阅读说明：本技术 缔合和可交换的低聚物及包含它们的组合物 (Associative and exchangeable oligomers and compositions containing them ) 是由 格雷戈里·德克鲁瓦 范妮·布赖恩德 于 2019-05-23 设计创作，主要内容包括：由混合至少一种低聚物A1和包含至少两个硼酸酯官能团的至少一种化合物A2而获得的组合物,所述低聚物A1由至少两种被二醇能官能团官能化的单体与至少一种第二单体的共聚获得。根据所使用的组合物A1和A2的比例,它们具有非常多样化的流变性质。由混合至少一种润滑油和这种缔合和可交换的聚合物组合物而获得的组合物,和这种组合物用于润滑机械零件的用途。(Composition obtained by mixing at least one oligomer a1 obtained by copolymerization of at least two monomers functionalized with glycol functional groups with at least one second monomer and at least one compound a2 comprising at least two borate functional groups. Depending on the proportions of the compositions A1 and A2 used, they have very diverse rheological properties. Compositions obtained by mixing at least one lubricating oil with such associative and exchangeable polymer compositions, and the use of such compositions for lubricating mechanical parts.)

1. A composition obtained by mixing at least

A polyglycol oligomer a1 having a number average molar mass greater than or equal to 600 g/mole and less than 10000 g/mole, said polyglycol oligomer a1 comprising repeating units corresponding to:

-at least two monomers M1,

and

at least one monomer M2, or

At least one monomer M3, or

At least one monomer M2 and at least one monomer M3,

and oligomer A1 contains less than 2 mole% of repeat units corresponding to one or more than one monomer M3,

and

compound a2 comprising at least two borate functional groups,

■ monomer M1 corresponds to the general formula (I):

wherein:

-R₁is selected from-H, -CH₃and-CH₂-CH₃；

-x is an integer from 1 to 18, preferably from 2 to 18;

-y is an integer equal to 0 or 1;

-X₁and X₂May be the same or different and are selected from hydrogen,Tetrahydropyranyl, methoxymethyl, t-butyl, benzyl, trimethylsilyl, and t-butyldimethylsilyl groups;

or

-X₁And X₂Forms a bridge with the oxygen atom having the formula:

wherein:

the asterisk (—) indicates the bond to the oxygen atom,

-R’₂and R "₂May be the same or different and is selected from hydrogen and C₁-C₁₁Alkyl, preferably methyl;

or

-X₁And X₂With an oxygen atom to form a boronic ester having the formula:

wherein:

the asterisk (—) indicates the bond to the oxygen atom,

-R”’₂is selected from C₆-C₃₀Aryl radical, C₇-C₃₀Aralkyl and C₂-C₃₀Alkyl, preferably C₆-C₁₈An aryl group;

■ monomer M2 corresponds to the general formula (II):

wherein:

-R₂is selected from-H, -CH₃and-CH₂-CH₃；

-R₃Selected from: -C (O) -O-R'₃、–O–R’₃、–S–R’₃and-C (O) -N (H) -R'₃WhereinR’₃Is C₁-C₃₀An alkyl group, a carboxyl group,

■ monomer M3 corresponds to the general formula (X):

wherein:

-Z₁、Z₂and Z₃May be the same or different and represents a hydrogen atom, C₁-C₁₂Alkyl and a radical of the group-OZ ' or-C (O) -O-Z ', in which Z ' is C₁-C₁₂An alkyl group.

2. The composition of claim 1, wherein the number average molar mass of oligomer a1 is from 600 g/mole to 9500 g/mole.

3. The composition of claim 1 or claim 2, wherein oligomer a1 comprises less than 1.5 mole% of repeat units corresponding to one or more than one monomer of formula (X) M3.

4. The composition according to any of the preceding claims wherein monomer M3 is styrene.

5. The composition of any of the preceding claims, wherein the average length of the side chains of oligomer a1 is from 8 to 20 carbon atoms, preferably from 9 to 18 carbon atoms.

6. The composition of any of the preceding claims, wherein the molar percentage of repeat units in oligomer a1 corresponding to monomer M1 in formula (I) is from 2% to 70%, preferably from 4% to 50%.

7. The composition according to any one of the preceding claims, wherein compound a2 is a compound of formula (III):

wherein:

-w₁and w₂Which may be the same or different, are integers selected from 0 and 1;

-R₄、R₅、R₆and R₇Which may be identical or different, represent a hydrocarbon radical chosen from hydrogen atoms, comprising from 1 to 30 carbon atoms, optionally substituted by one or more than one radical chosen from: a hydroxyl group, a group-OJ or-C (O) -O-J, wherein J is a hydrocarbyl group comprising 1 to 24 carbon atoms;

-L is a divalent bonding group selected from C₆-C₁₈Aryl radical, C₆-C₁₈Aralkyl and C₂-C₂₄A hydrocarbon chain.

8. The composition of any one of claims 1 to 6, wherein compound A2 is an oligomer comprising repeating units corresponding to:

● at least two monomers M4 of formula (IV):

wherein:

-t is an integer equal to 0 or 1;

-u is an integer equal to 0 or 1;

-M and R₈Are identical or different divalent bonding groups selected from C₆-C₁₈Aryl radical, C₇-C₂₄Aralkyl and C₂-C₂₄Alkyl, preferably C₆-C₁₈An aryl group;

x is selected from the group consisting of-O-C (O) -, -C (O) -O-, -C (O) -N (H) -, -N (H) -C (O) -, -S-, -N (H) -, -N (R'₄) -and-O-, wherein R'₄Is a hydrocarbon chain comprising from 1 to 15 carbon atoms;

-R₉is selected from-H, -CH₃and-CH₂-CH₃；

-R₁₀And R₁₁May be the same or different and represents a hydrocarbyl group selected from a hydrogen atom, comprising from 1 to 30 carbon atoms, optionally substituted by one or more groups selected from: a hydroxyl group, a group-OJ or-C (O) -O-J, wherein J is a hydrocarbyl group comprising 1 to 24 carbon atoms; and

● optionally at least one monomer M5 of formula (V):

wherein:

-R₁₂is selected from-H, -CH₃and-CH₂-CH₃；

-R₁₃Is selected from-C (O) -O-R'₁₃；–O–R’₁₃、–S–R’₁₃and-C (O) -N (H) -R'₁₃Wherein R'₁₃Is C₁-C₃₀An alkyl group, a carboxyl group,

● optionally at least one monomer M3 of the formula (X)

Wherein:

Z₁、Z₂and Z₃May be the same or different and represents a hydrogen atom, C₁-C₁₂Alkyl and a radical of the group-OZ ' or-C (O) -O-Z ', in which Z ' is C₁-C₁₂An alkyl group.

9. The composition according to claim 8, wherein the number average molar mass of oligomer A2 is from 600 g/mol to 10000 g/mol, preferably from 600 g/mol to 9500 g/mol.

10. A lubricant composition resulting from the mixing of at least:

-a lubricating oil; and

-a composition as defined in any one of claims 1 to 9.

11. Use of a lubricant composition according to claim 10 for reducing fuel consumption of a vehicle.

12. A method for reducing energy loss due to friction of a machine part comprising at least one step of contacting a machine part with the lubricant composition of claim 10.

13. A method for reducing fuel consumption of a vehicle comprising at least one step of contacting a mechanical part of a vehicle engine with the lubricant composition of claim 10.

Background

High molar mass polymers are widely used to increase the viscosity of solutions in many fields, such as the petroleum, paper and water treatment industries, the mining, cosmetics and textile industries, and all industrial techniques that generally use thickened solutions.

It is known that lubricant compositions, and more particularly engine lubricant compositions, can contain different types of additives to impart specific properties to the composition. With the establishment of the kyoto protocol, new environmental protection standards are forcing the automotive industry to manufacture vehicles with reduced pollutant emissions and fuel consumption. Therefore, the engines of these vehicles are subject to increasingly stringent technical limits: they spin significantly faster, at higher temperatures, and must consume less and less fuel. The properties of engine lubricants of motor vehicles have an impact on pollutant emissions and fuel consumption. Energy-efficient or "fuel-efficient" motor vehicle engine lubricants have been developed to meet these new demands.

Patent applications WO2015/110642, WO2015/110643 and WO2016/113229 disclose compositions obtained by mixing at least one copolymer a1 obtained by copolymerization of at least one monomer functionalized with a diol function and at least one compound a2 comprising at least two borate functional groups. These compounds may associate to optionally form a gel and exchange chemical bonds thermally and reversibly. The advantage of these additives is that the viscosity of the solutions containing them decreases as the temperature increases. These polymer compositions have a very diverse rheological behaviour depending on the proportions of the compounds A1 and A2 used. They may also contain a diol compound, which enables a better control of the association of the two copolymers.

In particular, these polymer compositions can be added to lubricating oils to lubricate mechanical parts. These copolymers enable the formulation of lubricant compositions with better control of the lubricant composition viscosity when compared to prior art lubricant compositions. In particular, when they are incorporated into base oils, these copolymers tend to reduce the viscosity drop of the mixture as the temperature increases. The presence of the glycol compound in these lubricant compositions enables better adjustment of the viscosity thereof.

Lubricant compositions are compositions that are applied to the surfaces of moving parts, particularly metal surfaces. They can reduce friction and wear between two parts that are in contact and move relative to each other. They also serve to dissipate some of the thermal energy generated by this friction. The lubricant composition forms a protective film between the surfaces of the parts to which it is applied.

Compositions for lubricating mechanical parts are generally formed from a base oil and additives. Base oils, particularly petroleum or synthetic oils, exhibit a change in viscosity when temperature changes.

In particular, when the temperature of the base oil increases, its viscosity decreases, and when the temperature of the base oil decreases, its viscosity increases. Now, in the hydrodynamic lubrication state, the thickness of the protective film is proportional to its viscosity and therefore also depends on the temperature. The composition has good lubricating properties if the thickness of the protective film remains substantially constant regardless of the conditions and duration of use of the lubricant.

In internal combustion engines, the lubricant composition may be subject to external or internal temperature changes. The external temperature variation is due to a variation in ambient air temperature, such as a temperature variation between summer and winter. The internal temperature variation is caused by the operation of the engine. The temperature of the engine is lower during its start-up phase than during prolonged use, especially in cold weather. Therefore, the thickness of the protective film may vary in these different environments.

Therefore, there is a need to provide lubricant compositions having good lubricating properties and viscosities that are less susceptible to temperature changes.

It is well known to add additives to increase the viscosity of lubricant compositions. The function of these additives is to modify the rheological behaviour of the lubricant composition. They can promote a more stable viscosity over the temperature range in which the lubricant composition is used. For example, these additives limit the viscosity reduction of the lubricant composition when the temperature is increased, while limiting the viscosity increase under cold conditions.

The additive for increasing viscosity (or the additive for increasing viscosity index) ensures good lubrication by limiting the influence on viscosity under cold conditions and by ensuring the minimum thickness of the film under hot conditions. Currently used additives for increasing viscosity are polymers such as Olefin Copolymers (OCP) and Polyalkylmethacrylate (PMA). These polymers have a high molar mass. Generally, the higher the molecular weight of these polymers, the proportionately greater the contribution to viscosity control.

However, a disadvantage of high molar mass polymers is their poorer permanent shear strength when compared with polymers of the same nature and of the same construction but of smaller size.

Lubricant compositions are now subjected to high shear stresses, particularly in internal combustion engines, where the friction surfaces have very small spacings and the pressures exerted on the parts are high. Shear stress on these high molar mass polymers leads to cleavage in the macromolecular chains. The thickening properties of the degraded polymer are reduced and the viscosity is irreversibly lowered. This poor permanent shear strength therefore results in a reduction in the lubricating properties of the lubricant composition.

Finally, the development of compositions with better oxidative stability, in particular better resistance to radical oxidation, has been sought.

The compositions described in patent applications WO2015/110642, WO2015/110643 and WO2016/113229 have very advantageous properties due to their ability to form thermoreversible associations. However, it has been found that under certain conditions, in particular at elevated temperatures, the association behavior of these copolymers is reduced. In particular, it has been observed that the viscosity index of the lubricant compositions containing them decreases and the circulation resistance (which may be defined as the temperature increase and decrease observed to occur continuously in the engine) deteriorates, leading to a loss of lubricant performance over time.

The applicant has therefore set the aim of preparing novel copolymers having improved properties compared with the copolymers of the prior art.

This objective is achieved by novel rheological additives that can associate to optionally form a gel and that can be exchanged. The additives of the invention have the advantage of thickening the medium in which they are dispersed and of maintaining this advantage at high temperatures, for example up to 150 ℃. These additives exhibit resistance to chemical degradation during elevated temperatures when compared to prior art additives. The lubricant compositions containing them show better stability of their cycle properties and better reproducibility of their lubricating properties over time.

This property is obtained by the combined use of two specific compounds, namely an oligomer bearing a diol function and optionally a styrene function, and a compound comprising a borate function.

By means of the composition of the invention, it is possible to provide a lubricant composition having good lubricating properties during the engine start-up phase (cold phase) and good lubricating properties when the engine is running at its use temperature (hot phase). These lubricant compositions make it possible to reduce the consumption of the fuel used in the vehicle. They have better resistance to mechanical degradation than the compositions of the prior art.

Disclosure of Invention

The invention relates to a composition obtained by mixing at least

Omicron having a number average molar mass greater than or equal to 600 grams/mole and less than 10000 grams/mole of polyglycol oligomer a1, said polyglycol oligomer a1 comprising repeat units corresponding to:

-at least two monomers M1,

and

at least one monomer M2, or

At least one monomer M3, or

At least one monomer M2 and at least one monomer M3,

and oligomer A1 contains less than 2% of repeating units corresponding to one or more than one monomer M3, and

compound a2 comprising at least two borate functional groups,

the monomer M1 corresponds to the general formula (I):

wherein:

-R₁is selected from-H, -CH₃and-CH₂-CH₃；

-x is an integer from 1 to 18, preferably from 2 to 18;

-y is an integer equal to 0 or 1;

-X₁and X₂Which may be the same or different, are selected from the group consisting of hydrogen, tetrahydropyranyl, methoxymethyl, t-butyl, benzyl, trimethylsilyl and t-butyldimethylsilyl;

or

-X₁And X₂Forms a bridge with the oxygen atom having the formula:

wherein:

the asterisk (—) indicates the bond to the oxygen atom,

-R’₂and R "₂Which may be identical or different, are selected from hydrogen and C₁-C₁₁Alkyl, preferably methyl;

or

-X₁And X₂With an oxygen atom to form a boronic ester having the formula:

wherein:

the asterisk (—) indicates the bond to the oxygen atom,

-R”’₂is selected from C₆-C₃₀Aryl radical, C₇-C₃₀Aralkyl and C₂-C₃₀Alkyl, preferably C₆-C₁₈An aryl group;

monomer M2, corresponding to general formula (II):

wherein:

-R₂is selected from-H, -CH₃and-CH₂-CH₃；

-R₃Selected from: -C (O) -O-R'₃、–O–R’₃、–S–R’₃and-C (O) -N (H) -R'₃Wherein R'₃Is C₁-C₃₀An alkyl group, a carboxyl group,

monomer M3, corresponding to general formula (X):

wherein:

-Z₁、Z₂and Z₃Which may be the same or different, represent a hydrogen atom, C₁-C₁₂Alkyl and a radical of the group-OZ ' or-C (O) -O-Z ', in which Z ' is C₁-C₁₂An alkyl group.

According to a preferred embodiment, the oligomer A1 has a number average molar mass of 600 g/mol to 9500 g/mol.

According to a preferred embodiment, oligomer a1 comprises less than 1.5 mole% of recurring units corresponding to one or more than one monomer M3 of formula (X).

According to a preferred embodiment, the monomer M3 is styrene.

According to a preferred embodiment, the side chains of oligomer a1 have an average length of 8 to 20 carbon atoms, preferably 9 to 18 carbon atoms.

According to a preferred embodiment, the molar percentage of recurring units in oligomer a1 corresponding to monomer M1 of formula (I) in the copolymer is from 2% to 70%, preferably from 4% to 50%.

According to a preferred embodiment, the oligomer a1 has a number average degree of polymerization of from 3 to 100, preferably from 3 to 50.

According to a preferred embodiment, the polydispersity index (Ip) of oligomer a1 is from 1.05 to 4.0, preferably from 1.10 to 3.8.

According to a first preferred embodiment, compound a2 is a compound of general formula (III):

wherein:

-w₁and w₂Which may be the same or different, are integers selected from 0 and 1;

-R₄、R₅、R₆and R₇Which may be identical or different, are chosen from hydrogen atoms, hydrocarbyl groups comprising from 1 to 30 carbon atoms, preferably from 4 to 18 carbon atoms, even more preferably from 6 to 14 carbon atoms, said hydrocarbyl groups being optionally substituted by one or more groups chosen from: a hydroxyl group and a group-OJ or-C (O) -O-J, J being a hydrocarbyl group comprising from 1 to 24 carbon atoms;

-L is a divalent bonding group selected from C₆-C₁₈Aryl radical, C₇-C₂₄Aralkyl and C₂-C₂₄A hydrocarbon chain.

According to another preferred embodiment, compound A2 is an oligomer, which is obtained by copolymerization of

At least two monomers M4 of formula (IV):

wherein:

-t is an integer equal to 0 or 1;

-u is an integer equal to 0 or 1;

-M and R₈Are identical or different divalent bonding groups selected from C₆-C₁₈Aryl radical, C₇-C₂₄Aralkyl and C₂-C₂₄Alkyl, preferably C₆-C₁₈An aryl group;

x is selected from the group consisting of-O-C (O) -, -C (O) -O-, -C (O) -N (H) -, -N (H) -C (O) -, -S-, -N (H) -, -N (R'₄) -and-O-, wherein R'₄Is a hydrocarbon chain comprising from 1 to 15 carbon atoms;

-R₉is selected from-H, -CH₃and-CH₂-CH₃；

-R₁₀And R₁₁Which may be identical or different, are chosen from hydrogen atoms, hydrocarbyl groups comprising from 1 to 30 carbon atoms, preferably from 4 to 18 carbon atoms, even more preferably from 6 to 14 carbon atoms, said hydrocarbyl groups being optionally substituted by one or more groups chosen from: a hydroxyl group and a group-OJ or-C (O) -O-J, J being a hydrocarbyl group comprising from 1 to 24 carbon atoms; and

optionally at least one monomer M5 of formula (V):

wherein:

-R₁₂is selected from-H, -CH₃and-CH₂-CH₃，R₁₃Is selected from-C (O) -O-R'₁₃、–O–R’₁₃、–S–R’₁₃and-C (O) -N (H) -R'₁₃Wherein R'₁₃Is C₁-C₃₀An alkyl group, a carboxyl group,

optionally at least one monomer M3 of formula (X):

wherein:

·Z₁、Z₂and Z₃Which may be the same or different, represent a hydrogen atom, C₁-C₁₂Alkyl and a radical of the group-OZ ' or-C (O) -O-Z ', in which Z ' is C₁-C₁₂An alkyl group.

According to a preferred embodiment, the oligomer a2 has a number average molar mass of 600 g/mol to less than 10000 g/mol, preferably 600 g/mol to 9500 g/mol, more preferably 600 g/mol to 5000 g/mol.

According to a preferred embodiment, in copolymer a2, at least one of the following two conditions is satisfied:

in formula (IV): when u is 1, R₉Is H and R₈Is represented by C₆-C₁₈Aryl or C₇-C₂₄Aralkyl, and the double bond of monomer M4 of formula (IV) is directly attached to the aryl group:

alternatively, oligomer a2 comprises at least one monomer M3 of formula (X).

Advantageously, when a2 comprises monomer M3 of formula (X), this monomer M3 is styrene.

Advantageously, the molar percentage of the styrene monomer (advantageously styrene) of formula (IV) and/or formula (X) in the borate oligomer a2 is from 2 to 50 mole%, preferably from 3 to 40 mole%, and more preferably from 5 to 35 mole% in the copolymer.

According to an advantageous embodiment, in the oligomer A2, the group R of the monomer of formula (IV)₁₀M, X and (R)₈)_u(wherein u equals 0 or 1) is from 8 to 38, preferably from 10 to 26.

According to an advantageous embodiment, the side chains of oligomer a2 have an average length of greater than or equal to 8 carbon atoms, preferably from 11 to 16 carbon atoms.

According to an advantageous embodiment, the molar percentage of oligomer a2 in the oligomer of monomer M4 of formula (IV) is from 4% to 50%, preferably from 4% to 30%.

According to an advantageous embodiment, the number average degree of polymerization of the oligomer a2 is from 2 to 100, preferably from 2 to 50.

According to an advantageous embodiment, the polydispersity index (Ip) of oligomer a2 is from 1.04 to 3.54, preferably from 1.10 to 3.10.

According to a preferred embodiment, the oligomer a1 is present in an amount of 0.1 to 50% by weight relative to the total weight of the composition.

According to a preferred embodiment, compound a2 is present in an amount ranging from 0.1% to 50% by weight relative to the total weight of the composition.

According to a preferred embodiment, the mass ratio of oligomer a1 and compound a2 (a1/a2 ratio) is from 0.002 to 500, preferably from 0.05 to 20, even more preferably from 0.1 to 10.

According to a preferred embodiment, the oligomer a1 is obtained by a process comprising at least the following steps:

-a step of controlled radical polymerization by reversible addition-fragmentation chain transfer in the presence of a thiocarbonylthio type transfer agent.

According to a more preferred embodiment, oligomer a1 is obtained after polymerization by a process comprising at least the following steps:

a step of aminolysis of the thiocarbonylthio residue to a thiol, followed by

-carrying out a michael addition reaction on an acrylate to convert a thiol into a thioether.

According to a preferred embodiment, the composition also comprises at least one exogenous compound a4 selected from polyols.

According to a preferred embodiment, the molar percentage of exogenous compound a4 is comprised between 0.025% and 5000%, preferably between 0.1% and 1000%, even more preferably between 0.5% and 500%, even more preferably between 1% and 150%, with respect to the borate functional group of compound a 2.

According to another preferred embodiment, the composition further comprises at least one exogenous compound a5 selected from corresponding to formula (XI):

wherein:

-Q represents a hydrocarbyl group selected from comprising 1 to 30 carbon atoms, optionally substituted with one or more than one group selected from: a hydroxyl group, a group-OJ or-C (O) -O-J, wherein J is a hydrocarbyl group comprising 1 to 24 carbon atoms;

-G₄and G₅Which may be identical or different, represent a radical chosen from a hydrogen atom, a hydrocarbon chain comprising from 1 to 24 carbon atoms, a hydroxyl group, a radical-OJ or-c (O) -O-J, J being a hydrocarbon radical comprising from 1 to 24 carbon atoms;

-g represents 0 or 1.

According to a preferred embodiment, the molar percentage of exogenous compound a5 is comprised between 0.025% and 5000%, preferably between 0.1% and 1000%, even more preferably between 0.5% and 500%, even more preferably between 1% and 150%, with respect to the diol functional groups of oligomer a 1.

The invention also relates to a lubricant composition obtained by mixing:

-a lubricating oil; and

-a composition as defined above and as detailed below.

According to a preferred embodiment, the lubricating oil is an oil selected from group I, group II, group III, group IV and group V of the API classification and mixtures thereof.

According to a preferred embodiment, the lubricant composition is further obtained by mixing with a functional additive selected from the group consisting of antioxidants, detergents, anti-wear additives, extreme pressure additives, viscosity index increasing polymers, pour point improvers, anti-foaming agents, anti-corrosion additives, thickeners, dispersants, friction modifiers, and mixtures thereof.

The invention also relates to a method for adjusting the viscosity of a lubricant composition, the method comprising at least:

-providing a composition as defined above and as detailed below,

-mixing the composition with lubricating oil.

The invention also relates to the use of a lubricant composition as defined above and as detailed below for reducing the fuel consumption of a vehicle.

The invention also relates to the use of a lubricant composition as defined above and as detailed below for increasing the mechanical durability of a lubricant.

The invention also relates to a method for reducing energy losses caused by friction of a mechanical part, comprising at least one step of contacting the mechanical part with a lubricant composition as defined above and as detailed below.

The invention also relates to a method for reducing the fuel consumption of a vehicle comprising at least one step of contacting a mechanical part of the vehicle engine with a lubricant composition as defined above and as detailed below.

Drawings

FIG. 1 schematically shows a random copolymer (P1), a gradient copolymer (P2) and a block copolymer (P3); each circle represents a monomer unit. The difference in chemical structure between the monomers is indicated by different colors (light grey/black).

FIG. 2 schematically illustrates a boronic acid ester bond exchange reaction between two polyglycol oligomers (A1-1 and A1-2) and two boronic acid diester oligomers (A2-1 and a 2-2) in the presence of a diol.

FIG. 3 schematically illustrates and represents the crosslinking of a composition according to the invention in Tetrahydrofuran (THF).

Figure 4 schematically illustrates the behavior of the composition of the invention according to an external stimulus, in this example temperature. The oligomer (2) bearing diol functions (function A) can be reversibly associated with the oligomer (1) bearing borate functions (function B) by transesterification. The organic group of the borate functional group (functional group B) exchanged during the transesterification reaction is a diol represented by a black crescent symbol. As the diol compound is released, it forms a borate chemical bond (3).

Fig. 5 is a graph showing the change in kinematic viscosity at 40 c as measured by shear rate applied to compositions a and F. The (. cndot.) curve corresponds to composition A. The (■) curve corresponds to composition F. The x-axis of the graph is denoted by s^-1The shear rate values are expressed and the y-axis represents the viscosity values in mpa.s.

Fig. 6 is a graph showing the change in kinematic viscosity at 100 c as measured by shear rate applied to compositions A, B and F. The (. cndot.) curve corresponds to composition A. The (■) curve corresponds to composition F. The x-axis of the graph is denoted by s^-1The shear rate values are expressed and the y-axis represents the viscosity values in mpa.s.

Fig. 7 is a graph showing the change in kinematic viscosity at 150c as measured by shear rate applied to compositions A, B and F. The (. cndot.) curve corresponds to composition A. The (■) curve corresponds to composition F. The x-axis of the graph is denoted by s^-1The shear rate values are expressed and the y-axis represents the viscosity values in mpa.s.

Experimental part

The following examples illustrate the invention but do not limit it.

1. Synthesis of

1.1.Synthesis of polyglycol oligomer

1.1.1. Monomer

Monomer M1: methacrylate with diol functional group (mono-diol):

the synthesis was carried out according to the protocol described in patent application WO 2018/096253 (experimental part § 1.1.1.).

Monomer M2: stearyl methacrylate (StMA):

octadecyl methacrylate ester ofAndand (7) selling.

Monomer M3: styrene:

styrene fromAnd (7) selling.

1.1.2. Synthesis of oligomer o-diol-2

The synthesis of oligomer o-diol-2 proceeds according to the following reaction scheme.

300mL of toluene was placed in a 1L reactor connected to a condenser, a thermometer and a nitrogen source. The reaction medium is degassed by sparging with nitrogen and stirred until the temperature reaches 100 ℃. Next, 10mL of a solution containing stearyl methacrylate (StMA), methacrylate with diol functional groups (mono-diol), styrene and ethyl 2-mercaptopropionate (solution 1) and 25mL of a toluene solution of Azobisisobutyronitrile (AIBN) (solution 2) were placed in the reactor. Once gas generation was observed, the remaining portions of solution 1 and solution 2 were added over 125 minutes. Table 1.1 below lists the amounts introduced. The progress of the reaction was monitored by SEC analysis. After 4 hours of polymerization at 100 ℃ the reaction medium is cooled to room temperature. The polymer was precipitated three times with 200mL of methanol. The volatiles were evaporated under reduced pressure at a temperature below 50 ℃. The product was then dried under vacuum at 40 ℃ for 72 hours to remove solvent residues. 96.3g of a pasty white solid are obtained. Yield: 80 percent.

Table 1.1: incorporation of O-diol-2 for the Synthesis of oligomer

Solution 1:	mass/volume
		Stearyl methacrylate	100.33g
Mono-diols	20.24g
		Styrene (meth) acrylic acid ester	0.45g
2-mercaptopropionic acid ethyl ester	6.92g
		Solution 2:	mass/volume
AIBN	1.42g
		Toluene	100mL

And (3) characterization:

the oligomer obtained comprised 22 mol% of recurring units containing a diol function, 77 mol% of StMA recurring units and 1 mol% of styrene recurring units consisting of¹H NMR (400MHz, CDCl 3).

The number average molar mass of the oligomer was about 3900g^-1And a polydispersity index of 1.26 as determined by SEC in THF at 40 ℃ using poly (methyl methacrylate) calibration.

1.2.Synthesis of boronic ester oligomers

1.2.1. Monomer

Monomer M4: monomers with borate function (mono-EB)

The synthesis was carried out according to the protocol described in patent application WO2016/113229 (experimental part § 2.1).

1.2.2. Synthesis of oligomer o-EB-1

The synthesis of oligomer o-EB-1 was performed according to the following reaction scheme.

Octadecyl methacrylate, monomer bearing borate functional groups (mono-EB), isopropanol, AIBN and toluene (solution 3) were placed in a 500mL reactor connected to a condenser, thermometer and nitrogen source. Table 1.3 below lists the amounts introduced. The reaction medium was degassed by sparging with nitrogen for 30 minutes, stirred and then warmed to 86 ℃. When the reaction medium was 75 ℃ and gas evolution was observed, a toluene solution of StMA and mono-EB (solution 4) was added dropwise over 80 minutes. The progress of the reaction was monitored by SEC analysis. After 3 hours of polymerization at 80 ℃ the medium was cooled to room temperature. The polymer was precipitated three times with 300mL of methanol. The volatiles were evaporated under reduced pressure at a temperature below 50 ℃. The product was then dried under vacuum at 40 ℃ for 72 hours to remove solvent residues. 115.6g of a pasty white solid were obtained. Yield: 87 percent.

Table 1.3: incorporation of the oligomer O-EB-1

And (3) characterization:

the oligomer obtained comprised 90 mol% of recurring units containing a borate functional group and 10 mol% of StMA recurring units consisting of¹H NMR(400MHz,CDCl₃) And (4) measuring.

The number average molar mass of the oligomer was about 7100g^-1And a polydispersity index of 1.74, as determined by SEC in THF at 40 ℃ using poly (methyl methacrylate) calibration.

1.3.Synthesis of boric acid diester molecule Di-EB

The synthesis of the molecule Di-EB proceeds according to the following reaction scheme.

The following were charged to a 500mL three-necked round bottom flask connected to a Dean-Stark apparatus, condenser and nitrogen source: 38mL of distilled water, 200mL of toluene, and 38.2g of 1-phenylene diboronic acid. The mixture obtained is in the form of a solid in suspension. 93.1g of 1, 2-dodecanediol are then added. 200mL of the remaining toluene was added to rinse the walls of the three-neck flask. The reaction medium is then heated until the solid dissolves. The medium is then placed under a nitrogen atmosphere, stirred and refluxed for 16 hours. The temperature of the reaction medium rose from 97 ℃ (boiling point of the water/toluene azeotrope) to 111 ℃ (boiling point of toluene). The water evaporated azeotropically was removed periodically from the Dean-Stark apparatus. The progress of the reaction was monitored by monitoring the reflux temperature and the amount of water removed from the Dean-Stark apparatus.

After 16 hours, the reaction medium is cooled to room temperature. The volatile substances were evaporated under reduced pressure below 30 ℃. The obtained white solid was dried for 2 hours using a rotary evaporator. 108.1g of a white solid was obtained. The yield was 94%.

And (3) characterization:

¹h NMR (400MHz, acetone-D6 with TCNB (2,3,4, 5-tetrachloronitrobenzene):

purity > 99%.

1.4.Synthesis of polyglycol Polymer p-diol (control)

The synthesis of the polyglycol polymer p-diol proceeds according to the following reaction scheme:

the following were introduced into a 4L reactor connected to a condenser, nitrogen source and 500mL dropping funnel: 734.4g anisole, 36.2g cumyl dithiobenzoate solution, 45.3g lauryl methacrylate, 45.2g stearyl methacrylate, 9.3g styrene and 2.7g mono-diol. 181.2g of lauryl methacrylate, 180.9g of stearyl methacrylate and 37.1g of styrene were placed in the dropping funnel.

The reactor, dropping funnel and remaining mono-diol (50.3g) were placed under a nitrogen atmosphere. The reaction medium is heated with stirring to a temperature T ═ 80 ℃. The progress of the reaction was monitored by SEC analysis. A solution of 0.2660g AIBN in 3mL anisole was slowly introduced over 15 minutes. The remaining mono-diol was then introduced into a syringe pump and the other monomers were introduced using a dropping funnel over about 30 hours.

Three solutions of 0.1362g, 0.1338g and 0.1450g AIBN in 3mL anisole solutions were prepared and then introduced over 10 minutes at t ═ 4 hours, t ═ 25 hours and t ═ 45 hours, respectively. After 48 hours, the reaction medium is cooled to room temperature and 150mL of THF and 25mL of n-butylamine are added. The reaction medium is maintained at room temperature for 4 hours and then 250mL of butyl acrylate are added. Stirring was continued at room temperature for 18 hours.

The product was then precipitated from 2L of methanol and after separation of the phases by settling, the supernatant was discarded. The precipitated polymer was dissolved in THF and then precipitated again from 2L of methanol. This operation was repeated three times. The polymer was dissolved in a minimum volume of THF and then 1000g of group III base oil was added to the polymer. The remaining solvent was removed by entrainment with nitrogen under mechanical stirring of the solution and 1355.6g of polyglycol p-diol were obtained. Polymer dilution 25.4%.

And (3) characterization:

the polymer thus obtained and diluted contained 68 mol% of StMA/dodecanol MA repeat units, 25 mol% of styrene repeat units and 7 mol% of hexanediol MA (mono-diol) repeat units, consisting of³C NMR(100MHz,CDCl₃) And (4) measuring.

The number average molar mass of the polymer was about 40000 g^-1And a polydispersity index of 1.46 as determined by SEC in THF at 40 ℃ using poly (methyl methacrylate) calibration.

1.5.Synthesis of Poly (boronate) Polymer p-EB (control)

The synthesis of the poly (boronate) polymer p-EB was performed according to the following reaction scheme.

1L of anisole, 3.56g of a cumyl dithiobenzoate solution, 900g of lauryl methacrylate and 76g of mono-EB were placed in a 2L reactor connected to a condenser and a nitrogen source. The reaction medium is placed under a nitrogen atmosphere, stirred and heated to 90 ℃. The reaction medium is heated with stirring and at T ═ 90 ℃. The progress of the reaction was monitored by SEC analysis. After 2 hours and 30 minutes of polymerization, the reaction medium is cooled to 0 ℃ and the product is precipitated from 4L of acetone, and after separation of the phases by settling, the supernatant is removed. The precipitated polymer was dissolved in THF and then precipitated again from 4L of acetone. This operation is repeated for the last time. The polymer was then dissolved in a minimum volume of THF and 900g of group III base oil was added to the polymer. The remaining solvent was removed by entrainment with nitrogen under mechanical stirring of the solution and 1381.0g of poly (boronate) p-EB were obtained. Polymer dilution 39.2%.

And (3) characterization:

the polymer thus obtained and diluted contained 94 mol% dodecanol MA repeating units and 6 mol%Of a boronic ester repeating unit of¹³C NMR(100MHz,CDCl₃) And (4) measuring.

The number average molar mass of the polymer was about 45000 g^-1And a polydispersity index of 1.39 as determined by SEC in THF at 40 ℃ using poly (methyl methacrylate) calibration.

2. Formulation of the composition

Each oligomer/polymer was dissolved in the base oil to obtain a solution containing 10 mass% pure oligomer/polymer. After dissolving the oligomer/polymer in the oil under magnetic stirring and heating at 80 ℃, these solutions were filtered through a 0.8 μm Millipore filter if necessary. They were used as stock solutions for preparing the following formulations.

2.1.Lubricant base oils

The lubricant base oil used in the test compositions was an oil from group III of the API classification sold by SK under the name Yubase 4 +.

It has the following characteristics:

-kinematic viscosity at 40 ℃ measured according to standard ASTM D445 of 18.51 cSt;

-a kinematic viscosity of 4.206cSt at 100 ℃ measured according to standard ASTM D445;

-a viscosity index of 135, measured according to standard ASTM D2270;

-Noack volatility (expressed in weight percentage) measured according to standard CEC L-40-93 of 13.4 mass%;

a flash point (expressed in degrees celsius) measured according to standard NF EN ISO 2592 of 234 ℃;

pour point (in degrees centigrade) measured according to standard NF T60-105 of-18 ℃.

2.2.Preparation of composition A (according to the invention)

8.00g of a stock solution containing 10 mass% of the borate ester oligomer o-EB-1 and 8.00g of a stock solution containing 10 mass% of the oligomer o-diol-2 were put into a flask and mixed with a magnetic stirrer for 5 minutes. The formulation thus contains 5 mass% of the boronate oligomer o-EB-1 and 5 mass% of the oligomer o-diol-2.

2.3.Preparation of composition B (according to the invention)

The amount of the compound prepared was adjusted so that the formulation contained 5 mass% of the boric acid diester molecule Di-EB and 10 mass% of the oligomer o-diol-2.

2.4. Preparation of composition F (control)

5.2g of a stock solution containing 10 mass% of the poly (boronate) polymer p-EB, 4.5g of a stock solution containing 10 mass% of the polyglycol polymer p-diol and 10.3g of the group III base oil were placed in a flask and mixed with a magnetic stirrer for 5 minutes. The formulation thus contained 2.6 mass% of poly (boronate) oligomer p-EB and 2.25 mass% of polyglycol p-diol.

3. Rheology study

3.1.Measuring device and arrangement

And (3) shear measurement:

low-shear (10 s) was measured at 40 ℃, 100 ℃ and 150 ℃ in steady state using a rheometer type DHR-2 from TA Instruments^-1、100s^-1、1000s^-1、5000s^-1And 10000s^-1) Kinematic viscosity, the rheometer was fitted with a cone-plate geometry (0.5-40 mm).

High shear (1X 10 at 40 ℃ C.) was measured using a USV high shear viscometer from PCS Instruments⁶s^-1、2×10⁶s^-1、3×10⁶s^-1、4×10⁶s^-11X 10 at 100 ℃ and 150 ℃⁶s^-1、4×10⁶s^-1、7×10⁶s^-1、10×10⁶s^-1) Kinematic viscosity.

Mechanical degradation test:

KRL mechanical degradation testing was performed at 60 ℃ for 20 hours according to standard CEC L-45-A-99, and kinematic viscosities were measured before and after the KRL testing. Kinematic viscosities of composition A, F and group III base oils were measured at 40 ℃ and 100 ℃ according to standard ASTM D445 with a capillary viscometer from Herzog.

Kinematic viscosity measurement:

the kinematic viscosities of the base oils of composition B and group III were measured at 40 ℃ and 100 ℃ according to the standard ASTM D445 with a capillary viscometer from the Herzog company.

3.2.Results

And (3) shear measurement:

FIGS. 5, 6 and 7 show the change curves of kinematic viscosity at 40 deg.C, 100 deg.C and 150 deg.C, respectively, measured as shear rate for composition A and composition F according to the invention.

When the shear rate is low (maximum 10000 s)^-1) When the rheological behavior of formulations a and F is the same. Composition F showed a significant decrease in kinematic viscosity when high shear rates were applied; this behavior shows poor shear strength for high molar mass polymers. Composition a comprising the oligomer combination according to the invention shows viscosity stability at high shear rates at 40 ℃ and 100 ℃, even at elevated temperatures up to 150 ℃. This illustrates the ability of the claimed oligomer mixture to thicken the medium in which it is dispersed and the technical effect of maintaining this ability under high temperature shear.

Mechanical degradation:

kinematic viscosities of compositions a and F were measured at 40 ℃ and 100 ℃ before and after KRL 20 hours mechanical degradation testing. The results obtained are collated in table 2.1.

Composition F, which contained 2.6 mass% of poly (borate ester) p-EB and 2.25 mass% of polyglycol p-diol, showed irreversible viscosity loss after shearing at 40 ℃ and 100 ℃. When using composition A containing the oligomers o-diol-2 and o-EB-1 according to the invention, no significant viscosity loss was observed. The composition retains its properties at elevated temperatures. These results show that the composition a according to the invention is better resistant to mechanical degradation than the composition F comprising a polymer of high molar mass.

The shear stability characterized by PSSI (permanent shear stability index) was calculated from the kinematic viscosity of the composition in oil after KRL 20 hours shear at 40 ℃ and 100 ℃ according to the following mathematical expression:

PSSI ═ KV after initial KV-KRL)/(initial KV-KV base oil) ] × 100.

The permanent shear stability index of composition F is greater than 40%. This indicates that certain high molar mass polymer molecules are destroyed under mechanical shear stress, resulting in irreversible viscosity loss of the formulation studied. In another aspect, composition A has only 2% PSSI at 40 ℃ and 1% PSSI at 100 ℃. This shows that the shear sensitive behaviour of the formulations according to the invention is slight and that they are resistant to mechanical degradation.

Table 2.1: measurement of kinematic viscosity at 40 ℃ and 100 ℃ before and after KRL 20-hour mechanical degradation test of composition A and composition F according to the invention

Kinematic viscosity measurement:

kinematic viscosities of composition B and group III base oils were measured at 40 ℃ and 100 ℃. The results obtained are collated in table 2.2.

Composition B, containing 5 mass% of boric acid diester molecules Di-EB and 10 mass% of oligomer o-diol-2, showed increased kinematic viscosity at 40 ℃ and 100 ℃. The viscosity increase observed at high temperature is more pronounced: the viscosity index is thus greatly increased.

Table 2.2: results of kinematic viscosity measurements of composition B according to the invention at 40 ℃ and 100 ℃

Detailed Description

One or more features after the expression "consisting essentially of … …" means that components or steps that do not significantly alter the characteristics and features of the invention other than the explicitly listed components or steps may be included in the methods or materials of the invention.

Unless expressly stated otherwise, the expression "X to Y" includes the extremes. Thus, the expression means that the target range includes the value X, Y and all values of X to Y.

Definition of：

The term "oligomer" refers to a macromolecule composed of a limited number of repeating units. These repeating units may all be the same or the oligomers may comprise different repeating units. Typically, the oligomer comprises from 2 to 100 repeating units and has a number average molar mass greater than or equal to 600 grams/mole and less than or equal to 10000 grams/mole.

The term "copolymer" refers to a linear or branched oligomer or macromolecule having a sequence formed by several repeating units (or monomer units), at least two of which have different chemical structures.

The term "monomeric unit" or "monomer" refers to a molecule that can be converted to an oligomer or macromolecule by binding to itself or to other molecules of the same type. Monomer means the smallest constitutional unit from which an oligomer or macromolecule is obtained by repetition.

The term "random oligomer or copolymer" refers to a macromolecule in which the sequence distribution of the monomer units follows a known statistical law. For example, when a copolymer or oligomer is formed from monomer units that are distributed in a markov distribution, it is random. FIG. 1 shows a schematic random copolymer (P1). The distribution of monomer units in the polymer chain depends on the reactivity of the polymerizable functional groups of the monomers and the relative concentration of the monomers.

The term "block copolymer or oligomer" refers to a macromolecule comprising or consisting of one or more than one block. The term "block" refers to a portion of a copolymer that contains several identical or different monomer units and has at least one structural or configurational feature that distinguishes it from its adjacent portions. FIG. 1 shows a schematic block copolymer (P3).

"gradient copolymer or oligomer" refers to a macromolecule having at least two monomer units of different structures in which the monomer composition gradually changes along the chain, gradually changing from one end of the polymer chain, which is rich in one monomer unit, to the other end, which is rich in the other comonomer. Fig. 1 shows a schematic gradient copolymer (P2).

The polyglycol oligomers of the invention may be random oligomers or gradient oligomers or block oligomers.

The polyborate oligomer of the present invention may be a random oligomer or a gradient oligomer or a block oligomer.

The term "copolymerization" refers to a process of converting a mixture of at least two monomer units of different chemical structures into an oligomer or copolymer.

In the remainder of the present patent application, "B" denotes a boron atom.

The term "C_i-C_jAlkyl "denotes a straight or branched saturated hydrocarbon chain containing from i to j carbon atoms. For example, the term "C₁-C₁₀Alkyl "means a straight or branched saturated hydrocarbon chain containing from 1 to 10 carbon atoms.

The term "C_x-C_yAryl "represents a functional group derived from an aromatic hydrocarbon-based compound containing x to y carbon atoms. Such functional groups may be monocyclic or polycyclic. As an example, C₆-C₁₈Aryl groups may be phenyl, naphthalene, anthracene, phenanthrene, and tetracene.

The term "C_x-C_yAlkenyl "denotes a straight or branched hydrocarbon chain comprising at least one unsaturated bond, preferably a carbon-carbon double bond, and comprising x to y carbon atoms.

The term "C_x-C_yAralkyl "means an aromatic hydrocarbon compound, preferably a monocyclic aromatic hydrocarbon compound, substituted with at least one straight or branched alkyl chain, wherein the total number of carbon atoms in the aromatic ring and its substituents is from x to y carbon atoms. As an example, C₇-C₁₈The aralkyl group may be selected from benzyl, tolyl, and xylyl.

The term "C substituted by a group Y_x-C_yAryl "denotes an aromatic hydrocarbon compound, preferably a monocyclic aromatic hydrocarbon compound, comprising x to Y carbon atoms, at least one carbon atom of the aromatic ring being substituted by a group Y.

The term "halogen" denotes a halogen atom selected from chlorine, bromine, fluorine and iodine.

In the specification, when it is stated that the copolymer or oligomer "contains monomers corresponding to the monomer M_iWhen the repeating unit "is used, it means that it may be directly derived from the monomer M_iCopolymerization with other comonomers, and i denotes the identity which identifies the various monomers illustrated below, but also indicates that it is possible to pass through the monomer M_iOther monomers obtained by copolymerization and possibly subsequently subjected to a chemical conversion step, so that it comprises structural units of the formula I with the monomers M_iStructures obtained by copolymerizationThe units are the same. For example, a monomer bearing an acid functional group, such as acrylic acid or methacrylic acid, may be first copolymerized with other monomers to form a copolymer, and then all or some of the acid functional group may be subsequently converted by any reaction, such as by esterification with an alkanol, or amidation with an alkylamine. A copolymer will then be obtained comprising repeating units corresponding to the alkyl acrylate or alkyl acrylamide monomers.

The term "copolymer/oligomer is produced directly or indirectly from … …" means that the process used to prepare the copolymer/oligomer may include one or more steps other than copolymerization, such as a deprotection step. It is noted that in the case of diol oligomers, a step of deprotection of the diol functions may optionally be carried out after copolymerization.

Throughout the description, the following expressions are not used preferably and equally: "oligomer results directly or indirectly from copolymerization" and "oligomer results from copolymerization".

Additive composition according to the invention:

one object of the present invention is a composition of exchangeable and associative compounds resulting from at least the mixing of:

a polyglycol oligomer a1, which is described below or is obtainable in particular by one of the methods described below;

compound a2 comprising at least two boronic acid ester functions described below.

Such additive composition enables control and regulation of the rheological behaviour of the added medium. The medium may be a hydrophobic medium, in particular a non-polar medium, such as a solvent, a mineral oil, a natural oil or a synthetic oil.

oPolyglycol oligomer A1

Polyglycol oligomer a1 is a hydrocarbon-based macromolecule comprising at least two diol functional groups and optionally one or more than one oxygen-based, nitrogen-based or sulfur-based functional group, for example from carboxylic acids, esters, ethers, amines, amides, thiols, thioethers, thioesters.

The number average molar mass of the polyglycol oligomer A1 is less than 10000 g/mol. Advantageously, the number average molar mass of the polyglycol oligomer a1 is less than 9500 g/mol.

Preferably, the number average molar mass of the polyglycol oligomer a1 is from 600 g/mol to less than 10000 g/mol, preferably from 600 g/mol to 9500 g/mol.

Number average molar masses were obtained by size exclusion chromatography using poly (methyl methacrylate) calibration. Size exclusion chromatography using poly (methyl methacrylate) calibration is described in the publication (Fontanlle, M.; Gnanou, Y., Chimie et physico-chip des polymers, second edition; Dunod: 2010; page 546).

Oligomer A1 comprises repeating units corresponding to monomer M1 of formula (I).

Oligomer a1 may comprise repeating units corresponding to monomer M2 of formula (II).

Oligomer a1 may comprise repeating units corresponding to monomer M3 of formula (X).

Advantageously, oligomer a1 does not contain any repeating units of aromatic type. The expression "oligomer a1 does not comprise any recurring units of aromatic type" means that oligomer a1 comprises less than 2 mol% of recurring units of aromatic type, in particular less than 2 mol% of recurring units corresponding to styrene. Advantageously, this definition corresponds to an oligomer a1 comprising less than 1.5 mol% of recurring units of aromatic type, in particular less than 1.5 mol% of recurring units corresponding to styrene.

Advantageously, the oligomer a1 comprises at least the recurring units corresponding to the monomer M1 of formula (I) and to the recurring units corresponding to the monomer M2 of formula (II), of a non-aromatic type. Advantageously, the number-average molar mass of the polyglycol oligomer A1 is less than 10000 g/mol, preferably less than 9500 g/mol. Preferably, the number average molar mass of a1 is between 600 g/mol and less than 10000 g/mol, advantageously between 600 g/mol and 9500 g/mol.

According to a preferred embodiment of the invention, the polyglycol oligomer a1 results directly or indirectly from the copolymerization of at least two first monomers M1 bearing diol functional groups and at least one second monomer M2 of the nonaromatic type, the chemical structure of said monomers M2 being different from that of the monomers M1.

According to a preferred embodiment, the polyglycol oligomer a1 consists essentially of monomers corresponding to at least two monomers M1 bearing diol functional groups and one or more than one monomer M2 which is chemically different from monomer M1.

·Monomer M1

Monomer M1 has the general formula (I):

wherein:

-R₁is selected from-H, -CH₃and-CH₂-CH₃preferably-H and-CH₃；

-x is an integer from 1 to 18, preferably from 2 to 18, more preferably from 3 to 8, even more preferably x is equal to 4;

-y is an integer equal to 0 or 1; preferably y is equal to 0;

-X₁and X₂Which may be the same or different, are selected from the group consisting of hydrogen, tetrahydropyranyl, methoxymethyl, t-butyl, benzyl, trimethylsilyl and t-butyldimethylsilyl;

or

-X₁And X₂Forms a bridge with the oxygen atom having the formula:

wherein:

the asterisk (—) indicates the bond to the oxygen atom,

-R’₂and R "₂Which may be identical or different, are selected from hydrogen and C₁-C₁₁An alkyl group;

or

-X₁And X₂With an oxygen atom to form a boronic ester having the formula:

wherein:

the asterisk (—) indicates the bond to the oxygen atom,

-R”’₂is selected from C₆-C₃₀Aryl radical, C₇-C₃₀Aralkyl and C₂-C₃₀Alkyl, preferably C₆-C₁₈Aryl, more preferably phenyl.

Preferably, when R'₂And R "₂Is C₁-C₁₁In the case of alkyl, the hydrocarbon chain is straight. Preferably, C₁-C₁₁The alkyl group is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and n-undecyl. More preferably, C₁-C₁₁The alkyl group is a methyl group.

Preferably, when R'₂Is C₂-C₃₀In the case of alkyl, the hydrocarbon chain is straight.

Among the monomers of formula (I), the monomers corresponding to formula (I-A) are preferred:

wherein:

-R₁is selected from-H, -CH₃and-CH₂-CH₃preferably-H and-CH₃；

-x is an integer from 1 to 18, preferably from 2 to 18, more preferably from 3 to 8, even more preferably x is equal to 4;

-y is an integer equal to 0 or 1; preferably y is equal to 0.

Among the monomers of formula (I), the monomers corresponding to formula (I-B) are preferred:

wherein:

-R₁is selected from-H, -CH₃and-CH₂-CH₃preferably-H and-CH₃；

-x is an integer from 1 to 18, preferably from 2 to 18, more preferably from 3 to 8, even more preferably x is equal to 4;

-y is an integer equal to 0 or 1; preferably y is equal to 0;

-Y₁and Y₂Which may be the same or different, is selected from tetrahydropyranyl, methoxymethyl, t-butyl, benzyl, trimethylsilyl and t-butyldimethylsilyl;

or

-Y₁And Y₂Forms a bridge with the oxygen atom having the formula:

wherein:

the asterisk (—) indicates the bond to the oxygen atom,

-R’₂and R "₂Which may be identical or different, are selected from hydrogen and C₁-C₁₁An alkyl group;

or

-Y₁And Y₂With an oxygen atom to form a boronic ester having the formula:

wherein:

the asterisk (—) indicates the bond to the oxygen atom,

-R”’₂is selected from C₆-C₃₀Aryl radical, C₇-C₃₀Aralkyl and C₂-C₃₀Alkyl, preferably C₆-C₁₈Aryl, more preferablyAnd (4) selecting phenyl.

Preferably, when R'₂And R "₂Is C₁-C₁₁In the case of alkyl, the hydrocarbon chain is straight. Preferably, C₁-C₁₁The alkyl group is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and n-undecyl. More preferably, C₁-C₁₁The alkyl group is a methyl group.

Preferably, when R'₂Is C₂-C₃₀In the case of alkyl, the hydrocarbon chain is straight.

The synthesis of the polyglycol oligomer (A1) may involve copolymerization of the protected form of monomer (I-B) with other comonomers, followed by deprotection of the diol functionality of monomer (I-B).

·Obtaining monomer M1

Monomer M1 of general formula (I) was obtained according to the methods described in WO2015/110642, WO2015/110643 and WO 2016/113229.

Examples of the synthesis of monomer M1 are described in the experimental part of patent applications WO2015/110642, WO2015/110643 and WO 2016/113229.

·Monomer M2

Monomer M2 has the general formula (II):

wherein:

-R₂is selected from-H, -CH₃and-CH₂-CH₃preferably-H and-CH₃；

-R₃Selected from: -C (O) -O-R'₃；–O–R’₃；–S–R’₃and-C (O) -N (H) -R'₃Wherein R'₃Is C₁-C₃₀An alkyl group.

Among the monomers of formula (II), monomers corresponding to formula (II-A) are preferred:

wherein:

-R₂is selected from-H, -CH₃and-CH₂-CH₃preferably-H and-CH₃；

-R”₃Is C₁-C₈An alkyl group.

Among the monomers of formula (II), monomers corresponding to formula (II-B) are preferred:

wherein:

-R₂is selected from-H, -CH₃and-CH₂-CH₃preferably-H and-CH₃；

-R”’₃Is C₉-C₃₀An alkyl group.

·Preparation of monomer M2

The monomers of the formulae (II), (II-A) and (II-B) are well known to the person skilled in the art. They are composed ofAndand (7) selling.

·Monomer M3

Monomer M3 has the general formula (X):

wherein:

-Z₁、Z₂and Z₃Which may be the same or different, represent a hydrogen atom, C₁-C₁₂Alkyl and a radical of the group-OZ ' or-C (O) -O-Z ', in which Z ' is C₁-C₁₂An alkyl group.

The term "C₁-C₁₂Alkyl "means a straight or branched saturated hydrocarbon chain containing from 1 to 12 carbon atoms. Preferably, the hydrocarbon chain is straight. Preferably, the hydrocarbon chain comprises 1 to 6 carbon atoms.

Advantageously, Z₁、Z₂And Z₃Which may be the same or different, represent a hydrogen atom, C₁-C₆Alkyl and a radical of-OZ ' or-C (O) -O-Z ', wherein Z ' is C₁-C₆An alkyl group.

More preferably, Z₁、Z₂And Z₃Which may be the same or different, represent a hydrogen atom, C₁-C₄Alkyl and a radical of the group-OZ ' or-C (O) -O-Z ', in which Z ' is C₁-C₄An alkyl group.

Among the preferred monomers M3, mention may be made of: styrene, p-tert-butylstyrene, p-methoxystyrene, p-acetoxystyrene and 2,4, 6-trimethylstyrene.

According to a preferred embodiment, M3 is styrene.

·Preparation of monomer M3

Certain monomers of formula (X), such as styrene, p-tert-butylstyrene, p-methoxystyrene, p-acetoxystyrene and 2,4, 6-trimethylstyrene, are well known to those skilled in the art. They are especially composed ofAnd (7) selling. Other monomers can be prepared from these commercially available monomers by synthetic methods well known to those skilled in the art.

·Other monomers

In addition to the repeating units corresponding to monomers M1, M2 and M3 detailed above, the oligomer a1 of the invention may comprise further repeating units derived from other comonomers in a proportion of not more than 20% by weight, preferably not more than 10% by weight, more preferably not more than 5% by weight, based on the total weight of the repeating units constituting the copolymer a 1.

·For obtaining polyglycol oligomer A1 method

The person skilled in the art is able to synthesize the polyglycol oligomer A1 on the basis of his general knowledge.

The copolymerization can be initiated in bulk or in solution in an organic solvent together with the free-radical-generating compound. For example, the oligomers of the invention are obtained by known free radical copolymerization processes, in particular controlled radical copolymerization, for example the process known as reversible addition-fragmentation chain transfer (RAFT) controlled radical polymerization and the process known as Atom Transfer Radical Polymerization (ATRP). Conventional free Radical and telomerization reactions can also be used to prepare The copolymers of The invention (Moad, G.; Solomon, D.H., The Chemistry of radial Polymerization, second edition; Elsevier Ltd: 2006; page 639; Matyaszewski, K.; Davis, T.P. handbook of radial Polymerization; Wiley-Interscience: Hoboken, 2002; page 936).

To control the length of the oligomer chain, methods known to those skilled in the art can be used, for example: the use of chain transfer agents, in particular mercaptans; controlling the monomer ratio according to their reactivity; kinetics of monomer introduction; the reaction temperature. Such a process is described in particular in US-5942642, US-5691284 and US-4009195.

The polyglycol oligomer a1 is advantageously prepared according to a preparation process comprising at least one polymerization step (a) in which at least the following are brought into contact:

i) two first monomers M1 of formula (I) as previously described;

II) optionally at least one second monomer M2 of formula (II) as previously described;

iii) optionally at least one third monomer M3 of formula (X) as previously described;

iv) at least one source of free radicals.

In one embodiment, the process may further comprise v) at least one chain transfer agent.

The term "free radical source" refers to a compound used to generate a chemical species with one or more than one unpaired outermost electron. Those skilled in the art can use what are known per se and are suitable for polymerization processes, in particularIs any source of free radicals for a controlled radical polymerization process. Among the free radical sources, preference is given, by way of example, to benzoyl peroxide, tert-butyl peroxide, diazo compounds such as azobisisobutyronitrile, peroxy compounds such as persulfates or hydrogen peroxide, redox systems such as Fe²⁺Or ascorbic acid/hydrogen peroxide, or a compound which can be cleaved photochemically or by ionizing radiation, such as ultraviolet light, or by beta-or gamma-radiation.

The term "chain transfer agent" denotes a compound aimed at ensuring the uniform growth of macromolecular chains through a reversible transfer reaction between a growth substance, i.e. a polymer chain terminated with carbon-based radicals, and a dormant species, i.e. a polymer chain terminated with a transfer agent. This reversible transfer process enables control of the molecular weight of the copolymer thus prepared. Preferably, in the process of the present invention, the chain transfer agent comprises a thiocarbonylthio group-S-C (═ S) -. As the chain transfer agent, there may be mentioned dithioesters, trithiocarbonates, xanthates and dithiocarbamates. Preferred transfer agents are cumyl dithiobenzoate or 2-cyano-2-propylbenzodithio (2-cyano-2-propyl benzodithionate).

The term "chain transfer agent" also denotes the following compounds: the purpose of this is to limit the growth of the macromolecular chains formed by the addition of the monomer molecules and to initiate new chains, thus enabling the final molecular weight to be limited, or even controlled. Transfer agents of this type are used in telomerization reactions. A preferred transfer agent is cysteamine.

In one embodiment, a method for preparing a polyglycol oligomer comprises:

-at least one polymerization step (a) as defined above, in which the monomers M1 and M2 are chosen from X representing hydrogen₁And X₂。

According to one embodiment (when radical polymerisation has been carried out with a RAFT chain transfer agent), the process comprises, after direct synthesis of the oligomer containing diol functions, a step of removing RAFT chain ends by aminolysis followed by michael addition.

The preferences and definitions described for the general formulae (I), (I-A), (I-B), (II-A), (II-B) and (X) also apply to the process described above.

·Properties of polyglycol oligomer A1

The polyglycol oligomer a1 is linear. Oligomer a1 has a backbone of polymerizable functional groups, in particular methacrylate functional groups and optionally a backbone of styrene or styrene-based functional groups, and hydrocarbon side chains optionally substituted with diol functional groups.

The advantage of the polyglycol oligomer a1 is sensitivity to external stimuli, such as temperature, pressure and shear rate; this sensitivity is reflected in a change in properties. The spatial conformation of the oligomer chain changes in response to a stimulus.

Advantageously, the average length of the side chains of the polyglycol oligomer a1 is from 8 to 20 carbon atoms, preferably from 9 to 18 carbon atoms. The term "average length of side chains" means the average length of side chains of the monomer M1 of formula (I) and the monomer M2 of formula (II) included in the copolymer composition. Side chains derived from the optional polyethylene monomer are not included in the calculation of the average length of the side chains. The person skilled in the art knows how to obtain such average lengths by appropriate selection of the type and proportions of the monomers constituting the polyglycol oligomer. Such a choice of average chain length enables to obtain oligomers which are soluble in the hydrophobic medium, independently of the temperature at which they are dissolved. The polyglycol oligomer a1 is therefore miscible in hydrophobic media. The term "hydrophobic medium" denotes a medium having little or no affinity for water, i.e. immiscible with water or with an aqueous medium.

Advantageously, the molar percentage of the recurring units in the polyglycol oligomer a1 corresponding to the monomer M1 of formula (I) in the copolymer is from 2% to 70%, preferably from 4% to 50%.

The mole percent of repeat units in the oligomer is directly obtained by adjusting the amount of monomer used to synthesize the oligomer.

Advantageously, the number average degree of polymerization of the polyglycol oligomer a1 is from 3 to 100, preferably from 3 to 50. The degree of polymerization is controlled in a known manner using controlled radical polymerization techniques, telomerization techniques, or by adjusting the amount of free radical source when preparing the copolymers of the invention by conventional radical polymerization.

Advantageously, the polydispersity index (Ip) of the polyglycol oligomer a1 is from 1.05 to 4.0, preferably from 1.10 to 3.8. The polydispersity index is obtained by size exclusion chromatography calibrated using poly (methyl methacrylate).

οCompound A2

·Boric acid diester compound A2

In one embodiment, compound a2 comprising two borate functional groups has the general formula (III):

wherein:

-w₁and w₂Which may be the same or different, are integers equal to 0 and 1,

-R₄、R₅、R₆and R₇Which may be the same or different, are selected from hydrogen and hydrocarbyl groups comprising 1 to 30 carbon atoms, preferably 4 to 18 carbon atoms, even more preferably 6 to 14 carbon atoms, optionally substituted with one or more groups selected from hydroxy and the group-OJ or-c (O) -O-J, J being a hydrocarbyl group comprising 1 to 24 carbon atoms, preferably J comprising 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms;

-L is a divalent bonding group selected from C₆-C₁₈Aryl radical, C₇-C₂₄Aralkyl and C₂-C₂₄A hydrocarbon chain. Preferably, the hydrocarbon chain is a straight chain alkyl group. Preferably, the hydrocarbon chain comprises from 6 to 16 carbon atoms. Preferably, L is C₆-C₁₈And (4) an aryl group.

In one embodiment of the invention, compound a2 is a compound of formula (III) above, wherein:

-w₁and w₂Which may be identical or different, are integers equal to 0 and 1;

-R₄and R₆Are identical and are hydrogen atoms;

-R₅and R₇Are identical and are hydrocarbyl groups, preferably straight-chain alkyl groups, containing from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 6 to 16 carbon atoms;

-L is a divalent bonding group and is C₆-C₁₈Aryl, preferably phenyl.

The boronic acid diester compound of formula (III) a2 as described above is obtained according to the methods described in WO2015/110642 or WO 2015/110643.

·Poly (boronate) oligomer Compound A2

In another embodiment, compound A2 comprising at least two borate functional groups is a poly (boronate) oligomer obtained from the copolymerization of at least two monomers M4 of formula (IV) as described below and

-at least one monomer M5 of formula (V) as described below;

and/or

-at least one monomer M3 of formula (X) as described below.

In the remainder of the present patent application, the expression "borate oligomer or copolymer" or "poly (borate) oligomer or copolymer" is equivalent and denotes the same copolymer.

Advantageously, the number average molar mass of the poly (boronate) copolymer is from 600 g/mol to 10000 g/mol.

Preferably, the number average molecular weight of the boronate oligomer a2 is from 600 g/mole to less than 10000 g/mole, advantageously from 600 g/mole to 9500 g/mole, more advantageously from 600 g/mole to 5000 g/mole.

Number average molar mass was measured by size exclusion chromatography calibrated using poly (methyl methacrylate). Size exclusion chromatography using poly (methyl methacrylate) calibration is described in the publication (Fontanlle, M.; Gnanou, Y., Chimie et physico-chemie des polymers, second edition; Dunod: 2010; page 546).

√Of formula (IV)Monomer M4

Monomer M4 of boronate oligomer compound a2 has the general formula (IV) wherein:

wherein:

-t is an integer equal to 0 or 1;

-u is an integer equal to 0 or 1;

-M and R₈Are identical or different divalent bonding groups and are selected from C₆-C₁₈Aryl radical, C₇-C₂₄Aralkyl and C₂-C₂₄Alkyl, preferably C₆-C₁₈An aryl group, a heteroaryl group,

x is selected from the group consisting of-O-C (O) -, -C (O) -O-, -C (O) -N (H) -, -N (H) -C (O) -, -S-, -N (H) -, -N (R'₄) -and-O-, wherein R'₄Is a hydrocarbon chain comprising from 1 to 15 carbon atoms; preferably, a hydrocarbon chain R'₄Is a straight chain alkyl group; preferably, R'₄Containing 1 to 8 carbon atoms;

-R₉is selected from-H, -CH₃and-CH₂-CH₃preferably-H and-CH₃；

-R₁₀And R₁₁Which may be identical or different, are chosen from hydrogen and a hydrocarbon radical comprising from 1 to 30 carbon atoms, preferably from 4 to 18 carbon atoms, even more preferably from 6 to 14 carbon atoms, optionally substituted by one or more groups chosen from: a hydroxyl group and a group-OJ or C (O) -O-J, J being a hydrocarbon group comprising from 1 to 24 carbon atoms; preferably, the hydrocarbon chain J comprises from 4 to 18 carbon atoms, preferably from 6 to 12 carbon atoms.

In one embodiment, monomer M4 has the general formula (IV), wherein:

-t is an integer equal to 0 or 1;

-u is an integer equal to 0 or 1;

-M and R₈Are divalent bonding groups and are not identical, M is C₆-C₁₈Aryl, preferably phenyl, R₈Is C₇-C₂₄Aralkyl, preferably benzyl;

-X is a functional group selected from-O-C (O) -, -C (O) -O-, -C (O) -N (H) -and-O-, preferably-C (O) -O-or-O-C (O) -;

-R₉is selected from-H and-CH₃preferably-H;

-R₁₀and R₁₁Is different, the radical R₁₀Or R₁₁Is H and the radical R₁₀Or R₁₁Is a hydrocarbon chain, preferably a straight chain alkyl group containing from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 6 to 12 carbon atoms.

In one embodiment, monomer M4 is a polyethylene monomer. In formula (IV): when u is 1, R₉Is H and R₈Is represented by C₆-C₁₈Aryl or C₇-C₂₄Aralkyl, and the double bond of monomer M4 of formula (IV) is directly attached to the aryl group.

√Synthesis of monomer M4 of formula (IV)

The monomer M4 of formula (IV) described above is obtained according to the method described in WO2015/110642 or WO 2015/110643.

√Synthesis of monomer M5 of general formula (V):

monomer M5 of boronic ester copolymer Compound A2 has the formula (V)

Wherein:

-R₁₂is selected from-H, -CH₃and-CH₂-CH₃preferably-H and-CH₃；

-R₁₃Is selected from-C (O) -O-R'₁₃、–O–R’₁₃、–S–R’₁₃and-C (O) -N (H) -R'₁₃Wherein R'₁₃Is C₁-C₂₅An alkyl group.

Preferably, R'₁₃Is a straight chain.

Among the monomers of formula (V), monomers corresponding to formula (V-A) are preferred:

wherein:

-R₂is selected from-H, -CH₃and-CH₂-CH₃preferably-H and-CH₃；

-R’₁₃Is C₁-C₂₅Alkyl, preferably straight-chain C₁-C₂₅Alkyl, even more preferably straight chain C₅-C₁₅An alkyl group.

√Preparation of monomer M5

The monomers of the formulae (V) and (V-A) are well known to the person skilled in the art. They are composed ofAndand (7) selling.

√Synthesis of Poly (boronate) oligomer Compound A2

One skilled in the art would be able to synthesize borate ester oligomers or copolymers based on common general knowledge. The copolymerization can be initiated in bulk or in solution in an organic solvent together with the free-radical-generating compound. For example, the boronate ester oligomers or copolymers of the present invention are obtained by known free radical copolymerization methods, particularly controlled radical copolymerization, for example, the so-called reversible addition-fragmentation chain transfer (RAFT) controlled radical polymerization method and the so-called Atom Transfer Radical Polymerization (ATRP) method. Conventional free Radical and telomerization reactions can also be used to prepare The copolymers or oligomers of The present invention (Moad, G.; Solomon, D.H., The Chemistry of radial Polymerization, second edition; Elsevier Ltd: 2006; page 639; Matyaszewski, K.; Davis, T.P. handbook of radial Polymerization; Wiley-Interscience: Hoboken, 2002; page 936).

Borate ester copolymers or oligomers prepared according to a process comprising at least one polymerization step (a) wherein at least the following are contacted:

i) two first monomers M4 of general formula (IV) as previously defined;

ii) optionally at least one monomer M5 of formula (V) as previously defined;

iii) optionally at least one monomer M3 of formula (X) as previously defined;

iv) at least one source of free radicals.

In one embodiment, the process may further comprise v) at least one chain transfer agent.

The preferences and definitions described for the formulae (IV), (V) and (X) also apply to the process.

The free radical source and chain transfer agent are those already described for the synthesis of polyglycol oligomers. The preferences described for the free radical source and the transfer agent also apply to this process.

√Properties of Poly (boronate) oligomer Compound A2

Advantageously, from the group R of the monomer M4 of formula (IV)₁₀、M、(R₈)_u(wherein u equals 0 or 1) and X has a total number of carbon atoms in the chain of 8 to 38, preferably 10 to 26.

Advantageously, the borate ester copolymer or oligomer has an average length of side chains of greater than 8 carbon atoms, preferably 11 to 16 carbon atoms. This chain length is capable of solubilizing the borate ester copolymer or oligomer in a hydrophobic medium. The term "average length of the side chains" means the average length of the side chains of each monomer constituting the copolymer or oligomer. The side chains derived from the styrene monomer are not taken into account in the calculation of the average length of the side chains. One skilled in the art would know how to obtain such average lengths by appropriate selection of the types and proportions of monomers that make up the borate ester copolymer or oligomer.

Advantageously, the molar percentage of monomer M4 of formula (IV) in the copolymer or oligomer of boronate ester oligomer a2 is from 4% to 50%, preferably from 4% to 30%.

Advantageously, the molar percentage of monomer M4 of formula (IV) in the borate oligomer a2 is from 4% to 50%, preferably from 4% to 30%, in the copolymer or oligomer, and the molar percentage of monomer M5 of formula (V) in the copolymer or oligomer is from 50% to 96%, preferably from 70% to 96%.

Advantageously, the molar percentage of monomer M3 of formula (X) in the borate oligomer a2 is from 2 to 50 mole%, preferably from 3 to 40 mole%, more preferably from 5 to 35 mole% in the oligomer.

Advantageously, the number average degree of polymerization of the borate oligomer is from 2 to 100, preferably from 2 to 50.

Advantageously, the borate oligomer has a polydispersity index (Ip) of from 1.04 to 3.54, preferably from 1.10 to 3.10. These values were obtained by size exclusion chromatography calibrated with poly (methyl methacrylate) using tetrahydrofuran as eluent.

The nature of compound a2 (particularly a boronate oligomer) is such that it can react with compounds bearing diol functional groups by transesterification in hydrophobic media, particularly in non-polar media. This transesterification reaction can be represented according to scheme 1 below:

thus, during the transesterification reaction, a boronic ester having a different chemical structure from the starting boronic ester is formed by the exchange of a hydrocarbyl group, which is represented below.

οExogenous Compound A4

According to one embodiment, the additive composition results from the mixing of at least:

a polyglycol oligomer A1,

-a compound A2 comprising at least two borate functional groups, which may be an oligomer, A2 comprising at least two borate functional groups and capable of associating with said polyglycol oligomer A1 through at least one transesterification reaction,

exogenous polyol compound a 4.

Advantageously, according to this embodiment of the invention, in the additive composition, the molar percentage of exogenous compound a4 with respect to the borate functional group of compound a2 is comprised between 0.025% and 5000%, preferably between 0.1% and 1000%, even more preferably between 0.5% and 500%, even more preferably between 1% and 150%.

The exogenous compound A4 is selected from polyols, in particular 1, 2-and 1, 3-diols and glycerol derivatives. For the purposes of the present invention, the term "exogenous compound" denotes a compound added to an additive composition resulting from the mixing of at least one polyglycol oligomer a1 and at least one compound a2, in particular a poly (borate) oligomer.

Compound a4 is selected from organic compounds that contain at least one diol group and are compatible with use in lubricant compositions. Preferably, compound a4 is selected from hydrocarbon compounds containing 2 to 30 carbon atoms.

Preferably, such exogenous compound a4 is selected from lubricant additives, such as compounds known to act as friction modifiers, thickeners, dispersants, or detergents in lubricant compositions.

The exogenous compound A4 can be chosen in particular from 1, 2-and 1, 3-diols and glycerol derivatives.

According to a preferred embodiment, the exogenous compound a4 can have the general formula (VI):

wherein:

w₃is an integer equal to 0 or 1 and,

R₁₄and R₁₅Which may be identical or different, are chosen from hydrogen and hydrocarbon chains containing from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 6 to 12 carbon atoms; preferably, the hydrocarbon chainIs straight chain alkyl. Preferably, it contains from 4 to 18 carbon atoms, preferably from 6 to 12 carbon atoms.

In one embodiment, the exogenous compound a4 has the general formula (VI), wherein:

-w₃is an integer equal to 0 or 1;

-R₁₄and R₁₅Which may be identical or different, are selected from the group consisting of-T, -CH₂-O-T and-CH₂-O-C (O) -T, T being selected from hydrogen and hydrocarbon chains, preferably linear alkyl chains, containing from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 6 to 12 carbon atoms.

In one embodiment, the exogenous compound a4 has the general formula (VI), wherein:

-w₃is an integer equal to 0 or 1;

-R₁₄and R₁₅Is different, the radical R₁₄Or R₁₅Is H and the radical R₁₄Or R₁₅Is a hydrocarbon chain, preferably a straight chain alkyl group containing from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 6 to 12 carbon atoms.

In another preferred embodiment, the exogenous compound is selected from the group consisting of a sugar and a sugar derivative.

The person skilled in the art will be able to select, on the basis of his general knowledge, one from among the sugars and sugar derivatives which is compatible with the lubricating oil.

Compounds of formula (VI) are commercially available from the following suppliers:Alfaand

οexogenous Compound A5

According to one embodiment, the additive composition results from the mixing of at least:

a polyglycol oligomer A1,

-a compound A2 comprising at least two borate functional groups, in particular a copolymer, advantageously an oligomer, A2 comprising at least two borate functional groups and capable of associating with said polyglycol oligomer A1 through at least one transesterification reaction,

the exogenous compound a5 is selected from those corresponding to formula (XI):

wherein:

-Q represents a hydrocarbon radical selected from comprising from 1 to 30 carbon atoms, optionally substituted by one or more than one group selected from: a hydroxyl group, a group-OJ or-C (O) -O-J, wherein J is a hydrocarbyl group comprising 1 to 24 carbon atoms;

-G₄and G₅Which may be identical or different, represent a radical chosen from a hydrogen atom, a hydrocarbon chain comprising from 1 to 24 carbon atoms, a hydroxyl group, a radical-OJ or-c (O) -O-J, J being a hydrocarbon radical comprising from 1 to 24 carbon atoms;

-g represents 0 or 1.

Advantageously, the exogenous compound a5 corresponds to formula (XIIA):

wherein:

-G₁、G₂、G₃、G₄and G₅Which may be identical or different, represent a radical chosen from a hydrogen atom, a hydrocarbon chain comprising from 1 to 24 carbon atoms, a hydroxyl group, a radical-OJ or-c (O) -O-J, J being a hydrocarbon radical comprising from 1 to 24 carbon atoms;

-g represents 0 or 1.

According to a preferred embodiment, the molar percentage of exogenous compound a5 is comprised between 0.025% and 5000%, preferably between 0.1% and 1000%, even more preferably between 0.5% and 500%, even more preferably between 1% and 150%, with respect to the diol functional groups of oligomer a 1.

According to a preferred embodiment, the exogenous compound a5 is selected from those corresponding to formula (XIIB):

according to a more preferred embodiment, the exogenous compound a5 is selected from those corresponding to formula (XIIB), wherein G ═ 0, G₄H and G₅Is represented by C₁-C₂₄An alkyl group.

The exogenous compound A5 released the diol fragment A6 of formula (XIII) in situ by transesterification.

√Properties of the novel additive composition of the invention

The additive composition of the invention results from the mixing of at least one polyglycol oligomer a1 as defined above, at least one compound a2 as defined previously and optionally at least one exogenous compound a4 or a5 as defined above, which has rheological properties that vary considerably with the temperature and the ratio of the compounds a1, a2 and optionally a4 and a5 used.

The polyglycol oligomers A1 and compound A2 as defined above have the advantage of having chemical bonds which can associate and exchange, in particular in hydrophobic media, in particular nonpolar hydrophobic media.

Under certain conditions, the polyglycol oligomer a1 and compound a2 as defined above may crosslink.

The polyglycol oligomer a1 and compound a2 also have the advantage of being interchangeable.

The term "associate" means that a borate type covalent chemical bond is established between the polyglycol oligomer a1 and the compound a2 comprising at least two borate functional groups. Depending on the functional groups of the polyglycol a1 and the compound a2 and depending on the composition of the mixture, the formation of covalent bonds between the polyglycol a1 and the compound a2 will optionally lead to the formation of a three-dimensional polymer network.

The term "chemical bond" means a borate covalent chemical bond.

The term "exchangeable" means that the compounds are capable of exchanging chemical bonds between themselves without changing the total number and nature of the chemical functional groups. The chemical exchange reaction (transesterification) is represented in scheme 2 below:

wherein:

r is a chemical group of compound A2,

the shaded circles represent the remaining chemical structure of compound a2,

the grid line rectangles represent the remaining chemical structure of the polyglycol oligomer a 1.

The boronic ester linkages of compound a2, optionally the boronic ester linkages formed by the transesterification reaction between the boronic ester of compound a2 and the exogenous compound a4 and the boronic ester linkages formed by the association reaction between the polyglycol oligomer a1 and the compound a2, can be exchanged with the diol functional groups possessed by compound A3 released in situ, and optionally with the diol functional groups possessed by the exogenous compound a4 and/or a5, to form new boronic esters and new diol functional groups without affecting the total number of boronic ester functional groups and diol functional groups. This other chemical bond exchange process is carried out by metathesis, by successive exchanges of the borate functional groups in the presence of a diol. FIG. 2 shows another chemical bond exchange process, in which it can be observed that polyglycol oligomer A1-1 (which associates with oligomer A2-1) exchanged two boronic acid ester bonds with boronic ester oligomer A2-2. Polyglycol oligomer A1-2 (which was associated with oligomer A2-2) exchanged two borate ester linkages with borate oligomer A2-1; the total number of borate bonds in the composition remains unchanged and is equal to 4. Oligomer A1-1 was then associated with oligomer A2-2. Oligomer A1-2 was then associated with oligomer A2-1. Oligomer A2-1 was exchanged with Polymer A2-2.

The term "crosslinked" refers to a copolymer or oligomer in the form of a network obtained by establishing bridges between macromolecular chains of the copolymer or oligomer in the form of a network. These linked chains are mostly distributed in three dimensions. The crosslinked copolymer or oligomer forms a three-dimensional network. In fact, the formation of a copolymer or oligomer network was confirmed by solubility testing. It can be confirmed that the formation of the copolymer network can be confirmed by placing the copolymer network in a solvent known to dissolve a non-crosslinked copolymer of the same chemical. If the copolymer swells rather than dissolves, the skilled person knows that a network is formed. Fig. 3 shows the solubility test.

The term "crosslinkable" refers to a copolymer or oligomer capable of being crosslinked.

The term "reversible crosslinking" refers to crosslinked copolymers or oligomers that form bridges by reversible chemical reactions. The reversible chemical reaction may move in one direction or the other, resulting in a structural change of the polymer network. The copolymer or oligomer may be transformed from an initial non-crosslinked state to a crosslinked state (three-dimensional copolymer network) and from a crosslinked state to a non-crosslinked state. In the context of the present invention, the bridges formed between the copolymer or oligomer chains are unstable. These bridges may be formed or exchanged by reversible chemical reactions. In the context of the present invention, the reversible chemical reaction is a transesterification reaction between the diol functional groups of the oligomer (copolymer a1) and the borate functional groups of the crosslinker (compound a 2). The bridges formed are borate linkages. These borate ester bonds are covalent bonds and are unstable due to the reversibility of the transesterification reaction.

The amount of borate bonds established between the polyglycol oligomer a1 and the compound a2 can be adjusted by the person skilled in the art by appropriate selection of the composition of the polyglycol oligomer a1, the compound a2 and the mixture.

In addition, the skilled person knows how to select the structure of compound a2 depending on the structure of oligomer a 1. Preferably, when the oligomer a1 comprises at least one monomer M1, wherein y ═ 1, compound a2 of general formula (III) or copolymer or oligomer a2 comprising at least one monomer M4 of formula (IV) will preferably be selected as w, respectively₁＝1、w₂1 and t 1.

The viscosity and rheological behavior of such compositions are modified by controlling the degree of association of polyglycol oligomer a1 and compound a2, especially the polyborate oligomer. When present, the exogenous compounds a4 and/or a5 can adjust the viscosity of the composition according to the intended use.

In a preferred embodiment of the present invention, the exogenous compound a4 has the same chemical species as the diol compound A3 released in situ by a transesterification reaction between the polyglycol oligomer a1 and compound a2, in particular a poly (boronate) oligomer. According to this embodiment, the total amount of free diol in the composition is strictly greater than the amount of diol compound released in situ. The term "free diol" denotes a diol functional group capable of forming a borate-type chemical bond by transesterification. For the purposes of this patent application, the term "total amount of free diols" denotes the total amount of diol functional groups that can form borate-type chemical bonds by transesterification.

According to this embodiment, the total amount of free diol is always equal to the sum of the moles (in moles) of diol functional groups of the exogenous diol compound a4 and the polyglycol oligomer a 1. In other words, in the additive composition there are present:

i moles of exogenous diol compound A4 and

j moles of polyalkylene glycol oligomer A1,

the total amount of free diol is in any case (and therefore independent of the degree of association between the polyglycol oligomer a1 and the compound a2 (in particular poly (boronate) oligomer a2) ═ i + j × average number of diols per a1 oligomer chain (units: moles).

The amount of diol released in situ in the transesterification reaction between a1 and a2 is equal to the amount of borate functional groups linking oligomers a1 and a 2.

The person skilled in the art knows how to select the chemical structure and the amount of exogenous compound a4 added to the additive composition, according to the molar percentage of the borate functional groups of compound a2, in particular according to the molar percentage of poly (borate) oligomers, in order to adjust the rheological behaviour of the composition.

Advantageously, the content of oligomer a1 in the composition is comprised between 0.1% and 50.0% by weight relative to the total weight of the composition, preferably between 0.25% and 40% by weight relative to the total weight of the final composition, and more preferably between 1% and 40% by weight relative to the total weight of the final composition.

Advantageously, the content of composition a2 in the composition ranges from 0.1% to 50.0% by weight relative to the total weight of the composition, preferably from 0.25% to 40% by weight relative to the total weight of the final composition, and more preferably from 1% to 40% by weight relative to the total weight of the final composition.

In one embodiment, oligomer a1 is present in the composition in an amount of 0.1 to 50.0% by weight, relative to the total weight of the composition, and compound a2, particularly a boronate oligomer, is present in the composition in an amount of 0.1 to 50% by weight, relative to the total weight of the composition.

Preferably, the mass ratio of polyglycol oligomer a1 and compound a2 (a1/a2 ratio) in the composition is from 0.002 to 500, preferably from 0.05 to 20, even more preferably from 0.1 to 10.

In one embodiment, the composition of the invention is in the form of a stock composition. The term "stock composition" refers to a composition from which a person skilled in the art can prepare a sub-solution by taking a quantity of stock solution, by adding the necessary amount of diluent (solvent, etc.) to obtain the desired concentration. Sub-compositions are thus obtained by diluting the stock composition.

The hydrophobic medium may be a solvent, mineral oil, natural oil or synthetic oil.

In one embodiment, the composition of the present invention may further comprise at least one additive selected from the group consisting of thermoplastics, elastomers, thermoplastic elastomers, thermosetting polymers, pigments, dyes, fillers, plasticizers, fibers, antioxidants, lubricant additives, compatibilizers, defoamers, dispersant additives, tackifiers, and stabilizers.

√The process for preparing the novel additive composition of the invention:

the novel additive compositions of the present invention are prepared by methods well known to those skilled in the art. For example, it will be apparent to those skilled in the art that:

-taking a desired amount of a solution comprising a polyglycol oligomer a1 as defined above;

-taking a desired amount of a solution comprising compound a2 as defined above; in particular a desired amount of a solution comprising a poly (boronate) oligomer as defined previously; and

-optionally taking a desired amount of a solution comprising exogenous compounds a4 and/or a5 as defined above;

-mixing the taken solutions simultaneously or sequentially to obtain the composition of the invention.

The order of addition of the compounds has no effect on the method of practice for preparing the additive composition.

√Use of the novel compositions of the invention

The composition of the invention can be used in any medium whose viscosity varies with temperature. The composition of the present invention is capable of thickening a liquid and adjusting the viscosity according to the use temperature. The additive composition according to the invention can be used in various fields, such as enhanced oil recovery, the paper industry, paints, food additives and cosmetic or pharmaceutical preparations.

They are more particularly advantageously used as lubricant additives in engines.

√Lubricant compositions according to the invention:

another subject of the invention relates to a lubricant composition obtained from the mixing of at least:

-a lubricating oil, which oil is,

a polyglycol oligomer A1 as defined previously,

-a compound A2 as defined previously comprising at least two borate functional groups and associable with the polyglycol oligomer A1 by at least one transesterification reaction,

-optionally exogenous compounds a4 and/or a5 as previously defined.

The preferred embodiments and definitions of the general formulae (I), (I-A), (I-B), (II-A), (II-B) and (X) also apply to the polyglycol oligomers A1 used in the lubricant compositions according to the invention.

The preferences and definitions of the formulae (III), (IV), (V) and (X) also apply to the borate compound A2 used in the lubricant compositions according to the invention.

An advantage of the lubricant composition according to the invention is a more stable viscosity against temperature variations with respect to the properties of the base oil. Advantageously, the viscosity of the lubricant composition is thus controlled and less dependent on temperature fluctuations. Additionally, for a certain use temperature, it is possible to adjust the viscosity of the lubricant composition and its rheological behavior by varying the amount of glycol compound or borate added to the lubricant composition. Finally, the lubricant compositions of the present invention have improved thermal stability, improved oxidation stability, improved viscosity index, improved cycle resistance, and better reproducibility of performance quality over time. They more particularly have better resistance to mechanical degradation.

οLubricating oil

The term "oil" denotes a fatty substance, which is at room temperature (25 ℃) and atmospheric pressure (760mmHg, i.e. 10)⁵Pa) of the liquid.

The term "lubricating oil" means an oil that reduces friction between two moving parts to facilitate operation of those parts. The lubricating oil may be of natural, mineral or synthetic origin.

The lubricating oil of natural origin may be an oil of vegetable or animal origin, preferably an oil of vegetable origin such as rapeseed oil, sunflower oil, palm oil, coconut oil and the like.

Lubricating oils of mineral origin are of petroleum origin and are extracted from petroleum fractions from the atmospheric and vacuum distillation of crude oil. Distillation is followed by refining operations such as solution extraction, deasphalting, solvent dewaxing, hydrotreating, hydrocracking, hydroisomerization, hydrofinishing, and the like. By way of example, mention may be made of paraffinic mineral base oils, such as Bright Stock Solvent (BSS), naphthenic mineral base oils, aromatic mineral oils, hydrorefined mineral base oils having a viscosity index of about 100, hydrocracked mineral base oils having a viscosity index of from 120 to 130, or hydroisomerized mineral base oils having a viscosity index of from 140 to 150.

Lubricating oils of synthetic origin (or synthetic base oils), as their name implies, are derived from chemical synthesis, e.g. by addition or polymerization of component products to themselves, or addition of one component product to another, e.g. esterification, alkylation, fluorination, etc., derived from petrochemistry, carbon chemistry and mineral chemistry, e.g. olefins, aromatics, alcohols, acids, halogen-based compounds, phosphorus-based compounds, silicon-based compounds, etc. By way of example, mention may be made of:

synthetic oils based on synthetic hydrocarbons, such as Polyalphaolefins (PAO), Internal Polyolefins (IPO), polybutenes and Polyisobutylenes (PIB), alkylbenzenes and alkylated polyphenyls;

synthetic oils based on esters, such as diesters or neopolyol esters;

synthetic oils based on polyalkylene glycols, such as monoalkylene glycols, polyalkylene glycols and polyalkylene glycol monoethers;

-synthetic oils based on phosphoric esters;

synthetic oils based on silicon derivatives, such as silicone oils or polysiloxanes.

Lubricating oils useful in the compositions of the present invention may be selected from any of the oils from group I to group V as specified in the API Guidelines (Base Oil interconvertibility Guidelines of the American Petroleum Institute (API)) (or equivalent oils according to the ATIEL classification (Association Technique de l' Industrie Europ ene des Lubrifiants)), summarized as follows:

measured according to standard ASTM D2007

Measured according to the standards ASTM D2622, ASTM D4294, ASTM D4927 and ASTM D3120

Measured according to standard ASTM D2270

The compositions of the present invention may comprise one or more than one lubricating oil. The lubricating oil or lubricating oil mixture is the main component in the lubricant composition. This is then referred to as a lubricant base oil. The term "major component" means that the lubricating oil or lubricating oil mixture constitutes at least 51% by weight relative to the total weight of the composition.

Preferably, the lubricating oil or mixture of lubricating oils represents at least 70% by weight relative to the total weight of the composition.

In one embodiment of the invention, the lubricating oil is selected from oils of group I, group II, group III, group IV and group V of the API classification and mixtures thereof. Preferably, the lubricating oil is selected from oils of group III, group IV and group V of the API classification and mixtures thereof. Preferably, the lubricating oil is an oil from group III of the API classification.

The kinematic viscosity of the lubricating oil is from 2cSt to 150cSt, preferably from 2cSt to 15cSt, measured at 100 ℃ according to standard ASTM D445.

οFunctional additive

In one embodiment, the composition of the present invention may further comprise one or more than one functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, antioxidants, viscosity index enhancing polymers, pour point modifiers, anti-foaming agents, thickeners, anti-corrosion additives, dispersants, friction modifiers, and mixtures thereof.

The functional additives to be added to the compositions of the present invention are selected according to the end use of the lubricant composition. These additives can be introduced in two different ways:

-each additive is added separately and sequentially to the composition,

-or all additives are added to the composition simultaneously; in this case, the additives are typically provided in the form of a package, referred to as an additive package.

When present, the functional additive or mixture of functional additives represents from 0.1% to 10% by weight relative to the total weight of the composition.

Detergent:

these additives reduce the formation of deposits on the surface of the metal parts by dissolving the byproducts of oxidation and combustion. These detergents which may be used in the lubricant composition according to the present invention are well known to those skilled in the art. These detergents, which are commonly used in formulating lubricant compositions, are generally anionic compounds comprising a lipophilic long hydrocarbon chain and a hydrophilic head. The associated cation is typically a metal cation of an alkali or alkaline earth metal. The detergents are preferably selected from alkali or alkaline earth metal salts of carboxylic acids, sulfonates, salicylates and naphthenates and phenates. The alkali and alkaline earth metals are preferably calcium, magnesium, sodium or barium. These metal salts may contain an approximately stoichiometric amount or an excess (an amount greater than the stoichiometric amount) of the metal. In the latter case, these detergents are referred to as overbased detergents. The excess metal which makes the detergent overbased is in the form of an oil-insoluble metal salt, for example a carbonate, hydroxide, oxalate, acetate or glutamate, preferably a carbonate.

Anti-wear and extreme pressure additives:

these additives protect the friction surface by forming a protective film that adsorbs onto these surfaces. There are a variety of antiwear and extreme pressure additives. Examples which may be mentioned include phosphorus-sulfur additives, such as metal alkyl thiophosphates, in particular zinc alkyl thiophosphates, more particularly zinc dialkyl dithiophosphates or ZnDTP, amine phosphates, polysulfides, in particular sulfur-based olefins, and metal dithiocarbamates.

V. antioxidant:

these additives retard the degradation of the composition. Degradation of the composition may be reflected in the formation of deposits, the presence of sludge, or an increase in the viscosity of the composition. Antioxidants act as free radical inhibitors or hydrogen peroxide destroyers. Phenolic or aminic antioxidants are commonly used.

Check corrosion inhibitor:

these additives cover the surface with a film that prevents oxygen from entering the metal surface. They can sometimes neutralize acids or certain chemical products to prevent metal corrosion. Examples which may be mentioned include, for example, dimercaptothiadiazoles (DMTD), benzotriazoles and phosphites (free sulphur scavenging).

V viscosity index enhancing polymer:

these additives ensure good cold resistance and minimum viscosity at high temperatures of the composition. Examples that may be mentioned include, for example, polymer esters, Olefin Copolymers (OCP) or Polymethacrylates (PMA).

V. pour point improver:

these additives improve the low temperature performance of the composition by slowing the formation of paraffin crystals. For example, they are polyalkyl (meth) acrylates, polyacrylates, polyacrylamides, polyalkylphenols, polyalkylnaphthalenes and polyalkylstyrenes.

V, antifoaming agent:

the function of these additives is to counteract the function of the detergent. Examples which may be mentioned include polymethylsiloxanes and polyacrylates.

V.thickener:

thickeners are additives used primarily for industrial lubrication and are capable of formulating lubricants with higher viscosity than engine lubricant compositions. Examples which may be mentioned include polyisobutenes having a weight-average molar mass of from 10000 g/mol to 100000 g/mol.

V. dispersant:

these additives ensure that suspension is maintained and insoluble solid contaminants are removed which are formed by oxidation by-products formed during use of the composition. By way of illustration, examples which may be mentioned include succinimide, PIB (polyisobutylene) succinimide and mannich bases.

V friction modifier:

these additives improve the coefficient of friction of the composition. By way of example, mention may be made of molybdenum dithiocarbamates and amines containing at least one hydrocarbon chain of at least 16 carbon atoms.

Content of compound in lubricant composition

Advantageously, the oligomer a1 is present in the lubricant composition in an amount of 0.25 to 40.0% by weight relative to the total weight of the lubricant composition, and preferably in an amount of 1 to 40% by weight relative to the total weight of the lubricant composition.

Advantageously, the content of compound a2 ranges from 0.25% to 40% by weight relative to the total weight of the lubricant composition, and preferably ranges from 1% to 40% by weight relative to the total weight of the lubricant composition.

Preferably, the mass ratio between the polyglycol oligomer a1 and the compound a2 (a1/a2 ratio) is from 0.002 to 500, preferably from 0.05 to 20, even more preferably from 0.1 to 10.

In one embodiment, the sum of the masses of oligomer a1 and compound a2 is between 0.2% and 50%, advantageously between 0.5% and 40%, relative to the total mass of the lubricant composition, preferably between 2% and 40%, relative to the total mass of the lubricant composition, and the mass of the lubricating oil is between 50% and 99.8%, relative to the total mass of the lubricant composition.

For engine applications, the sum of the masses of oligomer a1 and compound a2 advantageously represents from 1% to 35% relative to the total mass of the lubricant composition.

For transmission applications, the sum of the masses of oligomer a1 and compound a2 advantageously represents from 1% to 40% relative to the total mass of the lubricant composition.

In one embodiment, the molar percentage of exogenous compound a4 in the lubricant composition relative to the borate functional groups of compound a2 (particularly poly (borate) oligomers) is from 0.025% to 5000%, preferably from 0.1% to 1000%, more preferably from 0.5% to 500%, even more preferably from 1% to 150%.

In another embodiment, the molar percentage of exogenous compound a5 in the lubricant composition relative to the diol functional groups of compound a1 (particularly polyglycol oligomer) is from 0.025% to 5000%, preferably from 0.1% to 1000%, more preferably from 0.5% to 500%, even more preferably from 1% to 150%.

In one embodiment, the lubricant composition of the present invention results from the mixing of:

-0.25 to 40% by weight, relative to the total weight of the lubricant composition, of at least one polyglycol oligomer a1 as defined previously;

-0.25% to 40% by weight, relative to the total weight of the lubricant composition, of at least one compound a2 as previously defined; and

-optionally 0.1% to 10% by weight, relative to the total weight of the lubricant composition, of at least one exogenous compound a4 as previously defined;

-optionally 0.1% to 10% by weight, relative to the total weight of the lubricant composition, of at least one exogenous compound a5 as previously defined; and

-20 to 99.5% by weight, relative to the total weight of the lubricant composition, of at least one lubricating oil as previously defined.

In another embodiment, the lubricant composition of the present invention results from the mixing of:

-0.25 to 40% by weight, relative to the total weight of the lubricant composition, of at least one polyglycol oligomer a1 as defined previously;

-0.25% to 40% by weight, relative to the total weight of the lubricant composition, of at least one compound a2 as previously defined; and

-optionally 0.1% to 10% by weight, relative to the total weight of the lubricant composition, of at least one exogenous compound a4 as previously defined; and

-optionally 0.1% to 10% by weight, relative to the total weight of the lubricant composition, of at least one exogenous compound a5 as previously defined;

-0.5% to 15% by weight, relative to the total weight of the lubricant composition, of at least one functional additive as previously defined, and

-from 5% to 99% by weight, relative to the total weight of the lubricant composition, of at least one lubricating oil as previously defined.

Another subject of the invention is a composition at least for lubricating an engine, comprising, in particular consisting essentially of:

-from 70% to 99% by weight, preferably from 70% to 97% by weight, of a lubricating oil, and

-from 1% to 30% by weight, advantageously from 3% to 30% by weight, of a mixture of at least one oligomer a1 as defined previously and at least one borate compound a2 as defined previously; and

-optionally 0.1% to 10% by weight of at least one exogenous compound a4 as previously defined;

-optionally 0.1% to 10% by weight of at least one exogenous compound a5 as previously defined;

the composition has a kinematic viscosity at 100 ℃ measured according to standard ASTM D445 of from 3.8cSt to 26.1 cSt; the weight percentages are expressed relative to the total weight of the composition.

In the composition as defined above, at least for lubricating an engine, in particular in the presence of exogenous compounds a4 and/or a5, oligomer a1 and compound a2 as defined previously may reversibly associate and exchange; however, they do not form a three-dimensional network. They are not crosslinked.

In one embodiment, the composition for lubricating at least an engine may further comprise at least one functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, other antioxidants, anti-corrosion additives, viscosity index increasing polymers, pour point modifiers, anti-foaming agents, thickeners, dispersants, friction modifiers, and mixtures thereof.

In one embodiment of the invention, a composition is used at least for lubricating an engine, said composition comprising, in particular consisting essentially of:

-55 to 98.5% by weight of a lubricating oil, and

-1 to 30% by weight of a mixture of at least one oligomer a1 as defined previously and at least one compound a2 as defined previously; and

-optionally 0.1% to 10% by weight of at least one exogenous compound a4 as previously defined;

-optionally 0.1% to 10% by weight of at least one exogenous compound a5 as previously defined;

-0.5 to 15 wt% of at least one functional additive selected from detergents, anti-wear additives, extreme pressure additives, other antioxidants, anti-corrosion additives, viscosity index increasing polymers, pour point improvers, anti-foaming agents, thickeners, dispersants, friction modifiers and mixtures thereof;

the composition has a kinematic viscosity at 100 ℃ measured according to standard ASTM D445 of from 3.8cSt to 26.1 cSt; the weight percentages are expressed relative to the total weight of the composition.

The definitions and preferences for lubricating oil, for oligomer a1, borate compound a2 and exogenous compounds a4 and a5 also apply to compositions for at least lubricating an engine.

Another subject of the invention is a composition at least for lubricating a transmission, such as a manual or automatic transmission.

Another subject of the invention is a composition at least for lubricating a transmission, comprising, in particular consisting essentially of:

-50 to 95% by weight of a lubricating oil, and

-5 to 40% by weight of a mixture of at least one oligomer a1 as defined previously and at least one boronate compound a2 as defined previously; and

-optionally 0.1% to 10% by weight of at least one exogenous compound a4 as previously defined;

-optionally 0.1% to 10% by weight of at least one exogenous compound a5 as previously defined;

the kinematic viscosity of the composition, measured at 100 ℃ according to standard ASTM D445, is between 4.1cSt and 41cSt, the weight percentages being expressed relative to the total weight of the composition.

In the composition as defined above, at least for lubricating a transmission, the oligomer a1 and the compound a2 as defined previously may be reversibly associated and exchanged, in particular in the presence of exogenous compounds a4 and/or a 5; however, they do not form a three-dimensional network. They are not crosslinked.

In one embodiment, the composition for lubricating at least a transmission may further comprise at least one functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, other antioxidants, anti-corrosion additives, viscosity index increasing polymers, pour point modifiers, anti-foaming agents, thickeners, dispersants, friction modifiers, and mixtures thereof.

In one embodiment of the invention, a composition for lubricating at least a transmission comprises, in particular consists essentially of:

-50 to 94.9% by weight of a lubricating oil, and

-5 to 35% by weight of a mixture of at least one oligomer a1 as defined previously and at least one boronate compound a2 as defined previously; and

-optionally 0.1% to 10% by weight of at least one exogenous compound a4 as previously defined;

-optionally 0.1% to 10% by weight of at least one exogenous compound a5 as previously defined;

-0.1 to 15 wt% of at least one functional additive selected from detergents, anti-wear additives, extreme pressure additives, other antioxidants, anti-corrosion additives, viscosity index increasing polymers, pour point improvers, anti-foaming agents, thickeners, dispersants, friction modifiers and mixtures thereof;

the kinematic viscosity of the composition, measured at 100 ℃ according to standard ASTM D445, is between 4.1cSt and 41cSt, the weight percentages being expressed relative to the total weight of the composition.

The definitions and preferences for lubricating oil, for the para-oligomer a1, the boronate compound a2 and the exogenous compounds a4 and a5 also apply to the composition at least for lubricating a transmission.

√Process for preparing the lubricant composition of the present invention

The lubricant compositions of the present invention are prepared by methods well known to those skilled in the art. For example, it is possible for the person skilled in the art to:

-taking a desired amount of a solution comprising a polyglycol oligomer a1 as defined above;

-taking a desired amount of a solution comprising the boronic ester compound a2 as defined previously;

-optionally taking a desired amount of a solution comprising exogenous compounds a4 and/or a5 as defined above;

-mixing the solutions in a lubricant base oil simultaneously or sequentially to obtain the lubricant composition of the invention.

The order of addition of the compounds has no effect on the method of practice for preparing the lubricant composition.

√Properties of the Lubricant composition according to the invention

The lubricant compositions of the present invention result from the mixing of associative polymers that have the property of increasing the viscosity of the lubricating oil by association. An advantage of the lubricant composition according to the invention is that these associations or crosslinks are reversible and optionally the degree of association or crosslinking can be controlled by the addition of other diol compounds. In addition, they have improved thermal stability, improved viscosity index, improved oxidative stability, better cycle performance and better reproducibility of the quality of the properties over time, and better resistance to mechanical degradation.

One skilled in the art would know how to adjust various parameters of the various components of the composition to obtain a lubricant composition having a viscosity suitable for use.

The amount of borate linkages established between the polyglycol oligomer a1 and the compound a2 can be adjusted by the person skilled in the art by appropriate selection of the molar percentages of the polyglycol oligomer a1, the compound a2, optionally the exogenous compound a4 and/or a5, in particular the source compound a4 and/or a 5.

In addition, the skilled person knows how to select the structure of compound a2 depending on the structure of oligomer a 1. Preferably, when oligomer a1 comprises at least one monomer M1, wherein y ═ 1, compound a2 of general formula (III) or oligomer a2 comprising at least one monomer M4 of formula (IV) will preferably be selected as w, respectively₁＝1、w₂1 and t 1.

Moreover, the person skilled in the art knows in particular how to adjust:

the molar percentage of monomer M1 carrying diol functions in the polyglycol oligomer A1,

-the molar percentage of monomer M4 carrying a borate functional group in the borate oligomer A2,

average length of side chains of polyglycol oligomer A1,

-average length of side chains of boronate oligomer A2,

length of monomer M4 of boronate oligomer A2,

average degree of polymerization of polyglycol oligomer A1 and borate oligomer A2,

-the mass percentage of polyglycol oligomer A1,

-mass percentage of borate compound A2,

-optionally the amount of exogenous compound A4 and/or A5,

-…。

method for adjusting viscosity of lubricant composition

Another subject of the invention is a method for adjusting the viscosity of a lubricant composition, said method comprising at least:

-providing a lubricant composition resulting from the mixing of at least one lubricating oil, at least one polyglycol oligomer a1 and at least one compound a2, said compound a2 comprising at least two borate functional groups and being associable with said polyglycol oligomer a1 by at least one transesterification reaction, optionally adding to said lubricant composition at least one exogenous compound a4 and/or a 5.

For the purposes of the present invention, the term "adjusting the viscosity of the lubricant composition" means adjusting the viscosity according to the use of the lubricant composition. This process is described in detail in WO 2016/113229.

Other subject matter according to the invention

Another subject of the invention is the use of a lubricant composition as defined above for lubricating a mechanical part.

In the remainder of the description, percentages are expressed on a weight basis relative to the total weight of the lubricant composition.

The compositions of the present invention may be used to lubricate the surfaces of parts typically found in engines, such as piston systems, rings and sleeves.

The composition of the present invention can be used for engines or transmissions for light or heavy vehicles, and also for ships.

Another subject of the invention is a method for lubricating at least one mechanical part, in particular at least an engine or at least a transmission, said method comprising the step of contacting the mechanical part with at least one lubricant composition as defined above.

The definitions and preferences for lubricating oils, for oligomers A1, borate compounds A2 and, where appropriate, for exogenous compounds A4 and A5 also apply to the process for lubricating at least one mechanical part.