CN113227336A

CN113227336A - Compounds comprising polyamine, carboxylic acid and boron functional groups and their use as lubricant additives

Info

Publication number: CN113227336A
Application number: CN201980085624.9A
Authority: CN
Inventors: 瓦莱丽·杜瓦杨
Original assignee: Total Marketing Services SA
Current assignee: TotalEnergies Marketing Services SA
Priority date: 2018-11-09
Filing date: 2019-11-07
Publication date: 2021-08-06
Also published as: WO2020094800A1; KR20210088606A; JP2022512950A; EP3877490A1; US20220010232A1; SG11202104795QA

Abstract

A product resulting from the reaction of at least: -an alkali or alkaline earth metal hydroxybenzoate compound, optionally hydrocarbyl-substituted, which is optionally overbased, -a boron compound, -an amine component selected from a di-aliphatic alkyl (alkenyl) polyalkylamine composition comprising one or more than one polyalkylamine of formula (I) or formula (II). A lubricant composition comprising the product. Use of the product as a lubricant for two-stroke marine engines and four-stroke marine engines, more preferably for two-stroke marine engines.

Description

Compounds comprising polyamine, carboxylic acid and boron functional groups and their use as lubricant additives

The present invention relates to the reaction product of an alkali or alkaline earth metal salt of an acidic organic compound, a boron compound and an amine component. The invention also relates to lubricant compositions comprising the reaction product, to a method for the production thereof and to the use thereof.

Background

One of the main functions of a lubricant is to reduce friction. However, in general, lubricating oils require other characteristics to be effective. 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 oils used in low speed two-stroke crosshead engines. On the one hand, the cylinder oil ensures the lubrication of the cylinder-piston combination and, on the other hand, the system oil ensures the lubrication of all moving parts except the cylinder-piston combination. 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 is then hydrolysed upon contact with the moisture present in the combustion gases and/or 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, which is typically accomplished by reaction with basic sites contained in the lubricant.

The neutralizing capacity of an oil is measured by its BN or base number, characterized by its basicity. The basicity is measured according to the standard ASTM D-2896 and expressed as the milliequivalent of potash per gram of oil (also known as "mg KOH/g" or "BN point". BN is a standard criterion, the basicity of the cylinder oil being able to be adjusted to the sulphur content of the fuel oil used, in order to be able to neutralize all the sulphur contained in the fuel and 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 required for the marine oil. This is why there are on the market marine oils with BN varying from 5mg KOH/g to 140mg KOH/g. This basicity is provided by the overbased detergent which is neutral and/or due to insoluble metal salts, particularly metal carbonates. Detergents which are predominantly anionic are metal soaps, for example of the salicylate, phenate, sulphonate, carboxylate type, etc., which form micelles in which particles of the insoluble metal salt remain suspended. Conventional neutral detergents inherently have a BN which is typically less than 150mg KOH/g detergent, whereas conventional overbased detergents inherently have a BN which is in the standard way from 150 to 700mg KOH/g detergent. Their mass percentages in the lubricant are determined according to the desired BN level.

In certain areas, particularly coastal areas, environmental concerns have raised requirements with respect to limiting the sulfur content of fuel oils used on board ships. Therefore, the MARPOL directive 6 issued by IMO (international maritime organization) (rule for preventing air pollution caused by ships) is in effect in 5 months in 2005. It sets a global upper limit of 4.5 wt/wt% for the sulfur content of heavy fuel oil and creates 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, in order to comply with regulations. The symbol w/w represents the weight percentage of the compound relative to the total weight of the fuel oil or lubricating composition in which the compound is contained.

Recently, MEPC (marine environmental protection committee) held a conference at 2008, month 4, approved a proposed amendment to the regulation MARPOL directive 6. These proposals are summarized in the following table. They proposed a solution in which the limit on the maximum sulphur content became more severe, with the global maximum sulphur content decreasing from 4.5 wt/wt% to 3.5 wt/wt% since 2012. SECA (sulfur emission control zone) will become ECA (emission control zone), further reducing the maximum allowable sulfur content from 1.5 wt/wt% to 1.0 wt/wt% since 2010 and adding new limits related to NOx and particulate content.

Ships sailing on seafares have used different heavy fuel oils according to local environmental restrictions, so that their operating costs are optimized. This will continue regardless of the final level of maximum allowable sulfur content of the fuel oil. Therefore, most container ships under construction today utilize fuel tanks, on the one hand "open sea" fuel oil with a high sulphur content and on the other hand "SECA" fuel oil with a sulphur content of less than or equal to 0.1 w/w%. Switching between these two types of fuel oils may require adaptation to the operating conditions of the engine, in particular the use of appropriate cylinder lubricants.

Currently, marine lubricants having a BN of 70 or less than 70 are used in the presence of fuel oils having a high sulphur content (3.5 wt/wt% and less than 3.5 wt/wt%). Marine lubricants having a BN of 40 or less than 40 are used in the presence of fuel oils having a low sulphur content (0.1 wt/wt%). In both cases, sufficient neutralization capacity is achieved when the concentration of basic sites required by the neutral and/or overbased detergents of the marine lubricating oil is reached, but the lubricant must be replaced each time the fuel oil type is changed.

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 (0.1 w/w) and fixed lubrication levels poses the risk of destabilization of micelles of significant excess basic sites (high BN) and unused overbased detergents, which contain insoluble metal salts. This instability leads to the formation of deposits of insoluble metal salts (e.g., calcium carbonate) primarily on the piston crown and may ultimately lead to the risk of excessive wear of the liner finish type. Furthermore, the use of low BN cylinder lubricants is not sufficient to achieve the total neutralisation capacity in the presence of fuel oils with high sulphur content, and therefore can cause a serious corrosion risk.

Therefore, optimization of cylinder lubrication for low speed two-stroke engines requires selection of a lubricant having a BN suitable for fuel oil and engine operating conditions. This optimization reduces the flexibility of engine operation and requires a high degree of expertise on the crew in determining the conditions under which it is necessary to switch from one type of lubricant to another.

In fact, the standards for the operating conditions of marine engines, in particular two-stroke marine engines, are becoming more and more stringent. Thus, the direct contact of the lubricant with the engine, and in particular with the high temperature parts of the engine (e.g. the segment-piston-pump assembly), should ensure not only a high temperature resistance to reduce or prevent the formation of deposits in the high temperature parts of the engine, but also a good neutralisation of the sulphuric acid produced during the combustion of the fuel.

There is a need for a marine detergent which can be used in the presence of high sulphur fuels as well as low sulphur fuels and which has good sulphuric acid neutralising ability whilst maintaining good heat resistance and therefore a low risk of deposit formation in high temperature parts of the engine.

There is also a need for a marine lubricant having BN, in particular having BN less than or equal to BN 70, which can be used in the presence of high sulphur fuels as well as low sulphur fuels, and which has good sulphuric acid neutralisation whilst maintaining good heat resistance, so that the risk of deposit formation in high temperature parts of the engine is low.

There is also a need to have lubricants for marine engines, including lubricants for two-stroke marine engines, which over time, especially during their use, have no or little risk of viscosity increase.

It is an object of the present invention to provide a lubricant additive that overcomes all or part of the above disadvantages. It is another object of the present invention to provide lubricant additives that are easily formulated in lubricant compositions.

It is a further object of the present invention to provide a lubricant composition that overcomes all or part of the above disadvantages.

It is another object of the present invention to provide lubricant compositions whose formulation is easy to achieve.

It is another object of the present invention to provide a method for lubricating a marine engine, in particular a two-stroke marine engine using both low and high sulphur fuels.

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

It is another object of the present invention to provide a method for reducing deposit formation in high temperature parts of marine engines, in particular two-stroke marine engines.

Document US2015/0299606 discloses metal-free detergents and antioxidant additives that can be used in lubricating oils comprising the reaction product of an acidic organic compound, a boron compound, a polyamine such as polyethyleneimine and optionally an alkoxylated amine and/or alkoxylated amide.

US 2005/172543 discloses a composition comprising the reaction product of an acidic organic compound, a boron compound and a basic organic compound, and its use as a detergent additive for lubricants and hydrocarbon fuels.

EP 3072951 discloses a detergent composition for use in a lubricating oil composition, the detergent comprising:

-overbased calcium sulfonates, and

-a metal-free low ash detergent comprising the reaction product of:

-an acidic organic compound, which is,

a boron compound, and

-an amine component comprising one or more than one amine.

US2016/0281014 discloses a lubricating oil detergent composition comprising an overbased calcium sulfonate and a low ash detergent which is metal-free and comprises the reaction product of an acidic organic compound such as an alkylated salicylic acid, a boron compound and an amine component.

Document US 2017/313955 discloses a marine engine lubricating composition comprising at least one lubricant base oil and at least one lubricant of formula R₁R₂N-(CH₂)₃-[NH(CH₂)₃]_n-NH₂Wherein R is₁And R₂Represents a saturated, linear or branched alkyl group containing at least 14 carbon atoms, and n represents 0, 1 or 2.

EP1783134, EP2316823 and EP 2322591 disclose the preparation of medium to high TBN detergent-dispersant additives for lubricating oil applications for internal combustion engines. These additives comprise alkylhydroxybenzoate salts of alkali metals and/or alkaline earth metals, optionally overbased.

WO 2017/021426 a1 discloses one or more than one fatty amine soluble in a lubricant composition for preventing and/or reducing metal loss from marine engine parts.

None of these documents discloses the reaction product of an alkali or alkaline earth metal salt of an acidic organic compound, a boron compound and an amine component as defined below.

Additives that combine the alkylated salicylic acid, boron compound, and amine components provide satisfactory corrosion and abrasion resistance. However, for some of these compounds, increasing the amount of additives in the lubricating oil increases the viscosity of the oil at which neutralization occurs, thereby reducing the lubricating effect. Other compounds have proven satisfactory in controlling oil viscosity increase, but are less satisfactory in stain removal performance. Other compounds have also proven satisfactory in terms of stain removal performance, but have not been satisfactory in terms of oil viscosity increase when neutralization occurs.

Thus, there is a need for lubricant additives that provide both effective corrosion and wear resistance, which provide satisfactory rheology in use to enhance lubrication efficacy, and which provide high detergency performance to avoid deposit formation.

The reaction products of the present invention advantageously provide improved detergency and oxidative stability. In addition, the reaction product provides excellent detergency and cleanliness to the lubricating oil without reducing oil rheology in use. They provide excellent corrosion and wear resistance.

Disclosure of Invention

The present invention relates to a reaction product of at least:

-an alkali or alkaline earth metal hydroxybenzoate compound, optionally substituted with hydrocarbyl groups, which is optionally overbased,

-a boron compound, wherein the boron compound is selected from the group consisting of,

-an amine component selected from:

a di-fatty alkyl (alkenyl) polyalkylamine composition comprising one or more than one polyalkylamine of formula (I) or formula (II):

wherein,

each R is, independently of the other R, a linear or branched alkyl or alkenyl moiety having from 4 to 30 carbon atoms,

n and z are independently of one another 0, 1, 2 or 3, and

when z is greater than 0, o and p are independently of one another 0, 1, 2 or 3,

wherein the polyalkylamine composition comprises at least 3 wt.% of a branched compound of formula (I) or formula (II), relative to the total weight of polyalkylamine compound (I) and compound (II) in the composition, the branched compound being represented by:

-in formula (I), at least one of n and z is greater than or equal to 1,

-in formula (II), n is greater than or equal to 1.

The invention also relates to lubricant compositions comprising such reaction products and base oils.

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

According to an advantageous embodiment, the hydrocarbyl-substituted alkali metal and/or alkaline earth metal hydroxybenzoate compound is selected from monoalkyl (en) substituted salicylates, dialkyl (en) substituted salicylates, carboxylic acid-functionalized calixarene salts, in particular salicylic acid calixarene salts, and mixtures thereof.

According to a more advantageous embodiment, the alkali metal and/or alkaline earth metal hydroxybenzoate compounds, optionally substituted with hydrocarbon groups, are selected from alkali metal and/or alkaline earth metal salts of compounds of formula (III):

wherein:

x represents a hydrocarbon radical having from 1 to 50 carbon atoms and X can contain one or more than one heteroatom,

a is an integer, a represents 0, 1 or 2.

According to an advantageous variant, in formula (III), a represents 1 or 2.

According to another variant, in formula (III), a represents 0.

According to an even more advantageous embodiment, the alkali metal and/or alkaline earth metal hydroxybenzoate compounds, optionally substituted with hydrocarbon groups, are selected from alkali metal and/or alkaline earth metal salts of compounds of formula (IIIA):

according to an advantageous variant, in formula (IIIA), a represents 1 or 2.

According to another variant, in formula (IIIA), a represents 0.

According to an advantageous embodiment, the boron compound is selected from boric acid, boric acid complexes, boron oxide, trialkylborates in which the alkyl groups independently comprise from 1 to 4 carbon atoms, C₁-C₁₂Alkyl boric acid, C₁-C₁₂Dialkylboric acid, C₆-C₁₂Aryl boronic acids, C₆-C₁₂Diarylboronic acids, C₇-C₁₂Aralkyl boronic acid, C₇-C₁₂Diaroboronic acids or products derived from these compounds in which the alkyl group is substituted by one or more than one alkoxy unit, advantageously the boron compound is boric acid.

According to an advantageous embodiment, the polyalkylamine composition comprises at least 4 wt/wt%, at least 5 wt/wt%, at least 6 wt/wt%, at least 7 wt/wt% or at least 7.5 wt/wt% of a branched compound of formula (I) or formula (II), expressed as:

-in formula (I), at least one of n or z is greater than or equal to 1,

-in formula (II), n is greater than or equal to 1.

According to an advantageous variant, the polyalkylamine composition comprises at least 5% by weight, relative to the total weight of compound (I) and compound (II), of compounds of formula (I) and formula (II) having a linear structure, with linear meaning that n is 0 in formula (I) and formula (II) and z is 0 in formula (I).

According to another advantageous variant, the polyalkylamine composition further comprises a derivative of a polyalkylamine of formula (I) or formula (II), said derivative being an optionally methylated alkoxylate.

According to an advantageous embodiment, the polyalkylamine composition further comprises a derivative of a polyalkylamine of formula (I) or formula (II), said derivative being methylated.

Detailed Description

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

Unless explicitly stated otherwise, the expression "comprised between X and Y" includes the border. The expression indicates that the target range includes X and Y values and all values from X to Y.

"alkyl" refers to a saturated hydrocarbon chain that may be straight, branched, or cyclic.

"alkenyl" means a hydrocarbon chain that may be straight, branched, or cyclic and that contains at least one unsaturated bond, 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 an aromatic hydrocarbon functional group containing an alkyl chain substituent, preferably monocyclic.

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

"overbased" refers to a class of metal salts or complexes. These materials are also referred to as "basic", "superbasic", "complex", "metal complex", "high metal containing salt", and the like. Overbased products are metal salts or complexes characterized by a metal content in excess of that present according to the stoichiometry of the metal and the particular acidic organic compound (e.g., carboxylic acid) reacted with the metal.

The term "total base number" or "TBN" refers to the number of milliequivalents of KOH required to neutralize 1 gram of product. Thus, a high TBN reflects a strongly overbased product, and therefore, a higher base stock for neutralizing acids. The TBN of the product may be determined according to ASTM Standard No. D2896 or equivalent procedures.

Alkali metal or alkaline earth metal hydroxybenzoates

The alkali and/or alkaline earth metal hydroxybenzoate compounds, optionally substituted with hydrocarbyl groups, are alkali and/or alkaline earth metal salts of molecules comprising at least one benzoate moiety, and the aromatic ring carries at least one hydroxyl functional group and may carry an alkyl, alkenyl, aryl or aralkyl substituent. When present, the hydrocarbyl substituent and the hydroxyl functionality may be in the ortho, meta, or para positions relative to the carboxylic acid functional group and relative to each other. The hydrocarbyl substituent may contain 1 to 50 carbon atoms.

The alkali metal and/or alkaline earth metal hydroxybenzoate compounds include salicylic acid (hydroxy-2-benzoate), hydroxy-3-benzoate, hydroxy-4-benzoate, preferably salicylate.

The alkali metal and/or alkaline earth metal hydrocarbyl-substituted hydroxybenzoate compounds include, but are not limited to, monoalkyl (ene) -substituted salicylates, dialkyl (ene) -substituted salicylates, carboxylic acid-functionalized calixarene salts, particularly calixarene salicylate salts, and mixtures thereof.

Calixarenes are macrocyclic rings composed of several phenol units, which can be substituted in the para position and linked by methylene bridges. The cyclic oligomer comprising a ring formed and bridged by a methylene group- (CH)₂) Or a chain of 4 to 16 phenols linked like a bridge.

According to one variant, the alkali metal and/or alkaline earth metal hydroxybenzoate compounds are selected from alkali metal salts.

Preferably, the alkali metal is lithium, sodium or potassium, more preferably potassium.

According to a second variant, the alkali metal and/or alkaline earth metal hydroxybenzoate compounds are chosen from alkaline earth metal salts.

Preferably, the alkaline earth metal is calcium, barium, magnesium or strontium, more preferably calcium.

According to a first embodiment, the alkali metal and/or alkaline earth metal hydroxybenzoate compounds, optionally substituted with hydrocarbon groups, are selected from alkali metal and/or alkaline earth metal salts of compounds of formula (III):

wherein:

a is an integer, a represents 0, 1 or 2.

According to a first variant, a is 0.

According to another variant, a is 1 or 2.

When a is 2, the two hydrocarbyl groups may be the same or different.

Advantageously, a is 1.

Hydrocarbyl in formula (III) refers to alkyl, alkenyl, aryl, and aralkyl groups that may contain one or more than one heteroatom.

The hydrocarbyl group in formula (III) may be linear, branched or cyclic.

The heteroatom in X may be selected from O, N, S. For example, they may exist in one or more than one of the following forms: -OH, -NH₂or-SH substituents, or-O-, -NH-, -N ═ or-S-bridges.

Preferably, X does not comprise a heteroatom.

Preferably, X is selected from alkyl and alkenyl.

Advantageously, X represents an alkyl or alkenyl group having from 1 to 50 carbon atoms.

Preferably, X is selected from linear and branched alkyl and alkenyl groups.

Even more advantageously, X represents a linear alkyl group having from 1 to 50 carbon atoms.

Preferably, X comprises from 12 to 40 carbon atoms, even more preferably X comprises from 18 to 30 carbon atoms.

Advantageously, in formula (III), -OH and-COOH are in ortho position to the benzene ring, and the molecule of formula (III) is salicylic acid or a salicylic acid derivative of formula (IIIA):

wherein X and a have the same definitions as formula (III) and the most advantageous variants of these parameters are the same as formula (III).

Sodium salicylate is commercially available (CAS number: 54-21-7).

The alkali metal alkylhydroxybenzoate compounds may in particular be prepared by: neutralizing at least one alkylphenol with an alkali metal base to obtain an alkali metal alkylphenate, and then carboxylating the alkali metal alkylphenate with carbon dioxide.

The alkaline earth metal alkylhydroxybenzoate compound may then be obtained by acidifying an alkali metal alkylhydroxybenzoate to form an alkylhydroxybenzoic acid and further reacting the alkylhydroxybenzoic acid with a molar excess of alkaline earth metal base.

The preparation of alkali metal and/or alkaline earth metal alkylhydroxybenzoate compounds is disclosed in particular in EP 2316823.

According to a variant, in the reaction with the boron compound and the amine component, an alkali metal and/or alkaline earth metal hydroxybenzoate compound, optionally substituted with hydrocarbyl groups, may be used as a mixture with the alkylphenol.

According to this variant, the mixture may comprise up to 50 mole% of alkylphenol, based on the total moles of alkylphenol and alkali metal and/or alkaline earth metal hydroxybenzoate compound. Such mixtures and their preparation are disclosed, for example, in EP1783134 and EP 2316823.

Boron compound

The boron compound is selected from boric acid, alkyl boric acid, boric acid ester and alkyl boric acid ester, boron oxide, boric acid complex.

For example, the boron compound may be selected from boric acid, boric oxide, boric acid complexes, trialkylborates wherein the alkyl groups independently contain 1 to 4 carbon atoms, C₁-C₁₂Alkyl boric acid, C₁-C₁₂Dialkylboric acid, C₆-C₁₂Aryl boronic acids, C₆-C₁₂Diarylboronic acids, C₇-C₁₂Aralkyl boronic acid, C₇-C₁₂Diaralkyl boronic acids or products derived from these materials in which the alkyl group is substituted by one or more than one alkoxy unit.

The alkyl and alkoxy groups may be linear, branched or cyclic.

Boronic acid complexes are complexes with molecules containing one or more than one alcohol functionality.

Advantageously, the boron compound is boric acid.

Amine component

The amine component is a mixture or composition comprising one or more than one di-fatty alkyl (alkenyl) polyalkylamine (referred to as "polyalkylamine") of formula (I) or formula (II):

wherein,

n and z are independently of one another 0, 1, 2 or 3, and

wherein the polyalkylamine mixture or composition comprises at least 3 wt.% of a branched compound of formula (I) or formula (II), relative to the total weight of polyalkylamine compound (I) and compound (II) in the composition, the branched compound being represented by:

-in formula (I), at least one of n and z is greater than or equal to 1,

-in formula (II), n is greater than or equal to 1.

In one embodiment, the polyalkylamine mixture or composition comprises at least 4 weight percent (wt/wt%), suitably at least 5 wt/wt%, suitably at least 6 wt/wt%, suitably greater than 7 wt/wt%, suitably greater than 7.5 wt/wt%, suitably greater than 10 wt/wt%, suitably greater than 20 wt/wt% of the branched compound relative to the total weight of the compound of formula (I) or formula (II), wherein at least one of n or z is greater than or equal to 1. For the product of formula (I), this means that at least one of n or z must be greater than or equal to 1. For the product of formula (II), this means that n must be greater than or equal to 1.

It is noted that whenever n, o, p or z is 0, the hydrogen indicated at the chain end is covalently bound to the corresponding secondary nitrogen.

Preferably, the amine mixture or composition comprises a di-aliphatic alkyl (alkenyl) polyalkylamine compound of formula (I) or formula (II) wherein n, o, p and z are 1 or 2 when not 0, more preferably n, o, p and z are 1 when not 0.

According to an advantageous embodiment, the amine mixture or composition consists essentially of a di-aliphatic alkyl (alkenyl) polyalkylamine compound of formula (I) or formula (II), wherein n, o, p and z are independently 0, 1 or 2, more preferably n, o, p and z are independently 0 or 1.

According to another preferred embodiment, the amine mixture or composition consists essentially of a di-aliphatic alkyl (alkenyl) polyalkylamine compound of formula (I) or formula (II) and derivatives thereof, wherein n, o, p and z are independently 0, 1 or 2, more preferably n, o, p and z are independently 0 or 1.

Derivatives of compound (I) and compound (II) are described below.

Each R is independent of the other R and is preferably selected from linear and branched alkyl and alkenyl groups. Even more preferably, each R is independently of the other R and is selected from the group consisting of straight chain alkyl and straight chain alkenyl.

Each R is independently of the other R, preferably selected from alkyl and alkenyl groups comprising from 4 to 30 carbon atoms, even more preferably linear or branched alkyl and alkenyl groups having from 8 to 22 carbon atoms, preferably having from 14 to 18 carbon atoms, more preferably having from 16 to 18 carbon atoms.

According to one preferred variant, each R is selected, independently of the other R, from linear alkyl and alkenyl groups having from 14 to 22 carbon atoms, preferably from 14 to 18 carbon atoms, more preferably from 16 to 18 carbon atoms.

Although the groups R may be different, in one embodiment they are the same because the production of such materials is more economical. Regardless of whether the R groups are the same or not, they are independently preferably derived from chemical raw materials or natural sources, such as natural fats and oils. In particular, if a natural source is used, it is meant that each R may be a mixture of alkyl and alkenyl groups having different chain lengths. Suitable R groups are derived from animal and vegetable fats and oils, such as tallow, rapeseed, sunflower, soybean, linseed, olive, palm, castor, wood, corn, pumpkin, grape, jojoba, sesame, walnut, hazelnut, almond, shea, macadamia, cottonseed, alfalfa, rye, safflower, peanut, coconut, and copra oils, and mixtures thereof.

Preferably, the R groups are derived from tallow, coconut and palm oil. Preferably, the R groups represent aliphatic groups obtained from tallow oil and form the corresponding mixtures of fatty alkyl (alkenyl) polyamines.

The R group is derived from animal and vegetable fats and oils, and means that the R group corresponds to a mixture of fatty chains obtained by reducing fatty acids obtained from animal and vegetable fats and oils.

According to some variants, it may be beneficial to use hydrogenated R groups. However, for some feedstocks, a significant amount of unsaturation may remain even after hydrogenation. Suitably, fully hydrogenated tallow groups are used as R groups and the corresponding mixtures of di-aliphatic alkyl (alkenyl) polyalkylamines are formed. Alternatively, the R groups of the feedstock are unsaturated, wherein the unsaturated R groups may be fully or partially hydrogenated in the process of preparing the claimed di-fatty alkyl (alkenyl) polyalkylamine, which is a mixture of di-fatty alkyl polyalkyleneamines and di-fatty alkenyl polyalkyleneamines.

Alternatively, the R group of the starting material is unsaturated. Likewise, compounds of formula (I) and formula (II) wherein one R is fully saturated and the other R is unsaturated are amine products that may be used according to the present invention.

Thus, as used herein, "di-fatty alkyl (alkenyl) polyalkylamine" refers to di-fatty alkyl polyalkylalkylamines, di-fatty alkenyl polyalkylamines, fatty alkyl fatty alkenyl polyalkylamines, and mixtures thereof.

Derivatives of the di-fatty alkyl (alkenyl) polyalkylamine compositions of the present invention include products in which one or more than one NH moiety of the di-alkyl polyalkylamine of the present invention is methylated, alkoxylated or methylated and alkoxylated. Such products have been found to have desirable solubility, particularly in lubricating oils. The alkoxylated derivatives are suitably butoxylated, propoxylated and/or ethoxylated. If two or more different alkoxylating agents are used, they may be used in any order, for example EO-PO-EO, and the various alkoxy units may beHave a block nature and/or exist in a random manner. Suitably, primary-NH₂The groups are alkoxylated in a conventional manner with one or more than one alkylene oxide to form-NH-AO-H groups, wherein AO represents one or more than one alkylene-oxy unit. The resulting-NH-AO-H group may be further alkoxylated to form-N (AO-H)₂A group. Especially when large amounts of alkylene oxide are used (i.e. when more than 8 AO molecules per polyalkylamine molecule), one or more than one secondary amine functional group, if present, is usually also alkoxylated.

In one embodiment, all primary and secondary amine functional groups of the dialkylpolyamine are alkoxylated. In another embodiment, the di-aliphatic alkyl (alkenyl) polyalkylamine is derivatized by methylating one or more N-H functional groups in a conventional manner, for example, by reaction with formic acid and formaldehyde. In another embodiment, one or more than one O — H functional group of the alkoxylated di-aliphatic alkyl (alkenyl) polyalkylamine is methylated in a conventional manner.

Preference is given to compositions comprising mixtures of polyalkylamines of the formula (I). However, compositions comprising mixtures of polyalkylamines of formula (II) may be preferred because compositions comprising mixtures of polyalkylamines of formula (II) may be more economically prepared in particular cases. If appropriate, compositions comprising mixtures of polyalkylamines of the formula (I) and of the formula (II) are used.

The branched polyalkylamines can be produced using any conventional process steps, which are performed in the order and manner to obtain the disclosed mixtures.

A suitable process for their production is described in the experimental part of WO2017/148816, starting from diamines and involving two or more cycles, preferably two cycles for economic reasons, each comprising a cyanoethylation step and a hydrogenation step. This process is referred to as the two-step process hereinafter. However, in an alternative process, one equivalent of the dialkyl (alkenyl) -diamine is reacted in one step with two or more equivalents of acrylonitrile and then hydrogenated. In this case, optional additional cycles involving cyanoethylation and hydrogenation steps may be performed. Such a one-step process may be beneficial because it requires fewer reaction steps.

To increase branching in the two-cycle process, an acidic catalyst, such as HCl or acetic acid, is used. Also increasing the reaction temperature during cyanoethylation will result in increased branching during the process. In one embodiment of the multi-cycle process, the temperature of the later cyanoethylation step is higher than the temperature of the earlier cyanoethylation step to obtain the product with the desired branching. In one embodiment, more than 1 mole of acrylonitrile is used per mole of starting polyamine, which has been found to also increase branching of the resulting product to the desired level.

The temperature in each cyanoethylation step is suitably chosen to be from 70 ℃ to 125 ℃. In one embodiment, the reaction is carried out at a temperature of up to 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃ for economic reasons.

In order to maintain a homogeneous reaction mixture, a solvent is suitably used. Suitable solvents include C_1-4Alcohol and C_2-4A diol. Ethanol may be the solvent of choice for ease of handling. Unexpectedly, it was found that C_1-4Alcohol and C_2-4The glycol is not merely a solvent. They have also proven to be co-catalytically active in the cyanoethylation step.

The amount of solvent may vary within wide limits. For economic purposes, the amount is usually kept at a minimum. The amount of solvent, particularly in the cyanoethylation step, is suitably less than 50%, 40%, 30% or 25% by weight of the liquid reaction mixture. The amount of solvent, particularly in the cyanoethylation step, is suitably greater than 0.1%, 0.5%, 1%, 5% or 10% by weight of the liquid reaction mixture.

The amines as defined above may be prepared by the protocol disclosed in WO 2017/148816. They are commercially available from Akzo, especially as

The 2HBT article is commercially available as a reference.

Reaction product

The reaction of the alkali or alkaline earth metal hydroxybenzoate compound, optionally hydrocarbyl-substituted, boron compound and amine component may be carried out in any suitable manner.

For example, the reaction can be carried out by first combining the alkali or alkaline earth metal hydroxybenzoate (optionally hydrocarbyl-substituted) compound and boron compound in the desired proportions and in the presence of a suitable solvent.

Suitable solvents are, for example, naphtha and polar solvents, for example water and alcohols, such as methanol, ethanol, propanol, butanol.

Advantageously, the hydroxybenzoic acid compound substituted with a hydrocarbyl group is reacted: the molar ratio of boron compound is from about 15: 1 to about 1: 5, preferably from 5: 1 to 1: 2, more preferably from 4: 1 to 1: 1. The most preferred ratio is about 2: 1.

After a sufficient time, the boron compound dissolves. The amine component is then slowly added to the mixture to neutralize and form the desired reaction product.

Advantageously, the amine component is added in an amount such that the hydrocarbyl-substituted hydroxybenzoic acid compound: the molar ratio of amine components is about 15: 1 to about 1: 5, preferably 5: 1 to 1: 2, more preferably 4: 1 to 1: 1. the most preferred ratio is about 2: 1.

Advantageously, the amine component is added in such an amount that the boron compound: the molar ratio of amine components is from about 10: 1 to 1: 10, preferably from 5: 1 to 1: 5, even more preferably from 2: 1 to 1: 2. the most preferred ratio is about 1: 1.

The reaction may be advantageously carried out by maintaining the reaction medium at a temperature of from about 20 ℃ to about 100 ℃, for example from about 50 ℃ to about 75 ℃, typically for a period of from about 0.5 hour to 5 hours, more preferably from 1 hour to 4 hours.

After completion of the reaction, the solvent may be evaporated from the reaction medium, preferably by distillation under vacuum. Alternatively, the solvent may be kept mixed with the reaction product, which is used as it is.

Diluent oil may be added as needed to control viscosity, particularly during solvent removal by distillation.

The product resulting from this reaction will comprise a complex mixture of compounds. There is no need to separate the reaction product mixture to separate one or more specific components. Thus, the reaction product mixture may be used as such in the lubricating oil composition of the present invention.

In addition to the alkali or alkaline earth metal hydroxybenzoate compound (optionally hydrocarbyl-substituted), boron compound and amine component, the reaction may be carried out with other reactants.

However, according to the present invention, preferably, the reaction product results from the reaction of a mixture of reactants (excluding solvent) consisting essentially of at least one alkali or alkaline earth metal hydroxybenzoate compound (optionally hydrocarbyl-substituted), at least one boron compound and at least one amine component.

Even more preferably, the reaction product results from the reaction of a mixture of reactants (excluding solvent) consisting of at least one alkali or alkaline earth metal hydroxybenzoate compound (optionally hydrocarbyl-substituted), at least one boron compound and at least one amine component.

According to a second preferred embodiment, the reaction product results from the reaction of a mixture of reactants (excluding solvent) consisting essentially of at least one boron compound, at least one amine component, and a mixture comprising an alkali metal and/or alkaline earth metal hydroxybenzoate compound, optionally hydrocarbyl-substituted, and an alkylphenol.

Even more preferably, the reaction product results from the reaction of a mixture of reactants (excluding solvent) consisting of at least one boron compound, at least one amine component, and a mixture comprising an alkali metal and/or alkaline earth metal hydroxybenzoate compound, optionally hydrocarbyl-substituted, and an alkylphenol.

According to this second preferred embodiment, the mixture may comprise up to 50 mole% of the alkylphenol, based on the total moles of the mixture of the alkylphenol and the alkali metal and/or alkaline earth metal hydroxybenzoate compound.

Lubricant composition

The present invention also relates to the use of the reaction product as already disclosed above as an additive in a lubricating oil (or lubricant) composition. Also relates to lubricant compositions comprising such additives.

Advantageously, the lubricant composition comprises:

60% to 99.9% of at least one base oil,

from 0.1% to 20% of at least one reaction product of at least one alkali metal or alkaline earth metal hydroxybenzoate compound (optionally hydrocarbyl-substituted) as defined above, a boron compound and an amine component,

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

Even more advantageously, the lubricant composition comprises:

60% to 99.9% of at least one base oil,

from 0.1% to 15% of at least one reaction product of at least one alkali metal or alkaline earth metal hydroxybenzoate compound (optionally hydrocarbyl-substituted) as defined above, a boron compound and an amine component,

Base oil

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

Advantageously, the lubricant compositions according to the invention are marine engine lubricating oil compositions, preferably they are two-stroke marine engine lubricating oil compositions.

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

group 1 of these mineral oils 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 dewaxing or catalytic dewaxing, hydrotreating or hydrogenation.

The oils of groups 2 and 3 are obtained by more severe purification methods, such as hydrotreating, hydrocracking, a combination of hydrogenation and catalytic dewaxing. Examples of the synthetic base oils of groups 4 and 5 include polyalphaolefins, polybutenes, polyisobutylenes, alkylbenzenes.

These base oils may be used alone or as 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.

The kinematic viscosity of the 20-grade oil at 100 ℃ is 5.6mm²S to 9.3mm²/s。

The kinematic viscosity of 30-grade oil at 100 ℃ is 9.3mm²S to 12.5mm²/s。

The kinematic viscosity of 40-grade oil at 100 ℃ is 12.5mm²S to 16.3mm²/s。

The kinematic viscosity of 50-grade oil at 100 ℃ is 16.3mm²S to 21.9mm²/s。

The kinematic viscosity of 60-grade oil at 100 ℃ is 21.9mm²S to 26.1mm²/s。

Preferably, the lubricant composition according to the first and second aspects is a cylinder lubricant.

The viscosity grade of the cylinder oil for two-stroke marine diesel engines is from SAE-40 to SAE-60, with SAE-50 generally preferred, etcThe kinematic viscosity at 100 ℃ is 16.3mm²S to 21.9mm²And s. In general, conventional formulations of cylinder lubricants for two-stroke marine diesel engines have a grade SAE 40 to SAE 60, preferably SAE 50 (classified according to SAE J300) and comprise at least 50 wt.% of a lubricating base oil of mineral and/or synthetic origin, which is suitable for use in marine engines, for example belonging to the category API group 1. Their Viscosity Index (VI) is from 80 to 120; their sulfur content is greater than 0.03% and their saturates content is less than 90%.

The viscosity grade of the system oil for a two-stroke marine diesel engine is from SAE-20 to SAE-40, with SAE-30 generally preferred, equivalent to a kinematic viscosity at 100 ℃ of 9.3mm²S to 12.5mm²/s。

These viscosities may be achieved by mixing the additives with base oils, for example comprising group 1 mineral base oils, such as Neutral Solvent (e.g. 150NS, 500NS or 600NS) base oils and bright stock. Any other combination of mineral, synthetic or vegetable-derived base oils can be used, which as a mixture with additives has a viscosity matching the selected SAE grade.

The amount of base oil in the lubricant composition is from 30 to 90 wt.%, preferably from 40 to 90 wt.%, more preferably from 50 to 90 wt.%, relative to the total weight of the lubricant composition of the present invention.

In one embodiment of the invention, the lubricant composition has a Base Number (BN), determined according to the standard ASTM D-2896, of at most 50mg, preferably at most 40mg, advantageously at most 30 mg of potassium hydroxide per gram of lubricant composition, in particular from 10 mg to 40mg, preferably from 15 mg to 40mg of potassium hydroxide per gram of lubricant composition.

In another embodiment of the invention, the lubricant composition has a BN, determined according to standard ASTM D-2896, of at least 50, preferably at least 60, more preferably at least 70, advantageously from 70 to 100.

Additive:

optionally, the base oil may be replaced, in whole or in part, by one or more thickening additives which act to increase the cold and hot viscosity 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 chosen from those frequently used by the person skilled in the art.

In one embodiment, the lubricant composition further comprises an optional additive selected from a neutral detergent, an overbased detergent, an antiwear additive, an oil soluble fatty amine, a polymer, a dispersant additive, an antifoam additive, or mixtures thereof.

Detergents are generally 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 carboxylates, sulfonates, salicylates, naphthenates and phenates of alkali metals or alkaline earth metals, particularly preferably calcium, magnesium, sodium or barium. These metal salts may contain the metal in approximately stoichiometric amounts relative to the anionic group of the detergent. In this case, they are referred to as non-overbased or "neutral" detergents, although they may also have some basicity. The BN of these "neutral" detergents, as measured by ASTM D2896, is typically less than 150mg KOH/g detergent, or less than 100mg KOH/g detergent, or less than 80mg KOH/g detergent. So-called neutral detergents of this type may in part provide BN to the lubricating composition. For example, neutral detergents such as carboxylates, sulfonates, salicylates, phenates, naphthenates of alkali and alkaline earth metals (e.g., calcium, sodium, magnesium, barium) are used. When the metal is in excess (greater than stoichiometric amounts relative to the anionic group of the detergent), then these detergents are referred to as overbased detergents. Their BN is high, above 150mg KOH/g detergent, typically from 200 to 700mg KOH/g detergent, preferably from 250 to 450mg KOH/g detergent. The excess metal to provide overbased detergent properties is present in the form of an oil-insoluble metal salt, for example a carbonate, hydroxide, oxalate, acetate, glutamate, preferably a carbonate. In an overbased detergent, the metal of the insoluble salts may be the same as or different from the metal of the oil-soluble detergent. They are preferably selected from calcium, magnesium, sodium or barium. Thus, an overbased detergent is in the form of a micelle composed of an insoluble metal salt held in suspension in a lubricating composition by the detergent in the form of an oil soluble metal salt. These micelles may comprise one or more than one type of insoluble metal salt, which is stabilized by one or more than one type of detergent. Overbased detergents comprising a single type of metal salt soluble in the detergent are generally named according to the nature of the hydrophobic chain of the latter detergent. Thus, when the detergents are phenate, salicylate, sulfonate or naphthenate salts, respectively, they will be referred to as phenate, salicylate, sulfonate, naphthenate. If the micelle comprises several types of detergents, which differ from each other in their hydrophobic chain properties, the overbased detergent is referred to as a hybrid detergent. The overbased and neutral detergents may be selected from carboxylates, sulfonates, salicylates, naphthenates, phenates, and hybrid detergents combining at least two such 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 obtained by an insoluble metal salt selected from carbonates of alkali and alkaline earth metals, preferably calcium carbonate. The lubricating composition may comprise at least one overbased detergent as defined above and at least a neutral detergent.

The polymers are generally of 2000 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, having a high molecular weight (viscosity at 100 ℃ C., viscosity)>150) Poly-alpha-olefin, hydrogenated or non-hydrogenated styrene-olefin copolymer.

Antiwear additives protect surfaces from friction by forming a protective film that adsorbs onto these surfaces. The most commonly used are zinc dithiophosphates or DTPZn. Also within this class are various phosphorus compounds, sulfur compounds, nitrogen compounds, chlorine compounds, and boron compounds. There are a wide variety of antiwear additives, but the most widely usedGeneric classes are thiophosphorus additives, such as metal alkylthiophosphates, especially zinc alkylthiophosphates, more specifically zinc dialkyldithiophosphates or DTPZn. 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. DTPZn is typically present at a level of about 0.1 to 2 wt.%, relative to the total weight of the lubricating composition. Amine phosphates, polysulfides (including sulfurized olefins) are also widely used antiwear additives. Optionally the lubricating composition further comprises an antiwear extreme pressure additive of the nitrogen-sulphur type, for example a metal dithiocarbamate, in particular molybdenum dithiocarbamate. Glycerides are also antiwear additives. Mention may be made of monooleates, dioleates and trioleates, monopalmitates and monomyristates. In one embodiment, the antiwear additive is present in an amount ranging from 0.01 wt% to 6 wt%, preferably from 0.1 wt% to 4 wt%, relative to the total weight of the lubricating composition.

Dispersants are well known additives used in the formulation of lubricating compositions, particularly for use in the marine field. Their main role is to keep the particles initially present or present in the lubricant in suspension during use of the lubricant in the engine. They prevent their agglomeration by acting on steric hindrance. They may also act synergistically on 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 comprises at least one nitrogen, oxygen or phosphorus element. The succinic acid-derived compounds are particularly useful as dispersants in lubricant additives. Also used are in particular succinimides obtained by condensation of succinic anhydride and an amine, succinic esters obtained by condensation of succinic anhydride and an alcohol or polyol. 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 prepared by the polycondensation of alkyl-substituted phenols, formaldehyde and primary or secondary amines are also compounds useful 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 lubricating composition. Dispersants from the PIB succinimide family, such as borated or zinc-capped PIB succinimides, can be used.

Other optional additives may be selected from defoamers, for example polar polymers, for example 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 content of 0.1 wt% to 5 wt%, based on the total weight of the lubricating composition.

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

The fatty amine has the general formula (VI):

R’₁-[(NR’₂)-R’₃]_n-NR’₄R’₅， (VI)

wherein,

·R’₁denotes a saturated or unsaturated, linear or branched hydrocarbon radical comprising at least 12 carbon atoms, and optionally at least one heteroatom chosen from nitrogen, sulphur or oxygen,

·R’₂、R’₄and R'₅Independently represents a hydrogen atom or a saturated or unsaturated, linear or branched hydrocarbon radical, optionally comprising at least one heteroatom chosen from nitrogen, sulphur or oxygen,

·R’₃denotes a saturated or unsaturated, linear or branched hydrocarbon radical comprising at least 1 carbon atom, and optionally at least one heteroatom chosen from nitrogen, sulphur or oxygen (preferably oxygen),

n is an integer, n being equal to or greater than 1, preferably from 1 to 10, more preferably from 1 to 6, in particular selected from 1, 2 or 3.

Preferably, the fatty amine has the general formula (VI), wherein:

·R’₁represents a saturated or unsaturated, linear or branched hydrocarbon radical comprising from 12 to 22 carbon atoms, preferably from 14 to 22 carbon atoms, and optionally at least one heteroatom chosen from nitrogen, sulphur or oxygen, and/or

·R’₂、R’₄And R'₅Independently represent a hydrogen atom; a saturated or unsaturated, linear or branched hydrocarbon group containing 12 to 22 carbon atoms, preferably 14 to 22 carbon atoms, more preferably 16 to 22 carbon atoms; (R'₆-O)_p-H group, wherein R'₆Represents a saturated linear or branched hydrocarbon radical comprising at least 2 carbon atoms, preferably from 2 to 6 carbon atoms, more preferably from 2 to 4 carbon atoms, and p is greater than or equal to 1, preferably from 1 to 6, more preferably from 1 to 4; (R'₇-N)_i-H₂Group, wherein R'₇Represents a saturated linear or branched hydrocarbon radical comprising at least 2 carbon atoms, preferably from 2 to 6 carbon atoms, more preferably from 2 to 4 carbon atoms, and p is greater than or equal to 1, preferably from 1 to 6, more preferably from 1 to 4, and/or

·R’₃Represents a saturated or unsaturated, linear or branched alkyl group containing from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms.

In one embodiment, the fatty amine of formula (VI) is from 0.5 to 10 wt.%, preferably from 0.5 to 8 wt.%, relative to the total weight of the lubricant composition.

The optional additives, e.g. as defined above, comprised in the lubricant composition of the present invention may be incorporated into the lubricant composition as separate additives, in particular by adding them separately to the base oil. However, they may also be incorporated into additive concentrates for marine lubricant compositions.

Method for producing marine lubricants

The present disclosure provides a method for producing a marine lubricant as described above, comprising the steps of: the base oil is mixed with the reaction product of at least an alkali or alkaline earth metal hydroxybenzoate compound (optionally hydrocarbyl-substituted), boron compound and an amine component, as defined above.

Use of lubricating an engine

The present application also relates to the use of at least the reaction product of an alkali or alkaline earth metal hydroxybenzoate compound (optionally hydrocarbyl-substituted), a boron compound and an amine component, as described above, for lubricating an engine, preferably a marine engine. In particular, the present application relates to the use of at least the reaction product of an alkali or alkaline earth metal hydroxybenzoate compound (optionally hydrocarbyl-substituted), a boron compound and an amine component, as defined above, for lubricating two-stroke marine engines and four-stroke marine engines, more preferably two-stroke marine engines.

In particular, the reaction product of at least an alkali or alkaline earth metal hydroxybenzoate compound (optionally hydrocarbyl-substituted), a boron compound and an amine component as defined above is suitable for use in a lubricant composition as a cylinder oil or a system oil for lubricating two-stroke engines and four-stroke marine engines, more preferably two-stroke engines.

The present application also relates to a method for lubricating a two-stroke marine engine and a four-stroke marine engine, more preferably a two-stroke marine engine, comprising applying a marine lubricant as described above to the marine engine. In particular, lubricants are commonly applied to the cylinder wall for lubricating two-stroke engines by means of a pulse lubrication system or by means of injectors spraying the lubricant onto the annular groups of pistons. It has been observed that the application of the lubricant composition according to the invention to the cylinder wall provides enhanced corrosion protection, improved engine cleanliness.

Claims

1. A product resulting from the reaction of at least:

-an amine component selected from:

wherein,

n and z are independently of one another 0, 1, 2 or 3, and

wherein the polyalkylamine composition comprises at least 3 wt.%, relative to the total weight of polyalkylamine compounds (I) and (II) in the composition, of a branched compound of formula (I) or formula (II) represented by:

-in formula (I), at least one of n and z is greater than or equal to 1,

-in formula (II), n is greater than or equal to 1.

2. Product according to claim 1, wherein the alkali or alkaline earth metal hydroxybenzoate compound optionally substituted by hydrocarbon groups is selected from monoalkyl (ene) substituted salicylates, dialkyl (ene) substituted salicylates, carboxylic acid functionalized calixarene salts, in particular salicylic acid calixarene salts, and mixtures thereof.

3. The product according to claim 1 or claim 2, wherein the alkali or alkaline earth metal hydroxybenzoate compound, optionally substituted with hydrocarbyl groups, is selected from alkali and/or alkaline earth metal salts of compounds of formula (III):

wherein:

a is an integer, a represents 0, 1 or 2.

4. The product according to claim 3, wherein the alkali or alkaline earth metal hydroxybenzoate compound, optionally substituted with hydrocarbyl groups, is selected from alkali and/or alkaline earth metal salts of compounds of formula (IIIA):

5. the product according to claim 4, wherein the alkali metal and/or alkaline earth metal hydroxybenzoate compounds are selected from alkali metal and/or alkaline earth metal salicylates.

6. The product according to any of the preceding claims, wherein the boron compound is selected from boric acid, boric acid complexes, boron oxide, trialkyl borates whose alkyl groups independently comprise from 1 to 4 carbon atoms, C₁-C₁₂Alkyl boric acid, C₁-C₁₂Dialkylboric acid, C₆-C₁₂Aryl boronic acids, C₆-C₁₂Diarylboronic acids, C₇-C₁₂Aralkyl boronic acid, C₇-C₁₂Diaroboronic acids or products derived from these substances in which the alkyl group is substituted by one or more than one alkoxy unit, advantageously the boron compound is boric acid.

7. The product of any of the preceding claims, wherein the polyalkylamine composition comprises at least 4 wt/wt%, at least 5 wt/wt%, at least 6 wt/wt%, at least 7 wt/wt%, or at least 7.5 wt/wt% of a branched compound of formula (I) or formula (II), relative to the total weight of polyalkylamine compounds (I) and (II) in the composition, the branched compound represented by:

-in formula (I), at least one of n or z is greater than or equal to 1,

-in formula (II), n is greater than or equal to 1.

8. The product according to any one of the preceding claims, wherein the polyalkylamine composition comprises at least 5% by weight, relative to the total weight of compounds (I) and (II), of compounds of formula (I) and (II) having a linear chain structure, linear meaning that n is 0 in formula (I) and (II) and z is 0 in formula (I).

9. The product of any of the preceding claims wherein the polyalkylamine composition further comprises a derivative of a polyalkylamine of formula (I) or formula (II), said derivative being an optionally methylated alkoxylate.

10. The product of any of the preceding claims wherein the polyalkylamine composition further comprises a derivative of a polyalkylamine of formula (I) or formula (II), said derivative being methylated.

11. The product according to any one of the preceding claims, wherein each R is selected, independently of the other R, from linear or branched alkyl and alkenyl groups comprising from 8 to 22 carbon atoms, preferably having from 14 to 18 carbon atoms, more preferably having from 16 to 18 carbon atoms.

12. The product according to claim 11, wherein the R groups are derived from animal and vegetable fats and oils, such as tallow oil, rapeseed oil, sunflower oil, soybean oil, linseed oil, olive oil, palm oil, castor oil, wood oil, corn oil, pumpkin seed oil, grape seed oil, jojoba oil, sesame oil, walnut oil, hazelnut oil, almond oil, shea butter, macadamia nut oil, cottonseed oil, alfalfa oil, rye oil, safflower oil, peanut oil, coconut oil and copra oil, and mixtures thereof, preferably from tallow oil.

13. A lubricant composition comprising the product of any one of claims 1 to 12 and a base oil.

14. Use of the product according to any one of claims 1 to 12 or the lubricant composition according to claim 13 for lubricating two-stroke marine engines and four-stroke marine engines, more preferably two-stroke marine engines.