FR2984919B1 - METHOD FOR REDUCING THE BASICITY DEPLETION SPEED OF A LUBRICATING OIL COMPOSITION USED IN A MOTOR - Google Patents

Abstract

The invention relates to a method for reducing the basicity depletion rate of a lubricating oil composition comprising at least one overbased alkaline or alkaline earth metal detergent used in an engine. The method comprises adding to the lubricating oil composition one or more methylene bridged alkylphenols or ethoxylated methylene bridged alkylphenols. Field of application: Use of said lubricating oil composition in an engine to extend the life of the oil and better protect said engine for longer.

Description

FIELD OF THE INVENTION

The present invention provides a method for reducing the basicity depletion rate (as determined by ASTM D2896) of a lubricating oil composition used in an engine, the lubricating oil composition comprising at least one detergent based on overbased alkaline or alkaline earth metal, soluble in oil. In particular, the invention relates to a method for reducing the basicity depletion rate (as determined by ASTM D2896) of a lubricating oil composition used in an engine, the lubricating oil composition comprising at least an oil-soluble, overbased alkaline or alkaline earth metal detergent without increasing the sulfated ash content (SASH). Preferably, the lubricating oil composition is a marine engine cylinder lubricant, a piston engine oil, a gas engine oil, or a crankcase lubricating oil composition (including a vehicle engine oil). particular and a high performance diesel engine oil).

BACKGROUND OF THE INVENTION

Lubricating oil compositions include oil-soluble overbased detergents to provide alkalinity to neutralize sulfur-containing acids resulting from the presence of high sulfur fuels. They also prevent harmful deposits of carbon and sludge, which can lead to engine failures and repairs. Overbased detergents usually have a Total Base Number (TBN) of 50 to 500, preferably 250 to 450 mg KOH / g (ASTM D2896), and are usually metal-based detergents. overbased alkaline earth metals such as overbased calcium sulfonates, phenates and salicylates. It is important that the basicity of overbased detergents is maintained for as long as possible, as this ensures longer oil life and better engine protection for a longer period of time. It is also important that ash contents are not increased because excessive levels of sulphated ash can result in increased deposits on the pistons and exhaust gas circuits, including heat recovery systems and exhaust systems. post treatment.

The present invention relates to the problem of reducing the basicity depletion rate (as determined by ASTM D2896) of a lubricating oil composition used in an engine. The present invention also relates to the problem of reducing the basicity depletion rate (as determined by ASTM D2896) of a lubricating oil composition used in an engine without increasing the sulfated ash content.

SUMMARY OF L1 INVENTION

According to a first aspect of the present invention there is provided a method for reducing the rate of depletion (as determined by ASTM D2 8 96) of a lubricating oil composition used in an engine, the composition of lubricating oil comprising at least one oil-soluble overbased alkali or alkaline earth metal detergent, which process comprises adding to the lubricating oil composition one or more compounds of formula (I):

in which :

x is 1 to 50, preferably 1 to 40, more preferably 1 to 30; R1 and R2 are H, hydrocarbyl groups having 1 to 12 carbon atoms, or hydrocarbyl groups having 1 to 12 carbon atoms and at least one heteroatom; R represents a hydrocarbyl group having 9 to 100, preferably 9 to 70, preferably 9 to 50, carbon atoms; and n has a value of 0 to 10, or else alkaline earth metal salts of the compounds of formula (I).

In the compounds of formula (I), n is preferably 0. In the compounds of formula (I), x is preferably equal to 1. In the compounds of formula (I), R preferably has 9 to 20 atoms. carbon, more preferably 9 to 15. In the compounds of formula (I), R is preferably branched.

In the compounds of formula (I), R 1 is preferably H, R 2 is preferably H and R is preferably in the para position relative to the group -O- [CH 2 CH 2 O] nH.

The compounds of formula (I) are preferably methylene bridged alkylphenols or ethoxylated methylene bridged alkylphenols.

The compounds of formula (I) advantageously comprise less than 1 mol%, more preferably less than 0.5 mol% and preferably less than 0.1 mol% of unreacted alkylphenol.

In the compounds of formula (I), advantageously η = 1 for more than 60, more preferably more than 70, still more preferably more than 80, more preferably more than 90, or more preferably more than 95, mol%.

In the compounds of formula (I), preferably n> 2, which corresponds to di-oxyalkylated, tri-oxyalkylated and tetra-oxyalkyl compounds, for less than 5 mol%.

The alkaline earth metal salts of the compounds of formula (I) are, for example, the calcium, magnesium, barium or strontium salts. Calcium or magnesium is appreciated; calcium is particularly appreciated,

The lubricating oil composition has, for example, a total basic number (TBN) of 4 to 100 as measured by ASTM D2896, preferably a TBN of 5 to 75, more preferably 6 to 70.

The lubricating oil composition is preferably a marine engine cylinder lubricant, a piston engine oil, a gas engine oil or a crankcase lubricating oil composition (including a particular vehicle engine oil and a high performance diesel engine oil).

When the lubricating oil composition is a marine engine cylinder lubricant, the Total Base Number (TBN) (as measured by ASTM D2896) is preferably at least 20, more preferably at least 40 to about 70 mg KOH / g.

When the lubricating oil composition is a piston-sleeve engine oil, the TBN (as measured by ASTM D2896) is preferably at least 10, more preferably at least 20, and preferably 30 at 55 mg KOH / g.

When the lubricating oil composition is a gas engine oil, TBN (as measured by ASTM D2896) is preferably at least 4, more preferably 5 to 15 mg KOH / g.

When the lubricating oil composition is a crankcase oil, the TBN (as measured by ASTM D2896) is preferably at least 5, more preferably at least 6 to 18 mg KOH / g.

The lubricating oil composition is preferably a marine engine cylinder lubricant.

According to the present invention, it is also proposed the use of one or more compounds of formula (I):

wherein: x is 1 to 50, preferably 1 to 40, more preferably 1 to 30; R1 and R2 are H, hydrocarbyl groups having 1 to 12 carbon atoms, or hydrocarbyl groups having 1 to 12 carbon atoms and at least one heteroatom; R represents a hydrocarbyl group having 9 to 100, preferably 9 to 70, preferably 9 to 50, carbon atoms; and n is 0 to 10, or their alkaline earth metal salts, for reducing the basicity depletion rate (as determined by ASTM D2896) of a lubricating oil composition used in an engine, the lubricating oil composition comprising at least one oil-soluble overbased alkali or alkaline earth metal detergent.

DETAILED DESCRIPTION OF THE INVENTION

The compounds of formula (I) are the compounds represented below:

x is 1 to 50, preferably 1 to 40, more preferably 1 to 30;

R1 and R2 are H, hydrocarbyl groups having 1 to 12 carbon atoms, or hydrocarbyl groups having 1 to 12 carbon atoms and at least one heteroatom; R represents a hydrocarbyl group having 9 to 100, preferably 9 to 70, preferably 9 to 50, carbon atoms; and n has a value of 0 to 10, or their alkaline earth metal salts.

The alkaline earth metal salts of the compounds of formula (I) are, for example, the calcium, magnesium, barium and strontium salts. Calcium or magnesium is appreciated; calcium is particularly appreciated.

In the compounds of formula (I), n is preferably 0. In the compounds of formula (I), x is preferably equal to 1. In the compounds of formula (I), R preferably has 9 to 20 atoms. carbon, more preferably 9 to 15. In the compounds of formula (I), R is preferably branched. In the compounds of formula (I), R 1 and R 2 preferably represent H.

In the compounds of formula (I), R 1 is preferably H, R 2 is preferably H, R is preferably in the para position relative to the group -O- [CH 2 CH 2 O] nH and n is advantageously 1 or more and preferably, a value of 1 to 10. For further details concerning compounds of formula (I) wherein n is 1 or more, reference is made to EP 2374866A. In the compounds of formula (I), advantageously η = 1 for more than 60, more preferably more than 70, still more preferably more than 80, more preferably more than 90, or more preferably more than 95, mol%. In the compounds of formula (I), preferably n> 2, which corresponds to di-oxyalkylated, tri-oxyalkylated and tetra-oxyalkyl compounds, for less than 5 mol%.

The compounds of formula (I) advantageously comprise less than 1 mol%, more preferably less than 0.5 mol% and preferably less than 0.1 mol% of unreacted alkyl phenol.

The compounds of formula (I) have the advantage of being free of metals. In addition, they do not exhibit negative interactions with dispersants.

The compounds of formula (I) are preferably hydrocarbylphenol-formaldehyde condensation products. The term "hydrocarbyl" as used herein means that R is predominantly hydrogen and carbon atoms and is bonded to the rest of the molecule by a carbon atom, but does not exclude the presence of other atoms or groups in a proportion insufficient to alter the substantially hydrocarbon characteristics of the group. The hydrocarbyl group is preferably composed only of hydrogen and carbon atoms. Advantageously, the hydrocarbyl group is an aliphatic group, preferably an alkyl or alkylene group, especially an alkyl group, which may be linear or branched. R is preferably an alkyl or alkylene group. R is preferably branched.

The hydrocarbylphenol-aldehyde condensation product preferably has a weight average molecular weight (Mw), as measured by gel permeation chromatography (GPC), in the range of 1000 to less than 6000, preferably less than 4000. The hydrocarbylphenol-aldehyde condensation product preferably has a number average molecular weight (Mn), as measured by GPC, in the range of 900 to less than 4000, for example 3000. The ratio Mw / Mn is preferably in the range of 1.10 to 1.60.

The hydrocarbylphenol-aldehyde condensation product is preferably a product obtained by a condensation reaction between at least one aldehyde or a ketone or one of their reactive equivalents and at least one hydrocarbylphenol, in the presence of an acid catalyst such as, for example, for example, an alkylbenzenesulfonic acid. The product is preferably stripped to remove any unreacted hydrocarbylphenol, preferably less than 5% by weight, more preferably less than 3% by weight, still more preferably less than 1% by weight. mass, of hydrocarbylphenol unreacted. Most preferably, the product comprises less than 0.5% by weight, for example less than 0.1% by weight, of unreacted hydrocarbylphenol.

Although a basic catalyst can be used, an acidic catalyst is preferred. The acid catalyst may be selected from a wide range of acidic compounds such as, for example, phosphoric acid, sulfuric acid, sulfonic acid, oxalic acid and hydrochloric acid. The acid may also be present as a constituent of a solid material such as clay treated with an acid. The amount of catalyst used can vary from 0.05 to 10 or more than 10% by weight, for example from 0.1 to 1% by weight, of the total reaction mixture.

When n is 1 or greater in formula (I), the compounds are preferably prepared by oxyalkylation of a hydrocarbylphenol condensation product with ethylene carbonate (which is preferred), propylene carbonate or the like. butylene carbonate. The use of a carbonate for the oxyalkylation reaction allowed a much better adjustment of the "n" value and its amount compared to the use of ethylene oxide or propylene oxide. In addition, a suitable choice of catalyst can result in a product consisting almost entirely of a mono-oxyalkylated product (i.e., n = 1). Sodium salts, especially the hydroxide and carboxylates, such as stearate, are preferred.

In particular, the hydrocarbylphenol-aldehyde condensation product is preferably a branched dodecylphenol-formaldehyde condensation product, such as, for example, a tetrapropenyl-tetramer-phenol-formaldehyde condensation product.

The hydrocarbylphenol-aldehyde condensation product is preferably present in the additive concentrate in an amount of from about 0.1 to 20% by weight, preferably from about 0.1 to 15% by weight, and more preferably from about 0.1 to about 15% by weight. about 0.1 to 12% by weight, based on the weight of the concentrate.

The lubricating oil compositions of the present invention comprise a major amount of an oil of lubricating viscosity and a small amount of a compound of formula (I).

Lubricating viscosity oils useful in the context of the present invention may be selected from natural lubricating oils, synthetic lubricating oils and mixtures thereof. The lubricating oil can have a viscosity ranging from light distillate mineral oils to heavy lubricating oils, such as gasoline engine oils, mineral lubricating oils and high performance diesel engine oils. In general, the viscosity of the oil is from about 2 centistokes to about 40 centistokes, especially from about 4 centistokes to about 20 centistokes, as measured at 100 ° C.

Natural oils include animal oils and vegetable oils (eg castor oil, lard oil); liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral oils of paraffinic, naphthenic, and mixed paraffinic-naphthenic types. Lubricating viscosity oils derived from coal or shale also function as useful base oils. Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (for example polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly- (1-hexenes), poly (1-octenes), poly (1-decenes)); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di (2-ethylhexyl) benzenes); polyphenyls (for example biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and derivatives, analogs and homologs thereof. Also useful oils are synthetic oils obtained by a gas-to-liquid process from hydrocarbons synthesized by the Fischer-Tropsch process, which are commonly referred to as gas-to-liquid or "GTL" base stocks.

Alkylene oxide polymers and interpolymers and derivatives thereof wherein the terminal hydroxyl groups have been modified by esterification, etherification, or the like, represent another class of known synthetic lubricating oils. These oils are exemplified by polyoxyalkylene-type polymers prepared by polymerization of ethylene oxide or propylene oxide, and alkyl and aryl ethers of polyoxyalkylene-type polymers (e.g., a polyiso-propylene glycol methyl ether having a weight of 1000 molecular weight or a polyethylene glycol diphenyl ether having a molecular weight of 1000 to 1500); and their mono- and polycarboxylic esters, for example, acetic acid esters, C3 to C8 mixed fatty acid esters and the CX3 oxy acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils include the dicarboxylic acid esters (e.g., phthalic acid, succinic acid, alkylsuccinic acids and alkenylsuccinic acids, maleic acid, azelaic acid, suberic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenylmalonic acids) with various alcohols (eg butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, 2-ethylhexyl dimer of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles 2-ethylhexanoic acid.

Esters useful as synthetic oils also include those prepared from C5 to C12 monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.

Silicon-based oils such as polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxysilicone oils and silicate oils represent another useful class of synthetic lubricants; these oils include tetraethyl silicate, tetraisopropyl silicate, tetra (2-ethylhexyl) silicate, tetra (4-methyl-2-ethylhexyl) silicate, (p-tert-butylphenyl) silicate , Hexa- (4-methyl-2-ethylhexyl) disiloxane, poly (methyl) siloxanes and poly (methylphenyl) siloxanes. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans. The lubricating viscosity oil may comprise a Group I, Group II or Group III base lubricating oil or base oil mixtures of the aforementioned basic lubricating oils. Preferably, the oil of lubricating viscosity is a Group II or Group III base lubricating oil, or a mixture thereof, or a mixture of a Group I lubricating oil and one or Group II and Group III. Preferably, a dominant amount of lubricating oil of lubricating viscosity is a Group II, Group III, Group IV or Group V lubricating oil or a mixture thereof. The base lubricating oil, or base lubricating oil mixture, preferably has a saturated compound content of at least 65%, more preferably at least 75%, for example at least 85%. Most preferably, the base lubricating oil, or base lubricating oil blend, has a saturated compound content greater than 90%. Preferably, the oil or the mixture of oils will have a sulfur content of less than 1%, preferably less than 0.6%, preferably less than 0.4%, by weight.

Preferably, the volatility of the oil or the mixture of oils, as measured by the Noack volatility test (ASTM D5880), is less than or equal to 30%, advantageously less than or equal to 25%, more advantageously less than or equal to 20%, preferably less than or equal to 16%. Preferably, the viscosity number (VI) of the oil or oil mixture is at least 85, preferably at least 100, preferably about 105 to 140.

The definitions of the basic lubricating oils and base oils of this invention are the same as those contained in the publication of the American Petroleum Institute (API) entitled "Engine Oil Licensing and Certification System", Industry Services Department, Fourteenth Edition, December 1996, Addendum 1, December 1998. The said publication classifies basic lubricating oils as follows: (a) Group I lubricating oils contain less than 90% saturated compounds and / or more than 0.03% sulfur and have a viscosity number greater than or equal to 80 and less than 120 using the test methods specified in Table 1.

(b) Group II lubricating oils contain 90% or more saturated compounds and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 80 and less than 120 using the test methods specified in Table 1.

(c) Group III lubricating oils contain 90% or more saturated compounds and less than or equal to 0.03% sulfur and have a viscosity index greater than or equal to 120 using The test oils specified in Table 1. d) Group IV lubricating oils are polyalphaolefins (PAO). (e) Group V lubricating oils include all other basic lubricating oils not included in Group I, II, III or IV.

Table 1 - Basic Lubricating Oil Analysis Method

Metal-containing or ash-forming detergents act as both detergents for reducing or removing deposits and acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and prolonging the life of the product. of life of the engines. The detergents generally comprise a polar head with a long hydrophobic tail, the polar head comprising

a metal salt of an acidic organic compound. The salts may contain a substantially stoichiometric amount of the metal, in which case they are usually described as normal or neutral salts, and usually have a total base number or TBN (as measured by ASTM D2896) 0 to 80. A large amount of a metal base may be incorporated by reacting an excess of a metal compound (eg, an oxide or hydroxide) with an acid gas (eg, carbon dioxide). The resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base micelle (eg carbonate). These overbased detergents may have a TBN of 150 or more and usually have a TBN of 250 to 500 or more than 500.

The detergents which may be used include oil soluble, neutral and overbased sulphonates, phenates, sulfurized phenols, thiophosphonates, salicylates and naphthenes, and other oil-soluble carboxylates of a metal, particularly alkali or alkaline earth metals, for example sodium, potassium, lithium, calcium and magnesium. The most commonly used metals are calcium and magnesium, both of which may be present in detergents used in a lubricant, and mixtures of calcium and / or magnesium with sodium. Particularly suitable metal detergents are neutral and overbased calcium sulfonates having a TBN of 20 to 500, and neutral and overbased calcium sulphide phenates and phenates having a TBN of 50 to 450. It is possible to use detergents, whether overbased or neutral or mixed.

The sulfonates can be prepared from sulfonic acids which are usually obtained by sulfonation of alkyl-substituted aromatic hydrocarbons, such as those obtained by fractionation of petroleum or by alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogenated derivatives, such as chlorobenzene, chlorotoluene and chloronaphthalene. The alkylation can be carried out in the presence of a catalyst with alkylating agents having from about 3 to more than 70 carbon atoms. Alkarylsulfonates usually contain from about 9 to about 80 or more than 80 carbon atoms, preferably from about 16 to about 60 carbon atoms, per alkyl-substituted aromatic group.

Oil-soluble sulfonates or alkarylsulfonic acids can be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylates, sulfides, sulfates, nitrates, borates and ethers of the metal. The amount of metal compound is selected in relation to the desired TBN of the final product, but usually ranges from about 100 to 220% by weight (and is preferably at least 125% by weight) of the stoichiometrically required amount.

The metal salts of phenols and sulfurized phenols are prepared by reaction with a suitable metal compound such as an oxide or hydroxide and neutral or overbased products can be obtained by methods well known in the art. Sulfur phenols can be prepared by reacting a phenol with sulfur or a sulfur-containing compound such as hydrogen sulfide, sulfur monohalide or sulfur dihalide to form products which are generally mixtures of compounds in which 2 or more phenols are bridged by bridges containing sulfur.

The lubricating oil compositions of the present invention may further contain one or more ashless dispersants which effectively reduce the formation of deposits when used in engines when added to lubricating oils. Ashless dispersants useful in the compositions of the present invention include an oil soluble long chain polymer backbone having functional groups capable of associating with the particles to be dispersed. Usually, these dispersants comprise amine, alcohol, amide or ester polar groups attached to the polymer backbone, often by a bridging group. The ashless dispersant can be selected, for example, from oil-soluble salts, esters, amino esters, amides, imides and oxazolines of chain-substituted hydrocarbon-substituted mono- and polycarboxylic acids. long or their anhydrides; long chain hydrocarbon thiocarboxylate derivatives; long chain aliphatic hydrocarbons having polyamine groups attached directly thereto; and Mannich condensation products formed by condensing a long-chain substituted phenol with formaldehyde and a polyalkylene polyamine. The most commonly used dispersant is the well known succinimide dispersant, which is a condensation product of a hydrocarbyl substituted succinic anhydride and a poly (alkylene amine). Dispersants based on monosuccinimides and bis-succinimides (and mixtures thereof) are well known.

Preferably, the ashless dispersant is a "high molecular weight" dispersant having a number average molecular weight (Mn) greater than or equal to 4000, for example from 4000 to 20,000. The precise molecular weight ranges depend on the type of polymer used to form the dispersant, the number of functional groups present and the type of polar functional group used. For example, for a polyisobutylene derivatized dispersant, a high molecular weight dispersant is a dispersant formed with a number average molecular weight polymer skeleton of about 1680 to about 5600. Conventional polyisobutylene dispersants commercially available polyisobutylene polymers having a number average molecular weight ranging from about 900 to about 2300, functionalized with maleic anhydride (molecular weight = 98) and derivatized with polyamines having a weight Molecular weight of about 100 to 350. Lower molecular weight polymers can also be used to form high molecular weight dispersants by incorporating multiple polymer chains into the dispersant, which can be accomplished by methods known in the art. in this domain.

Preferred dispersant groups include poly-α-olefin dispersants derivatized with a polyamine, particularly ethylene / butene-alpha-olefin dispersants and polyisobutylene dispersants. Particularly preferred dispersants are ashless dispersants derived from a polyisobutylene substituted with succinic anhydride groups and reacted with polyethyleneamines, for example polyethylenediamine, tetraethylenepentamine; or a polyoxyalkylene polyamine, for example polyoxypropylenediamine, trimethylolaminomethane; a hydroxylic compound, for example pentaerythritol; and their associations. A particularly preferred dispersant combination is a combination (A) of a polyisobutylene substituted with succinic anhydride groups and reacted with (B) a hydroxyl compound, for example pentaerythritol; (C) a polyoxyalkylene polyamine, for example polyoxypropylenediamine; or (D) a polyalkylenediamine, for example polyethylenediamine and tetraethylenepentamine, using 0.3 to about 2 moles of (B), (C) and / or (D) per mole of (A). Another preferred dispersant combination comprises a combination (A) of a polyisobutenyl succinic anhydride with (B) a polyalkylene polyamine, for example tetraethylene pentamine, and (C) a polyhydric alcohol or a polyhydroxy-substituted aliphatic primary amine, for example pentaerythritol or trismethylolaminomethane, as described in the US Patent No. 3,632,511.

Another category of ashless dispersants comprises condensation products of the Mannich base type. In general, these products are prepared by condensing about one mole of an alkyl substituted mono- or polyhydroxybenzene with about 1 to 2.5 moles of one or more carbonyl compounds (eg, formaldehyde and paraformaldehyde) and about 0, 5 to 2 moles of a polyalkylene polyamine, as described, for example, in the US Pat. These condensation products of the Mannich base type may comprise a polymeric product resulting from a metallocene-catalyzed polymerization as a substituent on the benzene group, or they may be reacted with a compound containing such a polymer. substituted on a succinic anhydride in a manner similar to that described in the US Pat. No. 3,442,808. Examples of functionalized and / or derivatized olefinic polymers synthesized using metallocene catalyst systems are described in the publications mentioned above.

The dispersant can be further post-treated with a variety of conventional post-treatments such as boration, as generally described in U.S. patents. Nos. 3,087,936 and 3,254,025. Borating of the dispersant is readily accomplished by treating a nitrogen-acylated dispersant with a boron compound such as boron-derived oxide, boron halide, boron-derived acids and esters. of boron-derived acids in an amount sufficient to provide from about 0.1 to about 20 atomic proportions of boron for each mole of acylated nitrogen composition. Useful dispersants contain from about 0.05 to about 2.0% by weight, for example about 0.05 to about 0.7% by weight, of boron. It is believed that boron, which occurs in the product as dehydrated boric acid polymers (mainly (HBO2) 3), binds to the dispersant imides and diimides in the form of amine salts, e.g. metaborate of diimide. The borating can be carried out by adding about 0.5 to 4% by weight, for example about 1 to about 3% by weight (based on the weight of the acylated nitrogen compound), a boron compound, preferably boric acid, usually in the form of a suspension, to the acylated nitrogen compound and by heating with stirring at a temperature of from about 135 ° C to about 190 ° C, for example from 140 ° C to 170 ° C, for about 1 to about 5 hours, followed by nitrogen entrainment. Alternatively, the boron treatment can be carried out by adding boric acid to a hot reaction mixture of the dicarboxylic acid material and the amine while removing the water. Other post-reaction methods commonly known in the art can also be implemented.

The dispersant may also be further posttreated by reaction with an agent referred to as a "capping agent". Conventionally, nitrogenous dispersants have been "capped" to reduce the detrimental effect that these dispersants have on the fluorinated elastomer seals of the engines. Many capping agents and processes are known. Of the known "capping agents", those which convert the basic amino groups of the dispersants to non-basic groups (eg, amido or imido groups) are most suitable. The reaction of a nitrogenous dispersant and an alkyl acetoacetate (e.g., ethyl acetoacetate (EAA)) is described, for example, in U.S. Nos. 4,839,071, 4,839,072 and 4,579,675. The reaction of a nitrogenous dispersant and formic acid is described, for example, in U.S. Pat. No. 3,185,704. The reaction product of a nitrogenous dispersant and suitable capping agents is described in U.S. Pat. No. 4,663,064 (glycolic acid); 4,612,132, 5,334,321, 5,356,552, 5,716,912, 5,849,676, 5,861,363 (alkyl and alkylene carbonates, e.g., ethylene carbonate); 5,328,622 (monoepoxide); 5,026,495, 5,085,788, 5,259,906, 5,407,591 (poly (eg, bis) epoxides) and 4,686,054 (maleic acid or succinic anhydride). The foregoing list is not exhaustive and other methods for providing a cap for nitrogenous dispersants are known to those skilled in the art.

In order to adequately control the deposit on the pistons, a nitrogenous dispersant may be added in an amount to provide the lubricating oil composition with about 0.03% by weight to about 0.15% by weight, preferably about 0, 07 to about 0.12% by weight of nitrogen.

The ashless dispersants are basic in nature and, therefore, have TBN which, depending on the nature of the polar group and the borate or treatment with a dispersant capping agent or lack of boration or treatment, can range from about 5 to about 200 mg KOH / g. However, it is known that high levels of basic nitrogen of the dispersant have a detrimental effect on the fluoroelastomeric materials conventionally used to form the engine seals and, therefore, it is preferable to use the minimum amount of a dispersant necessary to make it possible to fight against deposits on the pistons, and to use practically no dispersant, or preferably not to use dispersant having a TBN greater than 5. Preferably, the quantity of dispersant used does not provide more than 4, preferably not more than 3 mg KOH / g of TBN to the lubricating oil composition. It is further preferred that the dispersant does not provide more than 30, preferably not more than 25,% of the TBN of the lubricating oil composition.

Additional additives may be incorporated into the compositions of the invention to enable them to meet particular requirements. Examples of additives which can be incorporated into the lubricating oil compositions are metal corrosion inhibitors, viscosity index improvers, oxidation inhibitors, friction modifiers, other dispersants, agents, and the like. antifoam, anti-wear agents and pour point depressants. Some are described in more detail below.

Metal dihydrocarbyldithiophosphates are frequently used as antiwear agents and antioxidants. The metal may be an alkali or alkaline earth metal or aluminum, lead, tin, molybdenum, manganese, nickel or copper. Zinc salts are most commonly used in a lubricating oil in amounts of 0.1 to 10, preferably 0.2 to 2% by weight, based on the total weight of the lubricating oil composition. They can be prepared by known techniques by first forming a dihydrocarbyl-dithiophosphoric acid (DDPA), usually by reacting one or more alcohols or phenol with P2S5 and then neutralizing the formed DDPA with a zinc. For example, a dithiophosphoric acid can be prepared by reacting mixtures of primary and secondary alcohols. Alternatively, it is possible to prepare multiple dithiophosphoric acids in which the hydrocarbyl groups on one are of a totally secondary character and the hydrocarbyl groups on the others are of a totally primary character. To prepare the zinc salt, it is possible to use any basic or neutral zinc compound but the oxides, hydroxides and carbonates are used most generally. Commercial additives frequently contain excess zinc due to the use of an excess of basic zinc compound in the neutralization reaction.

The preferred zinc dihydrocarbyl dithiophosphates are oil soluble salts of dihydrocarbyl dithiophosphoric acids and may be represented by the following formula:

wherein R and R 'may be the same or different hydrocarbyl radicals containing 1 to 18, preferably 2 to 12, carbon atoms, including radicals such as alkyl, alkenyl, aryl, arylalkyl and alkaryl radicals and cycloaliphatic radicals. Particularly preferred groups such as R and R 'are alkyl groups having 2 to 8 carbon atoms. Thus, the radicals can be, for example, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, amyl, n-hexyl, isohexyl, n-octyl, decyl, dodecyl, octadecyl, 2 radicals. ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl and butenyl. In order to achieve oil solubility, the total number of carbon atoms (i.e., R and R ') in dithio-phosphoric acid is generally approximately 5 or greater. therefore, zinc dihydrocarbyldithiophosphates may comprise zinc dialkyldithiophosphates. The present invention may be particularly useful when used with lubricant compositions containing phosphorus contents of from about 0.02 to about 0.12 mass%, for example from about 0.03 to about 0.10. % by weight, or from about 0.05 to about 0.08% by weight, based on the total mass of the composition. In a preferred embodiment, the lubricating oil compositions of the present invention contain a predominantly derived zinc dialkyldithiophosphate (eg greater than 50 mol%, for example more than 60 mol%) of secondary alcohols.

Oxidation inhibitors or antioxidants reduce the tendency of mineral oils to deteriorate in service. Oxidative deterioration can be evidenced by the presence of sludge in the lubricant,

deposits similar to gums on metal surfaces and by an increase in viscosity. These oxidation inhibitors include sterically hindered phenols, alkaline earth metal salts of alkylphenol thioesters preferably having C5-CX2 alkyl side chains, calcium nonylphenol sulfide, oil-soluble sulfur phenates and phenates, phosphosulfurized or sulphurized hydrocarbons, phosphorus esters, metal thiocarbamates, oil-soluble copper compounds, as described in the US Pat. No. 4,867,890 and compounds containing molybdenum.

Conventional aromatic oil-soluble amines having at least two aromatic groups directly attached to an amine nitrogen atom contain from 6 to 16 carbon atoms. The amines may contain more than two aromatic groups. Compounds having a total of at least three aromatic groups in which two aromatic groups are linked by a covalent bond or by an atom or group (for example an oxygen or sulfur atom, or a group -CO-, - SO2- or alkylene) and two are attached directly to an amine nitrogen atom are also considered to be aromatic amines having at least two aromatic groups attached directly to the nitrogen. The aromatic rings are usually substituted with one or more substituents selected from alkyl, cycloalkyl, alkoxy, aryloxy, acyl, acylamino, hydroxy and nitro groups.

Multiple antioxidants are commonly used in combination. In a preferred embodiment, the lubricating oil compositions of the present invention contain from about 0.1 to about 1.2% by weight of an amine antioxidant and from about 0.1 to about 3% by weight of an antioxidant. phenolic. In another preferred embodiment, the lubricating oil compositions of the present invention contain from about 0.1 to about 1.2% by weight of an amine antioxidant, from about 0.1 to about 3% by weight of a phenolic antioxidant and a molybdenum compound in an amount providing to the lubricating oil composition about 10 to about 1000 ppm molybdenum.

Representative examples of suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene, polymethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, interpolymers of styrene and acrylic esters, and partially hydrogenated styrene / isoprene, styrene / butadiene and isoprene / butadiene copolymers, as well as partially hydrogenated homopolymers of butadiene and isoprene.

Friction modifiers and fuel economy agents that are compatible with the other ingredients of the final oil may also be incorporated. Examples of such substances include glyceryl monoesters of higher fatty acids, for example glyceryl monooleate; esters of long-chain polycarboxylic acids with diols, for example the butanediol ester of a dimerized unsaturated fatty acid; oxazoline derivatives; and alkoxylated alkyl substituted monoamines, diamines and alkyl-etheramines, for example, ethoxylated tallow amine and ethoxylated tallow etheramine. Other known friction modifiers include oil soluble organic molybdenum compounds. These friction modifiers consisting of organic molybdenum compounds also provide advantageous oxidation and wear inhibition characteristics to a lubricating oil composition. Examples of such oil-soluble organic molybdenum compounds include dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates, sulfides, and the like, and mixtures thereof. Molybdenum dithiocarbamates, dialkyldithiophosphates, alkylxanthates and alkylthioxanthates are particularly preferred.

In addition, the molybdenum compound may be an acidic molybdenum compound. These compounds will react with a basic nitrogen compound, as measured by the ASTM D-664 or D-2896 assay procedure, and are usually hexavalent. Molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other alkali metal molybdates or other molybdenum salts, for example sodium molybdate, MoOC14, Mo02Br2, Mo203C16, molybdenum trioxide or similar molybdenum compounds are also included.

Among the molybdenum compounds useful in the compositions of this invention are organic molybdenum compounds of the formulas:

Mo (ROCS 2) 4 and Mo (RSCS 2) 4 wherein R represents an organic group selected from the group consisting of alkyl, aryl, aralkyl and alkoxyalkyl groups, generally having 1 to 30 carbon atoms, preferably 2 to 12 carbon atoms. carbon and most preferably alkyl groups of 2 to 12 carbon atoms. Dialkyldithiocarbamates of molybdenum are particularly preferred.

Another group of organic molybdenum compounds useful in the lubricating compositions of this invention are trinuclear molybdenum compounds, especially those of the formula Mo3SkLnQz and mixtures thereof, wherein the L symbols represent independently selected ligands having organic groups with a number of sufficient carbon atoms to make the compound soluble or dispersible in the oil, has a value of 1 to 4, k varies from 4 to 7, Q is selected from the group of neutral compounds yielding electrons such as water , amines, alcohols, phosphines and ethers and z is from 0 to 5 and includes non-stoichiometric values. At least 21 carbon atoms in total must be present among all organic groups of the ligand, for example at least 25, at least 30 or at least 35 carbon atoms.

A dispersant-viscosity index improver acts as both a viscosity index improver and a dispersant. Examples of dispersant-viscosity index improvers include the reaction products of amines, for example polyamines, with a hydrocarbyl-substituted mono- or dicarboxylic acid in which the hydrocarbyl substituent comprises a chain of sufficient length to imparting viscosity index improving properties to the compounds. In general, the dispersant-viscosity index improver may be, for example, a polymer of a C4 to C24 unsaturated ester of vinyl alcohol or unsaturated C3 to C10 monocarboxylic acid or a dicarboxylic acid. C4 to C10 with an unsaturated nitrogen monomer having 4 to 20 carbon atoms; a C2-C20 olefin polymer with an unsaturated C3-C10 mono- or dicarboxylic acid neutralized with an amine, a hydroxy-amine or an alcohol, or an ethylene polymer with a C3-C20 olefin having further subjected to grafting a C4 to C20 unsaturated nitrogen monomer thereon or grafting an unsaturated acid to the polymer backbone by reacting the carboxylic acid groups of the grafted acid with an amine, a hydroxy-amine or an alcohol.

Pour point depressants, also known as lubricating oil flow improvers (LOFIs), lower the minimum temperature at which the fluid flows or can be poured. These additives are well known. Typical examples of such additives which improve the low temperature fluidity of the fluid are Cs-C18 dialkyl fumarate / vinyl acetate copolymers and polymethacrylates. The foaming limitation can be provided by a polysiloxane antifoaming agent, for example a silicone oil or a polydimethylsiloxane.

Some of the aforementioned additives may have a multiplicity of effects; thus, for example, a single additive may act as a dispersant and an oxidation inhibitor. This approach is well known and does not require a more detailed description here.

In the present invention, it may also be preferable to incorporate an additive which maintains the stability of the viscosity of the mixture. Thus, although polar group-containing additives provide a suitably low viscosity in the premix stage, it has been observed that some compositions exhibit an increase in viscosity when stored for prolonged periods. Additives that are effective in controlling this increase in viscosity include long-chain hydrocarbons functionalized by reaction with mono- or dicarboxylic acids or anhydrides which are used in the preparation of ashless dispersants, as previously described.

When the lubricating compositions contain one or more of the aforesaid additives, each additive is usually mixed with the base oil in an amount that allows the additive to perform its desired role. Representative effective amounts of these additives, when used in various lubricants, are listed below. All listed values are given as a percentage by mass of active ingredient.

Marine Diesel Engine Cylinder Lubricant ("MDCL")

A marine diesel engine cylinder lubricant may use 10 to 35, preferably 13 to 30, preferably 16 to 24, wt.% Of a concentrate or additive formulation, the remaining percent being a lubricating oil of based. It advantageously comprises at least 50, more preferably at least 60, still more preferably at least 70,% by weight of an oil of viscosity suitable for lubrication on the basis of the total mass of the MDCL.

Fully formulated MDCLs preferably have a TBN of at least 20, for example from about 30 to about 100 mg KOH / g (ASTM D2896). More preferably, the compositions have a TBN of at least 40, e.g. from about 40 to about 70 mg KOH / g.

The MDCL preferably have a sulphated ash content (SASH) (ASTM D-874) of about 12% by weight or less, preferably about 11% by weight or less, more preferably about 10% or less. in bulk, for example equal to or less than 9% by weight.

The following examples may be mentioned as examples of conventional proportions of additives in an MDCL:

Piston-piston engine oil ("TPEO")

Piston-piston motor oil may use 7 to 35, preferably 10 to 28, more preferably 12 to 24, wt.% Of a concentrate or additive formulation, the remaining percent being a lubricating oil. basic.

Fully formulated piston-piston engine oils preferably have a TBN of at least 10, for example from about 15 to about 60 mg KOH / g (ASTM D2896). More preferably, the compositions have a TBN of at least 20, for example from about 30 to about 55 mg KOH / g.

Fully formulated piston-piston engine oils preferably have a sulphated ash content (SASH) (ASTM D-874) of approximately equal to or less than 7% by weight, preferably approximately equal to or less than 6.5% by weight. mass, for example equal to or less than 6.3% by weight.

The following proportions can be mentioned as typical proportions of additives in a TPEO:

Crankcase lubricant

Fully formulated housing lubricating oil compositions preferably have a TBN of at least 6, e.g. from about 6 to about 18 mg KOH / g (ASTM D2896). More preferably, the compositions have a TBN of at least 8.5, e.g. from about 8.5 or 9 to about 18 mg KOH / g.

The fully formulated crankcase lubricating oil compositions preferably have a sulfated ash content (SASH) (ASTM D-874) of about 1.1% or less by weight, preferably about 1.0% or less in bulk, more preferably approximately equal to or less than 0.8% by weight, for example equal to or less than 0.5% by weight.

The following examples may be mentioned as examples of conventional proportions of additives in a

crankcase lubricant (including a particular vehicle engine oil and a high efficiency diesel engine oil):

The fully formulated lubricating oil compositions of the present invention preferably have a sulfur content of less than about 0.4% by weight. For casing applications, the fully formulated lubricating oil compositions preferably have a sulfur content of less than about 0.35% by weight, more preferably less than about 0.3% by weight, for example less than about 0, 20% by weight. Preferably, the Noack volatility (ASTM D5880) of the fully formulated lubricating oil composition (lubricating viscosity oil plus all additives and additive diluent) will be no greater than 13, for example no more than 12 preferably not more than 10. The fully formulated lubricating oil compositions of the present invention preferably comprise not more than 1200 ppm of phosphorus, for example not more than 1000 ppm of phosphorus, or not more than 800 ppm of phosphorus. , by

example not more than 600 ppm of phosphorus, or not more than 500 or 400 ppm of phosphorus.

It may be desirable, although not essential, to prepare one or more additive concentrates, including additives (the concentrates sometimes referred to as additive formulations), which allows several additives to be added simultaneously to the oil to form the lubricating oil composition. A concentration for the preparation of a lubricating oil composition of the present invention may contain, for example, about 0.1 to about 30% by weight, preferably 0.5 to 30% by weight, of one or more several compounds of formula (I); about 10 to about 40% by weight of a nitrogenous dispersant; about 2 to about 20% by weight of an amine antioxidant, a phenolic antioxidant, a molybdenum compound or a mixture thereof; about 5 to 40% by weight of a detergent; and about 2 to about 20% by weight of a metal dihydrocarbyldithiophosphate.

The final composition can use 5 to 25% by weight, preferably 5 to 18% by weight, typically 10 to 15% by weight, of the concentrate, the remainder being an oil of viscosity suitable for lubrication and a viscosity modifier. .

All percentages by weight (and by weight) expressed herein (unless otherwise indicated) are based on the active ingredient (i.a.) content of the additive, and / or the additive formulation, excluding any associated diluent. However, the detergents are conventionally formulated in a diluent oil, which is not removed from the product, and the TBN of a detergent is typically provided for the active detergent in the associated diluent oil. As a result, the percentages by weight (and by weight), when referring to detergents are (unless otherwise indicated), the total percentage by weight (or by mass) of the active ingredient and the associated diluent oil .

This invention will be better understood by reference to the following examples, in which all parts are parts by weight (or by weight) unless otherwise indicated. EXAMPLES

It is important that the basicity introduced into the lubricating oil composition is maintained as long as possible. It is also important that the time after which the TBN and Total Acid Number (TAN) values intersect is as long as possible. Both measures ensure a longer oil life and better engine protection over a long period of time.

Beaker tests were carried out on three lubricating oil compositions: a reference oil, Example 1 and Example 2. The reference oil comprised 2.4 75% by weight of an overbased calcium sulfonate detergent. having a TBN of 425 mg KOH / g in a base oil. Example 1 comprised 2.475% by weight of an overbased calcium sulfonate detergent having a TBN of 425 mg KOH / g and 1.369% by weight poly {[2-hydroxy-5- (tetrapropenyl) -1 , 3-phenylene] methylene in a base oil. Example 2 comprised 2.475% by weight of an overbased calcium sulfonate detergent having a TBN of 425 mg KOH / g and 1.369% by weight poly {[2-hydroxyethoxy-5- (tetrapropenyl) -1 , 3-phenylene] methylene in a base oil. The three lubricating oil compositions all had a TBN of 10.5 mg KOH / g (ASTM D2896).

Poly {[2-hydroxy-5- (tetrapropenyl) -1,3-phenylene] -methylene was prepared as follows:

A paratetrapropenylphenol (known as "TPP") (1 molar equivalent, commercially available), an alkylbenzenesulfonic acid (0.0033 mol% relative to TPP) and toluene (30% by weight relative to TPP) ) were introduced into a reactor equipped with baffles, equipped with an overhead stirrer and a Dean and Stark reflux apparatus. A protective nitrogen atmosphere has been used constantly. Stirring was increased to 160-170 rpm and the temperature was raised to 110 ° C in 40 min. A 36.5% solution of formaldehyde (1.18 molar equivalents of formaldehyde relative to the TPP used) was introduced in 2 hours at a constant rate. The temperature was maintained at 110 ° C throughout the addition. After formaldehyde addition was complete, the temperature was raised to 120 ° C and held for 1 hour to remove remaining water. The reaction mixture was cooled to 90 ° C and then a 50% solution of sodium hydroxide (1.25 molar equivalents relative to alkylbenzenesulfonic acid) was charged in 0.5 h. The temperature was raised to 130 ° C in 0.5 h and maintained for an additional 1 h to remove water. With an apparatus equipped for distillation, the intermediate was heated to 130 ° C in 1 hour under vacuum to remove toluene. Mineral oil was used to bring the product back to 50% active ingredient.

Poly {[2-hydroxyethoxy-5- (tetrapropenyl) -1,3-phenylene] -methylene was prepared as follows:

A paratetrapropenylphenol (known as "TPP") (1 molar equivalent, commercially available), an alkylbenzenesulfonic acid (0.0033 mol% relative to TPP) and toluene (30% by weight relative to TPP) ) were introduced into a reactor equipped with baffles, equipped with an overhead stirrer and a Dean and Stark reflux apparatus. A protective nitrogen atmosphere has been used constantly. The stirring speed was increased to 160-170 rpm. The temperature was raised to 110 ° C in 40 min. A 36.5% solution of formaldehyde (1.18 molar equivalents of formaldehyde relative to the TPP used) was introduced in 2 hours at a constant rate. The temperature was maintained at 110 ° C throughout the addition. After formaldehyde addition was complete, the temperature was raised to 120 ° C and held for 1 hour to remove remaining water. The reaction mixture was cooled to 90 ° C and then a 50% solution of sodium hydroxide (2.22% by weight relative to TPP) was introduced over 0.5 h. The temperature was raised to 130 ° C in 0.5 h and held for an additional 1 h to remove water. With an apparatus equipped for distillation, the intermediate was heated to 130 ° C in 1 hour under vacuum to remove toluene. Xylene (30% by weight relative to TPP) was introduced while cooling to 90 ° C. The Dean and Stark apparatus has been passed from reflux distillation. Ethylene carbonate (1.02 molar equivalents relative to TPP) was introduced over 0.5 h using a separatory funnel. The temperature was raised to the reflux point at 165 ° C in 1 h. IR analysis was used to determine when the ethylene carbonate was consumed completely (usually after 2.5 h). The temperature was maintained at 165 ° C and vacuum distillation was used to remove xylene. Mineral oil was used to bring the product back to 50% active ingredient.

The beaker test included titration of the oil formulation with 1.0 M sulfuric acid, and analysis of TAN and TBN values. The flow rate of acid was 10 ml / h, the amount of oil was 250 g, the stirring speed was 300 rpm and the oil temperature was 95 ° C.

After testing each sample, a centrifugation step was used to remove the insoluble solids prior to the oil analysis.

The results are as follows:

The results are also shown in the attached figure.

The results show that the reference oil crosses the values of TAN and TBN much earlier than Examples 1 and 2. As a result, a depletion of the base in the reference oil is reached much earlier than in the base case examples 1 and 2. In fact, Examples 1 and 2 did not demonstrate crossing the values of TAN and TBN even at the end of the test after 2.5 hours. Once the lubricating oil compositions have shown a crossing of the TAN and TBN values, the composition has insufficient base rates to neutralize any acid produced by a motor, which causes engine wear. These results are unexpected since Examples 1 and 2 do not include any higher base amount than

reference at the beginning of the test (i.e. all the examples started the beaker test with a TBN of 10.5 mg KOH / g).

Claims (13)

1. Use of one or more compounds of formula (I): wherein: x is 1 to 50, preferably 1 to 40, more preferably 1 to 30; R1 and R2 are H, hydrocarbyl groups having 1 to 12 carbon atoms, or hydrocarbyl groups having 1 to 12 carbon atoms and at least one heteroatom; R represents a hydrocarbyl group having 9 to 100, preferably 9 to 70, preferably 9 to 50, carbon atoms; and n is 0 to 10, or their alkaline earth metal salts, for reducing the basicity depletion rate (as determined by ASTM D2896) of a lubricating oil composition used in an engine, the lubricating oil composition comprising at least one oil-soluble overbased alkali or alkaline earth metal detergent. 2. Use of one or more compounds of formula (I) according to claim 1, characterized in that n in the formula (I) is equal to 0. 3. Use of one or more compounds of formula (I) according to any one of the preceding claims, characterized in that x in the formula (I) is equal to 1. 4. Use of one or more compounds of formula (I) according to any one of the preceding claims, characterized in that R in the formula (I) has 9 to 20 carbon atoms, preferably 9 to 15. 5. Use of one or more compounds of formula (I) according to any one of the preceding claims, characterized in that R in formula (I) is branched. 6. Use of one or more compounds of formula (I) according to any one of the preceding claims, characterized in that R1 = H, R2 = H and R is in the para position relative to the group -O- [CH2CH2O] nH in formula (I) · 7. Use of one or more compounds of formula (I) according to any one of the preceding claims, characterized in that the compounds of formula (I) comprise less than 1% of moles, advantageously less than 0.5% by weight. moles and preferably less than 0.1 mol% unreacted alkylphenol. 8. Use of one or more compounds of formula (I) according to any one of the preceding claims, characterized in that η = 1 for more than 60, advantageously more than 70, advantageously more than 80, advantageously more than 90, or preferably more than 95 mol% of the compounds of formula (I). 9. Use of one or more compounds of formula (I) according to any one of the preceding claims, characterized in that the alkaline earth metal salts of the compounds of formula (I) are calcium or magnesium salts. 10. Use of one or more compounds of formula (I) according to any one of the preceding claims, characterized in that n> 2, which corresponds to di-oxyalkyl compounds, tri-oxyalkylated and tetra-oxyalkylated, for less than 5 mol% of the compounds of formula (I). 11. Use of one or more compounds of formula (I) according to any one of the preceding claims, characterized in that the compounds of formula (I) are methylene-bridged alkylphenols or ethoxylated methylene bridged alkylphenols. 12. Use of one or more compounds of formula (I) according to any one of the preceding claims, characterized in that the lubricating oil composition has a total basicity index (TBN) of 4 to 100 as measured by ASTM D2896, advantageously a TBN of 5 to 75, more preferably 6 to 70. 13. Use of one or more compounds of formula (I) according to any one of the preceding claims, characterized in that the lubricating oil composition is a marine engine cylinder lubricant, a piston-sleeve engine oil , a gas engine oil or a crankcase lubricating oil composition (including a particular vehicle engine oil and a high efficiency diesel engine oil).