thiophosphates, molybdenum thiocarbamates, molybdenum dithiocarbamates, and the like.

  Additional examples of ash-containing compounds include, but are not limited to, titanium-containing compounds and tungsten-containing compounds.

  Another suitable group of friction modifiers includes nitrogen-free compounds, polyol esters such as glycerol monooleate (GMO), glycerol monolaurate (GML), and the like.

  The amount of such friction modifying compound present in the lubricating composition can be any desired or effective amount. In one aspect, the amount included in the lubricating composition is from about 0.05 to about 3 weight percent, for example from about 0.2 to about 1.5 weight percent, based on the total weight of the lubricating composition. As a further example, it may be about 0.3 to about 1% by weight. In one aspect, the additive composition includes about 0.3% to about 18%, such as about 1.2% to about 8.9%, based on the total weight of the lubricating composition. %, For example, from about 1.8% to about 6% by weight. However, one of ordinary skill in the art will appreciate that any amount can be used.

  Suitable dispersants for use in the disclosed additive composition can be selected from any of the ashless dispersants known to those skilled in the art. Suitable ashless dispersants may include ashless dispersants such as succinimide dispersants, Mannich base dispersants and high molecular weight polyamine dispersants. Hydrocarbyl substituted succinic acylating agents can be used to generate hydrocarbyl substituted succinimides. Such hydrocarbyl-substituted succinic acylating agents include, but are not limited to, hydrocarbyl-substituted succinic acid, hydrocarbyl-substituted succinic anhydride, hydrocarbyl-substituted succinic acid halides (eg, acid fluoride and acid chloride), and hydrocarbyl-substituted An ester of succinic acid and a lower alcohol (for example, having 7 or less carbon atoms), that is, a hydrocarbyl-substituted compound that can function as a carboxylic acylating agent is included.

  The hydrocarbyl substituted acylating agent can be prepared by reacting maleic anhydride with a polyolefin or chlorinated polyolefin of appropriate molecular weight. It is also possible to use similar carboxylic reactants when producing such acylating agents. Such reactants include, but are not limited to, maleic acid, fumaric acid, malic acid, tartaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, ethyl maleic anhydride, anhydrous Dimethylmaleic acid, ethylmaleic acid, dimethylmaleic acid, hexylmaleic acid, etc. (including the corresponding acid halides and lower fatty esters) can be included.

  The molecular weight of such olefins can be varied depending on the intended use of the anhydrous substituted succinic acid. Typically, such anhydrous substituted succinic acid may have a hydrocarbyl group with about 8 to 500 carbon atoms. However, in the case of anhydrous substituted succinic acid used in the manufacture of lubricant dispersions, the hydrocarbyl group provided therein may typically have about 40-500 carbon atoms. When high molecular weight anhydrous substituted succinic acid is used, it is more accurate to refer to the number average molecular weight (Mn) because the olefins used in the production of such anhydrous substituted succinic acid have a low molecular weight. This is because the molecular weight resulting from the polymerization of various olefin monomers such as ethylene, propylene and isobutylene can include a mixture of various components.

  The molar ratio of maleic anhydride to olefin can vary widely. It can vary, for example, from about 5: 1 to about 1: 5, or such as from about 1: 1 to about 3: 1. When using olefins such as polyisobutylene and ethylene-alpha-olefin copolymers having a number average molecular weight of from about 500 to about 7000, or by way of example, from about 800 to about 3000 or more, the maleic anhydride is stoichiometric. An excess may be used, for example, 1.1 to 3 moles of maleic anhydride per mole of olefin. Unreacted maleic anhydride may be evaporated from the resulting reaction mixture.

Polyalkenyl succinic anhydride can be converted to polyalkyl succinic anhydride using normal reducing conditions such as catalytic hydrogenation. A suitable catalyst for catalytic hydrogenation is palladium on carbon. Similarly, polyalkenyl succinimide can be converted to polyalkyl succinimide using similar reducing conditions.

  As used herein, polyalkyl or polyalkenyl substituents on succinic anhydride may generally be substituents derived from polyolefins, such polyolefins being monoolefins, especially 1-mono-olefins such as Polymers or copolymers such as ethylene, propylene and butylene. The monoolefin used can have from about 2 to about 24 carbon atoms, or, as a further example, from about 3 to about 12 carbon atoms. Other suitable monoolefins include propylene, butylene, especially isobutylene, 1-octene and 1-decene. Polyolefins generated from such monoolefins include polypropylene, polybutene, polyisobutene, and polyalphaolefins generated from 1-octene and 1-decene.

  In some aspects, the ashless dispersant may include one or more alkenyl succinimides of amines having at least one primary amino group capable of forming an imide group. The alkenyl succinimide can be prepared by conventional methods such as heating an alkenyl succinic anhydride, acid, acid-ester, acid halide or lower alkyl ester with an amine containing at least one primary amino group. Can be generated. The production of alkenyl succinic anhydride can be easily carried out by heating a mixture of polyolefin and maleic anhydride to about 180-220 ° C. Such polyolefins are polymers or copolymers having a number average molecular weight generated from lower monoolefins such as ethylene, propylene, isobutene and the like, as measured by gel permeation chromatography (GPC), in the range of about 300 to about 3000. It may be.

  Amines that can be used in producing such ashless dispersants include at least one primary amino group and at least one additional primary or secondary amino group that can react to form an imide group. And / or any amine having at least one hydroxyl group. A few representative examples are: N-methyl-propanediamine, N-dodecylpropanediamine, N-aminopropyl-piperazine, ethanolamine, N-ethanol-ethylenediamine and the like.

Suitable amines may include alkylene polyamines such as propylene diamine, dipropylene triamine, di- (1,2-butylene) triamine and tetra- (1,2-propylene) pentamine. Further examples include ethylene polyamines that can be depicted by the formula H ₂ N (CH ₂ CH ₂ —NH) _n H, where n can be an integer from about 1 to about 10. These include ethylenediamine, diethylenetriamine (DETA), triethylenetetraamine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), etc., which include mixtures thereof (where n is Which is the average value of the mixture). Such ethylene polyamines have primary amine groups at each end so that mono-alkenyl succinimides and bis-alkenyl succinimides can be produced. Commercial ethylene polyamine mixtures contain small amounts of branched and cyclic species such as N-aminoethylpiperazine, N, N′-bis (aminoethyl) piperazine, N, N′-bis (piperazinyl) ethane and similar compounds There is a possibility. Such commercial mixtures may have an approximate overall composition that falls in the range corresponding to diethylenetriamine to tetraethylenepentamine. The molar ratio of polyalkenyl succinic anhydride to polyalkylene polyamine may be from about 1: 1 to about 3.0: 1.

In some aspects, such dispersants include polyethylene polyamines such as triethylenetetraamine or tetraethylenepentamine and hydrocarbon substituted carboxylic acids or anhydrides [polyolefins of appropriate molecular weight such as polyisobutene and unsaturated poly It is also possible to include reaction products of carboxylic acids or anhydrides, such as maleic anhydride, maleic acid, fumaric acid and the like (generated by reacting a mixture of two or more such materials). .

  Polyamines that are also suitable for use in preparing the dispersants described herein include N-arylphenylenediamines such as N-phenylphenylenediamines such as N-phenyl-1,4-phenylenediamine, N- Aminothiazoles such as phenyl-1,3-phenylenediamine and N-phenyl-1,2-phenylenediamine, such as aminothiazole, aminobenzothiazole, aminobenzothiadiazole and aminoalkylthiazole, aminocarbazole, aminoindole, aminopyrrole Amino-indazolinone, aminomercaptotriazole, aminoperimidine, aminoalkylimidazole such as 1- (2-aminoethyl) imidazole, 1- (3-aminopropyl) imidazole, and the like -Alkyl morpholine, and the like for example, 4- (3-aminopropyl) morpholine. Such polyamines are described in more detail in US Pat. Nos. 4,863,623 and 5,075,383, the disclosures of which are hereby incorporated by reference.

  Additional polyamines useful in generating the hydrocarbyl-substituted succinimide include polyamines having at least one primary or secondary amino group in the molecule and at least one tertiary amino group, such as US Patents These include those taught in US Pat. Nos. 5,634,951 and 5,725,612, the disclosures of which are incorporated herein by reference. Non-limiting examples of suitable polyamines include N, N, N ″, N ″ -tetraalkyldialkylenetriamine (two terminal tertiary amino groups and one central secondary amino group), N , N, N ′, N ″ -tetraalkyltrialkylenetetraamine (one terminal tertiary amino group, two internal tertiary amino groups and one terminal primary amino group), N, N, N ′, N ″, N ″ ′-pentaalkyltrialkylenetetraamine (one terminal tertiary amino group, two internal tertiary amino groups and terminal secondary amino group 1), tris (dialkylaminoalkyl) aminoalkylmethane (3 terminal tertiary amino groups and 1 terminal primary amino group), and similar compounds, where The alkyl groups are the same or different and each contains the number of carbon atoms Typically no more than about 12 and each may contain from about 1 to about 4 carbon atoms, by way of further example, such alkyl groups may be methyl and / or ethyl groups. Types of polyamine reactants can include dimethylaminopropylamine (DMAPA) and N-methylpiperazine.

  Suitable hydroxyamines for use herein include compounds, oligomers or polymers containing at least one primary or secondary amine that can react with the hydrocarbyl-substituted succinic acid or anhydride. Examples of hydroxyamines suitable for use herein include aminoethylethanolamine (AEEA), aminopropyldiethanolamine (APDEA), ethanolamine, diethanolamine (DEA), some propoxylated hexamethylenediamine (eg, HMDA). -2PO or HMDA-3PO), 3-amino-1,2-propanediol, tris (hydroxymethyl) aminomethane and 2-amino-1,3-propanediol.

  The molar ratio of amine to hydrocarbyl substituted succinic acid or anhydride may range from about 1: 1 to about 3.0: 1. Another example of an amine to hydrocarbyl substituted succinic acid or anhydride molar ratio can range from about 1.5: 1 to about 2.0: 1.

The dispersants indicated above may also be post-treated dispersants, which can be prepared, for example, by treating the dispersant with maleic anhydride and boric acid (eg, US Pat.
Or the dispersant is treated with nonylphenol, formaldehyde and glycolic acid (eg, as described in US Pat. No. 5,137,980). The disclosures of which are hereby incorporated by reference in their entirety.

  Mannich base dispersants are alkylphenols, typically alkylphenols having a long chain alkyl substituent on the ring, and one or more aliphatic aldehydes containing from about 1 to about 7 carbon atoms (eg, formaldehyde and derivatives thereof). ) And polyamines (especially polyalkylene polyamines). For example, by condensing them in a ratio of about 1 mole of long chain hydrocarbon-substituted phenol, about 1 to about 2.5 moles of formaldehyde, and about 0.5 to about 2 moles of polyalkylene polyamine, the Mannich base type ashless content Powders can be produced.

  The hydrocarbon source in producing the Mannich type polyamine dispersant is carbon dioxide produced from substantially saturated petroleum distillates and olefin polymers, such as mono-olefin polymers having from 2 to about 6 carbon atoms. It may be a hydrogen source. Such hydrocarbon sources generally contain, for example, at least about 40 carbon atoms, such that the dispersant is substantially oil soluble, and as a further example, the number of carbon atoms is at least 50. Olefin polymers having a GPC number average molecular weight in the range of about 600 to 5,000 may also be suitable. However, it is also possible to use polymers having a higher molecular weight. Suitable hydrocarbon sources can be isobutylene polymers and polymers made from a mixture of isobutene and raffinate streams.

  Suitable Mannich base type dispersants condense them in a ratio of about 1 mole of long chain hydrocarbon-substituted phenol, about 1 to about 2.5 moles of formaldehyde and about 0.5 to about 2 moles of polyalkylene polyamine. It may be a Mannich base type ashless dispersant.

  High molecular weight polyamine dispersants suitable for use as ashless dispersants are polymers containing basic amine groups and oil-soluble groups (eg, pendant alkyl groups having at least about 8 carbon atoms). Examples of such materials are interpolymers formed from various monomers such as decyl methacrylate, vinyl decyl ether or relatively high molecular weight olefins and aminoalkyl acrylates and aminoalkylacrylamides. Examples of high molecular weight polyamine dispersants are US Pat. Nos. 3,329,658; 3,449,250; 3,493,520; 3,519,565; 3,666,730; 3,687,849 and 3, No. 702,300. High molecular weight polyamines can include hydrocarbyl polyamines in which the hydrocarbyl group is composed of isobutene and the polymerization product of a raffinate I stream as described above. It is also possible to use PIB-amine and PIB-polyamine.

  Methods for producing ashless dispersants as described above are known to those skilled in the art and reported in the patent literature. The synthesis of various ashless dispersants of the type indicated above is described, for example, in US Pat. Nos. 2,459,112; 2,962,442, 2,984,550; 3,036,003; 3,163,603; 3, 166,516; 3,172,892; 3,184,474; 3,202,678; 3,215,707; 3,216,936; 3,219,666; 3,236,770; 254,025; 3,271,310; 3,272,746; 3,275,554; 3,281,357; 3,306,908; 3,311,558; 3,316,177; 3,376,281; 3,341,542; 3,346,493; 3,351,552; 3,355,270; 3,368,972; 3,381,002; 3,399,141 3,413,347; 3,415,750; 3,433,744; 3,438,757; 3,442,808; 3,444,170; 3,448,047; 3,448,048; 3,454,933; 3,454,555; 3,454,607; 3,459,661; 3,461,172; 3,467,668; 3,493 520; 3,501,405; 3,522,179; 3,539,633; 3,541,12; 3,542,680; 3,543,678; 3,558,743; 3,565,804; 3,567,637; 3,574,101; 3,576,743; 3,586,629; 3,591,598; 3,600,372; 3,630,904; 3,632,510; 6 32,511; 3,634,515; 3,649,229; 3,697,428; 3,697,574; 3,703,536; 3,704,308; 3,725,277; 3,725 441; 3,725,480; 3,726,882; 3,736,357; 3,751,365; 3,756,953; 3,793,202; 3,798,165; 3,798,247; 3,803,039; 3,804,763; 3,836,471; 3,862,981; 3,872,019; 3,904,595; 3,936,480; 3,948,800; 950,341; 3,957,746; 3,957,854; 3,957,855; 3,980,569; 3,985,802; 3,991,098; 4,006,089; 4,011, 80; 4,025,451; 4,058,468; 4,071,548; 4,083,699; 4,090,854; 4,173,540; 4,234,435; 4,354,950; No. 4,485,023; 5,137,980 and Re 26,433, which are incorporated herein by reference.

  One example of a suitable ashless dispersant is a borated dispersant. Ashless dispersant having basic nitrogen and / or having at least one hydroxyl group in the molecule, such as succinimide dispersant, succinamide dispersant, succinate ester dispersant, succinate ester-amide dispersant, Boron dispersants can be formed by subjecting Mannich base dispersants or hydrocarbylamine or polyamine dispersants to boronation ("boration"). Methods that can be used to boronate the various types of ashless dispersants described above are described in US Pat. Nos. 3,087,936; 3,254,025; 3,281,428; 3,282. 955; 2,284,409; 2,284,410; 3,338,832; 3,344,069; 3,533,945; 3,658,836; 3,703,536; 3,718,663; 4,455,243 and 4,652,387, the disclosures of which are hereby incorporated by reference in their entirety.

  For such borated dispersants, the borated dispersant is about 2 wt% or less of boron, such as about 0.8 wt% or less of boron, and as a further example, about 0.1 to about 0.7 wt% of boron. %, By way of further example, boron has been treated to contain from about 0.25 to about 0.7% by weight, and as a further example from about 0.35 to about 0.7% by weight boron. High molecular weight dispersants may be included. Such dispersants can be dissolved in oils of suitable viscosity for ease of handling. It should be understood that the weight percentages given here are weight percentages of the undispersed dispersant with no diluent oil added.

  It is also possible to react the dispersant further with organic acids, anhydrides and / or aldehyde / phenol mixtures. Use of such a method may improve compatibility with, for example, an elastic polymer seal. The borated dispersant may further include a mixture of borated dispersants. As a further example, the borated dispersant may also include a nitrogen-containing dispersant and / or may not contain phosphorus.

  In one aspect, a suitable dispersant for use in the disclosed lubricating oil composition can be an ethylene-propylene based dispersant. In particular, such a dispersant can be an ethylene-propylene copolymer grafted with maleic anhydride and reacted with n-phenylphenylenediamine.

  Also herein, anhydrous low molecular weight ethylene-alpha as described in US Pat. Nos. 5,075,383 and 6,117,825, the disclosures of which are incorporated herein by reference. -Olefin succinic dispersants are also suitable for use. Also, ethylene alpha-olefin heavys such as those described in US Pat. Nos. 5,266,223; 5,350,532 and 5,435,926, the disclosures of which are incorporated herein by reference. Combines are also suitable for use in the present disclosure. US Pat. Nos. 4,952,637, 5,356,999, 5,374,364 and 5,424,366, the disclosures of which are incorporated herein by reference. Such ethylene-propylene diene copolymers are also suitable.

  An anhydrous crosslinked low molecular weight ethylene-propylene succinic dispersant is also suitable for use in the present invention. Such cross-linking dispersants are similar to the anhydrous low molecular weight ethylene alpha-olefin succinic dispersants discussed above, but US Pat. No. 6,107,258 (the disclosure of which is incorporated herein by reference). As well as multifunctional polyamines to achieve advantageous crosslinking, as described in the specification.

  Suitable dispersants have been generated from ethylene-alpha-olefin polymers having a molecular weight of from about 300 to about 25,000, such as from about 1000 to about 15,000, and by way of further example from about 5,000 to about 15,000. Will be a dispersant.

  Dispersants in additional aspects are highly grafted as described in detail in US Pat. Nos. 5,139,688 and 6,107,257, the disclosures of which are hereby incorporated by reference. It can be an amine-derived functionalized ethylene-propylene copolymer.

The dispersant in one aspect can be a functionalized olefin copolymer. The preparation of such a polymer or copolymer substrate may be carried out using ethylene and propylene, or its preparation is made of ethylene and at least one of the C ₃ to C ₂₃ alpha-olefins. It is also possible to carry out using higher olefins.

Non-limiting examples of polymers suitable for use herein include copolymers formed from ethylene and at least one C ₃ to C ₂₃ alpha-olefin. In one aspect, a copolymer of ethylene and propylene can be used. Other alpha-olefins suitable for use in place of propylene for the purpose of forming a copolymer or in combination with ethylene and propylene for the purpose of forming a terpolymer include 1-butene, 2-butene, isobutene, 1 Pentene, 1-hexene, 1-octene and styrene, α, ω-diolefins such as 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, etc. branched chain alpha-olefins such as 4- Examples include methylbutene-1,5-methylpentene-1, 6-methylheptene-1, and the like, and mixtures thereof.

  The use of a third component can also result in more complex polymer substrates (often referred to as interpolymers). A third component commonly used in generating interpolymer substrates can be a polyene monomer selected from non-conjugated dienes and trienes. The non-conjugated diene component may be a diene having 5 to 14 carbon atoms in the chain. For example, such diene monomers can be characterized by the presence of vinyl groups in their structure, which can include cyclic and bicyclo compounds. Representative dienes include 1,4-hexadiene, 1,4-cyclohexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 1,5-heptadiene and 1,6-heptadiene. Octadiene is included. It is also possible to use a mixture of two or more dienes when producing such interpolymers. In one embodiment, a non-conjugated diene suitable for generating a terpolymer or interpolymer substrate can be 1,4-hexadiene.

  The triene component can have at least two unconjugated double bonds in the chain and can have up to about 30 carbon atoms. Typical trienes useful for use in producing the interpolymers of the present invention are 1-isopropylidene-3α, 4,7,7α-tetrahydroindene, 1-isopropylidene dicyclopentadiene, dihydro-isodicyclopentadiene and It may be 2- (2-methylene-4-methyl-3-pentenyl) (2.2.1) bicyclo-5-heptene.

Ethylene - propylene or higher alpha - olefins copolymers, ethylene about 15 to 80 mole percent and C ₃ from C ₂₃ alpha - may olefins from about 85 have comprise 20 mole percent, for example, ethylene to The molar ratio of C ₃ to C ₂₃ alpha-olefin is about 35 to 75 mole percent to about 65 to 25 mole percent, for example, the ratio of ethylene to C ₃ to C ₂₃ alpha-olefin is 50 to 70 mole percent to 50 To 30 mole percent, by way of further example, the ratio of ethylene to C ₃ to C ₂₃ alpha-olefin is 55 to 65 mole percent to 45 to 35 mole percent.

  The terpolymer variants of the polymers shown above can comprise about 0.1 to 10 mole percent of conjugated diene or toluene.

  The terms “polymer” and “copolymer” can be used generically for the purposes of including copolymers, terpolymers or interpolymers of ethylene. Such materials may contain small amounts of other olefin monomers as long as the basic properties of the ethylene copolymer are not substantially changed. One of ordinary skill in the art will understand how to make such functionalized olefin copolymers. For example, US Pat. No. 6,107,257 (the disclosure of which is incorporated herein by reference) discloses a method for producing a functionalized olefin copolymer.

The dispersant may also be a poly (meth) alkyl acrylate copolymer, which is (A) about 12 to about 18 weight percent methyl methacrylate, (B) about 75 to about 85 weight percent. (meth) may comprise units derived from acrylic acid C ₁₀ -C ₁₅ alkyl and (C) about 2 to dispersing the nitrogen-containing monomer of from about 5 weight percent. Such poly (meth) acrylate alkyl copolymers comprise (A) about 12 to about 18 weight percent methyl methacrylate, (B) about 75 to about 85 weight percent (meth) acrylic acid C ₁₀ −. C ₁₅ can comprise an alkyl and (C) the reaction product of dispersing the nitrogen-containing monomer from about 2 to about 5 weight percent.

(Meth) acrylic acid C ₁₀ -C ₁₅ alkyl as used herein refers to an acrylic or methacrylic acid alkyl ester having a linear or branched alkyl group having 10 to 15 carbon atoms per group. Meaning, but not limited to, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, meta Dodecyl pentadecyl acrylate and mixtures thereof are included.

Preparation of copolymerization monomers that are alkyl (meth) acrylates with 10 or more carbon atoms in the alkyl group is generally performed using standard esterification procedures with industrial quality long chain fatty alcohols. Such commercially available alcohols are mixtures of alcohols with varying chain lengths in the alkyl group. Consequently, for the purposes of this disclosure, not only is the individual alkyl (meth) acrylate product listed in the alkyl (meth) acrylate listed included, but the individual alkyl (meth) acrylate listed is present in a major amount. It is also intended to include alkyl (meth) acrylate mixtures.

  Dispersing nitrogen-containing monomers suitable for use herein include dialkylaminoalkyl (meth) acrylamides such as N, N-dimethylaminopropylmethacrylamide, N, N-diethylaminopropylmethacrylamide, N, N- Dimethylaminoethylacrylamide and N, N-diethylaminoethylacrylamide and the like, and dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl acrylate and thiomethacrylic acid N , N-dimethylaminoethyl and the like.

In one aspect, the poly (meth) alkyl acrylate copolymer consists essentially of the reaction product of (A), (B), and (C). However, those skilled in the art will recognize that other monomers that can be polymerized with the monomers (A), (B), and / or (C) disclosed herein are also low in the temperature of the fully formulated fluid. It will be understood that low concentrations may be present as long as the properties are not adversely affected. The amount of additional monomer present is typically less than about 5 weight percent, such as less than 3 weight percent, and as a further example less than 1 weight percent. This monomer, such as (meth) adding acrylic acid C ₂ -C ₉ alkyl, hydroxy or (meth) acrylic acid esters of alkyl containing alkoxy, ethylene, propylene, styrene, vinyl acetate at low concentrations It is intended to be within the scope of the disclosure. In one aspect, the sum of the weight percentages of (A), (B), and (C) corresponds to 100%.

  Such copolymers can be prepared using a variety of polymerization techniques, such techniques including free radical and anionic polymerization.

  Conventional free radical polymerization methods can be used to produce such copolymers. Polymerization of acrylic and / or methacrylic monomers can occur under a variety of conditions including bulk polymerization, solution polymerization (usually in an organic solvent, preferably in mineral oil), emulsification. Polymerization, suspension polymerization and non-aqueous dispersion techniques are included.

  Such a dispersant may be present in the lubricating oil composition in any necessary or effective amount. In one aspect, the lubricating oil composition is applied to the lubricating oil composition in an amount of from about 0.1% to about 10% by weight, such as from about 1% to about 7% by weight, as a further example. About 2 wt% to about 5 wt% may be included. In one aspect, the additive composition is combined with it from about 0.6% to about 59.5%, such as from about 5.95% to about 41.%, based on the total weight of the additive composition. 7% by weight, for example, from about 11.9% to about 29.8% by weight may be included.

  In accordance with various embodiments, a lubricating oil composition is disclosed comprising a major amount of a base oil and a minor amount of an additive composition, which comprises a friction modifier and a dispersant, wherein the additive The composition exhibits at least one of reduced thin film friction and improved fuel efficiency as compared to an additive composition without the friction modifier or the dispersant.

  Other components may optionally be present in the disclosed lubricating oil and / or additive composition. Non-limiting examples of other ingredients include anti-wear agents, cleaning agents, diluents, antifoaming agents, demulsifying agents, anti-foaming agents, corrosion inhibitors, extreme pressure agents, seal well agents, anti-wear agents. Oxidants, pour point depressants, rust inhibitors and friction modifiers are included.

  In one aspect, the disclosed lubricating oil composition can be applied as a lubricating oil to an engine, transmission or gear set. However, ordinary technicians in the field may aim to lubricate the disclosed lubricating composition anywhere, for example, to lubricate any surface, such as a surface where thin film friction may exist. It will be understood that it can be used. In another aspect, there is also disclosed a method of lubricating a machine, such as an engine, transmission, automotive gear, gear set, and / or shaft, and the method provides the machine with the lubricating oil composition disclosed herein. Comprising that.

  In accordance with various aspects, a method is disclosed for reducing a thin film friction exhibited by a fluid between surfaces, the method comprising adding a base oil and additive composition (which includes phosphorus-containing compounds, friction modifiers and dispersants) to the fluid. Providing a lubricating oil composition comprising a selected additive and a cleaning agent.

  In accordance with yet another aspect, a method is disclosed for reducing a thin film friction exhibited by a fluid between surfaces, the method including a base oil and additive composition (which includes a friction modifier and a dispersant) in the fluid. Providing a lubricating oil composition comprising).

  In various aspects, a method for improving fuel efficiency in a vehicle is disclosed that includes a base oil and an additive composition (which includes an additive selected from a phosphorus-containing compound, a friction modifier, and a dispersant). And a composition comprising a cleaning agent).

  In another aspect, a method for improving fuel efficiency in a vehicle is disclosed that includes a base oil and an additive composition (which comprises a friction modifier and a dispersant) in the vehicle. Providing a composition comprising:

  The present specification also discloses methods of lubricating machines, such as engines, transmissions, automotive gears, gear sets and / or axles, etc., using the disclosed lubricating oil compositions. In a further aspect, a method for improving fuel efficiency in a machine, such as an engine, transmission, automotive gear, gear set, and / or axle, is disclosed that includes the disclosed lubricating oil composition on the machine, such as an engine, Including in transmissions, automotive gears, gear sets and / or axles and the like.

  Furthermore, it is believed that the disclosed lubricating oil composition can be supplied to any machine where fuel economy is a problem.

-Effects of individual additives on thin film friction Individual additives such as detergents, phosphorus-containing compounds [PA (containing metal, containing phosphorus) and P-B (containing no metal) , Containing phosphorus)], friction modifiers, [FM-A (containing nitrogen), FM-B (containing no nitrogen) and FM-C (containing no nitrogen)] and dispersants [D-A ( When succinimide) and D-B (polymer)] were added to two base oils, namely Group II base oil (G2) and Group IV base oil (PA04), they showed to thin film friction The effect is shown in Table 1. The thin film friction was measured at a load of 100 ° C./20 N and a slide to roll ratio of 20% at 1.5 m / sec. Table 1 also shows the thin film friction change% when compared with the base oil. As can be seen, all additives except DA in G2 increased the thin film friction. However, the addition of DA to PA04 can increase thin film friction.

-Effect of additive composition on thin film friction of base oil G2 Table 2 shows phosphorus-containing compounds (PA and PB), friction modifiers (FM-A, FM-B and FM-C). And additives selected from dispersants (D-A and D-B) and additive compositions containing dispersants show the effect they have on thin film friction when placed in base oil G2. Table 2 also shows the actual and calculated percent change in thin film friction. When the additives are combined in a base oil, the calculated thin film indicated by the base oil by adding the percent change in thin film friction exhibited by the base oil when using each of the individual additives as shown in Table 1 The percent change in friction can be determined. For example, the calculated percent thin film friction change when the detergent and PA combination is placed in the base oil RLOP 100 would be 277% (130% + 147%). Table 2 shows the calculated percent thin film friction change determined from the effect exhibited by the individual additives. If the actual thin film friction change percentage when using such an additive combination is less than the calculated thin film friction change percentage, then the measured thin film friction will be unexpectedly low, and such additive combinations may be fuel economy. The characteristics are better than expected.

  In all cases shown in Table 2, additives and detergents selected from phosphorus-containing compounds (PA and PB), friction modifiers (FM-A and FM-B) and dispersants (DA) When the additive composition containing (cleaning agent) was added to the base oil G2, the actual thin film friction change percentage was lower than the calculated thin film friction change percentage. Therefore, when an additive composition containing an additive selected from phosphorus-containing compounds, friction modifiers and dispersants and a detergent is added to the base oil, the thin film friction is unexpectedly better than expected, thus fuel efficiency. Became better.

-Effect of additive composition on thin film friction of base oil PA04 Table 3 shows additive compositions containing friction modifiers (FM-A and FM-C) and dispersant (DA). It shows the effect it has shown on thin film friction when placed in base oil PA04. Table 3 also shows the actual and calculated percent change in thin film friction. In all cases shown in Table 3, when the additive composition containing the friction modifiers (FM-A and FM-C) and the dispersant (DA) is added to the base oil PA04, the actual percent thin film friction change Was lower than the percent thin film friction change calculated from the effect exhibited by the individual additives.

  At numerous places throughout this specification, reference has been made to a number of US patents, published foreign patent applications and published technical papers. All such presented materials are expressly incorporated into this disclosure as if set forth in detail herein.

  For purposes of this specification and the appended claims, unless otherwise indicated, numerical values representing amounts, percentages or ratios and other numerical values used in the specification and claims are subject to the term “about” modification in all cases. Should be understood. Accordingly, unless indicated to the contrary, the numerical parameters set forth in this specification and the appended claims are approximations that may vary depending upon the desired properties sought to be obtained with this disclosure. At a minimum, each numerical parameter is interpreted by applying the usual rounding technique in the light of the number of significant figures reported, rather than as an attempt to limit the application of the equivalent principle applied to the scope of the claims. It should be.

  The numerical ranges and parameters representing the broad range of this disclosure are approximate, but the numerical values given in the specific examples are reported as accurately as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard error found in their individual testing measurements. Moreover, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a “less than 10” range can include any and all subranges of the lowest value of zero and the highest value of 10 (inclusive), ie equal to zero or Any and all subranges having a minimum value above and a maximum value equal to or less than 10 may be included, such as a range of 1 to 5, for example.

  It should be noted that the singular forms “a”, “an” and “the” as used herein and in the appended claims encompass a plurality of indicating objects unless clearly and clearly limited to one indicating object. Thus, for example, reference to “an antioxidant” includes two or more different antioxidants. The term “inclusion” as used herein and grammatical variations thereof are not intended to be limiting, and enumerating items in a list may be used in place of or in addition to the listed items. It does not exclude other similar items that can be.

  The present invention is susceptible to considerable variations in this implementation. Accordingly, the above description is not intended and should not be construed as limiting the invention to the particular examples shown above. Rather, what is intended to be protected is the matter as set forth in the claims and their equivalents as permitted by law.

Applicants do not intend to dedicate all disclosed aspects to the public, and any of the disclosed modifications or variations may not literally fall within the scope of the claims, but that To the extent they are also considered part of this invention under the principle of equivalents.

Claims (33)

An additive composition comprising:
Detergents, and additives selected from phosphorus-containing compounds, friction modifiers and dispersants,
An additive composition that exhibits at least one of reduced thin film friction and improved fuel efficiency as compared to an additive composition containing neither the detergent nor the additive.   The additive composition according to claim 1, wherein the phosphorus-containing compound is a phosphorus-containing compound containing a metal.   The additive composition according to claim 2, wherein the metal-containing phosphorus-containing compound is a metal dihydrocarbyl dithiophosphate.   4. The additive composition of claim 3, wherein the metal dihydrocarbyl dithiophosphate is a zinc dialkyldithiophosphate.   The additive composition according to claim 1, wherein the phosphorus-containing compound is a phosphorus-containing compound containing sulfur.   6. The additive composition of claim 5, wherein the sulfur-containing phosphorus-containing compound is selected from thiophosphates, dithiophosphates, sulfur-containing neopentyl glycol phosphites and sulfur-containing neopentyl glycol phosphite salts.   The additive composition according to claim 1, wherein the friction modifier is at least one of a nitrogen-free compound, a nitrogen-containing compound, and an ash-containing compound.   The additive composition according to claim 7, wherein the nitrogen-free compound is a polyol ester.   The additive composition according to claim 8, wherein the polyol ester is selected from glycerol monooleate and glycerol monolaurate.   The additive composition according to claim 7, wherein the nitrogen-containing compound is a long-chain alkylene amine.   11. The additive composition of claim 10, wherein the long chain alkylene amine is selected from N-oleyl-trimethylene diamine, N-tallow-trimethylene diamine, coco-trimethylene diamine and mixtures thereof.   The additive composition according to claim 7, wherein the nitrogen-containing compound is diethanolamine.   The additive composition according to claim 7, wherein the ash-containing compound is a molybdenum-containing compound containing sulfur.   12. The additive composition of claim 11, wherein the molybdenum-containing compound is selected from molybdenum carboxylates, molybdenum amides, molybdenum thiophosphates, molybdenum thiocarbamates and mixtures thereof.   The additive composition according to claim 1, wherein the dispersant is at least one of succinimide, boronated succinimide, Mannich dispersant, functionalized olefin copolymer and poly (meth) acrylate copolymer.   16. The additive composition of claim 15, wherein the dispersant is a highly grafted amine derived functionalized ethylene-propylene copolymer. A lubricating oil composition comprising:
A major amount of base oil, and a minor amount of the additive composition of claim 1;
A lubricating oil composition comprising.   An engine, transmission or gear set lubricated with the lubricating oil composition of claim 17.   18. A method of dispensing lubricating oil to a machine, the method comprising supplying the lubricating oil composition of claim 17 to the machine.   The method of claim 19, wherein the machine is a gear.   The method of claim 19, wherein the machine is an engine. An additive composition comprising:
Friction modifiers, and dispersants,
An additive composition that exhibits at least one of reduced thin film friction and improved fuel efficiency as compared to an additive composition comprising no friction modifier or dispersant.   The additive composition according to claim 22, wherein the friction modifier is at least one of a compound not containing nitrogen, a nitrogen-containing compound, and an ash-containing compound.   The additive composition according to claim 22, wherein the dispersant is at least one of succinimide, boronated succinimide, Mannich dispersant, functionalized olefin copolymer and poly (meth) acrylate copolymer. A lubricating oil composition comprising:
A major amount of base oil, and a minor amount of the additive composition of claim 22;
A lubricating oil composition comprising.   26. An engine, transmission or gear set lubricated with the lubricating oil composition of claim 25.   26. A method of dispensing a lubricating oil to a machine, the method comprising supplying the lubricating oil composition of claim 25 to the machine.   28. The method of claim 27, wherein the machine is a gear.   28. The method of claim 27, wherein the machine is an engine. A method of reducing thin film friction exhibited by a fluid between surfaces, wherein the fluid includes a base oil, and a cleaning agent, and an additive selected from phosphorus-containing compounds, friction modifiers and dispersants,
An additive composition comprising
Providing a lubricating oil composition comprising: A method for reducing thin film friction exhibited by a fluid between surfaces, the additive composition comprising a base oil and a friction modifier and a dispersant in the fluid,
Providing a lubricating oil composition comprising: A method for improving fuel efficiency in a vehicle, wherein the vehicle comprises a base oil and an additive selected from a detergent and a phosphorus-containing compound, a friction modifier and a dispersant,
Providing a composition comprising: a. A method for improving fuel efficiency in a vehicle, comprising an additive composition comprising a base oil and a friction modifier and a dispersant in the vehicle;
Providing a composition comprising: a.