BRPI0719343A2 - LUBRICATING COMPOSITION OF LOW SULFUR CONTENT, LOW PHOSPHORUS CONTENT, LOW ASH CONTENT, SUITABLE FOR USE IN AN INTERNAL COMBUSTION ENGINE AND METHODS FOR LUBRICATING AN INTERNAL COMBUSTION ENGINE AND FOR PRODUCING COMPOSITION. - Google Patents

Description

LOW SULFUR CONTENT, LOW PHOSPHOR CONTENT, LOW GRAY CONTENT, SUITABLE FOR USE IN AN INTERNAL COMBUSTION ENGINE AND METHODS TO BRUSH AN INTERNAL COMBUSTION ENGINE AND TO PRODUCE COMPOSITION

Background of the Invention

The present invention relates to a low sulfur, low ash, low phosphorus lubricating composition and method for lubricating an internal combustion engine, which provides fuel economy and fuel economy retention and reduction of fuel. friction and wear.

Fuel economy is of great importance, and lubricants that can favor improved fuel economy, for example by reducing friction within an engine, are of significant value. The present invention provides a low sulfur, low ash, low phosphorus lubricating composition including an improved fuel economy additive package in an internal combustion engine. This improvement is accomplished by providing an additive package in which the friction modification component comprises exclusively or predominantly a tartrate.

U.S. Patent 4,237,022, Barrer, December 2, 1980, discloses utility tartrates as additives in lubricants and fuels for effective wheezing and friction reduction, as well as improved fuel economy.

US Patent 4,952,328, Davis et al., August 28, 1990, discloses internal combustion engine lubricating oil compositions comprising (A) lubricating viscosity oil, (B) a carboxylic derivative produced by the reaction of a succinic acylating agent with certain amines, and (C) a basic alkali metal salt of sulfonic or carboxylic acid. An illustrative lubricant composition (Lubricant III) includes base oil which includes viscosity index modifier; a basic magnesium alkylated benzene sulfonate; an overused sodium alkylbenzene sulfonate; a basic calcium alkylated benzene sulfonate; succinimide dispersant; and zinc salts of a phosphorodithioic acid.

U.S. Patent 4,326,972, Chamberlin, April 27, 1982, discloses lubricant compositions for improving fuel economy in internal combustion engines. The composition includes a specific sulfurized composition (based on an ester of a carboxylic acid) and a basic alkali metal sulfonate. Additional ingredients may include at least one detergent or dispersing agent capable of being dispersed in oil, a viscosity enhancing agent, and a specific salt of a phosphorous acid. Summary of the Invention The present invention provides a low sulfur, low phosphorus and low ash lubricating oil composition suitable for lubricating an internal combustion engine comprising the following components:

(a) a lubricating viscosity oil; and

(b) a condensation product of a material represented by formula I and an alcohol of 6 to 12 carbon atoms;

The

I

wherein each R is independently H or a hydrocarbyl group, or wherein the R groups together form a ring; and wherein if R is Η, the condensation product is optionally further functionalized by acylation or reaction with a boron compound;

wherein said lubricating composition is provided with a sulphated ash value of up to about 1.0, a phosphorus content of up to about 0.08 weight percent, and a sulfur content of up to about 0, 4 percent by weight.

The invention further provides a method of lubricating an internal combustion engine comprising providing the lubricant composition to the engine.

Detailed Description of the Invention Various preferred aspects and embodiments will be described below by way of non-limiting illustration.

The present invention provides a composition as described above. Often the composition has a total sulfur content in an aspect below

0.4 per cent by weight in another aspect below 0.3 per cent by weight, yet another aspect 0.2 per cent by weight or less and yet another aspect 0.1 per cent by weight weight, or less. Frequently, the major source of sulfur in the composition of the invention is derived from conventional diluent oil. A typical range for total sulfur content is 0.1 to 0.01 weight percent.

Often the composition has a total phosphorus content of less than or equal to 800 ppm, in another aspect equal to or less than 500 ppm, yet another aspect equal to or less than 300 ppm, yet another aspect equal to or less than 200 ppm and yet another aspect equal to or less than 100 ppm of the composition. A typical range for total phosphorus content ranges from 500

20 to 100 ppm.

Often the composition has a total sulfated ash content as determined by ASTM * D-874 of less than 1.0 weight percent in one aspect.

equal to or less than 0.7 weight percent, yet 25 in another respect equal to or less than 0.4 weight percent, in yet another aspect equal to or less than 0.3 per cent by weight and yet another aspect equal to or less than 0.05 per cent by weight of the composition. A typical range for the total sulfate ash content ranges from 0.7 to 0.05 weight percent. Lubricating Viscosity Oil

The composition of low sulfur, low phosphorus, low ash lubricating oil is comprised of one or more base oils which are generally present in a larger amount (i.e., an amount greater than about 50 percent by weight). In general, the base oil is present in an amount greater than about 60 per cent, or greater than about 70 per cent, or greater than about 80 per cent by weight. lubricating oil composition. The sulfur content of base oil is typically less than 0.2 percent by weight.

The low sulfur, low phosphorus, low ash lubricating oil composition may have a viscosity of up to about 16.3 mm2 / s at 100 ° C, and in an embodiment of 5 to 16.3 20 mm2 / s (cSt) at 100 ° C, and in an embodiment of 6 to 13 mm2 / s (cSt) at 100 ° C. According to one embodiment, the lubricating oil composition is provided with a SAE Viscosity Degree of OW, OW-20, OW-30, OW-40, OW-50, OW-60, 5W, 5W-20, 5W- 30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 25 10W-30, 10W-40, or 10W-50.

The low sulfur, low phosphorus, low ash lubricating oil composition may have a high temperature / high shear viscosity at 1500C when measured by the ASTM D4683 procedure up to 4 mm2 / s (cSt) , and in an embodiment of up to 3.7 mm2 / s (cSt), and in an embodiment of 2 to 4 mm2 / s (cSt), and in an embodiment of 2.2 to 3.7 mm2 / s (cSt) , and in one embodiment 2.7 to 3.5 mm2 / s (cSt).

The oil base used in the composition of low sulfur, low phosphorus, low ash oils may be a natural oil, synthetic oil or a mixture thereof, as the sulfur content of this oil does not exceed the previously stated sulfur concentration limit required for the low sulfur, low phosphorus, low ash lubricating oil composition of the invention. Natural oils that are of use include animal oils and vegetable oils (eg castor oil, lard oil) as well as mineral lubricating oils such as liquid petroleum oils and treated mineral lubricating oils. with solvent or paraffinic, naphthenic or paraffinic-naphthenic acid mixed. Oil derived from coal and shale clay is equally useful. Synthetic lubricating oils include hydrocarbon oils such as polymerized and interpolymerized olefins (for example polybutylenes, polypropylenes, isobutylene propylene copolymers, and the like); poly (1-hexenes), poly (1-octenes), poly (1-decenes), and others and mixtures thereof; alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dynenylbenzenes, di (2-ethylexyl) benzenes, and the like); polyphenyls (e.g., biphenyls, terphenyls, alkylated and the like polyphenyls); ethers of alkylated diphenyls and their analogous and homologous derivatives and the like.

Alkylene oxide polymers and interpolymers and derivatives thereof, where the terminal hydroxyl groups have been modified by esterification, etherification, and the like, constitute another class of known synthetic lubricating oils which may be used. These are exemplified by oils prepared by polymerization of ethylene oxide or propylene oxide from alkyl and aryl ethers of these polyoxyalkylene polymers (for example, methyl polyisopropylene glycol ether having an average molecular weight of about 1000, different polyethylene glycol ether having a molecular weight of about 500-1000, polypropylene glycol diethyl ether having a molecular weight of about 1000-1500 and others) or mono- and polycarboxylic esters thereof, for example, acetic acid esters, mixed C 3-8 fatty acid esters, or tetraethylene glycol carboxylic acid diester.

Another suitable class of synthetic lubricating oils that may be used include dicarboxylic acid esters (e.g. phthalic acid, succinic acid, alkyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, dimeric acidic acid, malonic acid, alkyl malonic acids, alkenyl malonic acids, and the like) with a variety of alcohols (eg butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-alcohol). ethylhexyl, ethylene glycol, diethylene glycol monoether, propylene glycol, and the like). Specific examples of these esters include dibutyl adipate, di (2-ethylexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, dioctyl azate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, 2-ethylexyl linoleic acid dimer diester, the complex ester 15 formed by the reaction of one mol of sebacic acid with two moles of tetraethylene glycol and two moles of similar 2-ethylexanoic acid.

Utility esters such as synthetic oils also include those manufactured from C5 to C12 monocarboxylic acids and polyols and polyols such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and the like.

The oil may be a poly alpha olefin (PAO). Typically, PAOs are derived from monomers having from 4 to 30, or from 4 to 20, or from 6 to 16 carbon atoms. Examples of utility PAOs include those derived from octene, decene, mixtures thereof, and the like. These PAOs may have a viscosity of 2 to 15, or 3 to 12, or 4 to 8 mm2 / s (cSt) at 100 ° C. Examples of utility PAOs include 4 mm 2 / s (cSt) polyolefins (100 c) at 100 ° C, 6 mm 2 / s (cSt) poly alpha-olefins 5 at 100 ° C, and mixtures thereof. Mixtures of mineral oil with one or more of the preceding PAOs may be used.

Unrefined, refined, second refining oils, whether natural or synthetic (as well as 10 mixtures of two or more of any of these) of the foregoing type may be used in the lubricants of the present invention. Unrefined oils are those obtained from a natural or synthetic source without further purification treatment. For example, an oil shale oil obtained directly from retort operations, a petroleum oil obtained directly from primary distillation or ester oil obtained directly from an esterification process and used without another. treatment will be an unrefined oil. Refined oils are similar to unrefined oils except that they have been further treated in one or more purification steps to improve one or more properties. Many of these purification techniques are known to those of skill in the art, such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation and the like. Second refining oils are obtained by processes similar to those used to obtain refined oils applied to refined oils that have already been used in service. These second refining oils are also known as reclaimed or reprocessed oils and are often further processed by techniques aimed at the removal of waste additives and oil decomposition products.

Additionally, oils prepared by a Fischer-Tropsch synthetic gas-to-liquid procedure are known and used.

Friction Modifier

The tartrates of the present invention may be prepared by the reaction of tartaric acid and one or more alcohols.

The alcohols useful for the preparation of tartrates may contain from 6 to 12, or from 6 to 10, or from 8 to 10 carbon atoms. The alcohols employed may be straight or branched, and if branched, branching may occur at any point in the chain and branching may be of any length. According to one embodiment, the alcohol is linear containing from 8 to 10 carbon atoms.

It is believed that the use of alcohols of at least 6 carbon atoms will lead to products having reduced volatility compared to those products prepared from shorter chain alcohols. It is also believed that the use of alcohols having at least one branch will promote solubility of the product in the oil. Accordingly, some embodiments of the invention employ the product prepared from branched alcohols of at least 6 carbon atoms, for example branched Cg-12 or Ce-ιο or branched Cs-10 alcohols, either in the form of simple materials or as mixtures. These branched alcohols may provide maximum solubility and compatibility in an oil. Specific examples include 2-ethylexanol and isotrideyl alcohol, of which the latter may represent a commercial class mixture of various isomers. Similarly, some embodiments of the invention employ the product prepared from linear alcohols of at least 6 carbon atoms, for example linear C6-12 or C10-10 alcohols or linear C8-10 alcohols, either as simple materials or as mixtures. Such linear alcohols may provide optimal friction performance for an oil.

The tartrates of the present invention may conveniently be prepared by reaction of tartaric acid or a reactive equivalent of tartaric acid (such as an ester, acid halide, or anhydride) with one or more of the corresponding alcohols by a broadly condensing process. known.

Similarly, the alkyl groups of the amines may be similarly straight or branched.

The tartaric acid used to prepare the tartrates of the invention may be the commercially available type (obtained from Sargent Welch), and is likely to exist in one or more isomeric forms, such as d-tartaric acid, 1-tartaric acid or tartaric mesoacid, often depending on the 5 (natural) source or method of synthesis (eg from maleic acid). These derivatives may also be prepared from functional equivalents for the diacid readily apparent to those skilled in the art, such as esters, acid chlorides, anhydrides and the like.

The tartrates of the present invention may be solids, semisolids or oils depending on the particular alcohol used in the preparation of tartrate. For use as additives in oil compositions comprising fuel and lubricating compositions the tartarates are advantageously soluble and / or stably dispersible in such oil compositions. Thus, for example, compositions intended for use in oils are typically oil soluble and / or capable of being stably dispersed in an oil in which they are to be used. The term "oil soluble" as used in this report and the appended claims does not necessarily mean that all compositions in question are miscible or soluble in all proportions in all oils. Rather, it is intended to be understood that a composition is soluble in an oil (mineral, synthetic, and the like) where it is intended to function to an extent that allows the solution to exhibit one or more of the desired properties. Similarly, such "solutions" need not be solutions in their own right in the physical or chemical sense. Rather, they may be microemulsions or colloidal dispersions which, for the purpose of this invention, exhibit properties sufficiently close to those of authentic solutions to be interchangeable with them within the context of this invention for practical purposes.

As indicated above, the tartrate compositions of this invention are useful as lubricant additives, where they may function as rust and corrosion inhibitors, friction modifiers, anti-wear agents and demulsifiers. oners. They can be employed in a variety of lubricants based on various viscous lubrication oils, including natural and synthetic lubricating oils and their mixtures. These lubricants include crankcase lubricating oils for spark-ignition or compression-ignition internal combustion engines, including car and truck engines, two-stroke engines, aviation piston engines, marine and rail diesel engines. , and the like. They can also be used on gas engines, stationary and similar power turbines and engines. Automatic transmission fluids, cross-shaft lubricants, gear lubricants, metalworking lubricants, hydraulic fluids and other oil and grease compositions may also benefit from incorporating the present compositions. invention.

Other friction modifiers may be

present in the lubricants of the present invention and may include polyol esters such as glycerol monoleages; oleyl amides; diethanol fatty amines and mixtures thereof. A list of friction modifiers is included in U.S. Patent No. 4,792,410.

Polyol esters include fatty acid glycerol esters. These can be prepared by a variety of methods widely known in the art. Many of these esters, such as glycerol monooleate and glycerol monebeate, are manufactured on a commercial scale. The esters of utility for this invention are oil soluble and are preferably prepared from C8 to C22 fatty acids or mixtures thereof as found in natural products. The fatty acid may be saturated or unsaturated. Certain compounds found in acids from natural sources may include lycanic acid containing a keto group. Utility C8 to C22 fatty acids are those of the formula R-COOH wherein R is alkyl or alkenyl.

The fatty acid glycerol monoester is of utility. Mixtures of mono and diesters may be used. Mixtures of mono- and diesters may contain at least about 40% of the monoester. Mixtures of glycerol mono- and diesters containing from about 40% to about 60% by weight of the monoester may be used. For example, commercial glycerol monooleate containing a mixture of about 45% to 55% by weight monoester and 55% to 45% diester may be used.

Useful fatty acids are oleic, stearic, isosteic, palmitic, myristic, palmitic, linoleic, lauric, linolenic and eleosteic acids, and acids from natural tallow, palm oil, olive oil, peanut oil.

Although tartrates and polyester esters, such as glycerol monooleate may appear to have superficially similar molecular structures, it is observed that certain combinations of these materials can effectively provide better performance, eg wear prevention, than each other. material used alone.

U.S. Patent No. 4,280,916 discusses fatty acid amides in detail. Suitable amides are C8-C24 aliphatic monocarboxylic amides which are widely known. The reaction of the fatty acid base compound with ammonia produces the amide grease. Fatty acids and amides derived therefrom may be either saturated or unsaturated. Important acids include C 12 lauric, C 16 palmitic and C 18 steric. Other important unsaturated fatty acids include oleic, linoleic and linolenic acids, all of which are Cig. According to one embodiment, the fatty amides of the present invention are those derived from unsaturated fatty acids Cig.

Fatty amines and long chain amines

Diethoxylated compounds such as N, N-bis- (2-hydroxyethyl) tallowamine are themselves generally useful as components of this invention. Both types of amines are commercially available. Fatty amines and ethoxylated fatty amines are described in more detail in U.S. Patent 4,741,848. Miscellaneous

Antioxidants (i.e. oxidation inhibitors) including retarded phenolic antioxidants such as 2,6, -di-t-butylphenol, and retarded phenolic esters such as the type represented by the following formula:

t-alkyl

and, in a specific embodiment,

wherein R3 is a normal or branched chain alkyl group containing 2 to 10 carbon atoms according to one embodiment 2 to 4 and in another embodiment 4 carbon atoms. According to one embodiment, R 3 is an n-butyl group. In another embodiment R 3 may be 8 carbon atoms, such as found in Irganox L-135TH from Ciba. The preparation of these antioxidants can be found in U.S. Patent 6,559,105.

Other antioxidants may include secondary aromatic amine antioxidants such as di-alkyl (e.g., dinonyl) diphenylamine, sulphorous phenolic antioxidants, oil-soluble copper compounds, phosphorus-containing antioxidants, molybdenum, such as Mo dithiocarbamates, organic sulphides, bisulphides, and polysulphides (such as the diels Alder sulphurized adduct 15 of butadiene and butyl acrylate). U.S. Patent 6,251,840 contains an extensive list of antioxidants.

The EP / anti-wear agent which is used in connection with the present invention is typically in the form of a zinc dialkyl dithiophosphate. Although there are an extremely large number of different types of anti-wear agents that can be used in connection with such functional fluids, the present inventors have found that zinc dialkyl dithiophosphate-type anti-wear agents work. - work particularly well in connection with the other components to achieve the desired characteristics. According to one embodiment, at least 50% of the alkyl groups (alcohol derivatives) in the dialkyl dithiophosphate are secondary groups, that is, derived from secondary alcohols. According to another embodiment, at least 50% of the alkyl groups are isopropyl alcohol derivatives.

Ash-free detergents and dispersants, depending on their constitution, may produce a non-volatile material in the combustion such as boric oxide or phosphorus pentoxide. However, the ash-free detergents and dispersants do not normally contain metal and therefore do not provide an ash containing metal in combustion. Many types of ash-free dispersants are known in the art. Such materials are commonly referred to as "ash-free" even though they may be associated with a metal ion from another in situ source.

(I) "Carboxylic dispersants" are those

reaction products of carboxylic acylating agents 20 (acids, anhydrides, esters, and the like) containing at least 34 and preferably at least 54 carbon atoms which are reacted with nitrogen-containing compounds (such as amines) , organic hydroxyl compounds (such as aliphatic compounds including monohydric and polyhydric alcohols, or aromatic compounds including phenols and naphthols), and / or basic inorganic materials. These reaction products include imide, amide, and carboxylic ester dispersant ester reaction products.

Carboxylic acylating agents include fatty acids, isoaliphatic acids (e.g. 8-methyl octadecanoic acid), dimer acids, 4 + 2 addition dicarboxylic acids and 2 + 2 addition products of a non-fatty acid. saturated with an unsaturated carboxylic reagent), trimer acids, tricarboxylic addition acids (Empol® 1040, Hystrene® 5460 and Unidyme® 60), and substituted hydrocarbyl acylating agents (from olefins and / or polyalkenes). According to one embodiment, the carboxylic acylating agent is a fatty acid. Fatty acids generally contain from 8 to 30, or from 12 to 24 carbon atoms. Carboxylic acylating agents are described in U.S. Patent Nos. 2,444,328, 3,219,666, 4,234,435 and 6,077,909.

The amine may be a mono- or polyamine. Monoamines generally have at least one hydrocarbyl group containing from 1 to 24 carbon atoms, or from 1 to 12 carbon atoms. Examples of monoamines include (C8-30) fatty amines (Armeens ™), primary ether amines (SURFAM® amines), tertiary-aliphatic primary amines (Primenes ™), hydroxyamines (primary, secondary or secondary lacanol amines). N- (hydroxyhydrocarbyl) amines, and hydroxyhydrocarbyl amines (Ethomeens ™ and Propomesen). Polyamines include alkoxylated diamines (Ethoduomeens ™), fatty diamines (Duomeens ™), alkylene polyamines (ethylene polyamines), hydroxyl containing polyamines, polyoxyalkylene polyamines (Jeffamines ™), condensed polyamines (a reaction of densification between at least one hydroxyl compound with at least one polyamine reagent containing at least one primary or secondary amino group), and heterocyclic polyamines. Utility amines include those disclosed in U.S. Patent 4,234,435 (Meinhart) and U.S. Patent 5,230,714 (Steckel).

The polyamines from which the dispersing agent is derived include mainly alkylene amines which conform for the most part to the formula.

A - N- (alkylene-N) t —H A A

where t is an integer typically less than 10, A is hydrogen or a hydrocarbyl group typically having up to 30 carbon atoms, and the alkylene group is typically an alkylene group having less than

8 carbon atoms. Alkylene amines mainly include methylene amines, ethylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines. They are typically exemplified by: ethylene diamine, diethylene triamine, triethylene tetramine, propylene diamine, decamethylene diamine, octamethylene diamine, di (heptamethylene) triamine, tripropylene tetramine, tetraethylene pentamine trimethylene diamine, pentaethylene hexamine, di (trimethylene) triamine. Also higher are homologues, such as those obtained by condensation of two or more previously polished alkylene amines. Particularly useful are tetraethylene pentamines.

Especially useful are ethylene amines, also called polyethylene polyamines. They are described in certain detail under the title "Ethylene Amines" in Encyclopedia of Chemical Technology, Kirk and Othmer, Vol. 5, pp. 898-905, Interscience Publishers, New York (1950).

In a similar way,

hydroxyalkyl-substituted alkylene, i.e. alkylene amines having one or more hydroxyalkyl substituents on nitrogen atoms. Examples of such amines include N- (2-hydroxyethyl) ethylene diamine, N, N bis (2-hydroxyethyl) ethylene diamine, 1- (2-

hydroxyethyl) piperazine, monohydroxypropyl) piperazine, dihydroxypropyl substituted tetraethylene pentamine, N- (3-hydroxypropyl) tetramethylene diamine, and 2-heptadecyl-1- (2-hydroxyethyl) imidazoline.

Similarly useful are counterparts such as

those which are obtained by condensation of the alkylene amines illustrated above or alkyl substituted hydroxy alkyl amines through amino radicals or through hydroxyl radicals. Condensed polyamines are formed by a condensation reaction between at least one hydroxyl compound with at least one polyamine reagent containing at least one primary or secondary amino group and are described in US Patents 5,230,714 and 5,296,154 ( Steckel).

Examples of such "carboxylic dispersants" are described in GB 1,306,529 and many US patents, which include the following: 3,219,666, 3,316,177, 3,340,281, 3,351,552, 3,381. 022, 3,433,744, 3,444,170, 3,467,668, 3,501,405, 3,542,680, 3,576,743, 3,632,511, 4,234,435, 6,077,909 and 6,165,235.

(2) Succinimide dispersants are a

species of carboxylic dispersants. They are the reaction product of a hydrocarbyl succinic acylating agent substituted with an organic hydroxyl compound or an amine containing at least one hydrogen bound to a nitrogen atom, or a mixture of said compound and amine. . The term "succinic acylating agent" refers to a hydrocarbon-substituted succinic acid or succinic acid producing compound (which term also encompasses the acid itself). These materials typically include hydrocarbyl substituted succinic acids, anhydrides, esters (including semiesters) and halides.

Succinic-based dispersants have a wide variety of chemical structures, typically including structures such as

O O

R1-CH-II Ü-CH-R1

\, /

N- [R2-NH] x-R2-N / \

CH2-C C-CH2

&

In the retro structure, each R 1 is independently a hydrocarbyl group, such as a polyolefin-derived group having an Mn of 500 or 700 to 10,000. Typically the hydrocarbyl group is an alkyl group, often a polyisobutyl group having a molecular weight of 500 or 700 to 5000, or alternatively 1500 or 20 2000 to 5000. Alternatively expressed, R1 groups may contain 40 to 500 atoms carbon atoms, for example at least 50, for example, 50 to 300 carbon atoms, such as aliphatic carbon atoms. R2 are alkylene groups, commonly ethylene (CaH4) groups. Such molecules are commonly derived from the reaction of an alkenyl acylating agent with a polyamine, and a wide variety of bonds between the two halves is possible in addition to the previously exposed simple imide structure, including a variety of amides and salts of quaternary ammonium. Succinimide dispersants are more fully described in U.S. Patent Nos. 4,234,435, 3,172,892 and 6,165,235.

The polyalkenes from which the substituent groups are derived are typically homopolymers and interpolymers of polymerizable olefin monomers of 2 to 16 carbon atoms; usually 2 to 6 carbon atoms. The amines that react with succinic acylating agents to form the dispersing carboxylic composition may be monoamines or polyamines as described above.

Succinimide dispersant is referred to as such as it usually contains nitrogen largely in the form of imide functionality, although it may be in the form of amine salts, amides, imidazolines, as well as mixtures thereof for preparation. In the succinimide dispersant, one or more succinic acid producing compounds and one or more of the amines, typically with water removal, are heated, optionally in the presence of a substantially liquid organic solvent / diluent. nourishment, usually liquid, at a high temperature, generally in the range of 80 ° C to the point of decomposition of the mixture or product; typically 100 ° C to 300 ° C.

Further details and examples of the procedures for preparing the succinimide dispersants of the present invention are included, for example, in U.S. Pat. 3,172,892, 3,219,666, 3,272,746, 4,234,435, 6,440,905 and 6,165,235.

(3) "Amine dispersants" are reaction products of relatively high molecular weight aliphatic halides and amines, preferably polyalkylene polyamines. Examples thereof are described, for example, in the following U.S. patents: 3,275,554, 3,438,757, 3,454,555, and 3,565,804.

(4) "Mannich Dispersants" are reaction products of alkyl phenols wherein the alkyl group

It contains at least 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines). The materials described in the following US patents are illustrative: 3,036,003, 10 3,236,770, 3,414,347, 3,448,047, 3,461,172, 3,539,633, 3,586,629, 3,591,598, 3,634,515, 3,725,480 , 3,726,882, and 3,980,569.

(5) Post-treated dispersants are obtained by reacting carboxylic, amine or

Mannich with reagents such as dimercaptothiadiazoles, urea, thiourea, carbon disulphide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or the like. Exemplary materials of this species are described in the following US patents: 3,200,107, 3,282,955, 3,367,943, 3,513,093, 3,639,242, 3,649,659, 3,442,808, 3,455,832, 3,579,450, 3,600,372, 3,702,757, and 3,708,422.

(6) Polymeric dispersants are interposed

polymers of oil solubilization monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, for example aminoalkyl acrylates or acrylamides and poly (oxyethylene) -substituted acrylates. Examples of polymer dispersants thereof are set forth in the following U.S. patents: 3,329,658, 3,449,250, 3,519,656, 3,666,730, 3,687,849, and 3,702,300.

The composition may also contain one or more detergents, which are usually salts, and specifically overbased salts. Overbased salts, or overbased materials are homogeneous single phase Newtonian systems characterized by an excess metal content than should be present according to the metal stoichiometry and the particular acid organic compound that reacted with the metal. The overbased materials are prepared by reacting an acidic material (typically an inorganic acid or lower carboxylic acid, preferably carbon dioxide) with a mixture comprising an acidic organic compound, a reaction medium comprising at least one inert organic solvent (such as mineral oil, naphtha, toluene, xylene) for said acid organic material, a stoichiometric excess of a metal base, and a promoter.

Acidic organic compounds useful in the preparation of the base compositions of the present invention include carboxylic acids, sulfonic acids, phosphorus-containing acids, phenols or mixtures thereof. Preferably, the acidic organic compounds are acids are carboxylic acids or sulfonic acids with sulfonic or thiosulfonic groups (such as hydrocarbyl-substituted benzenesulfonic acids), and hydrocarbyl-substituted salicylic acids. Another type of compounds useful in the preparation of the overbearing composition of the present invention comprises saloxarates. A description of the useful salicarates for the present invention can be found in WO 04/04850.

Metal compounds useful in the preparation

Most of the base salts are generally any Group 1 or Group 2 metal compounds (CAS version of the Periodic Table of the Elements). Group 1 metals in the metal compound include Group Ia alkali metals (eg sodium, potassium, lithium) as well as Group 1b metals such as copper. Group 1 metals are preferably sodium, potassium, lithium and copper, preferably sodium or potassium, and most preferably sodium. Metal base Group 2 metals include Group 2a alkaline earth metals (eg magnesium, calcium, strontium, barium) as well as Group 2b metals such as zinc or cadmium. Preferably the Group 2 metals are magnesium, calcium, barium or zinc, preferably magnesium or calcium, more preferably calcium.

Examples of the overbased detergent of the present invention include, but are not limited to, calcium sulfonates, calcium phenates, calcium salicylates, calcium salicarates, and mixtures thereof.

The amount of overlapped material, ie

The detergent, if present, is in accordance with 0.05 to 3 weight percent of the composition, or 0.1 to 3 percent, or 0.1 to 1.5 weight percent. - to, or 0.15 to 1.5 percent by weight.

Anti-foaming agents used to reduce or prevent stable foaming include silicones 10 or organic polymers. Examples of these and additional antifoam compositions are described in "Foam Control Agents" by Henry T. Kerner (Noyes Data Corporation, 1976), pages 125-162.

The compositions of the present invention are in practice employed as lubricants by providing the lubricant to an internal combustion engine (such as a stationary gasoline driven internal combustion engine) in such a way that during engine operation. The lubricant is distributed to the major engine parts 20, thereby lubricating the engine.

As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its normal sense, which is widely known to those skilled in the art. Specifically, it refers to a group that has a carbon atom that is directly linked to the rest of the molecule and has a predominantly hydrocarbon character. Examples of hydrocarbyl groups include: hydrocarbon substituents, i.e. aliphatic (e.g., alkyl or alkenyl), alicyclic substituents (e.g., cycloalkyl, cycloalkenyl), and aromatic-, aliphatic-, and alicyclic substituents substituted as well as cyclic substituents, wherein the ring is completed through another part of the molecule (for example, two substituents together form a ring); substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g. halo (especially chlorine and fluorine), hydroxyl, alkoxy , mercapto, alkyl mercapto, nitro, nitrous, and sulfoxyl); hetero substituents, that is, substituents which, although having a predominantly hydrocarbon character, in the context of this invention, contain other than carbon in a ring or chain otherwise composed of carbon atoms. Heteroatoms include sulfur, oxygen, nitrogen, and include substituents such as pyridyl, furyl, thienyl and imidazolyl. Generally, no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically there will be no non-hydrocarbon substituents on the hydrocarbyl group. It is known that some of the materials described above in this case may interact in the final formulation, so that the components of the final formulation may differ from those initially added. For example, metal ions (from, for example, a detergent) may migrate to other acidic or anionic sites of other molecules. Products formed in this manner, including products formed by employing the composition of the present invention in their intended use, may not be easily described. Nevertheless, all such modifications and reaction products are included within the scope of the present invention; The present invention encompasses a composition prepared by mixing the components described above in this context.

EXAMPLES

The invention will be further illustrated by the following examples, which set forth particularly advantageous embodiments. Although the examples are provided to illustrate the present invention, they are not intended to limit it.

Lubricants are evaluated in the 1% cumene hydroperoxide test in the High Frequency Alternative Motion Wear Apparatus (HFRR 1% CHP) 25 and in the Cameron-Plint High Temperature Alternative Motion Wear test for wear and friction reduction. The HFRR 1% CHP test is used to evaluate the friction and wear performance of lubricants containing reduced levels of phosphorus and sulfur. The wear mark diameter and percentage film thickness is measured using an alternating motion steel ball bearing which slides against a flat steel plate. This test is performed using 1% cumene hydroperoxide (CHP) in conjunction with the High Frequency Alternate Motion Wear Apparatus, which is a commercially available piece of tribology test equipment.

The Cameron-Plint High Temperature Alternative Motion Wear test is used to evaluate the friction and wear performance of lubricants. The wear mark diameter and the film thickness percentage are obtained by measuring by the use of an alternating motion steel ball bearing which slides against a flat steel plate. This test is performed using the Cameron-Plint Alternative Movement Wear Apparatus test, which is a commercially available piece of tribology test equipment.

The following formulations are prepared in a lubricating viscosity oil, where the amounts of additive components are in percent by weight unless otherwise indicated: 0.15% pour point lowering agent. (including about 35% diluent oil), 8% viscosity index improving agent (including about 91% diluent oil), 0.89% diluent oil, 5.1% succinimide dispersing agent (including about 47% diluent oil), 0.48% zinc dialkyl dithiophosphate (except for Cl, which contains 0.98%) (each including about 9% diluent oil), 1.53% calcium sulfonate detergent (including about 42% diluent oil), 0.1% glycerol monooleate (including about 0% diluent oil), 3.44% antioxidants (including about 5% 90% to 100 ppm of a foaming agent, and the res- tant base oil.

To the above formulation, add the components as shown in the following table and perform the 1% Cumene Hydroperoxide test on the High Frequency Alternative Movement Apparatus and the Cameron-Plint High Temperature 20 Alternative Motion Wear test. The results are shown in the following table.

* 1 TABLE I

C1 C2 Ex. 1 Ex.2 Ex.3 Ex.4 0.1% 0.05% 0.05% 0.05% 0.05% 0.05% PPPPPP Additional Component: Component 1 1% Component 2 1% Component 3 1% Component 4 1% Test: 1. HFRR Test 1% CHP Mark Diameter of 161, 285, 225 228 214 214 Wear (μηη) 185 295 Film Thickness 94.83 23.1 98 82 98 93 (%) 2. High Temperature Alteration Movement Wear Test Cameron-Plint Mark Diameter of 339 661 361 323 324 345 Wear (μηη) Film Thickness 100 62 58 58 79 5.7 (%) Component I: ( DL) Tartaric acid / C8-10 alcohol / 2-Ethylexyl Alcohol (50:50) (less water) Component 2: (DL) Tartaric acid / C8-10 alcohol / Tridecyl Alcohol (50:50) (less water)

Component 3: (DL) Tartaric Acid / C12-14 Alcohol / 2-Ethylexyl Alcohol (50:50) (less water)

Component 4: Ethylhexyl Tartrate

The results show that the formulations using tartrates of the present invention in a low sulfur, ash and phosphorus lubricant (Ex. 1-4) reduce wear compared to the 0.05 low SAPS formulation. percent by weight of phosphorus distributed to a composition (C2), which does not contain tartrates. They also provide equivalent wear protection compared to conventional GF-3 (Cl) formulations, which have 15 higher phosphorus content.

Lubricants are further evaluated in the HFRR Low PS test. The HFRR Low PS test is used to evaluate the friction and wear performance of lubricants containing reduced levels of phosphorus and sulfur. The wear mark diameter and film thickness percentage are measured by the use of an alternating motion steel ball bearing that slides against a flat steel plate. This test is performed using 25 to 1% cumene hydroperoxide (CHP) in conjunction with the High Frequency Alternative Movement Apparatus, which is a commercially available part of tribology testing equipment. The following formulations are prepared in a lubricating viscosity oil, where the amounts of additive components are in percent by weight unless otherwise indicated: 0.15% pour point lowering agent. (including about 35% diluent oil), 8% viscosity index enhancer (including about 91% diluent oil), 0.41% diluent oil, 5.0% succinimide dispersing agent (including about 47% diluent oil), 0.63% zinc dialkyl dithiophosphate (each including about 9% diluent oil), 1.53% overlying calcium sulfonate detergent (including about 42% % diluent oil), 2.2% antioxidants (including about 5% diluent oil), 90-100 ppm of a foaming agent, and the remaining base oil.

To the above formulation, the components are added as shown in the following table and the Low OS Alternate Motion Apparatus Low OS test is performed. The results are shown in the following table.

Table 2

C3 C4 C5 Ex. 5 Ex. 6 0.05% P 0.05% P 0.05% P 0.05% P 0.05% P Additional Components Component 5 0.5 1.0 Component 6 0.5 1 , 0 1. HFRR Test Low PS Brand Diameter 337 318 241 219 223 Wear (μπι) Film Thickness 38 37 61 87 90 Cell (%) Component 5: 50:50 GMO Mix: SNFO

Component 6: C8-10 Tartrate

The results show that formulations using tartrates of the present invention in a low sulfur, ash and phosphorus lubricant (Ex. 5-6) reduce wear compared to the 0.05 percent low SAPS formulation. percent by weight of phosphorus distributed to a composition (C3 -C5), which does not contain tartaric rats.

Each of the above documents

is incorporated by reference in this context. Except in the Examples, or where otherwise explicitly stated, all numerical quantities in this specification that specify quantities of materials, reaction conditions, molecular weights, number of carbon atoms, and the like should be understood as modi - by the word "approximately". Unless otherwise indicated, each chemical or composition referred to in this context shall be construed as a commercial grade material which may contain isomers, by-products, derivatives, and other like materials which are normally understood to be present in the commercial class. However, the quantity of each chemical component is shown

It is intended exclusively for any solvent or diluent oil which may be commonly present in commercial material unless otherwise indicated. It should be understood that the upper and lower amount, range and ratio limits set forth herein may be combined independently. Similarly, the bands and quantities for each element of the invention may be used in conjunction with the bands or quantities for any of the other elements. As used herein, the term "consisting essentially of 15" allows the inclusion of substances that do not materially affect the basic and novel characteristics of the composition under consideration.

Claims (12)

1. Low sulfur, low phosphorus, low ash lubricant composition suitable for use in an internal combustion engine, comprising: (a) a lubricating viscosity oil, and (b) ) a condensation product of a material represented by formula I and an alcohol having from 6 to 12 carbon atoms; <formula> formula see original document page 39 </formula> wherein each R is independently H, or a hydrocarbyl group, or wherein the R groups together form a ring; and wherein if R is Η, the condensation product is optionally further functionalized by acylation or reaction with a boron compound; wherein said lubricant composition has a sulfated ash value of up to about 1.0, a phosphorus content of up to about 0.08 weight percent, and a sulfur content of up to about 0 percent. 4 percent by weight. Composition according to Claim 1, characterized in that the alcohol is linear, branched or mixtures thereof and wherein the alcohol has from about 8 to about 10 carbon atoms. Composition according to Claim 1, characterized in that the condensation product (b) is a linear C8-10 alkyl tartrate ester. Composition according to Claim 1, characterized in that the amount of the condensation product is about 0.05 to about 5.0 per cent by weight. Composition according to Claim 1, characterized in that it further comprises a metal dialkyl dithiophosphate, wherein the metal dialkyl dithiophosphate is zinc dialkyl dithiophosphate wherein at least about 50 percent of its alkyl groups are groups. of secondary alkyls. Composition according to Claim 1, characterized in that it further comprises a dispersing agent, wherein the dispersing agent is a succinimide. Composition according to Claim 1, characterized in that it further comprises at least one calcium-based detergent, wherein the calcium-based detergent is selected from the group consisting of calcium sulphonates, phenol phenates. calcium, calcium salicylates, calcium salixarates and mixtures thereof. Composition according to Claim 1, characterized in that it further comprises at least one antioxidant, wherein the antioxidant is selected from the group consisting of retarded phenols, aryl amines and mixtures thereof. Composition according to Claim 1, characterized in that it further comprises additional friction modifiers other than (b), wherein the additional friction modifiers are selected from the group consisting of glycerol monooleates, oleyl amides, amines. diethanol greases as well as mixtures thereof. Composition according to Claim 1, characterized in that it further comprises a foaming agent. Method for lubricating an internal combustion engine, characterized in that it comprises feeding said engine a lubricating viscosity oil, and a condensation product of a material represented by formula I and an alcohol having a 6 to 12 carbon atoms; where in the product each R is independently H, or a hydrocarbyl group, or wherein the R groups together form a ring; or wherein if R is H then the resulting hydroxyl group is further functionalized by acylation or reaction with a boron compound; wherein said lubricant composition has a sulfated ash value of up to about 1.0, a phosphorus content of up to about 0.08 weight percent, and a sulfur content of up to about 0 percent. 4 percent by weight. A method of producing a lubricating composition comprising: (a) mixing a lubricating viscosity oil and a condensation product of a material represented by formula I and an alcohol having from 6 to 12 atoms of carbon; <formula> formula see original document page 42 </formula> wherein in the product each R is independently H, or a hydrocarbyl group, or wherein the R groups together form a ring; or wherein if R is H, then the condensation product is further functionalized by acylation or reaction with a boron compound; resulting in a lubricant composition wherein said lubricant composition is provided with a sulphated ash value of up to about 1.0, a phosphorus content of up to about 0.08 weight percent, and a sulfur content up to about 0.4 weight percent.