JP2019073703A - Lubrication of internal combustion engine - Google Patents

Abstract

To control and/or improve wear performance of lubricating oil for an internal combustion engine.SOLUTION: An alkylphenol detergent additive which is oxyalkylated and sulfurized is used to control and/or improve wear performance of the lubricating oil for an internal combustion engine.SELECTED DRAWING: None

Description

  The present invention relates to the lubrication of internal combustion engines.

  EP-A-2 682 451 ("451") contains an overbased sulfurized calcium phenate detergent additive having an oxyalkylated phenolic functional group derived from unreacted alkylphenol starting material and Lubricating compositions (including MDCL's) are described. See abstract and paragraph [0046]. These are stated to be for a range of internal combustion engines (spark-ignition or compression-ignition), for example automotive and marine engines. The latter include two-stroke marine diesel engines and marine trunk piston engines. However, nothing is said about additives having antiwear properties, in fact "451" refers to the antiwear functionality provided by different additives. See paragraph [0045].

It has now been found that the use of additives exemplified by oxyalkylated and sulfurized alkylphenol detergents in internal combustion engine lubricating oils provides beneficial anti-wear properties.
Therefore, in one aspect of the present invention, the control of the wear performance of the lubricating oil of an internal combustion engine, for example, when lubricating an engine cylinder of a two-stroke crosshead engine for marine diesel, and / or Or provide the use of oxyalkylated, sulfurized alkylphenol detergent additives to provide the improvement.
In a second aspect, the present invention provides a method of operating an internal combustion engine, the method comprising the steps of: supplying lubricating oil for an internal combustion engine to the engine during operation of the engine. The lubricating oil comprises oxyalkylated and sulfurized alkylphenol detergent additives, wherein the detergent additives provide control and / or improvement of the wear performance of the engine.

As used herein, the following terms and expressions, when used, have the meanings ascribed to them:
"Active ingredients" or "(ai)" refers to additive substances that are not diluents or solvents.
The term "comprising" or any of its synonyms specifies the stated feature, step or integer or the presence of a component, but one or more other features, steps, integers, components or groups of these The expression "consists of" or "consists essentially of" or its homonymous source means "comprises" or its homonym; The term "consisting essentially of", which can be included within the scope of the term, makes it possible to include the substance, which does not significantly affect the properties of the composition to which the substance is applied.
"Hydrocarbyl" means a substituent or group (e.g., an alkyl group) with the characteristic of one carbon atom and exclusively hydrocarbon directly attached to the remainder of the molecule. Heteroatoms may be present, provided that these atoms do not alter the essentially hydrocarbyl character of the group.
By "major amount" is meant at least 40 or 50% by weight, preferably at least 60% by weight, even more preferably at least 70% by weight of the composition.
By "minor amount" is meant less than 50% by weight, preferably less than 40% by weight, and even more preferably less than 30% by weight of a composition.

"TBN" means total base number as measured by ASTM D2896.
The term "oxyalkylation" or any of its homologous sources means adding an oxyalkyl group having the general formula-(R'O) _n- to a nucleophilic compound.
"Alkylene carbonate" means a compound having the following general structure:

Here, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen or a hydrocarbyl group.
Furthermore, if used herein,
"Calcium content" is as measured according to ASTM 4951;
"Phosphorus content" is as measured by ASTM D5185;
"Sulfated ash content" is as measured by ASTM D874;
"Sulfur content" is as measured by ASTM D2622;
“KV100” means kinematic viscosity at 100 ° C. as measured by ASTM D445.
Similarly, the various components used, essential and optimal and customary may react under the conditions of formulation, storage or use, and the invention likewise applies to any such reaction. It will be understood that it also provides the product that can or can be obtained as a result.
Furthermore, it is also understood that any upper and lower limits of the amounts, ranges and ratios described herein may be independently combined.

From now on, the above features of the invention will be discussed in more detail in the following.
Oil with Lubricating Viscosity The lubricating oil composition of the present invention comprises an oil with a large amount of lubricating viscosity. Such lubricating oils may range in weight from light distillate mineral oils to heavy lubricating oils in their viscosity. Generally, the viscosity of the oil is in the range of ^{2 to} 40 mm ² / sec, eg 3 to 15 mm ² / sec, as measured at 100 ° C., and a viscosity index of 80 to 100, eg 90 to 95 Have. The lubricating oil can comprise a large amount of a composition as defined above.
Natural oils are hydrorefined, solvent-treated or acid-treated of animal and vegetable oils (eg castor oil and lard oil), liquid petroleum-based oils and paraffinic, naphthenic and mixed paraffinic-naphthenic forms Contains mineral oil. Oils of lubricating viscosity derived from coal or shale also serve as useful base oils.
Synthetic lubricating oils are hydrocarbon oils and halo-substituted hydrocarbon oils, such as polymerized and copolymerized olefins (eg, polybutylene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutylene, poly (1-hexene), poly ( 1-octene), poly (1-decene)); alkylbenzenes (eg, dodecylbenzene, tetradecylbenzene, dinonylbenzene, di (2-ethylhexyl) benzene); polyphenyls (eg, biphenyl, terphenyl, alkylated polyphenols) And alkylated diphenyl ethers and alkylated diphenyl sulfides and their derivatives, analogues and homologues.

Alkylene oxide polymers and copolymers and their derivatives in which the terminal hydroxyl groups are modified by esterification, etherification etc. constitute another class of known synthetic lubricating oils. These are polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, and alkyl and aryl ethers of polyoxyalkylene polymers (e.g. methyl-polyisopropylene glycol ether having a molecular weight of 1,000 or having a molecular weight of 1,000 to 1,500) Diphenyl ethers of polyethylene glycols) and their mono- and poly-carboxylic acid esters, such as acetic acid esters of tetraethylene glycol, mixed C ₃ -C ₈ fatty acid esters and C ₁₃ oxo acid diesters.
Another suitable class of synthetic lubricating oils is dicarboxylic acids such as phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linole Esters of acid dimers, malonic acid, alkyl malonic acids, alkenyl malonic acids and various alcohols (eg butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol) including. Specific examples of such esters are dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, A complex ester formed by reacting diekosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, and 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid Including.

Similarly, esters useful as synthetic oils are esters prepared from C ₅ -C ₁₂ monocarboxylic acids and polyols and polyol esters such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol. including.
Silicon-based oils such as polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxy-silicone oils and silicate oils constitute another useful class of synthetic lubricating oils, such as Oils are tetraethyl silicate, tetraisopropyl silicate, tetra- (2-ethylhexyl) silicate, tetra- (4-methyl-2-ethylhexyl) silicate, tetra (p-tert-butylphenyl) silicate, hexa- (4-methyl) -2-ethylhexyl) disiloxane, poly (methyl) siloxane and poly (methylphenyl) siloxane. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
Unrefined, refined and re-refined oils can be used in the lubricating oil of the present invention. Unrefined oils are oils obtained directly from a natural or synthetic source without further purification treatment. For example, shale oil obtained directly from retorting operations, petroleum oil obtained directly from distillation or ester oil obtained directly from the esterification process, and used without further treatment, is an unrefined oil.

Publication of The American Petroleum Institute (API): "Engine Oil Licensing and Certification System", Industry Services Department, 14th Edition, 1996. 12 Mon, Addendum 1, December 1998 classifies basestock as follows:
a) Group I basestocks contain less than 90% saturates and / or more than 0.03% sulfur and using the test method specified in Table E-1 below , With a viscosity index of greater than 80 and less than 120.
b) Group II base stocks contain greater than or equal to 90% saturates and less than or equal to 0.03% sulfur and greater than or equal to 80 and 120 using the test method specified in Table E-1 below. It has a viscosity index of less than.
c) Group III base stocks contain greater than or equal to 90% saturates and less than or equal to 0.03% sulfur, and viscosities greater than or equal to 120 using the test method specified in Table E-1 below. It has an index.
d) The Group IV basestock is poly alpha-olefin (PAO).
e) Group V base stocks include all other base stocks not included in groups I, II, III or IV.

The analytical methods for basestock are shown in the following table:

The present invention preferably employs Group I or Group II base stocks or oils. Preferably, the oil having the above-mentioned lubricating viscosity in the present invention contains 50% by mass or more of the base stock. This can comprise 60% by weight or more, for example 70, 80 or 90% by weight or more of the base stock or mixtures thereof. The oil of lubricating viscosity may be substantially all of the base stock or mixtures thereof. However, the invention is not limited to the use of the above-mentioned basestocks and can therefore include, for example, the use of Group III, IV or V basestocks and brightstocks. Likewise, they also include hydrocarbon-derived base stocks synthesized by the Fischer-Tropsch method. In the Fischer-Tropsch process, synthesis gas (or "syngas") comprising carbon monoxide and hydrogen is first generated and then converted to hydrocarbons using a Fischer-Tropsch catalyst. These hydrocarbons typically require further processing in order to be useful as a base oil. For example, they may be hydroisomerized, hydrocracked and hydroisomerized, dewaxed, or hydroisomerized and dewaxed by methods known in the art. For example, the syngas can be natural gas or other gaseous carbonized by steam reforming if the basestock can be called a gas-to-liquid ("GTL") base oil. From gases such as hydrogen or, if the basestock can be called biomass-to-liquid ("BTL" or "BMTL") base oil, by gasification of the biomass or If the basestock can be called coal-to-liquid ("CTL") base oil, it can be produced by coal gasification.
Preferably, the oil having the above-mentioned lubricating viscosity in the present invention contains 50% by mass or more of the above-mentioned base stock. The oil may comprise 60% by weight or more, for example 70, 80 or 90% by weight or more of the base stock or mixtures thereof. The oil of lubricating viscosity can be substantially all of the base stock or mixtures thereof.

Detergent Additives Detergents are compound based additives comprising a polar part and a hydrophobic tail, often also referred to as surfactants. If the polar portion of the surfactant is acidic, it can optionally be neutralized in the presence of a metal base to form a detergent comprising a metal salt.
Optionally, a large amount of metal base is included by reacting an excess amount of metal compound, such as an oxide or hydroxide, with an acidic gas such as carbon dioxide, for the purpose of producing an overbased detergent. The detergent comprises neutralized surfactant as the outer layer of a metal base (e.g. carbonate) micelle. In the present invention, the detergent may be a surfactant, a partially neutralized surfactant, a fully neutralized surfactant or an overbased neutralized surfactant. .
When neutralized, the detergent is preferably an alkali metal or alkaline earth metal additive such as neutral or overbased oil-soluble or oil-dispersible phenolic calcium, magnesium, sodium or A barium salt, wherein any overbasing treatment is effected by an oil-insoluble salt of the metal, such as carbonate, basic carbonate, acetate, formate, hydroxide or oxalate, It is stabilized in an oily diluent by means of the oil-soluble salt of the surfactant. Preferably, the metal is calcium.
The TBN of the above cleaning agent is at least as low as 50 mg KOH / g, as medium, ie 50 to 150 mg KOH / g, or less on an active ingredient basis as a value measured by ASTM D2896. Ie, more than 150 mg KOH / g.

In the present invention, the sulfurized alkylphenol detergent additive is 10 to 50% by mass, for example 15 to 40% by mass or 20 to 30% by mass, of an alkylene carbonate based on the active ingredient based on the detergent additive. It may be oxyalkylated by the reaction.
When the lubricating oil is a marine diesel cylinder lubricating oil, the TBN of the lubricating oil is preferably in the range of 5-160, and the total detergent concentration in the additive package is preferably the effective. More than 50 and up to 99, for example 60 to 98, or 70 to 95 as a mass percentage of the whole component.
The lubricating oil may further comprise, for example, an overbased sulfonate (preferably calcium) detergent having a TBN in the range of 250 to 800 on an active ingredient basis, for example as a mass percentage of the total active ingredient. It can be included at a concentration of -95%, such as 30-90% or 40-85%.
The lubricating oil may further comprise non-sulfurized oxyalkylated alkylphenol, for example as a weight percentage of the whole active ingredient, at a concentration of 0.01 to 10%.
The lubricating oil may further comprise a borated or non-borated dispersant additive such as a polyalkenyl succinimide.

Engine The invention can be applied to a range of internal combustion engines (spark-ignition or compression-ignition), for example lubricating oils for automotive engines and marine engines. In connection with the latter, mention may be made of two-stroke marine diesel crosshead engines and marine trunk piston engines.
The cross-head engine is a low speed engine with a range from high power to very high power. These include two separately lubricated parts, whose piston / cylinder assembly is lubricated with very high viscosity oil (MDCL) using total loss lubrication, and its crankshaft is usually Is lubricated by a lower viscosity lubricant called system oil. The MDCL lubricates the inner wall of the engine cylinder and the piston ring pack.
Marine cylinder lubricating oils, as applicable, use overbased metal detergents as their main additive component to neutralize the acid generated from the high sulfur fuel used during operation of the engine Is formulated.
Wear is becoming increasingly problematic due to changes in the design of cross-head diesel engines. Thus, the MDCL needs to withstand varying engine operating temperatures and elevated combustion pressures that may affect how well the lubricant film is maintained on the cylinder liner wall. is there. As a result, this can lead to excessive wear. Additives that are abrasion resistant and compatible with the MDCL environment will have high value in the lubricating oil industry.

The invention will now be described in the following non-limiting examples.
Additive component
Non-Borated Dispersants Dispersants are one additive whose main function is to keep solid and liquid contaminants in suspension, thereby reducing sludge deposition while at the same time reducing these contaminants. Passivating and reducing engine deposits. For example, dispersants maintain the oil-insoluble material resulting from oxidation in suspension during use of the lubricating oil, thus preventing sludge flocculation and precipitation or deposition on metal parts of the engine. Do.
Generally, dispersants are non-metallic organic materials that are "ash-free" and do not form substantially ash upon combustion. These comprise long hydrocarbon chains with a polar head, the polarity of which is derived, for example, from the inclusion of O, P or N atoms. The hydrocarbon is an oleophilic group having, for example, 40 to 500 carbon atoms which imparts oil-solubility. Thus, the ashless dispersant can comprise an oil soluble polymeric backbone.
A preferred class of olefin polymers is constituted by polybutenes, in particular polyisobutene (PIB) or poly-n-butenes, which may be produced, for example, by the polymerization of a C ₄ purified stream.
Dispersants include, for example, derivatives of long chain hydrocarbon-substituted carboxylic acids, examples of which are derivatives of high molecular weight hydrocarbyl-substituted succinic acid. A notable class of dispersants is constituted, for example, by the above-mentioned acids (or derivatives) and a hydrocarbon-substituted succinimide prepared by reacting a nitrogen-containing compound, preferably a polyalkene polyamine, such as a polyethylene polyamine. . Particularly preferred are the reaction products of polyalkene polyamines with alkenyl succinic anhydrides, such as those described in US-A-3,202,678; -3,154,560; -3,172,892; -3,024,195; -3,024,237; -3,219,666; It is a thing.

Borated dispersants hydrocarbon-substituted succinimides, such as those mentioned above, are described, for example, in US Pat. No. 3,087,936 and -3,254,025 to improve their properties. Can be post-processed). For example, boration can be achieved by treatment with an acyl nitrogen-containing dispersant and a boron compound selected from boron oxide, boron halides, boron acids and esters of boron acids.
Sulfonate detergents Sulfonate detergents are metal salts, and when they are generally described as normal or neutral salts, can contain substantially stoichiometric amounts of the metals, and Will have a total base number of 0-80 or TBN (as can be measured by ASTM D2896). Large amounts of metal bases can be included by reacting excess metal compounds such as oxides or hydroxides with an acidic gas such as carbon dioxide. The resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base (e.g. carbonate) micelle. Such overbased sulfonate detergents can have a TBN of 150 or more, and typically 250 to 800 or more, based on the active ingredient.
The sulfonate detergents which can be used can be oil-soluble, neutral and overbased sulfonates of metals, in particular alkali or alkaline earth metals such as 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 lubricating oils.

Sulfonate detergent A
Sulfonate detergent A is an overbased calcium sulfonate detergent. This is characterized by a TBN of 500-600 on an active ingredient basis.
Sulfonate detergent B
Sulfonate detergent B is an overbased calcium sulfonate detergent. This is characterized by a TBN of 650-750 on an active ingredient basis.
Phenate detergent A
Phenate detergent A is an overbased sulfurized calcium phenate detergent derived from tetrapropenyl phenol. This detergent is synthesized according to a well-established one-step method (ie the sulfurization and overbasing steps are carried out simultaneously as described in EP 2682451 B1). This is characterized by a TBN of 400 to 450 on an active ingredient basis.

Generalized structure:

Phenate detergent B
Phenate detergent B is an overbased sulfurized calcium phenate detergent derived from tetrapropenyl phenol. This detergent is synthesized according to a well-established two-step method (i.e., the sulfidation and overbasing steps are performed independently as described in EP 2682451 B1 and U.S. Pat. No. 3,801,507). It has the same general structure as phenate detergent A. This is characterized by a TBN of 375-425 on an active ingredient basis.
Capped phenate detergent B
The capped phenate detergent B is derived from the phenate detergent B described above, which is subsequently 10 to 50% by weight, for example 15 to 40% by weight, based on the active ingredient, relative to the detergent additive or It was oxyalkylated by reaction with 20-30% by weight of alkylene carbonate. This is characterized by a TBN of 325-375 on an active ingredient basis.

Generalized Formula:

Antiwear Agents Antiwear agents reduce friction and excessive wear, and usually contain sulfur or phosphorus or both, and are based, for example, on compounds capable of depositing polysulfide films on the relevant surfaces. Of note are dihydrocarbyl dithiophosphates, such as zinc dialkyl dithiophosphates (ZDDPs). ZDDPs first form dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of P ₂ S ₅ with one or more alcohols or phenols, usually according to known techniques, and then this formed DDPA with a zinc compound It can be produced by neutralization. For example, dithiophosphoric acid can be prepared by reaction with a mixture of primary or secondary alcohols. Alternatively, multiple dithiophosphoric acids can be prepared where the hydrocarbyl group on one acid is completely secondary in character and the hydrocarbyl group on the other acid is completely primary in character. Although any basic or neutral zinc salt may be used to make the zinc salt, the oxides, hydroxides and carbonates are most commonly used. Commercial additives often contain an excess of zinc, since the basic zinc compound is used in excess in this neutralization reaction.

Formulation
Two sets of lubricating formulations (Sets 1 and 2) were prepared using the phenate detergent component described above, but it was noteworthy that they did not contain a sulfonate detergent.

  Two sets of MDCL formulations were made by blending various selections of the above components.

Each formulation in Set 3 contained 3.920 grams of borated dispersant, 21.000 grams of Sulfonate Cleaner A, and 0.280 grams of an antiwear agent. The reference formulation 3 'contains 2.380 g of phenate detergent A and has a total package volume of 28.00 g; the reference formulation 3''contains 2.290 g of phenate detergent B and 27.91 g Formulation 3 of the present invention (inventive examples) contained 2.540 g of capped phenate detergent B and had a total package volume of 28.16 g.
Each formulation in Set 4 contained 1.013 g of non-borated dispersant and 11.152 g of Sulfonate Detergent B. Reference formulation 4 'contains 9.127 g of phenate detergent A and has a total package volume of 21.80 g; reference formulation 4''contains 8.790 g of phenate detergent B and 21.46 g Formulation 4 of the present invention contained 9.730 g of capped phenate detergent B, and a total package of 22.40 g.

Testing Each formulation was tested using the HT-HFRR test. A laboratory rig based on HT-HFRR (EP 2719751 A2) was developed in order to evaluate cylinder oil with respect to its ability to prevent the failure of lubricating films at high temperatures.
The HT-HFRR rig is operated at high temperature and its coefficient of friction (Fc) is recorded. The coefficient of friction decreases with increasing temperature until the temperature at which the oil film starts to break, due to the viscosity decrease of the MDCL, and the coefficient of friction (Fc) starts to increase with increasing temperature . By evaluating the oil with known field performance in the HT-HFRR rig, one of the most critical points in predicting oil performance is the lowest coefficient of friction (Fc) recorded It was proved to be a temperature.
The above test was performed under the following conditions:
An electromagnetic vibrator vibrated the steel ball with small amplitude while pressing it against the stationary steel disc with a load of 4N.
The lower fixed disc was electrically heated and fixed below the MDCL. The temperature was ramped from 80 ° C. to 380 ° C. for 15 minutes.

Results The results are shown in Tables 1 and 2 below, which give the respective results for the set of formulations 1, 2, 3 and 4. The value of HT-HFRR is expressed as the temperature (° C.) at the lowest friction, where higher values indicate better wear protection performance.

  The above results show that in each of sets 1 and 2, in the absence of the sulfonate, antiwear agent or dispersant, the formulations of the present invention gave better results than the respective reference formulations. There is.

  The above results show that in each of Sets 3 and 4 the formulations according to the invention gave better results than the respective reference formulations.

Claims (17)

  Use of an oxyalkylated, sulfurized alkylphenol detergent additive in a lubricating oil for an internal combustion engine to provide control and / or improvement of the wear performance of the lubricating oil.   Said detergent additive is oxyalkylated by reaction with 10 to 50% by weight, for example 15 to 40% by weight, or 20 to 30% by weight alkylene carbonate, based on the active ingredient, with respect to the detergent additive Use according to claim 1, wherein   The use according to claim 2, wherein the alkylene carbonate is ethylene carbonate, propylene carbonate or butylene carbonate.   4. A detergent according to any one of the preceding claims, wherein said detergent comprises an alkali or alkaline earth metal, preferably calcium, when neutralized, partially neutralized or overbased. Use of. The oxyalkyl group has the formula:
-(R'O) _n-
5. The use according to any one of the preceding claims, wherein R 'is ethylene, propylene or butylene and n is independently 1-10.   6. The method according to any one of claims 1 to 5, wherein the phenyl group of said alkylphenol is substituted with one or more hydrocarbyl groups containing 9 to 100, preferably 9 to 70 or 9 to 50 carbon atoms. Use described.   The use according to any of the preceding claims, wherein the lubricating oil is a marine diesel cylinder lubricating oil.   The use according to claim 7, wherein the lubricating oil lubricates the inner wall of the engine cylinder and its piston ring pack.   The use according to any one of claims 7 and 8, wherein the lubricating oil TBN is in the range of 5-160.   10. Any of the claims 7-9, wherein the total detergent concentration in said lubricating oil is more than 50% to 99%, for example 60 to 98%, or 70 to 95% as a percentage by mass of the total active ingredient. Use according to paragraph 1.   The use according to any of the preceding claims, wherein the lubricating oil further comprises an overbased sulfonate detergent, preferably of calcium.   The use according to claim 11, wherein the sulfonate detergent has a TBN ranging from 250 to 800 on an active ingredient basis.   The lubricating oil preferably has a TBN in the range of 250 to 800 on an active ingredient basis, preferably a calcium overbased sulfonate detergent, as a percentage by weight of the total active ingredient, 20 to 95%, for example 30 The use according to any one of claims 7 to 10, further comprising a concentration of -90% or 40-85%.   The use according to any one of the preceding claims, wherein the lubricating oil further comprises non-sulfurized oxyalkylated alkylphenol, for example at a concentration of 0.01 to 10% as a percentage by weight of the total active ingredient.   The use according to any of the preceding claims, wherein the lubricating oil further comprises a borated or non-borated dispersant additive, such as a polyalkenyl succinimide.   A method of operating an internal combustion engine, comprising the step of supplying an internal combustion engine lubricating oil to the engine during operation of the engine, the lubricating oil being oxyalkylated and sulfurized alkylphenol detergent additive Such method, wherein the detergent additive provides control and / or improvement of the wear performance of the engine.   The engine is a marine diesel two-stroke cross-head engine, the lubricating oil is a lubricating oil for a marine diesel cylinder, and the supply of the lubricating oil comprises the engine cylinder, eg its inner wall and its piston ring 17. The method of claim 16, which is for a pack.