阅读说明：本技术 润滑剂组合物和胍鎓基离子液体用作润滑剂添加剂的用途 (Lubricant composition and use of guanidinium-based ionic liquids as lubricant additives ) 是由 莫代斯蒂诺·德菲欧 托马斯·舒伯特 博扬·伊雷夫 于 2020-04-15 设计创作，主要内容包括：胍鎓基离子液体在润滑剂组合物,尤其是用于润滑船用发动机的润滑剂组合物中用作洗涤剂的用途。润滑剂组合物包含胍鎓基离子液体。(Use of a guanidinium-based ionic liquid as a detergent in a lubricant composition, especially for lubricating a marine engine. The lubricant composition comprises a guanidinium-based ionic liquid.)

1. Use of a guanidinium-based ionic liquid as a detergent in a lubricant composition.

2. Use according to claim 1 for lubricating a marine engine.

3. Use according to claim 1 or 2, wherein the guanidinium-based ionic liquid corresponds to formula (I):

[CAT⁺][X^-]

(I)

wherein

[X^-]Represents one or more than one anionic species; [ CAT ]⁺]Is selected from the group consisting ofCation of (II):

wherein:

r1, R2 are each independently selected from H, C₁-C₃₀Straight or branched alkyl radical, C₃-C₈Cycloalkyl radical, C₆-C₁₂Aryl radical and C₇-C₁₂An aralkyl group optionally substituted with a functional group comprising oxygen and/or nitrogen atoms,

r3, R4, R5 and R6 are independently selected from C₁-C₃₀Straight or branched alkyl radical, C₃-C₈Cycloalkyl radical, C₆-C₁₂Aryl radical and C₇-C₁₂An aralkyl group optionally substituted with a functional group comprising oxygen and/or nitrogen atoms,

or any two of (R3, R4) or (R5, R6) together form a methylene chain- (CH)₂) p-, wherein p is an integer from 2 to 5.

4. Use according to claim 3, wherein in formula (II):

r1, R2 are each independently selected from H and C₁-C₆A linear or branched alkyl group,

r3, R4, R5 and R6 are independently selected from C₁-C₆A straight or branched alkyl group.

5. The use of claim 4, wherein [ CAT ™ ]⁺]Selected from:

6. use according to any one of claims 3 to 5, wherein [ X [ [ X ]^-]Selected from:

a) carboxylate radical Ra-COO^-Wherein Ra is selected from alkyl and alkenyl groups comprising 1 to 30 carbon atoms, aryl groups comprising 6 to 30 carbon atoms, aralkyl groups comprising 7 to 30 carbon atoms, optionally substituted with functional groups comprising oxygen and/or nitrogen atoms;

b) alcohol/phenolate RaRbHCO^-Wherein Ra is selected from alkyl and alkenyl groups comprising 1 to 30 carbon atoms, aryl groups comprising 6 to 30 carbon atoms, aralkyl groups comprising 7 to 30 carbon atoms, Rb is selected from H, alkyl and alkenyl groups comprising 1 to 30 carbon atoms, aryl groups comprising 6 to 30 carbon atoms, aralkyl groups comprising 7 to 30 carbon atoms, optionally substituted with functional groups comprising oxygen and/or nitrogen atoms;

c) hydroxycarboxylates HO-Rc-COO^-Wherein Rc is selected from alkylene and alkenylene groups comprising from 1 to 30 carbon atoms, arylene groups comprising from 6 to 30 carbon atoms, aralkylene groups comprising from 7 to 30 carbon atoms, optionally substituted with functional groups comprising oxygen and/or nitrogen atoms.

7. The use according to claim 6, wherein [ X [ ]^-]Selected from: 2-ethylhexanoate, 2-hydroxypropionate, tert-amylphenoxide, isooctylphenol, and dioctylaminophenol.

8. A lubricant composition comprising:

30.0% to 99.95% of at least one base oil,

from 0.05% to 15.0% of at least one guanidinium-based ionic liquid,

the percentages are defined as the weight of the components relative to the total weight of the composition.

9. The lubricant composition according to claim 8, wherein the lubricant composition comprises at least one detergent (Det) selected from neutral and overbased detergents having a total base number of from 20 to 450mg KOH/g according to ASTM D2896.

10. The lubricant composition of claim 9, wherein the lubricant composition comprises from 1 wt% to 35 wt% of neutral and overbased detergents, relative to the total weight of the lubricant composition.

11. The lubricant composition of any one of claims 8 to 10, wherein the weight percent of guanidinium-based ionic liquid relative to the total weight of the lubricant composition is selected such that the alternative BN provided by the oil-soluble guanidinium-based ionic liquid is at least 3% of the BN of the lubricant composition.

12. A lubricant composition according to any one of claims 8 to 11 having a Total Base Number (TBN) according to ASTM D2896 of greater than 5mg KOH/g.

13. Lubricant composition according to any one of claims 8 to 12, having a kinematic viscosity at 100 ℃ higher than or equal to 5.6mm²A number/s of less than or equal to 21.9mm²/s。

14. The lubricant composition according to any one of claims 8 to 13, wherein guanidinium-based ionic liquid corresponds to formula (I):

[CAT⁺][X^-]

(I)

wherein

[X^-]Represents one or more than one anionic species, [ CAT⁺]A cation selected from formula (II):

wherein:

r1, R2 are each independently selected from H, C₁-C₃₀Straight or branched alkyl radical, C₃-C₈Cycloalkyl radical, C₆-C₁₂Aryl radical and C₇-C₁₂Aralkyl group, which is optionalSubstituted with functional groups comprising oxygen and/or nitrogen atoms,

r3, R4, R5 and R6 are independently selected from C₁-C₃₀Straight or branched alkyl radical, C₃-C₈Cycloalkyl radical, C₆-C₁₂Aryl radical and C₇-C₁₂An aralkyl group optionally substituted with a functional group comprising oxygen and/or nitrogen atoms,

or any two of (R3, R4) or (R5, R6) together form a methylene chain- (CH)₂) p-, wherein p is an integer from 2 to 5.

15. The lubricant composition of claim 14, wherein [ X [ ]^-]Selected from:

a) carboxylate radical Ra-COO^-Wherein Ra is selected from alkyl and alkenyl groups comprising 1 to 30 carbon atoms, aryl groups comprising 6 to 30 carbon atoms, aralkyl groups comprising 7 to 30 carbon atoms, optionally substituted with functional groups comprising oxygen and/or nitrogen atoms;

b) alcohol/phenolate RaRbHCO^-Wherein Ra is selected from alkyl and alkenyl groups comprising 1 to 30 carbon atoms, aryl groups comprising 6 to 30 carbon atoms, aralkyl groups comprising 7 to 30 carbon atoms, Rb is selected from H, alkyl and alkenyl groups comprising 1 to 30 carbon atoms, aryl groups comprising 6 to 30 carbon atoms, aralkyl groups comprising 7 to 30 carbon atoms, optionally substituted with functional groups comprising oxygen and/or nitrogen atoms;

c) hydroxycarboxylates HO-Rc-COO^-Wherein Rc is selected from alkylene and alkenylene groups comprising from 1 to 30 carbon atoms, arylene groups comprising from 6 to 30 carbon atoms, aralkylene groups comprising from 7 to 30 carbon atoms, optionally substituted with functional groups comprising oxygen and/or nitrogen atoms.

16. A method of lubricating two-stroke marine engines and four-stroke marine engines, more preferably two-stroke marine engines, the method comprising applying to the marine engines a lubricant composition according to any one of claims 8 to 15.

17. A method for reducing and/or limiting and/or preventing and/or delaying the formation of deposits in internal parts of a combustion engine, in particular a marine engine, or for reducing deposits already present in internal parts of a combustion engine, in particular a marine engine, which method comprises applying a guanidinium-based ionic liquid.

18. The method of claim 17, wherein the guanidinium-based ionic liquid has formula (I):

[CAT⁺][X^-] (I)

wherein

[X^-]Represents one or more than one anionic species; [ CAT ]⁺]A cation selected from formula (II):

wherein:

r1, R2 are each independently selected from H, C₁-C₃₀Straight or branched alkyl radical, C₃-C₈Cycloalkyl radical, C₆-C₁₂Aryl radical and C₇-C₁₂An aralkyl group optionally substituted with a functional group comprising oxygen and/or nitrogen atoms,

r3, R4, R5 and R6 are independently selected from C₁-C₃₀Straight or branched alkyl radical, C₃-C₈Cycloalkyl radical, C₆-C₁₂Aryl radical and C₇-C₁₂An aralkyl group optionally substituted with a functional group comprising oxygen and/or nitrogen atoms,

or any two of (R3, R4) or (R5, R6) together form a methylene chain- (CH)₂) p-, wherein p is an integer from 2 to 5.

19. The method of claim 18, wherein in formula (II):

r1, R2 are each independently selected from H and C₁-C₆A linear or branched alkyl group, and

r3, R4, R5 and R6 are independently selected from C₁-C₆A straight or branched alkyl group.

20. The method of claim 18 or 19, wherein [ CAT ™ ]⁺]Selected from:

21. the method of any one of claims 18 to 20, wherein [ X [ ]^-]Selected from:

a) carboxylate radical Ra-COO^-Wherein Ra is selected from alkyl and alkenyl groups comprising 1 to 30 carbon atoms, aryl groups comprising 6 to 30 carbon atoms, aralkyl groups comprising 7 to 30 carbon atoms, optionally substituted with functional groups comprising oxygen and/or nitrogen atoms;

b) alcohol/phenolate RaRbHCO^-Wherein Ra is selected from alkyl and alkenyl groups comprising 1 to 30 carbon atoms, aryl groups comprising 6 to 30 carbon atoms, aralkyl groups comprising 7 to 30 carbon atoms, Rb is selected from H, alkyl and alkenyl groups comprising 1 to 30 carbon atoms, aryl groups comprising 6 to 30 carbon atoms, aralkyl groups comprising 7 to 30 carbon atoms, optionally substituted with functional groups comprising oxygen and/or nitrogen atoms;

c) hydroxycarboxylates HO-Rc-COO^-Wherein Rc is selected from alkylene and alkenylene groups comprising from 1 to 30 carbon atoms, arylene groups comprising from 6 to 30 carbon atoms, aralkylene groups comprising from 7 to 30 carbon atoms, optionally substituted with functional groups comprising oxygen and/or nitrogen atoms.

22. The method of claim 21, wherein [ X [ ]^-]Selected from: 2-ethylhexanoate, 2-hydroxypropionate, tert-amylphenoxide, isooctylphenol, and dioctylaminophenol.

Background

One of the main functions of a lubricant is to reduce friction. However, in general, lubricating oils require additional properties in order to be used effectively. For example, lubricants used in large diesel engines, such as marine diesel engines, are often subject to operating conditions that require special consideration.

There are two types of marine oil used in low speed two-stroke crosshead engines. On the one hand, the cylinder oil ensures the lubrication of the cylinder-piston assembly, and on the other hand, the system oil ensures the lubrication of all moving parts except the cylinder-piston assembly. Within the cylinder-piston assembly, the combustion residues containing acid gases are contacted with lubricating oil.

The acid gas is formed by the combustion of fuel oil; these acid gases are in particular Sulfur Oxides (SO)₂、SO₃) Which subsequently hydrolyses on contact with the moisture present in the combustion gases and/or in the oil. The hydrolysis produces sulfurous acid (HSO)₃) Or sulfuric acid (H)₂SO₄)。

To protect the surface of the piston liner and avoid excessive erosive wear, these acids must be neutralized, typically by reaction with basic sites included in the lubricant.

The neutralizing capacity of an oil is measured by its BN or base number, which is characterized by its basicity. Measured according to the standard ASTM D-2896 and expressed as milliequivalents of potash per gram of oil (also known as "mg KOH/g" or "BN point"). BN is a standard specification that allows the alkalinity of cylinder oil to be adjusted according to the sulphur content of the fuel oil used, in order to be able to neutralize all the sulphur contained in the fuel and to be able to be converted into sulphuric acid by combustion and hydrolysis.

Thus, the higher the sulfur content of the fuel oil, the higher the BN requirement of the marine oil. This is why marine oils with BN varying from 5mg KOH/g to 140mg KOH/g are found on the market.

The alkalinity is usually provided by detergents which are neutral and/or overbased by insoluble metal salts, particularly metal carbonates. Detergents which are predominantly anionic are metal soaps such as salicylates, phenolates, sulfonates, carboxylates and the like which form micelles in which particles of insoluble metal salt remain suspended. Common neutral detergents inherently have a BN typically less than 150mg KOH per gram of detergent, while common overbased detergents inherently have a BN between 150 and 700mg KOH per gram of detergent in the standard manner. Their mass percentages in the lubricant are determined with the desired BN level.

In certain areas, particularly coastal areas, environmental concerns have raised requirements regarding limiting the sulfur levels in fuel oils used in ships. Thus, MARPOL convention 6 (rules for preventing air pollution by ships) issued by IMO (international maritime organization) is in effect in 5 months of 2005. Which set a global upper limit of 4.5% w/w for the sulfur content of heavy fuel oil and establish a sulfur oxide emission control zone called SECA (sulfur emission control zone). Ships entering these areas must use fuel oil with a maximum sulphur content of 1.5% w/w or any other alternative treatment aimed at limiting SOx emissions to meet the regulations. The symbol w/w represents the weight percent of the compound relative to the total weight of the fuel oil or lubricant composition containing the compound.

Thereafter, MEPC (marine environmental protection committee) held the conference at 2008 and approved the proposed amendment to regular MARPOL annex 6. From 2012 onwards, the limits on maximum sulphur content became more severe, with the global maximum content decreasing from 4.5% w/w to 3.5% w/w. Since 2010, SECA (sulfur emission control zone) became ECA (emission control zone), the maximum allowable sulfur content was further reduced from 1.5% w/w to 1.0% w/w and new limits on the content of NOx and particulate matter were added. In 2020, the maximum sulphur content will be further reduced, as detailed in the table below.

Currently, marine lubricants of the grade with a BN of 100 or below 100 are used in the presence of fuel oils with a high sulphur content (below 3.5% w/w). In the presence of fuel oil having a low sulphur content (0.1% w/w), a grade of marine lubricant having a BN of 40 or less than 40 is used. In both cases, sufficient neutralization capacity is achieved due to the necessary concentration of alkaline sites provided by the neutral and/or overbased detergents of the marine lubricant being achieved.

Furthermore, each of these lubricants has limitations in use due to the following observations: the use of high BN cylinder lubricants in the presence of fuel oils with low sulphur content (0.1w/w) and at fixed lubrication levels, creates a significant excess of alkaline sites (high BN) and a risk of destabilization of micelles containing insoluble metal salts of unused overbased detergents. This instability can lead to the formation of deposits of insoluble metal salts (e.g., calcium carbonate), primarily on the piston crown, and can ultimately lead to the risk of excessive wear of the liner finish type. For this reason, when low sulfur fuels are used, the TBN of the lubricant should be relatively low, which also results in a reduction in detergent concentration. It is clear that lubricant formulators need other types of detergents that are ash free or have reduced ash content. Furthermore, in the presence of fuel oils with high sulphur content, the overall neutralisation capacity of the use of low BN cylinder lubricants is insufficient and can therefore cause a serious corrosion risk.

There is a need for a marine detergent that can be used in the presence of high sulphur fuels as well as low sulphur fuels and that has a good sulphuric acid neutralising capacity, while maintaining good heat resistance and therefore a low risk of deposit formation in the hot end parts of the engine.

There is also a need for a marine lubricant having BN, in particular having a BN 70 below or equal, which can be used in the presence of high as well as low sulphur fuels and has a good sulphuric acid neutralising capacity, while maintaining good heat resistance and therefore a low risk of deposit formation in the hot end parts of the engine.

There is also a need for a marine lubricant having improved wash performance, said improved wash performance being: the ability to keep the engine clean by limiting deposits in the internal parts of the combustion engine ("keep-clean") effect) or by reducing deposits already present in the internal parts of the combustion engine ("clean-up") effect.

It is an object of the present invention to provide a lubricant additive which overcomes all or part of the above disadvantages. It is another object of the present invention to provide a lubricant additive that is easy to formulate in a lubricant composition.

It is another object of the present invention to provide a method of lubricating marine engines, particularly two-stroke marine engines, which can be used with both low and high sulfur fuels.

It is another object of the present invention to provide a method of lubricating marine engines, particularly two-stroke marine engines using very low sulfur fuels.

It is another object of the present invention to provide a method of reducing the formation of deposits in the hot end parts of marine engines, particularly two-stroke marine engines.

Surprisingly, the applicant has found that the introduction of certain types of ionic liquids as detergents in conventional formulations of cylinder lubricants leads to a significant increase in the effectiveness of said conventional lubricants in the neutralization of sulfuric acid formed during the combustion of any type of fuel oil having a sulphur content of less than 4.5% in two-stroke marine engines. In particular, the improvement in properties is associated with a significantly increased rate or kinetics of neutralization of the sulfuric acid formed. This difference in performance between the conventional reference lubricant and the same lubricant with detergent added is characterized by a neutralization effectiveness index measured using the enthalpy test described in the examples below.

The use of some ionic liquids as additives in lubricants has been described in the prior art, however, guanidinium-based ionic liquids are not known to be useful as detergent additives in lubricant compositions for marine engines.

US2012/178658 discloses the use of an ionic liquid in a lubricant composition to reduce coking and sludge accumulation in an aircraft turbine. The ionic liquid can be represented by the formula C⁺A^-Is represented by the formula (I) in which C⁺Is a cation, A^-Is an anion. Preferred cations are quaternary ammonium cations and phosphonium cations. Preferred anions are fluorinated anions.

EP2022840 discloses the use of guanidinium-based ionic liquids for lubricating moving parts in wind turbines, in particular for gear lubrication.

US2011/077177 discloses a lubricant composition for marine engines comprising:

-a lubricating base oil which is a lubricating base oil,

at least one overbased detergent based on an alkali metal or alkaline earth metal, and

-from 0.01% to 10% of one or more than one surfactant compound.

The applicant has found that guanidinium-based ionic liquids have outstanding properties as detergent additives in the lubricant compositions of marine engines, in particular two-stroke marine engines. The ionic liquids used according to the invention in these lubricant compositions can keep the engine clean, in particular by limiting or preventing the formation of deposits in the internal parts of the combustion engine ("clean-keeping" effect) or by reducing deposits already present in the internal parts of the combustion engine ("cleaning" effect).

Disclosure of Invention

The present invention relates to the use of guanidinium-based ionic liquids as detergents in lubricant compositions.

According to a preferred embodiment, the use is for lubricating a marine engine.

According to a preferred embodiment, the present invention relates to the use of a guanidinium-based ionic liquid as a detergent in a lubricant composition for lubricating two-stroke marine engines and four-stroke marine engines, more preferably two-stroke marine engines.

Another object of the present invention is a lubricant composition comprising:

at least one base oil, at least one of which,

at least one guanidinium-based ionic liquid,

at least one detergent (Det) chosen from neutral and overbased detergents having a total base number of from 20 to 450mg KOH/g, according to ASTM D2896.

Another object of the present invention is a lubricant composition comprising:

30.0% to 99.95% of at least one base oil,

from 0.05% to 15.0% of at least one guanidinium-based ionic liquid,

the percentages are defined as the weight of the components relative to the total weight of the composition.

The invention also relates to a method of lubricating a two-stroke marine engine and a four-stroke marine engine, more preferably a two-stroke marine engine, comprising applying to the marine engine a lubricant composition as disclosed above.

Another object of the present invention is a method for reducing and/or limiting and/or preventing and/or delaying the formation of deposits in internal parts of a combustion engine, in particular a marine engine, or reducing deposits already present in internal parts of a combustion engine, in particular a marine engine, comprising applying a guanidinium-based ionic liquid or a lubricant composition as defined above.

According to a preferred embodiment, the guanidinium-based ionic liquid corresponds to formula (I):

[CAT⁺][X^-]

(I)

wherein

[X^-]Represents one or more than one anionic species; [ CAT ]⁺]Is a cation selected from formula (II):

wherein:

r1, R2 are each independently selected from H, C₁-C₃₀Straight or branched alkyl radical, C₃-C₈Cycloalkyl radical, C₆-C₁₂Aryl radicals or C₇-C₁₂An aralkyl group optionally substituted with a functional group comprising oxygen and/or nitrogen atoms,

r3, R4, R5 and R6 are independently selected from C₁-C₃₀Straight or branched alkyl radical, C₃-C₈Cycloalkyl radical, C₆-C₁₂Aryl radicals or C₇-C₁₂An aralkyl group optionally substituted with a functional group comprising oxygen and/or nitrogen atoms,

or any two of (R3, R4) or (R5, R6) together form a methylene chain- (CH)₂) p-, wherein p is an integer from 2 to 5.

According to a more preferred embodiment, in formula (II):

r1, R2 are each independently selected from H, C₁-C₆A linear or branched alkyl group,

r3, R4, R5 and R6 are independently selected from C₁-C₆A straight or branched alkyl group.

According to the most preferred embodiment, [ CAT⁺]Selected from:

according to a preferred embodiment, [ X ]^-]Selected from:

a) carboxylate radical Ra-COO^-Wherein Ra is selected from alkyl and alkenyl groups comprising 1 to 30 carbon atoms, aryl groups comprising 6 to 30 carbon atoms, aralkyl groups comprising 7 to 30 carbon atoms, optionally substituted with functional groups comprising oxygen and/or nitrogen atoms;

b) alcohol/phenolate RaRbHCO^-Wherein Ra is selected from alkyl and alkenyl groups comprising 1 to 30 carbon atoms, aryl groups comprising 6 to 30 carbon atoms, aralkyl groups comprising 7 to 30 carbon atoms, Rb is selected from H, alkyl and alkenyl groups comprising 1 to 30 carbon atoms, aryl groups comprising 6 to 30 carbon atoms, aralkyl groups comprising 7 to 30 carbon atoms, optionally substituted with functional groups comprising oxygen and/or nitrogen atoms;

c) hydroxycarboxylates HO-Rc-COO^-Wherein Rc is selected from alkylene and alkenylene groups comprising 1 to 30 carbon atoms, arylene groups comprising 6 to 30 carbon atoms, aralkylene groups comprising 7 to 30 carbon atoms, optionally substituted with functional groups comprising oxygen and/or nitrogen atoms.

According to a more preferred embodiment, [ X ]^-]Selected from: 2-ethylhexanoate, 2-hydroxypropionate, tert-amylphenoxide, isooctylphenol, and dioctylaminophenol.

According to a preferred embodiment, the lubricant composition comprises at least one detergent (Det) selected from neutral and overbased detergents having a total base number of from 20 to 450mg KOH/g according to ASTM D2896.

According to a preferred embodiment, the lubricant composition comprises from 1 wt% to 35 wt% of neutral and overbased detergents, based on the total weight of the lubricant composition.

According to a preferred embodiment, the weight percentage of guanidinium-based ionic liquid relative to the total weight of the lubricant composition is selected such that the alternative BN provided by the oil-soluble guanidinium-based ionic liquid is at least 3% of the BN of the lubricant composition.

According to a preferred embodiment, the lubricant composition has a Total Base Number (TBN) according to ASTM D2896 of more than 5mg KOH/g.

According to a preferred embodiment, the lubricant composition is inKinematic viscosity at 100 ℃ higher than or equal to 5.6mm²A number/s of less than or equal to 21.9mm²/s。

The compounds of formula (I) as defined above and below greatly improve the wash performance of the lubricant composition.

The compounds of formula (I) as defined above and below allow to keep the internal parts of the engine clean and clean in a very efficient way.

Detailed Description

The term "consisting essentially of … …" followed by one or more features means that in addition to the explicitly listed components or steps, components or steps that do not materially affect the properties and characteristics of the invention may be included in the methods or materials of the invention.

Unless explicitly stated otherwise, the expression "comprising X to Y" includes the border. The expression is meant that the target range includes both X and Y values as well as all values from X to Y.

An "ionic liquid" is a salt in liquid form having an organic or inorganic cation and an anion. Typically the ionic liquid has a melting point below 100 ℃.

"alkyl" means a saturated hydrocarbyl chain which may be straight, branched or cyclic.

"alkenyl" means a hydrocarbyl chain which may be straight, branched or cyclic and which contains at least one unsaturation, preferably a carbon-carbon double bond.

"aryl" refers to an aromatic hydrocarbon functional group. The functional group may be monocyclic or polycyclic. As examples of aryl groups, mention may be made of: phenyl, naphthyl, anthryl, phenanthryl and tetracenyl.

"aralkyl" means a hydrocarbyl radical containing an aromatic functional group (preferably a monocyclic ring) attached to an alkyl chain, the aralkyl group being attached to the rest of the molecule through the aryl or alkyl portion of the radical.

"hydrocarbyl" refers to a compound or fragment of a compound selected from the group consisting of: alkyl, alkenyl, aryl, aralkyl. Where indicated, some hydrocarbyl groups contain heteroatoms.

Guanidinium-based ionic liquids

The guanidinium-based ionic liquid is a salt of a guanidinium cation with an organic or inorganic anion. Preferably, the guanidinium-based ionic liquid is a salt of a guanidinium cation with an organic anion.

The guanidinium-based ionic liquid is advantageously chosen from compounds of formula (I):

[CAT⁺][X^-]

(I)

wherein

[CAT⁺]Represents a guanidinium ion; [ X ]^-]Represents one or more than one anionic species.

More preferably, [ CAT⁺]A cation selected from formula (II):

wherein:

r1, R2 are each independently selected from H, C₁-C₃₀Straight or branched alkyl radical, C₃-C₈Cycloalkyl radical, C₆-C₁₂Aryl radicals or C₇-C₁₂An aralkyl group optionally substituted with a functional group comprising oxygen and/or nitrogen atoms,

r3, R4, R5 and R6 are independently selected from C₁-C₃₀Straight or branched alkyl radical, C₃-C₈Cycloalkyl radical, C₆-C₁₂Aryl radicals or C₇-C₁₂An aralkyl group optionally substituted with a functional group comprising oxygen and/or nitrogen atoms,

or any two of (R3, R4) or (R5, R6) together form a methylene chain- (CH)₂) p-, wherein p is an integer from 2 to 5.

According to a preferred embodiment, R1 ═ R2.

Advantageously, in formula (II), R1, R2 are each independently selected from H or C₁-C₆A straight or branched alkyl group. More advantageously, R1, R2 are each independently selected from H or C₁-C₃A straight or branched alkyl group. Even if the temperature is too highEven more advantageously, R1, R2 are each independently selected from H, methyl, ethyl.

Preferably, (R1, R2) is selected from: (-H, -H), (-CH)₃，-CH₃)、(-CH₂CH₃，-CH₂CH₃)。

According to a preferred embodiment, R3 ═ R4 ═ R5 ═ R6.

According to a preferred embodiment, R3, R4, R5, R6 are each independently selected from C₁-C₆A straight or branched alkyl group. More advantageously, R3, R4, R5, R6 are each independently selected from C₁-C₃A straight or branched alkyl group. Even more advantageously, R3, R4, R5, R6 are each independently selected from methyl, ethyl. Preferably, one of the following conditions is satisfied:

·R3＝R4＝R5＝R6＝-CH₃

·R3＝R4＝R5＝R6＝-CH₂-CH₃。

for example, the guanidinium cation may be selected from:

[X^-]any counter ion compatible with the application is meant.

According to the invention, [ X ]^-]May comprise one or more anions selected from: halide, perhalide, pseudohalide, sulfate, sulfite, sulfonate, sulfonimide, phosphate, phosphite, phosphonate, methide, carboxylate, hydroxycarboxylate, alcohol/phenoxide, oxazolate, carbonate, carbamate, thiophosphate, thiocarboxylate, thiocarbamate, thiocarbonate, xanthate, thiosulfonate, thiosulfate, nitrate, nitrite, perchlorate, halometalate, amino acid, and borate.

According to a preferred embodiment, [ X ]^-]Represents a counter ion selected from:

a) carboxylate radical Ra-COO^-；

b) Alcohol/phenolate RaRbHCO^-；

c) Hydroxycarboxylates HO-Rc-COO^-；

d) Selected from [ HSO₄]^-、[SO₄]^2-、[RaOSO₂O]^-Sulfate anions of (a);

e) selected from [ HSO₃]^-、[SO₃]^2-、[RaOSO₂]^-Sulfite anion of (a);

f) selected from [ RaSO₂O]^-The sulfonate anion of (a);

g) selected from [ (RaSO)₂)₂N]^-Sulfonimide group anion of (a);

h) is selected from [ H₂PO₄]^-、[HPO₄]^2-、[PO₄]^3-、[RaOPO₃]^2-、[(RaO)₂PO₂]Phosphate anion of (a);

i) is selected from [ H₂PO₃]^-、[HPO₃]^2-、[RaOPO₂]^2-、[(RaO)₂PO]^-Phosphite anions of (a);

j) selected from [ RaPO ]₃]^2-、[RaP(O)(ORa)O]^-Phosphonate anion of (a);

k) selected from [ (RaSO)₂)₃]^-Methide radical anion of (a);

l) a borate anion selected from bis (oxalato) borate, bis (malonato) borate;

m) an azolate anion selected from the group consisting of 3, 5-dinitro-1, 2, 4-triazolate, 4-nitro-1, 2, 3-triazolate, 2, 4-dinitroimidazoliate, 4, 5-dicyanoimidazolium, 4-nitroimidazolide, tetrazolium;

n) is selected from thiocarbonate (e.g., [ RaOCS₂]) Thiocarbamate (e.g., [ Ra ]₂NCS₂]^-) Thiocarboxylate (e.g., [ RaCS ]₂]^-) Thiophosphate (e.g., [ (RaO)₂PS₂]^-) Thiosulfonate (e.g., [ R ]aS(O)₂S]^-) And thiosulfate (e.g., [ RaOS (O))₂S]^-A sulfur-containing anion of (a); and

o) nitrate ([ NO ]₃]^-) Or nitrite ([ NO ]₂]^-) An anion;

wherein the content of the first and second substances,

ra is selected from alkyl and alkenyl groups comprising from 1 to 30 carbon atoms, aryl groups comprising from 6 to 30 carbon atoms, aralkyl groups comprising from 7 to 30 carbon atoms, optionally substituted with functional groups comprising oxygen and/or nitrogen atoms,

rb is selected from H, alkyl and alkenyl groups comprising from 1 to 30 carbon atoms, aryl groups comprising from 6 to 30 carbon atoms, aralkyl groups comprising from 7 to 30 carbon atoms, optionally substituted with functional groups comprising oxygen and/or nitrogen atoms,

rc is selected from alkylene and alkenylene groups containing 1 to 30 carbon atoms, arylene groups containing 6 to 30 carbon atoms, aralkylene groups containing 7 to 30 carbon atoms, optionally substituted with functional groups containing oxygen and/or nitrogen atoms.

According to one embodiment, [ X ]^-]Comprising one or more than one anion selected from the group consisting of: sulfate, sulfite, sulfonate, sulfonimide, phosphate, phosphite, phosphonate, methide, carboxylate, hydroxycarboxylate, alcohol/phenolate, oxazolate, carbonate, carbamate, thiophosphate, thiocarboxylate, thiocarbamate, thiocarbonate, xanthate, nitrate, nitrite, amino acid, and borate.

Advantageously, [ X ]^-]Comprising one or more than one anion selected from carboxylate, hydroxycarboxylate, alcohol/phenolate.

According to an even more preferred embodiment, [ X ] is^-]Represents a counter ion selected from:

a) carboxylate radical Ra-COO^-Wherein Ra is selected from the group consisting of alkyl and alkenyl groups comprising 1 to 30 carbon atoms, aryl groups comprising 6 to 30 carbon atoms, aralkyl groups comprising 7 to 30 carbon atoms, optionally oxygen-containing and-Or a functional group of a nitrogen atom;

b) alcohol/phenolate RaRbHCO^-Wherein Ra is selected from alkyl and alkenyl groups comprising 1 to 30 carbon atoms, aryl groups comprising 6 to 30 carbon atoms, aralkyl groups comprising 7 to 30 carbon atoms, Rb is selected from H, alkyl and alkenyl groups comprising 1 to 30 carbon atoms, aryl groups comprising 6 to 30 carbon atoms, aralkyl groups comprising 7 to 30 carbon atoms, optionally substituted with functional groups comprising oxygen and/or nitrogen atoms;

c) hydroxycarboxylates HO-Rc-COO^-Wherein Rc is selected from alkylene and alkenylene groups comprising 1 to 30 carbon atoms, arylene groups comprising 6 to 30 carbon atoms, aralkylene groups comprising 7 to 30 carbon atoms, optionally substituted with functional groups comprising oxygen and/or nitrogen atoms.

When [ X ]^-]Represents a carboxylate radical Ra-COO^-Advantageously Ra is chosen from alkyl and alkenyl groups comprising 6 to 15 carbon atoms, aryl groups comprising 6 to 15 carbon atoms, aralkyl groups comprising 7 to 20 carbon atoms. For example, [ X ]^-]Can represent 2-ethylhexanoate.

When [ X ]^-]Represents a hydroxycarboxylate radical HO-Rc-COO^-When it is advantageous [ X ]^-]Selected from alpha-hydroxy acids, beta-hydroxy acids, gamma-hydroxy acids, wherein Rc is selected from alkylene and alkenylene groups containing from 1 to 15 carbon atoms, arylene groups containing from 6 to 15 carbon atoms, aralkylene groups containing from 7 to 20 carbon atoms. For example, [ X ]^-]Lactate, also known as 2-hydroxypropionic acid, may be represented.

When [ X ]^-]Means alcohol/phenolate RaRbHCO^-When it is advantageous [ X ]^-]Selected from the group consisting of alkyl phenolates, amino phenolates, and mixtures thereof. More advantageously, [ X ]^-]Selected from alkylphenates containing from 7 to 20 carbon atoms, and aminophenolates in which the amine group is substituted by at least one alkyl group containing from 1 to 18 carbon atoms, preferably from 2 to 12 carbon atoms. For example, [ X ]^-]Can represent tert-pentylphenoxide, isooctylphenol and dioctylaminophenol.

The molecules of formula (I) may be prepared by any method known to the skilled person, such as for example m.g. bogdanov et al, z.naturforsch.2010,65b, 37-48; Y.Gao et al, Inorg.chem.2005,44, 1704-1712. An exemplary synthesis is disclosed in the experimental section.

For use in lubricant compositions, the guanidinium-based ionic liquid must preferably be soluble in the base oil, which is the major part of the lubricant composition. The compound is oil soluble when it is soluble at room temperature in a concentration of at least 0.01% by weight relative to the weight of the base oil.

To verify whether guanidinium-based ionic liquids are oil-soluble, a test is disclosed in the experimental section.

Advantageously, the weight percentage of guanidinium-based ionic liquid relative to the total weight of the lubricant composition is selected such that the BN provided by these compounds contributes at least 0.5 milligrams of potash per gram of lubricant, preferably at least 2 milligrams of potash per gram of lubricant, more preferably at least 3 milligrams of potash per gram of lubricant, still more preferably from 3 to 40 milligrams of potash per gram of lubricant to the total BN of the lubricant composition.

Advantageously, the weight percentage of guanidinium-based ionic liquid relative to the total weight of the lubricant composition is selected such that the alternative BN provided by the oil-soluble guanidinium-based ionic liquid is at least 3%, preferably at least 5%, preferably from 10% to 50%, of the BN of the lubricant composition.

In a preferred embodiment of the invention, the weight percentage of guanidinium-based ionic liquid relative to the total weight of the lubricant composition is from 0.05% to 15%, preferably from 0.1% to 12%, advantageously from 0.5% to 10%, even more preferably from 1% to 8%.

Lubricant composition

The present invention also relates to the use of the guanidinium-based ionic liquids disclosed above as additives in lubricating oil (or lubricant) compositions.

The invention also relates to a part of the lubricant composition for two-stroke and four-stroke marine engines comprising said additive.

Advantageously, the lubricant composition comprises, preferably consists essentially of:

30.0% to 99.95% of at least one base oil,

from 0.05% to 15.0% of at least one guanidinium-based ionic liquid as defined above,

the percentages are defined as the weight of the components relative to the total weight of the composition.

Even more advantageously, the lubricant composition comprises, preferably essentially consists of:

from 50.0% to 99.0% of at least one base oil,

from 1.0% to 10.0% of at least one guanidinium-based ionic liquid as defined above,

the percentages are defined as the weight of the components relative to the total weight of the composition.

According to another preferred embodiment, the present invention relates to a lubricant composition comprising, preferably consisting essentially of:

at least one base oil, at least one of which,

at least one guanidinium-based ionic liquid compound as defined above,

at least one detergent selected from neutral and overbased detergents having a total base number of from 20 to 450mg KOH/g according to ASTM D2896.

Advantageously, according to this embodiment, the lubricant composition comprises, preferably essentially consists of:

30.0% to 94.0% of at least one base oil,

from 0.05% to 15% of at least one guanidinium-based ionic liquid as defined above,

from 1% to 35% of at least one detergent chosen from neutral and overbased detergents having a total base number of from 20mg KOH/g to 450mg KOH/g according to ASTM D2896,

the percentages are defined as the weight of the components relative to the total weight of the composition.

Advantageously, the lubricant composition comprises, preferably consists essentially of:

from 50% to 90% of at least one base oil,

from 1% to 10% of at least one guanidinium-based ionic liquid as defined above,

from 5% to 35% of at least one detergent chosen from neutral and overbased detergents having a total base number of from 20 to 450 according to ASTM D2896,

the percentages are defined as the weight of the components relative to the total weight of the composition.

Base oil

Typically, the lubricating oil compositions according to the present invention comprise as a first component an oil of lubricating viscosity, also referred to as a "base oil". The base oil for use herein may be any presently known or later-discovered oil of lubricating viscosity for use in formulating lubricating oil compositions for any application, such as engine oils, marine cylinder oils, functional fluids such as hydraulic oils, gear oils, transmission fluids such as automatic transmission fluids, turbine lubricants, trunk piston engine oils, compressor lubricants, metal working lubricants, and other lubricating oil and grease compositions.

Advantageously, the lubricant composition according to the invention is a marine engine lubricating oil composition; preferably, it is a two-stroke marine engine lubricating oil composition.

Generally, the oils, also referred to as "base oils", used to formulate the lubricant compositions according to the invention may be mineral oils, synthetic oils or oils of vegetable origin, and mixtures thereof. The mineral or synthetic oils commonly used in applications belong to one of the classes defined in the API classification, summarized as follows:

group 1 mineral oils may be obtained by distilling selected naphthenic or paraffinic crude oils, and then purifying these distilled oils by methods such as solvent extraction, solvent dewaxing or catalytic dewaxing, hydrotreating or hydrogenation.

The group 2 and group 3 oils are obtained by more severe purification methods such as a combination of hydrotreating, hydrocracking, hydrogenation and catalytic dewaxing. Examples of synthetic base oils from 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.

The lubricant compositions of the present invention have a viscosity grade of SAE-20, SAE-30, SAE-40, SAE-50 or SAE-60, classified according to SAEJ 300.

20-grade oil has a kinematic viscosity of 5.6mm at 100 ℃²S to 9.3mm²Is between/s.

The kinematic viscosity of 30-grade oil at 100 ℃ is 9.3mm²S to 12.5mm²Is between/s.

The kinematic viscosity of 40-grade oil at 100 ℃ is 12.5mm²S to 16.3mm²Is between/s.

The kinematic viscosity of 50-grade oil at 100 ℃ is 16.3mm²S to 21.9mm²Is between/s.

The kinematic viscosity of 60-grade oil at 100 ℃ is 21.9mm²S to 26.1mm²Is between/s.

Preferably, the lubricant composition is a cylinder lubricant.

Advantageously, the amount of base oil in the lubricant composition of the present invention is from 30 to 99.95 wt.%, preferably from 40 to 99%, more preferably from 50 to 94% of the total weight of the lubricant composition.

Detergent composition

The above ionic liquids function as detergents in lubricant compositions. They have the advantage of allowing the use of smaller amounts of metal detergents. Thus, the ionic liquids used according to the invention make it possible to obtain compositions having the ability to neutralize low-sulphur fuel compositions and high-sulphur fuel compositions, but in both cases they avoid the formation of deposits. According to the present invention, the ionic liquid is preferably used in combination with at least one detergent, preferably at least one metal detergent, which does not belong to the class of ionic liquids.

Detergents for nonionic liquids are typically anionic compounds containing a long lipophilic hydrocarbon chain and a hydrophilic head, where the associated cation is typically a metal cation of an alkali or alkaline earth metal. The detergents are preferably selected from alkali metal or alkaline earth metal (particularly preferably calcium, magnesium, sodium or barium) salts of carboxylic acids, sulfonates, salicylates, naphthenates and phenates. These metal salts may contain metal in approximately stoichiometric amounts with the anionic groups of the detergent. In this case, they are referred to as non-overbased or "neutral" detergents, although they also contribute some alkalinity. These "neutral" detergents generally have a BN, as measured according to ASTM D2896, of less than 150mg KOH/g of detergent, or less than 100mg KOH/g of detergent, or less than 80mg KOH/g of detergent. So-called neutral detergents of this type may contribute in part to the BN of the lubricant composition. For example, neutral detergents such as carboxylates, sulfonates, salicylates, phenates, naphthenates of alkali metals and alkaline earth metals, e.g., calcium, sodium, magnesium, barium, are used. When the metal is in excess (greater than the stoichiometric amount relative to the anionic groups of the detergent) these are so-called overbased detergents. Their BN is high, above 150mg KOH/g detergent, typically from 200mg KOH/g detergent to 700mg KOH/g detergent, preferably from 250mg KOH/g detergent to 450mg KOH/g detergent. The excess metal providing high alkaline detergent properties is in the form of an insoluble metal salt in the oil, e.g. carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate. In overbased detergents, the metal of these insoluble salts may be the same or different from the metal of the oil soluble 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, which are kept suspended in the lubricant composition by the detergent in the form of soluble metal salts in the oil. These micelles may contain one or more than one type of insoluble metal salt, stabilized by one or more than one type of detergent. Overbased detergents comprising a single type of detergent-soluble metal salt are generally named according to the nature of the hydrophobic chain of the previous detergent. Thus, when the detergents are phenates, salicylates, sulfonates or naphthenates, respectively, they will be referred to as phenates, salicylates, sulfonates, naphthenates types. If the micelle contains several types of detergents, which differ from each other by the nature of their hydrophobic chains, such overbased detergents are referred to as mixed types. The overbased and neutral detergents may be selected from carboxylates, sulfonates, salicylates, naphthenates, phenates, and mixed detergents combining at least two of these types of detergents. Overbased and neutral detergents include compounds based on metals selected from calcium, magnesium, sodium or barium, preferably calcium or magnesium. Overbased detergents may be overbased by a metal-insoluble salt selected from the group consisting of alkali metal and alkaline earth metal carbonates, preferably calcium carbonate. The lubricant composition may comprise at least one overbased detergent and at least one neutral detergent as defined above.

Advantageously, the composition according to the invention comprises from 1% to 35% by weight of detergent, more advantageously from 5% to 35%, preferably from 8% to 35%, even more preferably from 10% to 35%, these percentages being percentages by weight of detergent of the nonionic liquid relative to the total weight of the lubricant composition.

Preferably, the composition according to the invention comprises from 1% to 35% by weight of detergent, more advantageously from 5% to 35%, preferably from 8% to 35%, even more preferably from 10% to 35%, these percentages being percentages by weight of neutral and overbased detergent relative to the total weight of the lubricant composition, which are preferably selected from neutral and overbased detergents having a total base number of from 20 to 450mg KOH/g according to ASTM D2896.

Advantageously, the weight percentages of the neutral and overbased detergents relative to the total weight of the lubricant are selected such that the BN provided by these neutral and overbased detergents contributes up to 40 milligrams of potash per gram of lubricant, preferably 5 to 40 milligrams of potash per gram of lubricant, more preferably 20 to 40 milligrams of potash per gram of lubricant, relative to the total BN of the lubricant.

Additive:

optionally, the base oil may be replaced, in whole or in part, by one or more thickening additives which function to increase both the hot and cold viscosities of the composition, or by additives which improve the Viscosity Index (VI).

The lubricant composition of the invention may comprise at least one optional additive, in particular selected from additives frequently used by the person skilled in the art.

In one embodiment, the lubricant composition further comprises an optional additive selected from an anti-wear additive, an oil soluble fatty amine, a polymer, a dispersant additive, an anti-foam additive, or mixtures thereof.

The polymer is typically of 2000 daltons to 50000 daltons (M)_n) A low molecular weight polymer of (2). The polymer is selected from the group consisting of PIB (2000 daltons), polyacrylates or polymethacrylates (30000 daltons), olefin copolymers, olefin and alpha-olefin copolymers, EPDM, polybutene, polyalphaolefins having a high molecular weight (viscosity at 100 ℃), and mixtures thereof>150) Hydrogenated or non-hydrogenated styrene-olefin copolymers.

The anti-wear additive protects the surface from rubbing by forming a protective film that adsorbs on the surface. The most commonly used are zinc dithiophosphates or ZnDTP. Also within this class are various phosphorus, sulfur, nitrogen, chlorine and boron compounds. The antiwear additives are of a wide variety, but the most widely used class is the sulfur-phosphorus additives, such as metal alkyl thiophosphates, particularly zinc alkyl thiophosphates, more particularly zinc dialkyl dithiophosphates or ZnDTP. Preferred compounds are of the formula Zn ((SP (S) (OR))₁)(OR₂))₂Wherein R is₁And R₂Is an alkyl group, preferably having 1 to 18 carbon atoms. ZnDTP is typically present at a level of about 0.1 to 2 wt.%, relative to the total weight of the lubricant composition. Amine phosphates, polysulfides, including sulfurized olefins, are also widely used anti-wear additives. Antiwear and extreme pressure additives of the nitrogen and sulfur type may also optionally be present in the lubricant composition, for example metal dithiocarbamates, particularly molybdenum dithiocarbamates. Glycerides are also anti-wear additives. Mention may be made of monooleates, dioleates and trioleates, monopalmitates and monomyristates. In one embodiment, the amount of antiwear additive isIs 0.01 to 6 wt.%, preferably 0.1 to 4 wt.%, relative to the total weight of the lubricant composition.

Dispersants are well known additives used in formulating lubricant compositions, particularly for applications in the marine field. Their main function is to keep in suspension the particles that are originally present or that appear during use of the lubricant in the engine. They prevent their agglomeration by using steric hindrance. They may also have a synergistic effect on neutralization. Dispersants used as lubricant additives typically contain polar groups associated with longer hydrocarbon chains, typically containing 50 to 400 carbon atoms. The polar group typically contains at least one nitrogen, oxygen, or phosphorus element. The succinic acid-derived compounds are particularly useful as dispersants in lubricant additives. In particular, succinimides obtained by condensation of succinic anhydride with amines, succinic esters obtained by condensation of succinic anhydride with alcohols or polyols are also used. These compounds can then be treated with various compounds including sulfur, oxygen, formaldehyde, carboxylic acids, and boron-containing compounds or zinc to produce, for example, borated succinimides or zinc-terminated succinimides. Mannich bases obtained by polycondensation of phenols substituted with alkyl groups, formaldehyde and primary or secondary amines are also compounds used as dispersants in lubricants. In one embodiment of the invention, the dispersant content may be greater than or equal to 0.1% by weight, preferably from 0.5% to 2% by weight, advantageously from 1% to 1.5% by weight, relative to the total weight of the lubricant composition. Dispersants from the PIB succinimide family, such as borated or zinc capped, may be used.

Other optional additives may be selected from defoamers, for example polar polymers such as polydimethylsiloxanes, polyacrylates. They may also be selected from antioxidants and/or rust inhibiting additives such as organometallic detergents or thiadiazoles. These additives are known to the person skilled in the art. These additives are typically present in a weight content of 0.1% to 5%, based on the total weight of the lubricant composition.

In one embodiment, the lubricant composition according to the present invention may further comprise an oil-soluble fatty amine.

The optional additives as defined above contained in the lubricant composition of the present invention may be introduced into the lubricant composition as separate additives, in particular they are added separately in the base oil. However, they may also be integrated in additive concentrates for marine lubricant compositions.

Process for preparing lubricant compositions, especially marine lubricant compositions

The present disclosure provides a method of preparing a lubricant composition as disclosed above, in particular a marine lubricant, comprising the step of mixing a base oil with a guanidinium-based ionic liquid component as defined above and optionally additives.

Characteristics of the Lubricant composition

The components disclosed above are formulated to provide a composition that advantageously has the following characteristics:

advantageously, the composition has a Total Base Number (TBN) higher than 5mg KOH/g according to ASTM D2896. Preferably, the composition has a Total Base Number (TBN) of from 5mg KOH/g to 100mg KOH/g. More advantageously, the composition has a Total Base Number (TBN) higher than 10mg KOH/g according to ASTM D2896. Preferably, the composition has a Total Base Number (TBN) value of from 10 to 100mg KOH/g, preferably from 15 to 75mg KOH/g, more preferably from 20 to 60mg KOH/g, even more preferably from 25 to 40mg KOH/g.

Preferably, the kinematic viscosity at 100 ℃ of the lubricant composition according to the invention is higher than or equal to 5.6mm²A number/s of less than or equal to 21.9mm²S, preferably greater than or equal to 12.5mm²A number/s of less than or equal to 21.9mm²S, more preferably greater than or equal to 14.3mm²A number/s of less than or equal to 21.9mm²S, advantageously 16.3mm²S to 21.9mm²(ii)/s, wherein the kinematic viscosity at 100 ℃ is evaluated according to ASTM D445.

Preferably, the lubricant composition according to the invention is a cylinder lubricant.

Advantageously, the lubricant composition is a cylinder lubricant for a two-stroke diesel marine engine and has a viscosity grade SAE-40 toSAE-60, corresponding to a kinematic viscosity of 16.3mm at 100 ℃²S to 21.9mm²/s。

Even more advantageously, the lubricant composition is a cylinder oil for a two-stroke diesel marine engine and has a viscosity grade SAE-50, corresponding to a kinematic viscosity of 16.3mm at 100 ℃²S to 21.9mm²/s。

Generally, a conventional formulation of a cylinder lubricant for a two-stroke marine diesel engine is of SAE 40 to SAE 60 grade, preferably SAE 50 (classified according to SAE J300), and comprises at least 50 wt% of a lubricating base oil of mineral and/or synthetic origin suitable for use in a marine engine, which is for example of the API class 1 category.

These viscosities can be achieved by blending the additive with a base oil, for example a base oil comprising a group 1 mineral base oil such as Neutral Solvent (e.g. 150NS, 500NS or 600NS) base oil and bright stock. Any other combination of mineral, synthetic or vegetable-derived base oils can be used, with mixtures of additives having viscosities comparable to the chosen SAE grade.

Applicants have found that cylinder lubricants can be formulated in which a substantial portion of the BN is provided by an oil-soluble guanidinium-based ionic liquid, while maintaining performance levels comparable to standard formulations having equivalent BN.

The properties discussed herein are in particular the ability to neutralize sulfuric acid, measured using the enthalpy test described in the examples below.

The cylinder lubricant according to the present invention is suitable for use in both high-sulfur and low-sulfur fuel oils due to the alternative BN provided by the oil-soluble guanidinium-based ionic liquid that does not form hard deposits causing wear of parts, optionally in combination with highly alkaline and neutral detergent.

Use for lubricating an engine

The present application also relates to the use of a guanidinium-based ionic liquid as defined above for lubricating an engine, preferably a marine engine. In particular, the present invention relates to the use of a guanidinium-based ionic liquid as defined above for lubricating two-stroke marine engines and four-stroke marine engines, more preferably two-stroke marine engines.

In particular, the guanidinium-based ionic liquids as defined above are suitable for use in lubricant compositions as cylinder oil or system oil for lubricating two-stroke engines and four-stroke marine engines, more preferably two-stroke engines.

The invention relates in particular to the use of a guanidinium-based ionic liquid as defined above as detergent additive in lubricant compositions, especially in marine lubricants.

In particular, the guanidinium-based ionic liquids of the present invention are used in lubricant compositions, especially in marine lubricants, to reduce and/or limit and/or prevent and/or retard the formation of deposits in the internal parts of the marine engine (maintenance cleaning effect) and/or reduce deposits already present in the internal parts of the marine engine (cleaning effect).

The invention also relates to the use of the above lubricant composition for lubricating two-stroke engines and four-stroke marine engines, more preferably two-stroke engines.

The present application also relates to a method of lubricating two-stroke marine engines and four-stroke marine engines, more preferably two-stroke marine engines, comprising applying to the marine engine a guanidinium-based ionic liquid or lubricant composition as disclosed above.

In particular, two-stroke engines are typically lubricated by applying a guanidinium-based ionic liquid or lubricant composition to the cylinder wall by a pulse lubrication system, or by injecting a guanidinium-based ionic liquid or lubricant composition onto a set of piston rings by an injector. It has been observed that the application of the guanidinium-based ionic liquid or lubricant composition according to the invention to the cylinder wall provides increased corrosion protection and improved engine cleanliness.

The invention also relates to a method for reducing and/or limiting and/or preventing and/or delaying the formation of deposits in or reducing deposits already present in internal parts of a combustion engine, in particular a marine engine, which comprises applying a guanidinium-based ionic liquid, in particular of the formula (I) or a lubricant composition as defined above.

Measurement of the difference in properties between a conventional reference lubricant and a lubricant according to the invention:

this measurement is characterized by a neutralization effectiveness index measured according to the enthalpy test method described precisely in the examples, in which the progress of the exothermic neutralization reaction is monitored by the increase in temperature observed when the lubricant containing basic sites is disposed in the presence of sulfuric acid.

Experimental part

I-materials and methods:

ionic liquid 1,1,3, 3-tetramethylguanidine 2-ethylhexanoate (IL1)：

The ionic liquid is prepared by the following method:

1151.8g (10mol, 1.00 eq.) of 1,1,3, 3-tetramethylguanidine were slowly added to 1.5L of methanol at 0 ℃ with stirring and cooling. When the solution was cooled to Room Temperature (RT), 1442.1g (10mol, 1.00 eq.) of 2-ethylhexanoic acid was added slowly over 4 hours using a piston pump with cooling. The temperature of the reaction mixture was always kept below 20 ℃. After the addition was complete, the reaction mixture was stirred at room temperature for a further 24 hours, and then the pH of the medium was adjusted to pH 9 by adding either 1,1,3, 3-tetramethylguanidine or 2-ethylhexanoic acid. To purify the resulting mixture, activated carbon (50g) was added and stirred at room temperature for a further 13 hours. Filtering the activated carbon with a glass filter, evaporating the solvent at 38 ℃ under reduced pressure, and obtaining a yellowish oil at 35 ℃ and 1X 10^-2Further drying was carried out in vacuo at mbar for 36 hours until the water content was below 0.1% as measured by karl fischer titration.

The base number of IL1 was 214mg KOH/g according to ASTM D2896.

To verify that the guanidinium-based ionic liquid is oil-soluble, the following tests were performed:

100mL of a lubricant composition comprising a guanidinium-based ionic liquid and a base oil was introduced into two reaction tubes.

One tube was kept at room temperature (between 15 and 25 ℃) and the other reaction tube was placed in an oven at 60 ℃.

The guanidinium-based ionic liquid is considered oil-soluble if the lubricant composition of both reaction tubes is clear after one month.

Base oil:

base oil 1: group I mineral oil designated 600NS having a viscosity of 120cSt at 40 ℃ measured according to ASTM D7279

A detergent:

dtg 1: phenolate in accordance with ASTM D2896, TBN 250mg KOH/g

Dtg 2: salicylate in accordance with ASTM D2896, TBN 250mg KOH/g

Additive:

antifoaming Agent (AF)

II-preparation of the Lubricant compositions:

the components listed in table 1 were mixed at 60 ℃. The percentages disclosed in table I correspond to weight percentages based on the total weight of the composition.

TABLE 1

Test method 1-neutralization kinetics：

This example describes an enthalpy test that can measure the neutralization effectiveness of a lubricant on sulfuric acid, quantified by dynamic monitoring of the kinetics or rate of reaction.

The principle is as follows: the acid-base neutralization reaction is generally exothermic and therefore the heat obtained by the reaction of sulfuric acid with the lubricant to be tested can be measured. The heat generation is monitored by the temperature change over time in a DEWAR-type adiabatic reactor. From these measurements, an index can be calculated that quantifies the effectiveness of the lubricant with the additive according to the invention compared with a lubricant as reference.

The index is calculated relative to a reference oil, the value of which is given as 100. The ratio between the neutralization reaction times of the reference sample (Sref) and the measurement sample (Smes) is as follows:

neutralization effectiveness index (Sref/Smes x 100)

These values of the neutralization reaction time are determined from the curve of the temperature rise over time, taken during the neutralization reaction, which is of the order of a few seconds. The time period S is equal to the difference t between the time at the end temperature of the reaction and the time at the initial temperature of the reaction_f-t_i. Time t at reaction initiation temperature_iCorresponding to the first temperature increase after the start of stirring. Time t at the final temperature of the reaction_fIs the time from which the temperature signal remains stable for a period of time greater than or equal to half the reaction time. The lubricant of the invention is therefore even more effective, since it results in a short neutralization time and therefore a high index.

The equipment used was: the geometry of the reactor and stirrer and the operating conditions are chosen such that they are in a chemical state in which the influence of diffusion constraints in the oil phase is negligible. In the configuration of the apparatus used, therefore, the height of the fluid must be equal to the internal diameter of the reactor and the agitator screw must be located at about 1/3 f of the height of the fluid. The apparatus consists of a cylindrical 250ml adiabatic reactor with an internal diameter of 48mm and an internal height of 150mm, and a stirring rod with a screw equipped with inclined blades and a diameter of 22 mm; the diameter of the blade is 0.3 to 0.5 times the diameter of the DEWAR, i.e. 9.6 to 24 mm. The position of the screw was fixed at a distance of 15mm from the bottom of the reactor. The stirring system is driven by a motor with variable speed from 10r.p.m. to 5000r.p.m. and a system for acquiring the variation of temperature with time.

The system is suitable for measuring reaction times of about 5 to 20 seconds and for measuring temperature increases of several tens of degrees starting from a temperature of about 20 to 35 c, preferably about 30 c. The location of the system for acquiring the temperature in the DEWAR is fixed. The stirring system is arranged to ensure that the reaction is carried out under a chemical state: in the configuration of the present experiment, the rotation speed was set to 2000r.p.m, and the position of the system was fixed. Furthermore, the chemical state of the reaction also depends on the height of the oil introduced into the DEWAR, which must be equal to the diameter of the latter and which, within the framework of the present experiment, corresponds to a mass of 70g of lubricant tested.

3.5g of 95% sulfuric acid concentrate and 70.0g of the lubricant to be tested are introduced into the reactor. After placing the stirring system in the reactor so that the acid and lubricant are thoroughly mixed in a reproducible manner in both tests, the collection system then begins stirring to monitor the reaction. 3.5g of acid were introduced into the reactor. 70.0g of lubricant was then introduced and heated to a temperature of about 30 ℃. The collection system is then activated and the agitation system is then adjusted to be in a chemical state.

Implementation of enthalpy test-calibration:

in order to calculate the effectiveness index of the lubricant according to the invention by the method described above, we chose as reference the neutralization reaction time measured on a cylinder oil of BN 25 for a two-stroke marine engine (measured by ASTM D-2896), which oil does not contain any detergent additive according to the invention. The oil is obtained from a mineral base oil and has a density at 15 ℃ of 880Kg/m³To 900Kg/m³In the meantime. A concentrate comprising calcium salicylate having BN equal to 250mg KOH/g, defoamer, calcium phenate having BN equal to 250mg KOH/g, is added to the base oil, wherein the amount of concentrate is the amount needed to obtain lubricant having BN 25mg KOH/g. The viscosity of the lubricant thus obtained at 100 ℃ was 12.5mm²S to 16.3mm²And s. The neutralization reaction time (referred to as Href) of this oil was around 100 seconds, and the neutralization effectiveness index was designated as 100.

Implementation of neutralization validation test

This example describes the effect of the additive according to the invention on a formulation of constant BN at 25mg KOH/g. Reference is made to BN 25mg KOH/g, without IL1 according to the invention and referred to in the preceding examples as Href.

Samples of BN 25mg KOH/g with additive to be tested were prepared starting from the additive-free lubricant referred to in the previous examples as Href. These samples were obtained by mixing in a beaker at a temperature of 60 ℃ with sufficient stirring to homogenize the lubricant mixture.

Table 2 below shows the values of the effectiveness index of various samples prepared in this way.

TABLE 2

	BN	Neutralization effectiveness index
			Href	25	100
C1	25	704

Test method 2-Heat resistance and Wash Performance of the Lubricant compositions:

the heat resistance of the lubricant composition according to the invention was evaluated by means of the ECBT test on aged oils.

Lubricant composition C₁The heat resistance of (c) is thus evaluated by the ECBT test on aged oils, via which the mass (in mg) of the deposit produced under the given conditions is determined. The smaller the mass, the better the heat resistance and, therefore, the better the cleanliness of the engine.

This test simulates the behavior of a lubricant composition when injected onto a hot workpiece of an engine, particularly the piston crown.

The test was carried out at a temperature of 310 ℃.

The test used an aluminum beaker in the form of a simulated piston. Placing the beakers in a glass container; the lubricant composition is maintained at a controlled temperature of about 60 ℃. The lubricant is placed in these containers, which are themselves equipped with metal brushes partially immersed in the lubricant. The brush was rotated at 1000rpm to produce a spray of lubricant onto the inner surface of the beaker. The beaker was maintained at a temperature of 310 ℃ by means of resistance heating regulated by a thermocouple. This spray of lubricant lasted 12 hours throughout the test.

The test is described in detail in The publication "Research and Development of Marine Lunents in ELF ANTAR France-The release of laboratory tests-in simulation field Performance" published in Ship Propulsion conference 2000 in Amsterdam, 3.29.30.2000.

This process makes it possible to simulate the formation of deposits in the piston ring assembly. The result is the weight of the deposit measured on the beaker in mg.

Lubricant C according to the invention₁Providing 190mg of deposit, while the comparative lubricant Href provides 360mg of deposit.

Thus, the ionic liquids defined in the present invention have a washing action, since they allow to reduce deposits in engine components.