阅读说明：本技术 脂肪胺用于减少和/或控制船用引擎中异常气体燃烧的用途 (use of fatty amines for reducing and/or controlling abnormal gas combustion in marine engines ) 是由 让-巴蒂斯特·马丁 瓦莱丽·杜瓦扬 于 2018-05-03 设计创作，主要内容包括：本发明涉及可溶于包含至少一种洗涤剂的润滑剂组合物中的一种或多种脂肪胺用于减少和/或控制船用引擎中的异常气体燃烧的用途,胺/洗涤剂重量比在0.01与0.5之间。本发明还涉及一种用于减少和/或控制船用引擎中异常气体燃烧的方法,其中气体与可溶于包含至少一种洗涤剂的润滑剂组合物中的一种或多种脂肪胺接触,胺/洗涤剂重量比在0.01与1之间、优选在0.01与0.9之间、更优选在0.02与0.8之间、例如在0.03与0.8之间、尤其在0.01与0.5之间、优选在0.01与0.4之间、例如在0.02与0.4之间。(The present invention relates to the use of one or more fatty amines soluble in a lubricant composition comprising at least one detergent in a amine/detergent weight ratio between 0.01 and 0.5 for reducing and/or controlling abnormal gas combustion in a marine engine. The invention also relates to a method for reducing and/or controlling abnormal gas combustion in a marine engine, wherein the gas is contacted with one or more fatty amines soluble in a lubricant composition comprising at least one detergent, the amine/detergent weight ratio being between 0.01 and 1, preferably between 0.01 and 0.9, more preferably between 0.02 and 0.8, such as between 0.03 and 0.8, especially between 0.01 and 0.5, preferably between 0.01 and 0.4, such as between 0.02 and 0.4.)

1. Use of one or more fatty amines soluble in a lubricant composition comprising at least one detergent in an amine/detergent weight ratio between 0.01 and 1 for reducing and/or controlling abnormal gas combustion in a marine engine.

2. Use according to claim 1, wherein the fatty amine is selected from:

-an amine of formula (I):

R₁-[(NR₂)-R₃]_q-NR₄R₅， (I)

Wherein:

R₁Is a saturated or unsaturated, linear or branched hydrocarbon group having at least 12 carbon atoms, and optionally at least one heteroatom selected from nitrogen, sulfur or oxygen;

R₂、R₄Or R₅independently a hydrogen atom or a saturated or unsaturated, linear or branched hydrocarbon group, and optionally comprising at least one heteroatom selected from nitrogen, sulphur or oxygen;

R₃Is a saturated or unsaturated, linear or branched hydrocarbon radical having one or more carbon atoms and optionally containing at least one heteroatom selected from nitrogen, sulfur or oxygen, preferably oxygen;

q is equal to or higher than 0, preferably q is 1 or higher, more preferably it is an integer between 1 and 10, further preferably between 1 and 6, advantageously it is selected from 1, 2 or 3;

-a mixture of fatty polyalkylamines comprising one or more polyalkylamines of formulae (III) and/or (IV):

Wherein:

R, which are identical or different, are linear or branched alkyl groups having from 8 to 22 carbon atoms;

n and z are each independently 0, 1, 2 or 3; and is

When z is higher than 0, o and p are each independently 0, 1, 2 or 3,

the mixture comprises at least 3% by weight of a branched compound such that at least one of n or z is 1 or higher, or a derivative thereof; or

-mixtures of fatty amines of formula (I), (III) and/or (IV).

3. Use according to any one of the preceding claims, in which the fatty amine represents from 0.1% to 10% by weight, preferably from 0.1% to 6%, for example from 0.5% to 6%, relative to the total weight of the lubricant composition.

4. Use according to any one of the preceding claims, wherein the composition comprises at least one dispersant.

5. use according to any of the preceding claims for reducing and/or controlling abnormal gas combustion in a two-stroke or four-stroke, marine pure gas or dual fuel engine.

6. use according to any one of the preceding claims for reducing and/or controlling abnormal gas combustion in a marine engine caused by auto-ignition of the lubricant composition.

7. Use according to any one of the preceding claims, for any type of gas, in particular gases having a low Methane Number (MN), preferably a methane number lower than 80, more advantageously lower than 60.

8. Use of a lubricant composition comprising:

-at least one base oil;

-at least one fatty amine;

-at least one detergent,

An amine/detergent weight ratio of between 0.01 and 1, preferably between 0.01 and 0.9, more preferably between 0.02 and 0.8, for example between 0.03 and 0.8, for:

-reducing and/or controlling abnormal gas combustion in a marine engine, preferably for reducing and/or controlling abnormal gas combustion in a two-stroke or four-stroke, pure gas or dual fuel marine engine; and/or

-reducing and/or controlling abnormal gas combustion in a marine engine caused by auto-ignition of the lubricant composition.

9. Use according to claim 8, wherein the fatty amine is as described in claim 2.

10. Use according to claim 8 or 9, wherein the fatty amine represents from 0.1% to 10% by weight, preferably from 0.1% to 6% by weight, for example from 0.5% to 6% by weight, relative to the total weight of the lubricant composition.

11. use according to any one of claims 8 to 10, wherein the detergent represents from 4% to 30% by weight, preferably from 5% to 25% by weight, for example from 6% to 25% by weight, relative to the total weight of the lubricant composition.

12. Use according to any one of claims 8 to 11, further comprising a dispersant.

[ technical field ] A method for producing a semiconductor device

the present invention relates to reducing and/or controlling abnormal gas combustion in marine engines.

The subject of the present invention is the use of one or more fatty amines soluble in a lubricant composition for reducing and/or controlling abnormal gas combustion in a marine engine.

Another subject of the invention is a method for reducing and/or controlling abnormal gas combustion in a marine engine, wherein the gas is contacted with one or more fatty amines soluble in the lubricant composition.

another subject of the invention is a lubricant composition and its use for reducing and/or controlling abnormal gas combustion in a marine engine.

[ background of the invention ]

The marine propulsion industry is striving to improve the efficiency of pneumatic marine engines that have been operated under increasing operational loads. However, the low rotation speed associated with the high load may promote the occurrence of the abnormal combustion phenomenon, possibly resulting in damage to the engine. Pre-ignition, characterized by auto-ignition of the air-gas premix prior to a normal ignition command, results in an abnormal rise in pressure in the gas engine cylinder.

Generally, the combustion of a gas or more specifically an air-gas mixture in a marine engine is initiated by controlled ignition resulting from contact between an electric arc and the gas or pilot injection of a liquid fuel that propagates a flame via ignition. The controlled ignition may be obtained directly in the combustion chamber of the marine engine or in a pre-combustion chamber of the marine engine adjacent to the engine combustion chamber.

Controlled gas combustion is the term used when it is initiated directly by controlled ignition. Such controlled combustion is typically characterized by controlled expansion of the flame front throughout the combustion chamber. Controlled combustion may also be referred to as normal combustion.

However, in some cases, the air-gas mixture may pre-auto-ignite prior to controlled ignition, particularly by auto-ignition of the lubricant composition in the combustion chamber. In this case, it is referred to as uncontrolled pre-ignition phenomenon. This uncontrolled pre-ignition phenomenon translates into abnormal gas combustion, characterized by uncontrolled expansion of the flame front throughout the combustion chamber.

This abnormal gas combustion causes a drastic increase in the temperature and pressure in the combustion chamber. It has been determined that these unusually high temperatures and pressures can have a significant negative impact on the efficiency and overall performance of the marine engine and may even cause irreversible damage to the internal parts of the engine: cylinders, pistons, spark plugs and valves in marine engines.

in the field of 2-stroke engines, it is known, inter alia from US3544466, to use amines in lubricant compositions, in particular to premix the lubricant with gasoline before adding to the engine. It is also known from GB973679 to use amines in lubricant compositions to improve engine lubricity. The related application relates to 2-stroke gasoline engines in which a lubricant is mixed with the gasoline prior to addition to the engine. These previous generations of engines differ significantly from current marine engines, which do not require premixing the lubricant with the fuel prior to addition. Both patent applications thus relate to most engines in terms of engine design, addition of lubricant premixed with fuel, and lubrication system.

throughout the course of the research, the applicant has proposed that abnormal gas combustion may result in particular from the auto-ignition of the lubricant composition during the gas compression cycle and/or from the combustion of the gas when the marine engine is running.

Accordingly, there is a need to provide a lubricant composition that overcomes all or some of the aforementioned disadvantages.

Lubricant compositions for marine engines conventionally comprise detergents.

the applicant has surprisingly found that the presence of a fatty amine soluble in the lubricant composition in a specific weight ratio to the detergent allows to reduce and/or control the abnormal gas combustion in a marine engine.

the fatty amines comprised in the lubricant composition are known per se in the applications WO2009/153453 and WO 2014/180843 filed by the applicant. The applicant has now found a novel use of these fatty amines.

The applicant has therefore observed that the use of one or more soluble fatty amines in a specific weight ratio with respect to the detergent in a lubricant composition allows to reduce and/or control the abnormal gas combustion in a marine engine.

abnormal combustion means combustion of gases in the combustion chamber caused by uncontrolled pre-ignition. Abnormal combustion translates into uncontrolled expansion of the flame front throughout the combustion chamber. Abnormal combustion also translates to a pressure level in the combustion chamber that is at least 10%, preferably at least 20%, more preferably at least 30% higher than the nominal pressure of gas combustion in the marine engine.

Nominal pressure means the maximum pressure to which the engine parts are subjected during controlled gas combustion in the combustion chamber without risk of deterioration of all or some of the engine internal parts, such as cylinders, pistons, spark plugs and valves.

gas means a mixture of gas and air. Within the meaning of the present invention, a mixture of gas and air is formed upstream of or in the combustion chamber before ignition of the marine engine. The step allowing to obtain a mixture of gas and air is called the premixing step. Within the meaning of the present invention, the terms gas and air mixture have equivalent meanings and can be used instead of each other.

The term homogeneous gas combustion is used when premixing gas with air. Within the meaning of the present invention, the terms "gas combustion", "combustion of a gas and air mixture", "homogeneous gas combustion" or "homogeneous combustion of a gas and air mixture" have an equivalent meaning and can be used instead of each other.

Marine engine means a two-stroke or four-stroke marine engine which is pneumatic only (also called pure gas engine) or which operates with gas and fuel and is also called dual fuel engine.

the engine of the present invention is particularly a 2-stroke or 4-stroke engine in which the lubricant is not premixed with the fuel prior to addition.

[ summary of the invention ]

A first subject of the invention relates to the use of one or more fatty amines soluble in a lubricant composition comprising at least one detergent, the amine/detergent weight ratio being between 0.01 and 1, preferably between 0.01 and 0.9, more preferably between 0.02 and 0.8, such as between 0.03 and 0.8, in particular between 0.01 and 0.5, preferably between 0.01 and 0.4, such as between 0.02 and 0.4, for reducing and/or controlling abnormal gas combustion in a marine engine.

In the present invention, "between xxx and yyy" means that the values xxx and yyy are included in the range.

in a particular embodiment of the invention, the fatty amine is selected from:

-an amine of formula (I):

R₁-[(NR₂)-R₃]_q-NR₄R₅，(I)

Wherein:

R₁Is a saturated or unsaturated, linear or branched hydrocarbon group having at least 12 carbon atoms, and optionally at least one heteroatom selected from nitrogen, sulfur or oxygen;

R₂、R₄or R₅Independently a hydrogen atom or a saturated or unsaturated, linear or branched hydrocarbon group, and optionally comprising at least one heteroatom selected from nitrogen, sulphur or oxygen;

R₃Is a saturated or unsaturated, linear or branched hydrocarbon radical having one or more carbon atoms and optionally containing at least one heteroatom selected from nitrogen, sulfur or oxygen, preferably oxygen;

q is equal to or higher than 0, preferably q is 1 or higher, more preferably it is an integer between 1 and 10, further preferably between 1 and 6, advantageously it is selected from 1, 2 or 3;

-a mixture of fatty polyalkylamines comprising one or more polyalkylamines of formulae (III) and/or (IV):

wherein:

R, which are identical or different, are linear or branched alkyl groups having from 8 to 22 carbon atoms;

n and z are each independently 0, 1, 2 or 3; and is

When z is higher than 0, o and p are each independently 0, 1, 2 or 3,

The mixture comprises at least 3% by weight of a branched compound such that at least one of n or z is 1 or higher, or a derivative thereof, or

-mixtures of fatty amines of formula (I), (III) and/or (IV).

Advantageously, the fatty amine (is) has formula (I):

R₁-[(NR₂)-R₃]_q-NR₄R₅，

Wherein:

R₁Is a saturated or unsaturated, linear or branched alkyl group having from 12 to 22 carbon atoms, preferably from 14 to 22 carbon atoms, and optionally at least one heteroatom selected from nitrogen, sulfur or oxygen; and/or

R₂、R₄Or R₅Independently a hydrogen atom, a saturated or unsaturated, linear or branched alkyl group having between 1 and 22 carbon atoms, preferably between 14 and 22 carbon atoms, more preferably between 16 and 22 carbon atoms; or (R)₆-O)_r-H group, wherein R₆Is a saturated, linear or branched alkyl group having at least 2 carbon atoms, preferably between 2 and 6 carbon atoms, more preferably between 2 and 4 carbon atoms, and r is an integer of 1 or more, preferably between 1 and 6, more preferably between 1 and 4; and/or

R₃is a saturated or unsaturated, linear or branched alkyl group having between 2 and 6 carbon atoms, preferably between 2 and 4 carbon atoms.

more advantageously, the fatty amine has formula (I), wherein:

q is 1, 2 or 3;

R₁Is a saturated or unsaturated, linear or branched alkyl group having from 12 to 20 carbon atoms, preferably from 14 to 20 carbon atoms, and optionally at least one heteroatom selected from nitrogen, sulfur or oxygen;

R₂independently a hydrogen atom or a saturated, linear or branched alkyl group having from 1 to 20 carbon atoms, preferably from 16 to 20 carbon atoms, more preferably from 16 to 18 carbon atoms;

R₃Is a saturated, straight-chain alkyl group having between 2 and 6 carbon atoms, preferably between 2 and 4 carbon atoms;

R₄and R₅Is a hydrogen atom or a methyl group, preferably a hydrogen atom.

advantageously, the fatty amine has formula (I), wherein:

q is equal to 3;

R₁Is a saturated or unsaturated, linear or branched alkyl group having from 12 to 20 carbon atoms, preferably from 14 to 20 carbon atoms, more preferably from 16 to 20 carbon atoms, and optionally at least one heteroatom selected from nitrogen, sulfur or oxygen;

R₂Independently a hydrogen atom or a saturated straight or branched alkyl group having 16 to 18 carbon atoms;

R₃Is an ethyl or propyl group;

R₄And R₅is a hydrogen atom.

more preferably, the fatty amine is also of formula (I), wherein:

q is 1, 2 or 3;

R₁is a saturated or unsaturated, linear or branched alkyl group having from 14 to 20 carbon atoms, preferably from 16 to 20 carbon atoms;

R₂、R₄And R₅Independently is a hydrogen atom or (R)₆-O)_r-H group, wherein R₆Is a saturated, straight-chain alkyl group having between 2 and 6 carbon atoms, preferably between 2 and 4 carbon atoms, and r is an integer between 1 and 6, preferably between 1 and 4;

R₃Are saturated, straight-chain alkyl groups having between 2 and 6 carbon atoms, preferably between 2 and 4 carbon atoms.

Advantageously, the fatty amine is also of formula (I), wherein:

q is equal to 3;

R₁Is a saturated or unsaturated, linear or branched alkyl group having from 14 to 20 carbon atoms, preferably from 16 to 20 carbon atoms;

R₂、R₄And R₅Independently is a hydrogen atom or (R)₆-O)_r-H group, wherein R₆is a saturated, straight-chain alkyl group having between 2 and 4 carbon atoms, and r is an integer between 1 and 4;

R₃is an ethyl or propyl group.

Preferably, the fatty amine is a mixture of fatty polyalkylamines comprising one or more polyalkylamines of formulae (III) and/or (IV):

wherein:

R, which are identical or different, are linear or branched alkyl groups having from 8 to 22 carbon atoms;

n and z are each independently 0, 1, 2 or 3; and is

when z is higher than 0, o and p are each independently 0, 1, 2 or 3,

The mixture comprises at least 3% by weight of a branched compound such that at least one of n or z is 1 or higher, or a derivative thereof.

In a particular embodiment of the invention, the fatty amine represents from 0.1 to 10% by weight, preferably from 0.1 to 6%, for example from 0.5 to 6%, relative to the total weight of the lubricant composition.

In another particular embodiment of the invention, the marine engine is a two-stroke or four-stroke, pure gas or dual fuel engine.

in another particular embodiment of the invention, the use of one or more fatty amines soluble in the lubricant composition allows for the reduction and/or control of abnormal gas combustion in a marine engine caused by auto-ignition of the lubricant composition.

In another particular embodiment of the invention, the use of one or more fatty amines soluble in the lubricant composition allows to reduce and/or control the anomalous gas combustion of any type of gas, in particular of gases having a low Methane Number (MN), preferably a methane number lower than 80, more advantageously lower than 60.

[ detailed description ] embodiments

aliphatic amines

the fatty amines of the present invention, which are soluble in the lubricant composition, allow for the reduction and/or control of abnormal gas combustion in marine engines.

In a particular embodiment of the invention, the fatty amine has the formula (I):

R₁-[(NR₂)-R₃]_q-NR₄R₅，

Wherein:

R₁Is a saturated or unsaturated, linear or branched hydrocarbon group having at least 12 carbon atoms, and optionally at least one heteroatom selected from nitrogen, sulfur or oxygen;

R₂、R₄or R₅Independently a hydrogen atom or a saturated or unsaturated, linear or branched hydrocarbon group, and optionally comprising at least one heteroatom selected from nitrogen, sulphur or oxygen;

R₃Is a saturated or unsaturated, linear or branched hydrocarbon group comprising one or more carbon atoms and optionally at least one heteroatom selected from nitrogen, sulfur or oxygen;

q is equal to 0 or higher, preferably q is 1 or higher, more preferably it is an integer between 1 and 10, more preferably between 1 and 6, advantageously it is selected from 1, 2 or 3.

"fatty amines" according to the invention means the following amines: comprising one or more saturated or unsaturated, linear or branched hydrocarbon radicals and optionally at least one heteroatom selected from nitrogen, sulphur or oxygen, preferably oxygen. For example, the fatty amine of the present invention may be an amine of formula (I).

"fatty amine(s)" according to the invention means a mixture of fatty amines in which at least one fatty amine has the formula (I).

Preferably, the fatty amine is of formula (I), wherein:

R₁Is a saturated or unsaturated, linear or branched alkyl group having from 12 to 22 carbon atoms, preferably from 14 to 22 carbon atoms, and optionallyAt least one heteroatom selected from nitrogen, sulfur or oxygen; and/or

R₂、R₄Or R₅independently a hydrogen atom, or a saturated or unsaturated, linear or branched alkyl group having between 1 and 22 carbon atoms, preferably between 14 and 22 carbon atoms, more preferably between 16 and 22 carbon atoms; or (R)₆-O)_r-H group, wherein R₆Is a saturated, linear or branched alkyl group having at least 2 carbon atoms, preferably between 2 and 6 carbon atoms, more preferably between 2 and 4 carbon atoms, and r is an integer of 1 or more, preferably between 1 and 6, more preferably between 1 and 4; and/or

R₃is a saturated or unsaturated, linear or branched alkyl group having between 2 and 6 carbon atoms, preferably between 2 and 4 carbon atoms.

Advantageously, the fatty amine has formula (I), wherein:

q is 1, 2 or 3;

R₁is a saturated or unsaturated, linear or branched alkyl group having from 14 to 20 carbon atoms, preferably from 16 to 20 carbon atoms, and optionally at least one heteroatom selected from nitrogen, sulfur or oxygen;

R₂Independently a hydrogen atom or a saturated, linear or branched alkyl group having from 1 to 20 carbon atoms, preferably from 16 to 20 carbon atoms, more preferably from 16 to 18 carbon atoms;

R₃Is a saturated, straight-chain alkyl group having between 2 and 6 carbon atoms, preferably between 2 and 4 carbon atoms;

R₄And R₅Is a hydrogen atom or a methyl group, preferably a hydrogen atom.

In particular, the fatty amine has formula (I), wherein:

q is equal to 3;

R₁Is a saturated or unsaturated, linear or branched alkyl group having from 14 to 20 carbon atoms, preferably from 16 to 20 carbon atoms, and optionally at least one radical selected from nitrogena heteroatom of sulfur or oxygen;

R₂Independently a hydrogen atom or a saturated straight or branched alkyl group having 16 to 18 carbon atoms;

R₃is an ethyl or propyl group;

R₄and R₅Is a hydrogen atom.

Advantageously, the fatty amine has formula (I), wherein:

q is 1, 2 or 3;

R₁Is a saturated or unsaturated, linear or branched alkyl group having from 14 to 20 carbon atoms, preferably from 16 to 20 carbon atoms;

R₂、R₄And R₅Independently is a hydrogen atom or (R)₆-O)_r-H group, wherein R₆is a saturated, straight-chain alkyl group having between 2 and 6 carbon atoms, preferably between 2 and 4 carbon atoms, and r is an integer between 1 and 6, more preferably between 1 and 4;

R₃Are saturated, straight-chain alkyl groups having between 2 and 6 carbon atoms, preferably between 2 and 4 carbon atoms.

in particular, the fatty amine has formula (I), wherein:

q is equal to 3;

R₁is a saturated or unsaturated, linear or branched alkyl group having from 14 to 20 carbon atoms, preferably from 16 to 20 carbon atoms;

R₂、R₄And R₅independently is a hydrogen atom or (R)₆-O)_r-H group, wherein R₆Is a saturated, straight-chain alkyl group having between 2 and 4 carbon atoms, and p is an integer between 1 and 4;

R₃is an ethyl or propyl group.

generally, the fatty amines of the present invention are simply obtained from carboxylic acids. These acids are dehydrated in the presence of ammonia to obtain nitriles and then subjected to catalytic hydrogenation, resulting in the production of fatty amines, among others.

Within the meaning of the present invention, the fatty amines of formula (I) are obtained from at least one carboxylic acid, preferably at least one fatty acid.

Within the meaning of the present invention, the number of carbon atoms of the alkyl group of the fatty amine corresponds to the number of carbon atoms of the carbon chain of the carboxylic acid, preferably to the number of carbon atoms of the carbon chain of the fatty acid.

Within the meaning of the present invention, one and the same fatty amine of formula (I) may be substituted by several alkyl groups obtained from several identical or different carboxylic acids, preferably from several identical or different fatty acids.

In a particular embodiment of the invention, the alkyl group is obtained from a fatty acid selected from the group consisting of: octanoic acid, pelargonic acid, decanoic acid, undecylenic acid, lauric acid, tridecenoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid, pentacosanoic acid, cerotic acid, heptacosanoic acid, montanic acid, nonacosanoic acid, melissic acid, hentriacontanoic acid, laccerotic acid, and derivatives thereof; or unsaturated fatty acids such as palmitoleic acid, oleic acid, erucic acid, nervonic acid, linoleic acid, alpha-linolenic acid, c-linolenic acid, di-homo-c-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and derivatives thereof.

Preferably, the fatty acids are derived from the hydrolysis of triglycerides contained in vegetable or animal oils such as coconut, palm, olive, peanut, rapeseed, sunflower, soybean, cotton, linseed oil, tallow. Natural oils (e.g., rapeseed oil or sunflower oleate) may have been genetically modified to enrich their content in certain fatty acids.

generally, the fatty amines of formula (I) of the present invention are preferably obtained from natural plant or animal sources. Treatment to produce fatty amines from natural oils can result in the production of a mixture of primary, tertiary and secondary polyamines.

In another particular embodiment of the invention, when several fatty amines are used to reduce and/or control the abnormal gas combustion in a marine engine, said fatty amines form a mixture of fatty amines comprising all or part of the compounds satisfying the following formulae (Ia), (Ib), (Ic) and (Id) in different proportions:

R₁-NR₄R₅(Ia)，

R₁-[(NR₂)-R₃]-NR₄R₅(Ib)，

R₁-[(NR₂)-R₃]₂-NR₄R₅(Ic)，

R₁-[(NR₂)-R₃]₃-NR₄R₅(Id)

wherein:

R₁Is a saturated or unsaturated, linear or branched hydrocarbon group having at least 12 carbon atoms, and optionally at least one heteroatom selected from nitrogen, sulfur or oxygen;

R₂、R₄Or R₅independently a hydrogen atom or a saturated or unsaturated, linear or branched hydrocarbon group, and optionally comprising at least one heteroatom selected from nitrogen, sulphur or oxygen;

R₃Is a saturated or unsaturated, linear or branched hydrocarbon radical having one or more carbon atoms and optionally containing at least one heteroatom selected from nitrogen, sulfur or oxygen, preferably oxygen.

The radical R of an aliphatic amine of formulae (Ia), (Ib), (Ic) and (Id)₁、R₂、R₃、R₄、R₅And R₆The preferences and advantages of (a) are as defined hereinbefore for the fatty amines of formula (I) of the present invention.

In another particular embodiment, the mixture of aliphatic amines is in purified form, i.e. comprises predominantly a single type of amine of formula (Ia), (Ib), (Ic) or (Id), for example predominantly a monoamine of formula (Ia), a diamine of formula (Ib), a triamine of formula (Ic) or predominantly a tetramine of formula (Id). In particular, the mixture of fatty amines comprises predominantly tetraamines of formula (Id).

In a particular embodiment of the invention, the mixture of fatty amines comprises essentially:

a monoamine of formula (Ia), or

a diamine of the formula (Ib), or

a triamine of the formula (Ic), or

A tetraamine of formula (Id),

Wherein the radical R₁、R₂、R₃、R₄、R₅And R₆As defined above.

In another embodiment of the invention, the mixture of fatty amines comprises predominantly monoamines of the formula (Ia) wherein:

R₁Is a saturated or unsaturated, linear or branched alkyl group having from 12 to 20 carbon atoms, preferably from 14 to 20 carbon atoms, more preferably from 16 to 20 carbon atoms;

R₄And R₅Independently a hydrogen atom or a saturated, linear or branched alkyl group having from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms, more preferably a methyl group.

in another embodiment of the invention, the mixture of fatty amines comprises predominantly a diamine of formula (Ib) wherein:

R₁is a saturated or unsaturated, linear or branched alkyl group having from 12 to 20 carbon atoms, preferably from 14 to 20 carbon atoms, more preferably from 16 to 20 carbon atoms;

R₂Is a saturated, linear or branched alkyl group having from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms, more preferably a methyl group;

R₃Is an ethyl or propyl group;

R₄And R₅Independently a hydrogen atom or a saturated, linear or branched alkyl group having from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms, more preferably a methyl group.

Preferably, the mixture of fatty amines comprises predominantly formula R₁-NH₂Monoamines of formula (IIa), formula R₁-[(NR₂)-R₃]-NH₂(IIb) diamine of the formula R₁-[(NR₂)-R₃]₂-NH₂(IIc) triamines, or of the formula R₁-[(NR₂)-R₃]₃-NH₂(IId) a tetraamine wherein:

R₁Or R₂Is an at least saturated or unsaturated alkyl group obtained from fatty acids derived from tallow, or soybean oil, or coconut oil or (oleic) sunflower seed oil;

R₃Is a saturated or unsaturated, linear or branched hydrocarbon radical having at least 2 carbon atoms.

within the meaning of the invention when R₁Or R₂Is a saturated alkyl group, said saturated alkyl group being obtained from a saturated fatty acid or an unsaturated fatty acid subjected to hydrogenation, in particular from all these double bonds.

Advantageously, essentially comprises the formula R₁-[(NR₂)-R₃]₃-NH₂(IId) the mixture of fatty amines of tetraamines is in the form of:

At least one fatty amine of formula (IId), wherein R₁Is a saturated or unsaturated, linear or branched alkyl group having from 14 to 16 carbon atoms; r₂Is a hydrogen atom; and R is₃Is a saturated straight chain alkyl group having 2 to 6 carbon atoms;

at least one fatty amine of formula (IId), wherein R₁is a saturated or unsaturated, linear or branched alkyl group having at least 18 carbon atoms; r₂Is a hydrogen atom; and R is₃is a saturated straight-chain group having 2 to 6 carbon atoms; and

At least one fatty amine of formula (IId), wherein R₁Is a saturated or unsaturated, linear or branched alkyl group having at least 20 carbon atoms; r₂Is a hydrogen atom; and R is₃is a saturated straight chain alkyl group having 2 to 6 carbon atoms.

In particular, mainly comprising the formula R₁-[(NR₂)-R₃]₃-NH₂(IId) the mixture of fatty amines of tetraamines is in the form of:

At least one fatty amine of formula (IId), wherein R₁Is a saturated or unsaturated, linear or branched alkyl group having from 14 to 16 carbon atoms; r₂is a hydrogen atom; and R is₃Is a saturated straight-chain alkyl group having 2 to 6 carbon atoms；

at least one fatty amine of formula (IId), wherein R₁Is a saturated or unsaturated, linear or branched alkyl group having at least 18 carbon atoms; r₂Is a hydrogen atom; and R is₃Is a saturated straight chain alkyl group having 2 to 6 carbon atoms; and

At least one fatty amine of formula (IId), wherein R₁Is a saturated or unsaturated, linear or branched alkyl group having at least 20 carbon atoms; r₂Is a hydrogen atom; and R is₃is a saturated straight-chain alkyl group having 2 to 6 carbon atoms,

the sum of the contents by weight of said fatty amines of formula (IId) is higher than 90% with respect to the mixture of said fatty amines.

Advantageously, essentially comprises the formula R₁-[(NR₂)-R₃]₃-NH₂(IId) the mixture of fatty amines of tetraamines is also in the form of:

At least one fatty amine of formula (IId), wherein R₁Is an unsaturated, linear or branched alkyl group having from 16 to 20 carbon atoms, preferably from 18 to 20 carbon atoms; r₂Is a hydrogen atom; and R is₃is a saturated straight chain alkyl group having 2 to 6 carbon atoms; and

At least one fatty amine of formula (IId), wherein R₁Is a saturated linear or branched alkyl group having 16 to 20 carbon atoms, preferably 18 to 20 carbon atoms; r₂is a hydrogen atom; and R is₃Is a saturated straight chain alkyl group having 2 to 6 carbon atoms.

in particular, mainly comprising the formula R₁-[(NR₂)-R₃]₃-NH₂(IId) the mixture of fatty amines of tetraamines is in the form of:

At least one fatty amine of formula (IId), wherein R₁Is an unsaturated, linear or branched alkyl group having from 16 to 20 carbon atoms, preferably from 18 to 20 carbon atoms; r₂Is a hydrogen atom; and R is₃Is a saturated straight chain alkyl group having 2 to 6 carbon atoms;

At least one fatty amine of formula (IId), whereinR₁Is a saturated linear or branched alkyl group having 16 to 20 carbon atoms, preferably 18 to 20 carbon atoms; r₂Is a hydrogen atom; and R is₃Is a saturated straight chain alkyl group having 2 to 6 carbon atoms.

The sum of the contents by weight of said fatty amines of formula (IId) is higher than 90% with respect to the mixture of said fatty amines.

Preferably, the mixture of fatty amines does not comprise fatty amines other than the fatty amine according to formula (IId).

In a particular embodiment of the invention, when only one fatty amine is used to reduce and/or control abnormal gas combustion in a marine engine, the fatty amine corresponds to one of the following formulae:

A monoamine of formula (IIa), or

A diamine of the formula (IIb), or

A triamine of the formula (IIc), or

A tetraamine of formula (IId),

Wherein:

R₁Is a saturated straight or branched hydrocarbon group having at least 14 carbon atoms;

R₂independently a hydrogen atom or a saturated straight or branched hydrocarbon group having at least 14 carbon atoms;

R₃is a saturated straight chain hydrocarbon group having at least 2 carbon atoms.

in this embodiment, the fatty amine is preferably a tetraamine of formula (IId) wherein:

R₁Is a saturated straight or branched alkyl group having between 14 and 18 carbon atoms;

R₂independently a hydrogen atom or a saturated straight or branched hydrocarbon group having between 14 and 18 carbon atoms;

R₃is a saturated straight-chain hydrocarbon group having between 2 and 6 carbon atoms.

In this embodiment, the fatty amine is advantageously a tetraamine of formula (IId) wherein:

R₁is a saturated straight or branched alkyl group having between 16 and 18 carbon atomsA group;

R₂Independently a hydrogen atom or a saturated straight or branched hydrocarbon group having between 16 and 18 carbon atoms;

R₃Is an ethyl or propyl group.

Preferably, when the fatty amine is a mixture of polyalkylamines of formula (III) and/or (IV), the mixture of polyalkylamines comprises at least 5% by weight of compounds having a pure linear structure, since these compounds have proven to have acceptable viscosity characteristics, in particular an increased acceptable viscosity when using lubricants comprising this mixture of polyalkylamines of formula (III) and/or (IV).

In one embodiment, when the fatty amine is a mixture of polyalkylamines of formula (III) and/or (IV), the mixture of polyalkylamines comprises at least 4% by weight (w/w%), preferably at least 5 w/w%, preferably at least 6 w/w%, preferably more than 7 w/w%, preferably more than 7.5 w/w%, preferably more than 10 w/w%, preferably more than 20 w/w% of branched compounds, wherein at least one of n or z is equal to or higher than 1.

For the product of formula (III), this means that n must be equal to or higher than 1 for the branched product.

Preferably, when the fatty amine is a mixture of polyalkylamines of formula (III) and/or (IV), the hydrogen atom present at the chain end is covalently bonded to the corresponding secondary nitrogen atom when n, o, p or z is equal to 0.

Preferably, when the fatty amine is a mixture of polyalkylamines of formula (III) and/or (IV), the mixture comprises a compound of formula (III) and/or (IV) wherein n, o, p and z are equal to 1 or 2 when they are different from 0, preferably n, o, p and z are equal to 1 when they are different from 0.

In a preferred embodiment, when the fatty amine is a mixture of polyalkylamines of formula (III) and/or (IV), the mixture predominantly comprises compounds of formula (III) and/or (IV), wherein n, o, p or z is independently 0, 1 or 2, preferably n, o, p or z is independently 0 or 1.

In a preferred embodiment, when the fatty amine is a mixture of polyalkylamines of formula (III) and/or (IV), the mixture predominantly comprises compounds of formula (III) and/or (IV) and derivatives thereof, wherein n, o, p and z are independently 0, 1 or 2, preferably n, o, p and z are independently 0 or 1.

Derivatives of the compounds of formula (III) and/or (IV) are described below.

In a preferred embodiment, each R group is independently a straight or branched alkyl group and has from 14 to 22 carbon atoms, preferably from 14 to 20 carbon atoms, preferably from 16 to 20 carbon atoms.

Generally, the fatty amines of formulae (III) and (IV) according to the invention are obtained simply from carboxylic acids. These acids are dehydrated in the presence of ammonia to obtain nitriles and then subjected to catalytic hydrogenation, resulting in the production of fatty amines, among others.

Within the meaning of the present invention, the fatty amines of the formulae (III) and (IV) are obtained from at least one carboxylic acid, preferably at least one fatty acid.

Within the meaning of the present invention, the number of carbon atoms of the alkyl group of the fatty amines of formulae (III) and (IV) corresponds to the number of carbon atoms of the carbon chain of the carboxylic acid, preferably to the number of carbon atoms of the carbon chain of the fatty acid.

in a particular embodiment of the invention, when the fatty amine is a mixture of polyalkylamines of formulae (III) and/or (IV), the alkyl group R is obtained from a fatty acid selected from: octanoic acid, pelargonic acid, decanoic acid, undecylenic acid, lauric acid, tridecenoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid, pentacosanoic acid, cerotic acid, heptacosanoic acid, montanic acid, nonacosanoic acid, melissic acid, hentriacontanoic acid, laccerotic acid, and derivatives thereof; or unsaturated fatty acids such as palmitoleic acid, oleic acid, erucic acid, nervonic acid, linoleic acid, alpha-linolenic acid, c-linolenic acid, di-homo-c-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and derivatives thereof.

preferably, the fatty acids are derived from the hydrolysis of triglycerides contained in vegetable or animal oils such as coconut, palm, olive, peanut, rapeseed, sunflower, soybean, cotton, linseed oil, tallow. Natural oils (e.g., rapeseed oil or oleic sunflower oil) may have been genetically modified to enrich them for certain fatty acid content.

the composition of the derivatives of fatty dialkyl polyalkylamines of formulae (III) and/or (IV) of the present invention comprises the following compounds: wherein one or more NH segments of the fatty polyalkylamines of the present invention are methylated, alkoxylated or both. Such compounds have been found to have advantageous solubility, particularly in lubricating oils. Advantageously, the alkoxylated derivative is butylated, propoxylated and/or ethoxylated. If two or more alkoxylating agents are used, they may be used in any order, for example EO-PO-EO, and the different alkoxy units may be of polyhedral type and/or be present randomly. Advantageously, the primary NH is alkoxylated with one or more alkylene oxides in a conventional manner₂a group to form a group-NH-AO-H, wherein AO represents one or more alkylene-oxy repeat units. the-NH-AO-H group obtained may also be alkoxylated to form-N (AO-H)₂A repeating unit. Specifically, when a large amount of alkylene oxide is used (i.e., more than 8 moles of alkylene oxide per mole of polyalkylamine), one or more secondary amines, if present, are typically alkoxylated.

In one embodiment, all primary and secondary amine functional groups of the dialkylpolyamines of formula (III) and/or (IV) are alkoxylated. In another embodiment, the fatty dialkyl polyalkyl amines are obtained by methylating one or more NH functional groups in a manner known to those skilled in the art (e.g., by reaction with formic acid and formaldehyde). In one embodiment, one or more of the OH functional groups of the alkoxylated fatty dialkyl polyalkylamine are methylated in a conventional manner.

However, mixtures of the polyalkylamines of formula (IV) are preferred because it may be more economical to prepare mixtures of the polyalkylamines of formula (IV). Mixtures of polyalkylamines of the formula (III) and/or (IV) are used where appropriate.

The branched polyalkylamines of the invention can be prepared by any synthetic method known to the skilled worker. One conventional method uses a diamine, andAnd involves two or more cycles, preferably two for economic reasons, each comprising a cyanoethylation step and a hydrogenation step. In the remainder of this document, the process is referred to as a two-step process. In an alternative process, one equivalent of the dialkyl diamine may be reacted with two or more equivalents of acrylonitrile in a single step, followed by hydrogenation. In this case, optional additional cycles involving cyanoethylation and hydrogenation can be envisaged. This single step process may be advantageous because fewer intermediate steps are required. To increase branching in the two-step process, an acid catalyst, such as HCl or acetic acid, is used. In addition, the increase in reaction temperature during cyanoethylation also leads to an increase in branching in the process. When the multi-cycle process is carried out, the temperature of the subsequent cyanoethylation step is higher than that of the preceding cyanoethylation step, allowing the compound having the desired branching to be obtained. In one embodiment, more than one mole of acrylonitrile is used per mole of initial polyamine, which allows the branching of the desired product to be increased to the desired level. Suitably, and in order to maintain a homogeneous reaction mixture, a solvent is used. Preferred solvents comprise C_1-4Alcohol and C_2-4a diol. Preferably, ethanol is used, since it makes handling particularly easy. Surprisingly, C has been demonstrated_1-4Alcohol and C_2-4the diol is not only a solvent, but also co-catalytically active in the cyanoethylation step. The amount of solvent employed may vary over a wide range. For economic reasons, it is preferred to use the minimum amount. The amount of solvent, especially in the cyanoethylation step, is preferably less than 50, 40, 30 or 25% by weight relative to the liquid reaction mixture. The amount of solvent, especially in the cyanoethylation step, is preferably higher than 0.1, 0.5, 1, 5 or 10% by weight relative to the liquid reaction mixture.

With respect to the detergents used in the lubricant compositions, these detergents are well known to the skilled person.

In one particular embodiment of the invention, the detergents typically used in the formulation of lubricant compositions are anionic compounds comprising long lipophilic hydrocarbon chains and hydrophilic heads. The associated cation is typically a metal cation of an alkali or alkaline earth metal.

the detergent is preferably selected from the group consisting of alkali or alkaline earth metal salts, carboxylates, sulfonates, salicylates, naphthenic acids and phenates.

the alkali and alkaline earth metals are preferably calcium, magnesium, sodium or barium.

These metal salts may contain the metal in a suitable stoichiometric amount. In this case the term non-overbased or "neutral" detergents is used, although they also contribute a certain amount of alkalinity. These "neutral" detergents typically have a BN, measured according to ASTM D2896, of less than 150mg KOH/g, or less than 100, or less than 80mg KOH/g.

This type of so-called neutral detergent may contribute in part to the BN of the lubricant of the present invention. For example, neutral detergents of the carboxylate, sulfonate, salicylate, phenate, naphthenate type with alkali and alkaline earth metals (e.g. calcium, sodium, magnesium, barium) can be employed.

If the metal is in excess (in an amount above the stoichiometric amount) the detergent will be a so-called overbased detergent. They have a high BN, above 150mg KOH/g, usually between 200 and 700mg KOH/g, and generally between 250 and 450mg KOH/g.

The excess metal imparting overbased properties to the detergent is in the form of an oil-insoluble metal salt, for example a carbonate, hydroxide, oxalate, acetate, glutamate, preferably a carbonate.

The metals of these insoluble salts may be the same as those of the oil insoluble detergent, or they may be different from the oil insoluble detergent, in one and the same overbased detergent. They are preferably selected from calcium, magnesium, sodium or barium.

the overbased detergent is thus in the form of micelles consisting of insoluble metal salts that are kept suspended in the lubricant composition by the detergent in the form of oil-soluble metal salts.

These micelles may contain one or more types of insoluble metal salts that are stabilized by one or more types of detergents.

Overbased detergents comprising a single type of soluble metal salt are generally named according to the hydrophobic chain type of the latter detergent.

Thus, depending on whether the detergent is a carboxylate, phenate, salicylate, sulfonate or naphthenate, respectively, they are considered to be of the carboxylate, phenate, salicylate, sulfonate, naphthenate type.

if the micelles contain several types of detergents with different types of hydrophobic chains, the overbased detergent is said to be of the mixed type.

for use in the lubricant composition according to the invention, the oil-soluble metal salt is preferably a carboxylate, phenate, sulphonate, salicylate and mixed phenate-sulphonate and/or calcium salicylate, magnesium salicylate, sodium salicylate or barium salicylate detergent.

Insoluble metal salts which contribute to the overbased nature are carbonates of alkali and alkaline earth metals, preferably calcium or magnesium carbonate.

overbased detergents for use in the lubricant compositions of the present invention are preferably carboxylate, phenate, sulfonate, salicylate and mixed phenate-sulfonate-salicylate detergents overbased by calcium or magnesium carbonate.

Preferably, the lubricant composition comprises from 4 to 30% by weight of detergent, preferably from 5 to 25%, for example from 6 to 25%, relative to the total weight of the lubricant composition.

Lubricant composition

The fatty amine or mixture of fatty amines of the invention which allows to reduce and/or control abnormal gas combustion in marine engines is contained in the lubricant composition. The lubricant composition comprises:

-at least one base oil, preferably a lubricating base oil for marine engines;

-at least one detergent containing an alkali or alkaline earth metal overbased with a metal carbonate.

accordingly, the lubricant composition of the present invention comprises:

-at least one base oil, preferably a lubricating base oil for marine engines;

-at least one detergent containing an alkali or alkaline earth metal overbased with a metal carbonate;

-at least one fatty amine, in particular as defined above;

the amine/detergent weight ratio is between 0.01 and 1, preferably between 0.01 and 0.9, more preferably between 0.02 and 0.8, for example between 0.03 and 0.8.

Preferably, the lubricant composition has 70 milligrams or less of potassium hydroxide, preferably 60 milligrams or less of BN per mole of lubricant, as determined according to standard ASTM D-2896.

Advantageously, the lubricant composition has a BN of between 5 and 70 mg of potassium hydroxide, preferably between 10 and 60 mg of potassium hydroxide per mole of lubricant, determined according to the standard ASTM D-2896.

In one embodiment of the invention, the weight percentage of the fatty amine relative to the total weight of the cylinder lubricant is selected such that the BN contributed by the fatty amine represents a contribution of 1 to 20 milligrams of potassium hydroxide per gram of lubricant relative to the total BN of the cylinder lubricant.

The BN contribution (in mg of potassium hydroxide per gram of final lubricant or BN "score") contributed by the fatty amine in the cylinder lubricant according to the invention is calculated from the intrinsic BN of the fatty amine, measured according to the standard ASTM D-2896, and the weight percentage of the fatty amine in the final lubricant:

BN amine lubricant ═ x.BN amine/100

BN amine lubricant-the amine contribution to the BN of the final lubricant

x ═ weight% of amine in final lubricant

Inherent BN of BN amine ═ amine only (ASTM D-2896)

In another embodiment of the invention, the fatty amine represents from 0.1% to 10% by weight, preferably from 0.1% to 6%, for example from 0.5% to 6%, relative to the total weight of the lubricant composition.

Preferably, the lubricant composition further comprises at least one neutral detergent, in particular as defined above.

preferably, the lubricant composition comprises from 4% to 30% by weight of detergent, preferably from 5% to 25%, for example from 6% to 25%, relative to the total weight of the lubricant composition.

In a particular embodiment of the invention, the base oil contained in the lubricant composition is selected from oils of mineral, synthetic or vegetable origin and mixtures thereof.

The mineral or synthetic oils generally used in the present application belong to one of the categories defined in the API classification, such as outlined in the table below.

The mineral oils of group 1 may be obtained by distillation of selected naphthenic or paraffinic crude oils, followed by purification of these distillates by methods such as solvent extraction, solvent or catalytic dewaxing, hydrotreating or hydrogenation.

the oils of groups 2 and 3 are obtained by more severe purification methods, such as a combination of hydrotreating, hydrocracking, hydrogenation and catalytic dewaxing.

Examples of the synthetic base oils in groups 4 and 5 include polyalphaolefins, polybutenes, polyisobutylenes, alkylbenzenes.

These base oils may be used alone or in a mixture. Mineral oils may be combined with synthetic oils.

Cylinder oils for diesel 2-stroke marine engines have viscosity grades SAE-40 to SAE-60, generally SAE-50 equivalent to a kinematic viscosity at 100 ℃ between 16.3mm2/s and 21.9mm 2/s.

The 40 grade oil has a kinematic viscosity at 100 ℃ between 12.5mm2/s and 16.3mm 2/s.

The grade 50 oil has a kinematic viscosity at 100 ℃ between 16.3mm2/s and 21.9mm 2/s.

The 60 grade oil has a kinematic viscosity at 100 ℃ between 21.9V and 26.1V.

According to industry practice, cylinder oils for diesel 2-stroke marine engines may be formulated to have a kinematic viscosity at 100 ℃ of between 18 and 21.5, preferably between 19 and 21.5.

This viscosity can be obtained by mixing additives with base oils, for example containing mineral base oils from group 1, such as neutral solvent base oils (e.g. 500NS or 600NS) and Brightstock and/or mineral base oils from group 2. Any other combination of mineral, synthetic base oils or vegetable origin can be used, mixed with additives, having a viscosity compatible with SAE-50 grade.

In general, conventional formulations of cylinder lubricants for low speed diesel 2-stroke marine engines are of SAE 40 to SAE 60 grade, preferably SAE 50 grade (classified according to SAE J300) and comprise at least 50% by weight of one or more lubricating base oils of mineral and/or synthetic origin, which are adapted for use in marine engines, e.g. API class 1 group 1 and/or group 2, i.e. obtained by distillation of the selected crude oil, followed by purification by methods such as solvent extraction, solvent or catalytic dewaxing, hydrotreating or hydrogenation. For group 1 base oils, the Viscosity Index (VI) is between 80 and 120, the sulphur content is higher than 0.03% and the saturates content is lower than 90%. For the base oils in group 2, the Viscosity Index (VI) is between 80 and 120; the sulfur content thereof is 0.03% or less and the saturates content thereof is 90% or more.

in a particular embodiment of the invention, the lubricant composition may further comprise one or more thickening additives that act to increase the hot and cold viscosities of the composition, or additives that increase the Viscosity Index (VI).

Preferably, these additives are most often low molecular weight polymers having a molecular weight of about 2000 to 50000 daltons (Mn).

They may be selected from PIB (in the 2000 dalton region), polyacrylates or polymethacrylates (in the 30000 dalton region), olefin copolymers, copolymers of olefins and alpha-olefins, EPDM, polybutenes, high molecular weight polyalpha-olefins (viscosity at 100 ℃ >150), styrene-olefin copolymers, hydrogenated or not.

in a particular embodiment of the invention, one or more of the base oils contained in the lubricant compositions of the invention may be partially or fully substituted by these additives.

In this case, the polymer used to replace, in whole or in part, one or more of the base oils is preferably a thickener of the PIB type previously described (sold, for example, under the trade name Indopol H2100).

in a particular embodiment of the present invention, the lubricant composition may further comprise an anti-wear additive.

Preferably, the antiwear additive is zinc dithiophosphate or DTPZn. Within this class, various phosphorus, sulfur, nitrogen, chlorine and boron containing compounds have also been found.

There is a broad class of antiwear additives, but the most commonly used of this class are phosphorus-sulfur additives such as metal alkyl thiophosphates, especially zinc alkyl thiophosphates, and more specifically zinc dialkyl dithiophosphates or DTPZn.

amine phosphates, polysulfides (especially sulfur-containing olefins) are also conventionally employed antiwear additives.

In lubricant compositions, antiwear and extreme pressure additives of the nitrogen and sulfur containing type are also commonly found, such as metal dithiocarbamates, especially molybdenum dithiocarbamates. Glycerides are also antiwear additives. Mention may be made, for example, of monooleates, dioleates and trioleates, monopalmitates and monomyristates.

In a particular embodiment of the invention, the lubricant composition may further comprise at least one dispersant.

It is well known that dispersants can be used as additives in the formulation of lubricant compositions, particularly in the marine field. Their primary function is to maintain in suspension the particles initially present or present in the lubricant composition when used in an engine. They prevent their agglomeration by acting on steric hindrance. They may also have a synergistic effect on the neutralization.

Dispersants used as lubricant additives typically contain polar groups associated with relatively long hydrocarbon chains, typically containing from 50 to 400 carbon atoms. The polar group typically contains at least one element of nitrogen, oxygen, or sulfur.

succinic acid-derived compounds are dispersants and are widely used as lubricant additives. In particular, a succinimide obtained by condensing succinic anhydride with an amine, a succinic ester obtained by condensing succinic anhydride with an alcohol or a polyhydric alcohol are used.

These compounds can then be treated with various compounds, especially sulfur, oxygen, formaldehyde, carboxylic acids, and boron or zinc containing compounds to produce, for example, a borate containing succinimide or a zinc terminated succinimide.

Mannich bases obtained by polycondensing phenols substituted with alkyl groups, formaldehyde and primary or secondary amines are also compounds used as dispersants in lubricants.

dispersants from the succinimide PIB family, such as bromide-containing or zinc-capped, may be used.

In a particular embodiment of the invention, the lubricant composition may also include any type of functional additive suitable for use in the lubricant composition, such as anti-foam additives for counteracting the effects of detergents, which may be polar polymers such as polymethylsiloxanes, polyacrylates, antioxidants and/or anti-corrosion additives, such as organometallic detergents or thiadiazoles. These are known to the person skilled in the art.

in the present invention, the lubricant composition refers to compounds that are employed separately prior to mixing, it being understood that the compounds may or may not retain the same chemical form prior to and after mixing. Preferably, the lubricants of the invention obtained by mixing separately employed compounds are not in the form of emulsions or microemulsions.

Marine engine

The use of one or more fatty amines soluble in the lubricant composition in a specific weight ratio relative to the detergent of the lubricant composition allows for the reduction and/or control of abnormal gas combustion in marine engines.

In one particular embodiment of the invention, the marine engine is a two-stroke or four-stroke pure gas engine or a dual fuel engine.

In a particular embodiment of the invention, the use of one or more fatty amines of the invention in a particular weight ratio with respect to the detergent of the lubricant composition allows to reduce and/or control the abnormal gas combustion in the marine engine caused by the auto-ignition of the lubricant composition.

In a particular embodiment of the invention, the use of one or more fatty amines soluble in the lubricant composition in a specific weight ratio with respect to the detergent of the lubricant composition allows to reduce and/or control the anomalous gas combustion of any type of gas, in particular of gases having a low Methane Number (MN), preferably a methane number lower than 80, more advantageously lower than 60.

generally, it is known that the lower the Methane Number (MN) of the gas, the more the phenomenon of abnormal gas combustion increases.

The different embodiments, variations, preferences and advantages described above may be employed separately or in combination to achieve the first subject matter of the invention.

Method of producing a composite material

A second subject of the invention covers a method for reducing and/or controlling the abnormal gas combustion in a marine engine, wherein the gas is contacted with one or more fatty amines soluble in a lubricant composition comprising at least one detergent, the amine/detergent weight ratio being between 0.01 and 1, preferably between 0.01 and 0.9, more preferably between 0.02 and 0.8, for example between 0.03 and 0.8.

The fatty amine, detergent and lubricant compositions are as defined above.

the different embodiments, preferences, advantages, variants described for the first subject matter of the invention, which encompasses the use of one or more fatty amines soluble in a lubricant composition to reduce and/or control abnormal gas combustion in a marine engine, apply separately or in combination to the second subject matter of the invention encompassing the above-described method.

the invention also relates to the use of the lubricant composition of the invention to reduce and/or control abnormal gas combustion in a marine engine, preferably a two-stroke or four-stroke, pure gas or dual fuel engine.

the invention also relates to the use of the lubricant composition of the invention to reduce and/or control abnormal gas combustion in a marine engine caused by auto-ignition of the lubricant composition.

the use of the invention relates to any type of gas, in particular a gas having a low Methane Number (MN), preferably a methane number below 80, more advantageously below 60.

The invention also relates to a method for reducing and/or controlling abnormal gas combustion in a marine engine comprising lubricating the engine with the lubricant composition of the invention. Preferably, the marine engine is of the two-stroke or four-stroke pure gas type or of the dual fuel type.

The invention also relates to a method for reducing and/or controlling abnormal gas combustion in a marine engine caused by auto-ignition of a lubricant composition comprising engine lubrication with a lubricant composition of the invention.

the process of the invention relates to any type of gas, in particular a gas having a low Methane Number (MN), preferably a methane number below 80, advantageously below 60.

The invention is illustrated by way of non-limiting examples.

The test carried out to measure the pre-ignition frequency of the gas mixture in contact with the lubricant composition was carried out in a single-cylinder gas engine comprising a combustion chamber with a bore diameter of 108mm, a stroke of 115mm, a compression ratio of 11.4, corresponding to 1054cm³The single cylinder capacity of (a).

The speed of the single cylinder gas engine was 1000 rpm. The operating point selected is equal to an indicated mean effective pressure of 23bar, corresponding to an application representative of a heavy engine load.

Single cylinder gas engines have spark plug ignition systems that use "open-cell" technology to accurately repeat the ignition command every engine combustion cycle. The single cylinder gas engine is also equipped with a cylinder pressure sensor to measure the pressure change in the cylinder, determine the maximum cylinder pressure value at each engine cycle, and calculate the energy released during the combustion cycle.

Before a test for measuring abnormal gas combustion in a combustion chamber was performed, a mixture was prepared, which was formed of a gas having a methane number equivalent to 70% and air containing nitrogen and oxygen at an excess air ratio (air/gas) of 1.6 with respect to the stoichiometric ratio for gas combustion.

in order to make the effect of the lubricant on the abnormal combustion phenomena visible, the air-gas mixture is heated to a temperature of about 55 ℃, then gradually raised, in particular up to a maximum temperature of 110 ℃, and compressed at 3.6 bar on entering the single-cylinder gas engine.

FIG. 1 illustrates the percent pre-ignition caused by a lubricant as a function of inlet temperature.

FIG. 2 illustrates the frequency of abnormal combustion as a function of inlet temperature.

fig. 3 illustrates the time to reach auto-ignition as a function of temperature at top dead center.