Compositions comprising thermally associated exchangeable copolymers

Abstract

The present invention relates to a composition obtained by mixing at least one polyglycol comb copolymer A1 and a compound A2 containing at least two borate functional groups, wherein the polyglycol comb copolymer A1 comprises a main chain and side chains, at least a portion of the side chains of the copolymer A1 consisting of oligomers. Depending on the ratio of the compounds A1 and A2 used, the composition according to the invention exhibits very different rheological properties. The invention also relates to a composition obtained by mixing at least one lubricating oil with such a composition of associative and exchangeable polymers, and the use of the composition for lubricating machine parts.

Description

Technical Field

[0001] The present invention relates to a composition comprising at least one comb-type polyglycol copolymer A1 and at least one compound A2 comprising at least two borate functional groups. Depending on the ratio of the compounds A1 and A2 used, this composition exhibits very different rheological properties. The present invention also relates to a composition obtained by mixing at least one lubricating oil with this polymer composition and to the use of this composition in lubricating machine parts.

[0002] The present invention relates to the field of associative and exchangeable polymers and to the field of lubricants. Prior art

[0003] High molar mass polymers are widely used to increase the viscosity of solutions in many areas, for example in the petroleum, paper, water treatment, mining, cosmetics and textile industries, as well as in all industrial technologies where thickening solutions are commonly used.

[0004] In fact, these high molecular weight polymers show the disadvantage of significant irreversible degradation under mechanical stress, compared to the same polymers of smaller size. These shear stresses on polymers of high molar mass lead to the scission of macromolecular chains. The thickening properties of the polymer thus degraded decrease or disappear, and the viscosity of the solution containing it decreases irreversibly. This low shear strength leads to a deterioration of the properties of solutions based on polymers of high molar mass.

[0005] Applications WO2015 / 110642, WO2015 / 110643 and WO2016113229 disclose a composition obtained by mixing at least one copolymer A1 obtained by copolymerization of at least one monomer functionalized by a diol functional group with at least one compound A2 comprising at least two borate functional groups. These compounds may associate to form a gel and exchange chemical bonds in a thermoreversible manner. These additives present the advantage of a reduced drop in the viscosity of the solution containing them when the temperature increases. Depending on the ratio of the compounds A1 and A2 used, these polymer compositions present very different rheological properties. They may additionally contain exogenous compounds, which make it possible to better control the association of the two compounds.

[0006] In particular, these polymer compositions can be added to lubricating oils to lubricate mechanical parts. These copolymers allow the formulation of lubricating compositions whose viscosity is better controlled than that of prior art lubricating compositions. In particular, when these copolymers are introduced into base oils, they tend to reduce the viscosity drop of the mixture when the temperature increases.

[0007] Lubricating compositions are compositions applied to the surfaces of moving parts, in particular between metal surfaces. They make it possible to reduce friction and wear between two parts that are in contact and moving with each other. They also serve to dissipate a portion of the heat energy generated by this friction. Lubricating compositions form a protective film between the surfaces of the parts to which they are applied.

[0008] Compositions for lubricating mechanical parts generally consist of base oils and additives. Base oils, especially those of petroleum or synthetic origin, exhibit changes in viscosity when the temperature changes.

[0009] This is because, when the temperature of the base oil increases, its viscosity decreases, and when the temperature of the base oil decreases, its viscosity increases. In fact, under hydrodynamic lubrication conditions, the thickness of the protective film is proportional to the viscosity and therefore also depends on the temperature. If the thickness of the protective film remains substantially constant, the composition exhibits good lubrication properties regardless of the condition of the lubricant and the length of time it is used.

[0010] In an internal combustion engine, the lubricating composition may be subjected to external or internal temperature changes. External temperature changes are caused by changes in the temperature of the ambient air, such as the temperature change between summer and winter. Internal temperature changes are caused by the operation of the engine. The temperature during the start-up phase of the engine (especially in cold weather) is lower than the temperature in continuous use. Therefore, the thickness of the protective film can vary under these different circumstances.

[0011] Therefore, it is necessary to provide a lubricating composition having good lubricating properties, the viscosity of which is not significantly affected by temperature changes.

[0012] It is known to add viscosity modifiers which improve the viscosity of lubricating compositions. The function of these additives is to modify the rheology of the lubricating composition. They enable greater stability of the viscosity to be obtained within the temperature range in which the lubricating composition is used. For example, these additives limit the decrease in viscosity of the lubricating composition when the temperature rises, while limiting the increase in viscosity under cold conditions.

[0013] Viscosity improvers (or viscosity index improvers) ensure good lubrication by limiting the effect on viscosity in cold conditions and ensuring minimum film thickness in hot conditions. Currently used viscosity improvers are polymers such as olefin copolymers (OCPs) and polyalkyl methacrylates (PAMs). Generally, the higher their molecular weight, the greater the contribution of these polymers to viscosity control.

[0014] However, polymers of high molar mass show the disadvantage of low resistance to permanent shear compared to polymers of the same kind and of the same structure but of smaller size.

[0015] In practice, lubricating compositions are subject to high shear stresses, in particular in internal combustion engines, where the spacing of moving surfaces is small and the pressures exerted on the parts are high. These shear stresses on polymers of high molar mass lead to the breaking of macromolecular chains. The thickening properties of the polymers thus degraded decrease, and the viscosity irreversibly decreases. This low resistance to permanent shearing therefore leads to a deterioration in the lubricating properties of the lubricating composition.

[0016] Finally, attempts have been made to develop compositions that exhibit greater stability towards oxidation, in particular greater resistance to oxidation by free radicals.

[0017] Document US 2011 / 319305 describes comb copolymers comprising olefinic repeating units having a molecular weight greater than 500 g / mol and repeating units having a molecular weight less than 500 g / mol and their use in hydraulic fluids.

[0018] Document EP 0 570 073 describes an additive for lubricating oils of the polyalkyl(acrylate) ester type, some of the monomers of which contain boron-based functionality.

[0019] In applications WO2015 / 110642, WO2015 / 110643 and WO2016113229, it is pointed out that the random diol copolymer A1 is a comb-type copolymer, that is, the copolymer has a main chain (also called a backbone) and hydrocarbon side chains extending from both sides of the main chain, and the side chains are optionally hydroxylated. It can be seen that the side chains of these copolymers in the prior art are not polymers or oligomers, so these copolymers are not comb-type copolymers in the usual sense of the art (IUPAC Commission on Macromolecular Nomenclature, Glossary of basic terms in polymer science, 1996 Recommendations, website https: / / www.gfp.asso.fr / wp-content / uploads / glossaire.pdf ). In practice, these copolymers are linear copolymers whose non-polymeric hydrocarbon side chains have an average length ranging from 8 to 20 carbon atoms.

[0020] The compositions described in applications WO2015 / 110642, WO2015 / 110643 and WO2016113229 exhibit very advantageous properties due to their ability to form thermoreversible associations. However, it is desirable to further improve these properties; in particular, attempts have been made to reduce the sensitivity of the viscosity of the composition with respect to temperature, in order to provide compositions that exhibit better viscosity stability between high and low temperatures. It is also attempted to provide compositions that exhibit a greater range of viscosity adjustment.

[0021] Furthermore, it has been found that under certain conditions, in particular at high temperatures, the associative behavior of these copolymers is reduced. In particular, a decrease in the viscosity index and a poorer resistance to cycling (defined as the successive rise and fall in temperature as observed in an engine) have been observed for lubricating compositions containing them, leading to a loss of lubrication performance over time.

[0022] The Applicant Companies therefore set themselves the goal of preparing novel copolymers which exhibit improved properties relative to the copolymers of the prior art.

[0023] This object is achieved by novel rheological additives which can associate to form a gel and exchange in a thermoreversible manner. Unlike base oils which become thinner at elevated temperatures, the additives of the invention exhibit the advantage of thickening the medium in which the additive is dispersed at elevated temperatures and of maintaining this advantage at elevated temperatures, for example up to 150° C. These additives comprise a comb-type polydiol copolymer A1, at least a portion of whose side chains is of oligomeric or polymeric type, and a compound A2 comprising at least two borate functional groups. These additives allow a greater adjustment range of the viscosity as a function of temperature. The lubricating compositions comprising them have a reduced viscosity sensitivity with respect to temperature and a higher viscosity stability with respect to temperature variations. This feature is due to the combined use of two specific compounds, one being a comb-type copolymer with diol functional groups and optionally styrene functional groups, and the other being a compound comprising borate functional groups.

[0024] By means of the composition of the invention, it is possible to provide a lubricating composition which has good lubricating properties during the engine starting phase (cold phase) and has good lubricating properties when the engine is running at its operating temperature (hot phase). Summary of the invention

[0025] The present invention relates to a composition obtained by mixing at least the following substances

[0026] ο Comb-type polyglycol copolymer A1

[0027] and

[0028] o a compound A2 comprising at least two borate functional groups,

[0029] The comb-type polyglycol copolymer A1 includes a main chain and side chains, and at least a part of the side chains of the copolymer A1 is composed of oligomers.

[0030] Another subject of the present invention is a lubricating composition obtained by mixing at least:

[0031] - Lubricating oil, and

[0032] - A composition as defined in detail above and below.

[0033] The present invention also relates to a method for adjusting the viscosity of a lubricating composition, the method comprising at least:

[0034] - providing a composition as defined above and below in detail,

[0035] - Mix the composition with lubricating oil.

[0036] According to a preferred embodiment, the side chains consisting of oligomers represent 3% to 95% by weight, preferably 15% to 95% by weight, relative to the total weight of copolymer A1.

[0037] According to a preferred embodiment, at least a portion of the side chains of copolymer A1 consists of oligomers comprising more than 30 carbon atoms, preferably at least 50 carbon atoms, more preferably at least 70 carbon atoms.

[0038] According to yet another preferred embodiment, the side chains consisting of oligomers comprising more than 30 carbon atoms represent from 3% to 95% by weight, preferably from 15% to 95% by weight, relative to the total weight of copolymer A1.

[0039] According to a preferred embodiment, at least a part of the side chains of the copolymer A1 is composed of oligomers having a degree of polymerization of 5 to 1000, preferably 5 to 500, more preferably 5 to 200.

[0040] According to a preferred embodiment, at least a portion of the side chains of the copolymer A1 is constituted by oligomers O1 comprising polyolefin segments.

[0041] According to a preferred embodiment, the side chains of the copolymer A1 composed of the oligomer O1 comprise polyolefin segments having from 30 to 500 carbon atoms, preferably from 50 to 400 carbon atoms, even more preferably from 50 to 200 carbon atoms.

[0042] According to a preferred embodiment, the side chains comprising polyolefin segments represent 3% to 85% by weight, preferably 15% to 70% by weight, relative to the total weight of copolymer A1.

[0043] According to a further preferred embodiment, the oligomer O1 is present in the copolymer A1 in the form of repeating units corresponding to one or more than one monomer M6 of the general formula (IX):

[0044]

[0045] in:

[0046] Q1 is selected from -H, -CH3 and -CH2-CH3;

[0047] Q2 is selected from the group consisting of -Q', -O-Q', -C(O)-O-Q', -OC(O)-Q', -S-(CH2)2-C(O)-O-Q', -S-Q', -N(H)-C(O)-Q' and -C(O)-N(H)-Q', wherein Q' is a polyolefin,

[0048] n represents an integer from 0 to 1,

[0049] A represents a group selected from -A1-, -O-(-A2-O-) n' -A1-, -C(O)-O-(-A2-O-) n' -A1-、-OC(O)-(-A2-O-) n' -A1-、-S-(-A2-O-) n' -A1-, -N(H)-C(O)-(-A2-O-) n' -A1- and -C(O)--N(H)-(-A2-O-) n' -A1- divalent group, wherein

[0050] A1 is selected from C1 to C 30 Alkyl, C6 to C 30 Aryl or C6 to C 30 A divalent aralkyl group,

[0051] A2 is a divalent group selected from C2 to C4 alkyl groups,

[0052] n' is an integer, and n' represents 0 or 1.

[0053] According to a preferred embodiment, at least a portion of the side chains of the copolymer A1 are constituted by oligomers O2 comprising repeating units of monomers M2 corresponding to the general formula (II):

[0054]

[0055] in:

[0056] R2 is selected from -H, -CH3 and -CH2-CH3;

[0057] R3 is selected from: -C(O)-O-R'3, -O-R'3, -S-R'3 and -C(O)-N(H)-R'3, wherein R'3 is C1 to C 30 alkyl.

[0058] According to yet another preferred embodiment, at least a portion of the oligomers O2 comprise repeating units corresponding to the monomer M1 of the general formula (I):

[0059]

[0060] in:

[0061] -R1 is selected from -H, -CH3 and -CH2-CH3;

[0062] -y is an integer equal to 0 or 1;

[0063] -Y represents a group consisting of C1 to C 20 a divalent linking group of an alkyl chain, which optionally comprises one or more than one ether-O-bridge;

[0064] - X1 and X2 are the same or different and are selected from hydrogen, tetrahydropyranyl, methoxymethyl, tert-butyl, benzyl, trimethylsilyl and tert-butyldimethylsilyl;

[0065] or

[0066] -X1 and X2 form a bridge of the following formula with the oxygen atom:

[0067]

[0068] in:

[0069] -asterisk ( * ) represents a bond to an oxygen atom,

[0070] - R'2 and R"2 are the same or different and are selected from hydrogen and C1 to C 11 Alkyl, preferably methyl;

[0071] or

[0072] -X1 and X2 form a boric acid ester with the oxygen atom:

[0073]

[0074] in:

[0075] -asterisk ( * ) represents a bond to an oxygen atom,

[0076] -R"'2 is selected from C6 to C 30 Aryl, C7 to C 30 Arylalkyl and C2 to C 30 Alkyl, preferably C6 to C 18 Aryl.

[0077] According to yet another preferred embodiment, the monomer M1 is selected from monomers of formula (Ia):

[0078]

[0079] Here, x is an integer of 1 to 18, preferably 2 to 18.

[0080] According to one embodiment, when a part of the side chains of copolymer A1 is constituted by oligomers comprising repeating units corresponding to monomers M1 and / or M2, these oligomers have a degree of polymerization of 5 to 500, preferably 10 to 400, more preferably 20 to 200.

[0081] According to a preferred embodiment, when the side chains of copolymer A1 are composed of oligomers O1 comprising polyolefin segments having 30 to 105 carbon atoms, the repeating units of copolymer A1 contain greater than 5 mol % of monomers M6 of general formula (IX), preferably greater than 6 mol % of monomers M6 of general formula (IX), even more preferably greater than 6.5 mol % of monomers M6 of general formula (IX).

[0082] According to a preferred embodiment, the main chain of the copolymer A1 comprises recurring units corresponding to at least one monomer M2 of the general formula (II):

[0083]

[0084] in:

[0085] R2 is selected from -H, -CH3 and -CH2-CH3;

[0086] R3 is selected from: -C(O)-O-R'3, -O-R'3, -S-R'3 and C(O)-N(H)-R'3, wherein R'3 is C1 to C 30 alkyl.

[0087] According to yet another preferred embodiment, the main chain of the copolymer A1 comprises repeating units corresponding to at least one monomer M1 of the general formula (I):

[0088]

[0089] in:

[0090] -R1 is selected from -H, -CH3 and -CH2-CH3;

[0091] -y is an integer equal to 0 or 1;

[0092] -Y represents a group consisting of C1 to C 20 a divalent linking group of an alkyl chain, which optionally comprises one or more than one ether-O-bridge;

[0093] - X1 and X2 are the same or different and are selected from hydrogen, tetrahydropyranyl, methoxymethyl, tert-butyl, benzyl, trimethylsilyl and tert-butyldimethylsilyl;

[0094] or

[0095] -X1 and X2 form a bridge of the following formula with the oxygen atom:

[0096]

[0097] in:

[0098] -asterisk ( * ) represents a bond to an oxygen atom,

[0099] - R'2 and R"2 are the same or different and are selected from hydrogen and C1 to C 11 Alkyl, preferably methyl;

[0100] or

[0101] -X1 and X2 form a boric acid ester with the oxygen atom:

[0102]

[0103] in:

[0104] -asterisk ( * ) represents a bond to an oxygen atom,

[0105] R"'2 is selected from C6 to C 30 Aryl, C7 to C 30 Arylalkyl and C2 to C 30 Alkyl, preferably C6 to C 18 Aryl.

[0106] According to yet another preferred embodiment, the monomer M1 is selected from monomers of the general formula (Ia):

[0107]

[0108] Here, x is an integer of 1 to 18, preferably 2 to 18.

[0109] According to a preferred embodiment, the copolymer A1 comprises recurring units corresponding to at least one monomer M3 of the general formula (X):

[0110]

[0111] in:

[0112] - Z1, Z2 and Z3 are the same or different and represent a hydrogen atom, a C1 to C 12 alkyl or -OZ' or -C(O)-O-Z' group, wherein Z' is C1 to C 12 alkyl.

[0113] According to yet another preferred embodiment, the monomer M3 is styrene.

[0114] According to yet another preferred embodiment, the repeating unit corresponding to the monomer of formula (X) is 2 mol% to 50 mol% relative to the total moles of the repeating units constituting copolymer A1.

[0115] According to one preferred embodiment, the main chain of the comb copolymer A1 comprises at least two repeating units corresponding to the monomer M2 of formula (II) having different R3 groups.

[0116] According to a further preferred embodiment, one of the monomers M2 of the copolymer A1 has the general formula (II-A):

[0117]

[0118] in:

[0119] -R2 is selected from -H, -CH3 and -CH2-CH3,

[0120] -R"3 is C1 to C8 alkyl,

[0121] The other monomer M2 of copolymer A1 has the general formula (II-B):

[0122]

[0123] in:

[0124] -R2 is selected from -H, -CH3 and -CH2-CH3,

[0125] -R"'3 is C9 to C 30 alkyl,

[0126] According to a preferred embodiment, at least a portion of the side chains of the comb copolymer A1 are oligomers O1 comprising polyolefin segments, and the main chain of the comb copolymer A1 comprises at least one repeating unit corresponding to a monomer M2 of the general formula (II-A):

[0127]

[0128] in:

[0129] -R2 is selected from -H, -CH3 and -CH2-CH3,

[0130] -R"3 is C1 to C8 alkyl.

[0131] According to a preferred embodiment, the repeating unit corresponding to the monomer M2 is 10 mol% to 90 mol%, preferably 30 mol% to 80 mol%, relative to the total moles of the repeating units constituting the copolymer A1.

[0132] According to a preferred embodiment, the repeating unit corresponding to the monomer M1 is 1 mol% to 50 mol%, preferably 5 mol% to 30 mol%, relative to the total moles of the repeating units constituting the copolymer A1.

[0133] According to one preferred embodiment, the degree of branching of copolymer A1 is between 0.1 mol % and 10 mol %. The degree of branching is calculated by taking into account only oligomeric side chains comprising more than 30 carbon atoms.

[0134] Preferably, copolymer A1 exhibits a degree of branching of 0.5 to 5 mol % when the oligomer chain is an olefin having more than 100 carbon atoms and of 5 to 10 mol % when the oligomer chain is an olefin having 30 to 100 carbon atoms.

[0135] According to a preferred embodiment, the comb copolymer A1 comprises non-oligomeric side chains whose average length is from 1 to 10 carbon atoms, preferably from 3 to 8 carbon atoms.

[0136] According to a preferred embodiment, the number average degree of polymerization of the main chain of the comb copolymer A1 is from 40 to 2000, preferably from 40 to 1000.

[0137] According to a preferred embodiment, the number average degree of polymerization of the oligomeric side chains of the comb copolymer A1 is from 8 to 1,000.

[0138] According to a first embodiment, compound A2 is a compound of formula (III):

[0139]

[0140] in:

[0141] - w1 and w2 are the same or different and are integers from 0 to 1;

[0142] - R4, R5, R6 and R7 are identical or different and represent a group chosen from a hydrogen atom or a hydrocarbon radical containing 1 to 30 carbon atoms, which is optionally substituted by one or more groups chosen from: a hydroxyl group or an -OJ or -C(O)-OJ radical, in which J is a hydrocarbon radical containing 1 to 24 carbon atoms;

[0143] -L is selected from C6 to C 18 Aryl, C6 to C 18 Arylalkyl and C2 to C 24 A divalent linking group of a hydrocarbon chain.

[0144] According to a second embodiment, compound A2 is a copolymer comprising at least:

[0145] The repeating unit corresponding to the monomer M4 of formula (IV):

[0146]

[0147] in:

[0148] -t is an integer equal to 0 or 1;

[0149] -u is an integer equal to 0 or 1;

[0150] -M and R8 are divalent linking groups which are the same or different and are selected from C6 to C 18 Aryl, C7 to C 24 Arylalkyl and C2 to C 24 Preferably, M is C6 to C 18 Aryl, R8 is C7 to C 24 Aralkyl;

[0151] -X is a functional group selected from -OC(O)-, -C(O)-O-, -C(O)-N(H)-, -N(H)-C(O)-, -S-, -N(H)-, -N(R'4)- and -O-, wherein R'4 is a hydrocarbon chain containing 1 to 15 carbon atoms;

[0152] -R9 is selected from -H, -CH3 and -CH2-CH3;

[0153] -R 10 and R 11 are identical or different and represent a group chosen from a hydrogen atom or a hydrocarbon radical containing from 1 to 30 carbon atoms, optionally substituted by one or more than one group chosen from: a hydroxyl group or an -OJ or -C(O)-OJ group, in which J is a hydrocarbon radical containing from 1 to 24 carbon atoms;

[0154] The repeating unit corresponding to the monomer M5 of formula (V):

[0155]

[0156] in:

[0157] -R 12 is selected from -H, -CH3 and -CH2-CH3,

[0158] -R 13 Selected from C6 to C 18 Aryl and R' 13 、-C(O)-OR' 13 、-OR' 13 、-SR' 13 and -C(O)-N(H)-R' 13 C6 to C 18 Aryl, where R' 13For C1 to C 30 alkyl.

[0159] According to a preferred embodiment, when compound A2 is a copolymer comprising at least two borate functional groups, it is a comb-type copolymer comprising a main chain and side chains, at least a portion of the side chains of copolymer A2 being constituted by oligomers.

[0160] According to a preferred embodiment, when compound A2 is a copolymer, at least one of the following three conditions is met:

[0161] In formula (IV): u=1, R9 is H, and R8 represents C6 to C 18 Aryl or C7 to C 24 Aralkyl, and the double bond of the monomer M4 of formula (IV) is directly connected to the aryl group;

[0162] Or, in formula (V): R 12 Indicates H, R 13 Selected from C6 to C 18 Aryl and R' 13 C6 to C 18 Aryl, R' 13 Indicates H or C1 to C 25 Alkyl, the double bond of the monomer M5 of formula (V) is directly connected to the aromatic group;

[0163] Or, the copolymer A2 comprises at least one third monomer M3 having the formula (X):

[0164]

[0165] in:

[0166] Z1, Z2 and Z3 are the same or different and represent a hydrogen atom, a C1 to C 12 alkyl or -OZ' or -C(O)-O-Z' group, wherein Z' is C1 to C 12 alkyl.

[0167] Advantageously, when A2 comprises a third monomer M3 of formula (X), this monomer M3 is styrene.

[0168] Advantageously, the borate copolymer A2 has in the copolymer a styrene monomer of formula (IV), (V) and / or (X), advantageously styrene, in a molar percentage of 0.05 to 30 mol %, preferably 0.1 to 25 mol %.

[0169] According to a preferred embodiment, the content of copolymer A1 is from 0.1% to 50% by weight relative to the total weight of the composition.

[0170] According to a preferred embodiment, the content of compound A2 is 0.1 wt % to 50 wt % relative to the total weight of the composition.

[0171] According to a preferred embodiment, the weight ratio of copolymer A1 to compound A2 (A1 / A2 ratio) is from 0.005 to 200, preferably from 0.05 to 20, more preferably from 0.1 to 10.

[0172] According to a preferred embodiment, copolymer A1 is obtained by a process comprising at least the following steps:

[0173] - Stage of reversible addition-fragmentation chain transfer radical polymerization in the presence of transfer agents of thiocarbonylthio type.

[0174] According to yet another preferred embodiment, after the polymerization, the copolymer A1 is obtained by a process comprising at least the following steps:

[0175] - Aminolysis step of thiocarbonylthio residue to give thiol, then

[0176] -Michael addition of acrylates to convert thiols to thioethers.

[0177] According to a preferred embodiment, the composition further comprises at least one exogenous compound A4 chosen from polyols.

[0178] According to a preferred embodiment, the molar percentage of the exogenous compound A4 relative to the borate functional groups of the copolymer A2 is 0.025% to 5000%, preferably 0.1% to 1000%, more preferably 0.5% to 500%, more preferably 1% to 150%.

[0179] According to another preferred embodiment, the composition further comprises at least one exogenous compound A5 selected from the group corresponding to formula (XI):

[0180]

[0181] in:

[0182] -Q represents a group selected from hydrocarbon radicals containing 1 to 30 carbon atoms, which are optionally substituted by one or more than one group selected from: hydroxyl or -OJ or -C(O)-OJ radicals, wherein J is a hydrocarbon radical containing 1 to 24 carbon atoms,

[0183] -G4 and G5 are the same or different and represent a group selected from a hydrogen atom, a hydrocarbon chain containing 1 to 24 carbon atoms, a hydroxyl group or -OJ or -C(O)-OJ, wherein J is a hydrocarbon group containing 1 to 24 carbon atoms,

[0184] -g means 0 or 1.

[0185] According to a preferred embodiment, the lubricating oil is selected from one of the oils of API Class I, Class II, Class III, Class IV or Class V and mixtures thereof.

[0186] According to a preferred embodiment, the lubricating composition comprises at least one functional additive selected from antioxidants, detergents, anti-wear additives, load-bearing additives, polymers that can increase the viscosity index, pour point improvers, defoamers, anti-corrosion additives, thickeners, dispersants, friction modifiers and mixtures thereof. DETAILED DESCRIPTION

[0187] The expression "consisting essentially of" followed by one or more characteristics means that in addition to the components or phases explicitly listed, components or phases may be included in the methods or materials of the invention that do not significantly change the nature and characteristics of the invention.

[0188] Unless expressly stated otherwise, the expression "X to Y" includes the end values. Therefore, the expression indicates that the target interval includes the values ​​X, Y and all values ​​in the range from X to Y.

[0189] definition :

[0190] "Oligomer" is understood to refer to a macromolecule consisting of a limited number of repeating units. These repeating units can be all the same, or the oligomer can contain different repeating units. Typically, an oligomer contains 2 to 1000 repeating units. Most commonly, an oligomer is produced by the polymerization or copolymerization of a limited number of monomers. An oligomer contains a main chain and can contain side chains, also referred to as pendant chains.

[0191] The main chain of a polymer or oligomer is a straight chain, on which all other chains can be considered as side chains. When several chains can be considered as the main chain, the one that gives the simplest representation of the molecule is the one designated as the main chain. The term "main chain" within the meaning of the present invention does not necessarily mean that the chain length of the main chain is greater than the chain length of the side chains.

[0192] The side chain is a substituent of the macromolecular chain. The substituent can be a low molecular weight molecule, oligomer or polymer. Preferably, according to the present invention, the oligomer side chain contains at least 30 carbon atoms, preferably at least 50 carbon atoms, more preferably at least 70 carbon atoms.

[0193] "Copolymer" is understood to mean a linear or branched oligomer or macromolecule having a sequence consisting of several repeating units (or monomeric moieties), wherein at least two units have different chemical structures.

[0194] "Monomeric moiety" or "monomer" is understood to mean a molecule that can be converted into an oligomer or macromolecule by combining with itself or with other molecules of the same type. A monomer represents the smallest building block, the repetition of which gives rise to an oligomer or macromolecule.

[0195] "Comb polymer", also known as branched copolymer, is understood to refer to a polymer having a main chain and at least one side chain or pendant chain connected to the main chain at a point (called a branching point) between the two ends of the main chain. Unlike linear polymers comprising non-polymeric side groups or pendant groups, the side chains of comb polymers are oligomers, polymers or copolymers. Preferably, according to the present invention, the comb polymer comprises at least two, preferably at least three side chains or pendant chains. The degree of branching within the meaning of the present invention means the branching of oligomer side chains with more than 30 carbon atoms.

[0196] "Random copolymer" is understood to mean an oligomer or macromolecule in which the sequential distribution of monomer units obeys known statistical laws. For example, when a copolymer is formed from monomer units, the copolymer is random and its distribution is a Markovian distribution. A diagram of a random polymer (P1) is shown in FIG. Figure 1 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.

[0197] "Block copolymer" is understood to mean an oligomer or macromolecule comprising one or more than one block or formed by blocks. "Block" means a part of a copolymer which comprises several identical or different monomer units and has at least one unique structural or configurational feature which allows it to be distinguished from adjacent parts. The diagram of block polymer (P3) is shown in Figure 1 shown.

[0198] "Gradient copolymer" means a copolymer of at least two monomer units of different structures, wherein the monomer composition gradually changes along the polymer chain, thereby gradually transitioning from one end of the polymer chain rich in one monomer unit to the other end rich in another comonomer. The schematic diagram of the gradient polymer (P2) is as follows Figure 1 shown.

[0199] The polyglycol copolymers of the present invention are random copolymers or gradient copolymers. They can show a gradient distribution of certain monomers and a statistical or virtual statistical distribution of other monomers. They are different from block copolymers.

[0200] "Copolymerization" is understood to mean a process by which a mixture of at least two monomer units having different chemical structures can be converted into oligomers or copolymers.

[0201] Polyolefins are known to those skilled in the art. They can be obtained by polymerizing olefins and / or dienes composed of carbon and hydrogen, for example C2 to C 10 Olefins such as ethylene, propylene, n-butene, isobutene, cyclobutene, cycloheptene, cyclooctene or norbornene, and / or C4 to C 10 Diolefins, such as butadiene, isoprene, cyclooctadiene or norbornadiene. According to the present invention, the following are included in the definition of polyolefins: hydrogenated polyolefins, hydrogenated poly(diolefins), partially or fully hydrogenated olefins, polyolefins, hydrogenated polyolefins and hydrogenated polyolefin-co-polyolefin copolymers.

[0202] In the context of this patent application, "B" represents a boron atom.

[0203] “C i To C j "Alkyl" is understood to mean a saturated straight or branched hydrocarbon chain containing i to j carbon atoms. For example, "C1 to C 10 "Alkyl" is understood to mean a saturated, linear or branched hydrocarbon chain containing from 1 to 10 carbon atoms.

[0204] “C x To C y "Aryl" is understood to mean a functional group derived from an aromatic compound containing x to y carbon atoms. The functional group may be monocyclic or polycyclic. For example, C6 to C 18 Aryl groups may be phenyl, naphthyl, anthracenyl, phenanthrenyl and naphthacene.

[0205] “C x To C y "Alkenyl" is understood to mean a straight-chain or branched hydrocarbon chain comprising at least one unsaturated bond, preferably a carbon-carbon double bond, and comprising x to y carbon atoms.

[0206] “C x To C y "Arylalkyl" is understood to mean an aromatic compound substituted by at least one linear or branched alkyl chain, preferably a monocyclic aromatic compound, the total number of carbon atoms of the aromatic ring and its substituents being x to y carbon atoms. For example, C7 to C 18 The aralkyl group may be selected from benzyl, tolyl and xylyl.

[0207] "C substituted by Y group x To C y The term "aryl" is understood to mean an aromatic compound containing x to y carbon atoms, preferably a monocyclic aromatic compound, at least one carbon atom of the aromatic ring of which is substituted by a Y group.

[0208] "Halo" or "halogen" is understood to mean a halogen atom selected from chlorine, bromine, fluorine and iodine.

[0209] In the specification, when it is stated that a copolymer "comprises the monomers corresponding to M i When the repeating unit is ", this means that the copolymer can be directly composed of monomer M i The copolymerization of i represents the parameter that distinguishes the following different monomers from other comonomers, and the copolymer can also be obtained by removing the monomer M i The monomers other than M are copolymerized and then undergo a chemical transformation stage, so the structural units contained in it are the same as those obtained by monomer M. i For example, a monomer having acid functionality, such as acrylic acid or methacrylic acid, can first be copolymerized with other monomers to form a copolymer, and then all or part of the acid functionality can be converted, for example, by any reaction such as esterification with an alkanol or amidation with an alkylamine. A copolymer containing repeating units corresponding to the alkanol acrylate or alkyl acrylamide monomer will then be obtained.

[0210] Composition of the additive according to the invention:

[0211] The subject of the invention is a composition of associative and thermoreversibly exchangeable compounds, which is composed of at least the following substances:

[0212] - a comb-type polyglycol copolymer A1 as described below or in particular obtainable by one of the following processes;

[0213] - Compound A2 comprising at least two borate functional groups.

[0214] Such a combination of additives makes it possible to control and adjust the rheological behavior of the medium to which the additives are added.The medium may be a hydrophobic, in particular a nonpolar medium, such as a solvent, a mineral oil, a natural oil or a synthetic oil.

[0215] Comb-type polyglycol copolymer A1

[0216] The comb-type polyglycol copolymer A1 includes a main chain to which side chains are connected, and at least a part of the side chains of the copolymer A1 is composed of an oligomer.

[0217] The side chains of the comb copolymer A1 according to the invention differ from the side chains of the polyol copolymers of the prior art used as a mixture with boric esters in that at least a portion of the side chains consists of oligomers.

[0218] "Side chains consisting of oligomers" are understood to mean that at least part of the side chains is an oligomer of one or more than one monomer. At least it is not excluded that the side chains include other functional groups, for example a functional group or a series of functional groups connecting the side chains to the main chain.

[0219] Side chain of copolymer A1

[0220] The side chains of the copolymer A1 composed of oligomers exhibit a degree of polymerization which is different from zero, unlike the side chains of copolymers of the same type known from the prior art.

[0221] Preferably, the side chains consisting of oligomers represent 3% to 95% by weight, preferably 15% to 95% by weight, more preferably 20% to 95% by weight, relative to the total weight of copolymer A1.

[0222] Preferably, at least a portion of the side chains of copolymer A1 consist of oligomers comprising more than 30 carbon atoms, preferably at least 50 carbon atoms, more preferably at least 70 carbon atoms.

[0223] Preferably, the side chains consisting of oligomers comprising more than 30 carbon atoms represent 3% to 95% by weight, preferably 15% to 95% by weight, more preferably 20% to 95% by weight, relative to the total weight of copolymer A1.

[0224] Preferably, the degree of polymerization of at least a part of the side chains of the copolymer A1 composed of the oligomer is 5 to 1,000, preferably 5 to 500, and more preferably 5 to 200.

[0225] More preferably, the side chains consisting of oligomers having a degree of polymerization of 5 to 1000 account for 3 to 95% by weight, preferably 15 to 95% by weight, more preferably 20 to 95% by weight, relative to the total weight of the copolymer A1.

[0226] All the oligomer side chains of the copolymer A1 may be of the same type or of different types.

[0227] Copolymer A1 may contain oligomeric side chains and side chains which are not oligomeric.

[0228] Preferably, the side chains of copolymer A1 which are not oligomeric compounds represent 5 to 97 wt. %, preferably 5 to 85 wt. %, more preferably 5 to 80 wt. %, more preferably 5 to 75 wt. %, relative to the total weight of copolymer A1.

[0229] According to a first alternative form, at least part of the side chains of the copolymer A1 are constituted by oligomers O1 comprising polyolefin segments. The polyolefin segments may be obtained from polyolefin macromonomers or from functionalized monomers onto which polyolefin functional groups are grafted.

[0230] Preferably, the side chains comprising polyolefin segments represent 8% to 50% by weight, preferably 10% to 40% by weight, relative to the total weight of copolymer A1.

[0231] For example, the side chain comprising a polyolefin segment may be composed of repeating units corresponding to the monomer M6 of the general formula (IX) derived from a polyolefin.

[0232] According to another alternative form, a portion of the side chains of copolymer A1 is constituted by oligomers O2 comprising recurring units corresponding to monomers chosen from monomers M2 of general formula (II).

[0233] For example, according to this alternative form, a portion of the side chains of the copolymer A1 is constituted by an oligomer O2 comprising recurring units corresponding to monomers selected from the group consisting of the following general formulae:

[0234] - a monomer M1 of the general formula (I),

[0235] - a monomer M2 of the general formula (II).

[0236] The copolymer A1 may comprise both side chains of the oligomer O1 type comprising polyolefin segments and of the oligomer O2 type comprising repeating units of monomers corresponding to the monomers M2 selected from the group consisting of the monomers of the general formula (II).

[0237] Main chain of copolymer A1

[0238] The main chain of the comb copolymer A1 preferably comprises repeating units corresponding to the monomer M1 of the general formula (I).

[0239] The main chain of the comb copolymer A1 may comprise repeating units corresponding to the monomer M2 of the general formula (II).

[0240] Preferably, the main chain of the comb copolymer A1 comprises recurring units of monomers M3 corresponding to at least one of the general formula (X) defined above. According to this alternative, the other monomers participating in the construction of the comb polyglycol copolymer A1 must be compatible with the copolymerization of the monomers M3.

[0241] Copolymer A1 may be a random copolymer or a gradient copolymer.

[0242] Advantageously, the comb-type polydiol copolymer A1 is obtained directly or indirectly from the (co)polymerization of at least one diol monomer M1, which is introduced into the main chain or side chain of the copolymer A1, or into both the main chain and the side chain.

[0243] "Directly or indirectly obtained" is understood to mean that the process for preparing the copolymer may include one or more than one different copolymerization stage, such as a deprotection stage. It is worth noting that the copolymerization may optionally be followed by a deprotection step of the diol functional groups.

[0244] Throughout the specification, the following expressions may be used interchangeably in an equivalent manner: "polyglycol copolymer A1 is obtained directly or indirectly by copolymerization" and "polyglycol copolymer A1 is obtained by copolymerization".

[0245] Distribution of monomers in the main chain and side chains

[0246] Monomers M1, M2 and M3 may be present in the main chain and / or in the side chain. In the side chain, they are present in the form of oligomers. Optionally, other monomers may be present in the main chain and / or in the side chain.

[0247] Monomer M6 can be used in the copolymerization of the main chain and can provide oligomeric side chains.

[0248] When the monomers M1, M2 and / or M3 are incorporated into the main chain of the copolymer A1 according to the invention, the side chains of the monomers M1, M2 and M3 form the non-oligomeric side chains of the copolymer A1.

[0249] The comb copolymer A1 comprises non-oligomeric side chains, preferably having an average length of 1 to 10 carbon atoms, more preferably 3 to 8 carbon atoms.

[0250] When the comb copolymer A1 comprises oligomeric side chains composed of monomers M1 or monomers M2, these monomers preferably have an average length of 1 to 10 carbon atoms.

[0251] The "average length" is understood to mean the average length of the alkyl segments of the side chains of the monomers M1 of formula (I) and the monomers M2 of formula (II) which participate in the formation of the copolymer A1. When calculating the average length of the side chains of the comb copolymer A1, the side chains resulting from styrene monomers are not taken into account. A person skilled in the art knows how to obtain this average length by appropriately selecting the types and proportions of the monomers that constitute the polyglycol copolymer.

[0252] Unless otherwise indicated, the preferences expressed below for the selection of monomers M1, M2 and M3 are valid both when they are present in the form of repeating units in the main chain and when they are present in a side chain.

[0253] Monomer M1

[0254] The first monomer M1 of the comb copolymer (A1) of the present invention has the general formula (I):

[0255]

[0256] in:

[0257] -R1 is selected from -H, -CH3 and -CH2-CH3, preferably -H and -CH3;

[0258] -Y represents a group consisting of C1 to C 20A divalent linking group of an alkyl chain, which optionally contains one or more than one ether-O-bridge; preferably, Y represents a group selected from: -(CH2) x -or-(CH2) x' -O-(CH2) x "-chain

[0259] in

[0260] - x is an integer from 1 to 18, preferably from 2 to 18, more preferably from 3 to 8; more preferably, x is equal to 4;

[0261] - x' and x" are integers from 1 to 17, x'+x" is an integer from 2 to 18, more preferably an integer from 3 to 8; advantageously, x' is an integer from 1 to 4, x"=1; more preferably, x'=2, x"=1;

[0262] - y is an integer equal to 0 or 1; preferably, y is equal to 0;

[0263] - X1 and X2 are the same or different and are selected from hydrogen, tetrahydropyranyl, methoxymethyl, tert-butyl, benzyl, trimethylsilyl and tert-butyldimethylsilyl;

[0264] or

[0265] -X1 and X2 form a bridge of the following formula with the oxygen atom:

[0266]

[0267] in:

[0268] -asterisk ( * ) represents a bond to an oxygen atom,

[0269] - R'2 and R"2 are the same or different and are selected from hydrogen and C1 to C 11 alkyl;

[0270] or

[0271] -X1 and X2 form a boric acid ester with the oxygen atom:

[0272]

[0273] in:

[0274] -asterisk ( * ) represents a bond to an oxygen atom,

[0275] -R"'2 is selected from C6 to C 30 Aryl, C7 to C 30 Arylalkyl and C2 to C 30 Alkyl, preferably C6 to C 18 Aryl, more preferably phenyl.

[0276] Preferably, when R'2 and R"2 are C1 to C 11 When C1 to C 11 The alkyl group is selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and n-undecyl. 11 The alkyl group is methyl.

[0277] Preferably, when R"'2 is C2 to C 30 In the case of an alkyl group, the hydrocarbon chain is a straight chain.

[0278] More preferably, the monomer M1 corresponds to the general formula (Ia):

[0279]

[0280] wherein x is an integer from 1 to 18, preferably from 2 to 18, more preferably from 3 to 8; more preferably, x is equal to 4.

[0281] Among the monomers of formula (I), the monomers corresponding to formula (IA) are part of the preferred monomers:

[0282]

[0283] in:

[0284] -R1 is selected from -H, -CH3 and -CH2-CH3, preferably -H and -CH3;

[0285] -Y represents a divalent linking group selected from: -(CH2) x -or-(CH2) x' -O-(CH2) x "-chain

[0286] in

[0287] x is an integer from 1 to 18, preferably from 2 to 18, more preferably from 3 to 8; more preferably, x is equal to 4;

[0288] x' and x" are integers from 1 to 17, x'+x" is an integer from 2 to 18, more preferably an integer from 3 to 8; advantageously, x' is an integer from 1 to 4, x"=1; more preferably, x'=2, x"=1;

[0289] - y is an integer equal to 0 or 1; preferably, y is equal to 0.

[0290] Among the monomers of formula (IA), those corresponding to formula (Ia-A) are part of the preferred monomers:

[0291]

[0292] wherein R1, x and y have the same definitions and the same preferences as in formula (IA).

[0293] Among the monomers of formula (I), the monomers corresponding to formula (IB) are part of the preferred monomers:

[0294]

[0295] in:

[0296] -R1 is selected from -H, -CH3 and -CH2-CH3, preferably -H and -CH3;

[0297] -Y represents a group selected from -(CH2) x -or-(CH2) x' -O-(CH2) x "-chain divalent linking group,

[0298] in

[0299] x is an integer from 1 to 18, preferably from 2 to 18, more preferably from 3 to 8; more preferably, x is equal to 4;

[0300] x' and x" are integers from 1 to 17, x'+x" is an integer from 2 to 18, more preferably an integer from 3 to 8; advantageously, x' is an integer from 1 to 4, x"=1; more preferably, x'=2, x"=1;

[0301] - y is an integer equal to 0 or 1; preferably, y is equal to 0;

[0302] - Y1 and Y2 are the same or different and are selected from tetrahydropyranyl, methoxymethyl, tert-butyl, benzyl, trimethylsilyl and tert-butyldimethylsilyl;

[0303] or

[0304] -Y1 and Y2 form a bridge of the following formula with the oxygen atom:

[0305]

[0306] in:

[0307] -asterisk ( * ) represents a bond to an oxygen atom,

[0308] - R'2 and R"2 are the same or different and are selected from hydrogen and C1 to C 11 alkyl;

[0309] or

[0310] Y1 and Y2 form a boric acid ester with the oxygen atom:

[0311]

[0312] in:

[0313] -asterisk ( * ) represents a bond to an oxygen atom,

[0314] -R"'2 is selected from C6 to C 30 Aryl, C7 to C 30 Arylalkyl and C2 to C 30 Alkyl, preferably C6 to C 18 Aryl, more preferably phenyl.

[0315] Preferably, when R'2 and R"2 are C1 to C 11 When C1 to C 11 The alkyl group is selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and n-undecyl. 11 The alkyl group is methyl.

[0316] Preferably, when R"'2 is C2 to C 30 In the case of an alkyl group, the hydrocarbon chain is a straight chain.

[0317] Among the monomers of formula (IB), those corresponding to formula (Ia-B) are part of the preferred monomers:

[0318]

[0319] wherein R1, x, y, Y1 and Y2 have the same definitions and the same preferences as in formula (IB).

[0320] Examples of preferred diol monomers of formula (I) are shown below:

[0321]

[0322] The synthesis of the comb-type polyglycol copolymer (A1) may comprise copolymerizing the protected form of the monomer (IB) with other comonomers and then deprotecting the diol functional group of the monomer (IB).

[0323] Obtain monomer M1

[0324] The monomer M1 of the general formula (I) is obtained according to the methods described in WO2015 / 110642, WO2015 / 110643 and WO2016113229.

[0325] Examples of the synthesis of monomer M1 are described in the experimental parts of applications WO2015 / 110642, WO2015 / 110643 and WO2016113229.

[0326] Monomer M2

[0327] The second monomer M2 of the comb copolymer A1 of the invention has the general formula (II):

[0328]

[0329] in:

[0330] -R2 is selected from -H, -CH3 and -CH2-CH3, preferably -H and -CH3;

[0331] -R3 is selected from C6 to C 18 Aryl and C6 to C6 substituted with R'3, -C(O)-O-R'3, -O-R'3, -S-R'3 and -C(O)-N(H)-R'3 18 Aryl, wherein R'3 is C1 to C 30 alkyl.

[0332] Preferably, R'3 is C1 to C 30 Alkyl, the hydrocarbon chain is straight chain.

[0333] Among the monomers of formula (II), the monomers corresponding to formula (II-A) are part of the preferred monomers:

[0334]

[0335] in:

[0336] -R2 is selected from -H, -CH3 and -CH2-CH3, preferably -H and -CH3;

[0337] - R"3 is a C1 to C8 alkyl group; preferably, R"3 is a straight chain.

[0338] Preferably, the units corresponding to monomer (IIA) are present in the main chain of copolymer A1.

[0339] Among the monomers of formula (II), monomers corresponding to formula (II-B) are also part of the preferred monomers:

[0340]

[0341] in:

[0342] -R2 is selected from -H, -CH3 and -CH2-CH3, preferably -H and -CH3;

[0343] -R"'3 is C9 to C 30 Alkyl; preferably, R"'3 is a straight chain.

[0344] Preferably, the units corresponding to monomer (IIB) are present in the oligomeric side chains of copolymer A1.

[0345] Obtain monomer M2

[0346] The monomers of formula (II), (II-A) and (II-B) are well known to those skilled in the art. and sell.

[0347] Monomer M3

[0348] The third monomer of the comb copolymer A1 of the present invention has the general formula (X):

[0349]

[0350] in:

[0351] - Z1, Z2 and Z3 are the same or different and represent a hydrogen atom, a C1 to C 12 alkyl or -OZ' or -C(O)-O-Z' group, wherein Z' is C1 to C 12 alkyl.

[0352] "C1 to C 12 "Alkyl" is understood to mean a saturated, linear or branched hydrocarbon chain containing from 1 to 12 carbon atoms. Preferably, the hydrocarbon chain is linear. Preferably, the hydrocarbon chain contains from 1 to 6 carbon atoms.

[0353] Advantageously, Z1, Z2 and Z3 are identical or different and represent a group chosen from a hydrogen atom, a C1 to C6 alkyl group or an -OZ' or -C(O)-O-Z' group, wherein Z' is a C1 to C6 alkyl group.

[0354] More preferably, Z1, Z2 and Z3 are identical or different and represent a group selected from a hydrogen atom, a C1 to C4 alkyl group or a -OZ' or -C(O)-O-Z' group, wherein Z' is a C1 to C4 alkyl group.

[0355] Preferred monomers M3 may be mentioned: styrene, p-(tert-butyl)styrene, p-methoxystyrene, p-acetoxystyrene or 2,4,6-trimethylstyrene.

[0356] According to a preferred embodiment, M3 is styrene.

[0357] Get monomer M3

[0358] Some monomers of formula (X), such as styrene, p-(tert-butyl)styrene, p-methoxystyrene, p-acetoxystyrene or 2,4,6-trimethylstyrene, are well known to those skilled in the art. They are mainly composed of Other monomers can be prepared from these commercially available monomers by synthetic methods well known to those skilled in the art.

[0359] · Monomer M6

[0360] Monomer M6 has the general formula (IX):

[0361]

[0362] in:

[0363] Q1 is selected from -H, -CH3 and -CH2-CH3;

[0364] Q2 is selected from the group consisting of -Q', -O-Q', -C(O)-O-Q', -OC(O)-Q', S-Q', -S-(CH2)2-C(O)-O-Q', -N(H)-C(O)-Q' and C(O)-N(H)-Q', wherein Q' is a polyolefin,

[0365] n represents an integer from 0 to 1,

[0366] A represents a group consisting of: -A1-, -O-(-A2-O-) n' -A1-, -C(O)-O-(-A2-O-) n' -A1-、-OC(O)-(-A2-O-) n' -A1-、-S-(-A2-O-) n' -A1-, -N(H)-C(O)-(-A2-O-) n' -A1- and -C(O)-N(H)-(-A2-O-) n' -A1- divalent group, wherein

[0367] A1 is selected from C1 to C 30 Alkyl, C6 to C 30 Aryl or C6 to C 30 A divalent aralkyl group,

[0368] A2 is a divalent group selected from C2 to C4 alkyl groups,

[0369] n' is an integer, and n' represents 0 or 1.

[0370] For example, A2 can be selected from:

[0371] -CH2-CH2-, -CH2-CH2-CH2-, -CH2-C(CH3)H-.

[0372] Preferably, A2 is a straight chain; more preferably, A2 represents -CH2-CH2-.

[0373] Preferably, in formula (IX), Q1 represents -H.

[0374] Preferably, in formula (IX), Q2 is selected from -Q', -S-(CH2)2-C(O)-O-Q' or -C(O)-O-Q' groups, wherein Q' is a polyolefin.

[0375] According to a first alternative form, n=0 and Q1=CH3.

[0376] According to a preferred second alternative form, n=1, n'=0, Q1=H, and A1 is selected from C1 to C 12 Alkyl, C6 to C 12 Aryl or C6 to C 12 A divalent group of aralkyl.

[0377] Preferably, according to the second alternative form, n=1, Q1=H and A=p-phenyl.

[0378] Polyolefin-based macromonomers such as those of formula (IX) are known. These repeat units comprise at least one Q' group derived from a polyolefin.

[0379] Preferably, in formula (IX), Q' represents a polyolefin or a hydrogenated polyolefin derived from an olefin or from a diene, such as ethylene, propylene, n-butene, isobutylene, butadiene, isoprene, cyclobutene, cycloheptene or cyclooctene.

[0380] The repeating units M6 derived from polyolefin-based macromonomers preferably contain at least 90% by weight, more preferably at least 92.5% by weight, preferably at least 95% by weight, of groups derived from olefins and / or dienes, relative to the weight of the repeating units M6. The polyolefin groups Q' may also be present in hydrogenated form.

[0381] Preferably, Q' represents a polyolefin selected from hydrogenated polybutadiene, having a number average molecular weight of 400 to 50,000 g / mol, preferably 500 to 50,000 g / mol, more preferably 1000 to 10,000 g / mol, in particular 1500 to 5000 g / mol, more preferably 500 to 5000 g / mol or 700 to 3000 g / mol.

[0382] Preferably, Q' represents a polyolefin comprising 30 to 500 carbon atoms, preferably 50 to 400 carbon atoms, or 70 to 200 carbon atoms.

[0383] · The repeating unit corresponding to monomer M6 is obtained

[0384] The repeating units corresponding to monomer M6 can be obtained by any method known to those skilled in the art.

[0385] The monomer M6 can be obtained by the reaction of acrylic acid with alcohol Q'OH, the reaction of acryloyl chloride with alcohol Q'OH or the reaction of acrylic anhydride with alcohol Q'OH, wherein Q1 represents H, Q2 represents -C(O)-O-Q', and Q' is a polyolefin.

[0386] The monomer M6 can be obtained by reaction of methacrylic anhydride with an alcohol Q'OH or by reaction of methacrylic acid with an alcohol Q'OH, wherein Q1 represents CH3, Q2 represents -C(O)-O-Q', and Q' is a polyolefin.

[0387] Alternatively, repeating units corresponding to monomer M6, wherein Q1 represents H and CH3, Q2 represents -C(O)-O-Q', and Q' is a polyolefin or a hydrogenated polyolefin, can be introduced after polymerization by functionalizing the main chain, for example in the following order:

[0388] Acrylic acid or methacrylic acid is copolymerized with other monomers, such as monomer M1 of formula (I) and optionally monomer M2 of formula (II) and / or monomer M3 of formula (X), respectively, to form the main chain of the comb copolymer A1,

[0389] • Esterification of at least a portion of the acid functional groups of the (meth)acrylic monomers by reaction with an alcohol Q'OH.

[0390] The polyolefin alcohols used can be prepared in particular by synthesizing hydroxy-terminated polybutadiene as described in US Pat. No. 5,159,123 and then hydrogenating, for example, by the process described in US Pat. No. 7,148,292. Among the commercially available polyolefin alcohols that can be used, mention may be made of the polybutadiene Krasol HLBH 5000M sold by Cray Valley.

[0391] For other alternative forms of Q2, those skilled in the art similarly use conventional reactions to functionalize the polymerizable groups before or after the main chain polymerization of copolymer A1, in particular by esterification or amidation reactions, by thiol-ene coupling reactions, by Michael addition reactions between thiol functional groups and acrylate, acrylamide or maleimide functional groups, and the like.

[0392] · Side chains based on M1 / M2 / M3 oligomers :

[0393] According to a first embodiment, the copolymer A1 comprises side chains formed by oligomers comprising recurring units corresponding to monomers chosen from the monomers M2 of general formula (II).

[0394] Preferably, according to this alternative form, the copolymer A1 comprises side chains formed from oligomers obtained directly or indirectly from monomers chosen from the monomers M2 of general formula (II).

[0395] According to a second embodiment, the copolymer A1 comprises side chains formed by oligomers comprising recurring units corresponding to monomers chosen from:

[0396] - a monomer M1 of the general formula (I),

[0397] - a monomer M2 of the general formula (II).

[0398] Preferably, according to this alternative form, the copolymer A1 comprises side chains formed from oligomers obtained directly or indirectly from monomers chosen from:

[0399] - a monomer M1 of the general formula (I),

[0400] - a monomer M2 of the general formula (II).

[0401] According to a preferred embodiment, the copolymer A1 comprises side chains formed by oligomers comprising repeating units corresponding to monomers selected from:

[0402] - a monomer M1 of the general formula (I),

[0403] - a monomer M2 of the general formula (II),

[0404] - a monomer M3 of the general formula (X).

[0405] Preferably, according to this alternative form, the copolymer A1 comprises side chains formed from oligomers obtained directly or indirectly from monomers chosen from:

[0406] - a monomer M1 of the general formula (I),

[0407] - a monomer M2 of the general formula (II),

[0408] - a monomer M3 of the general formula (X).

[0409] · Obtain side chains based on M1 / M2 / M3 oligomers:

[0410] Oligomeric side chains can be obtained directly by copolymerization of:

[0411] -monomers involved in the main chain,

[0412] and

[0413] at least one oligomer comprising a polymerizable functional group and repeating units corresponding to the monomer M2 of the general formula (II), and optionally a monomer M1 of the general formula (I) and / or a monomer M3 of the general formula (X).

[0414] According to a preferred embodiment, the side chains are obtained by copolymerizing the monomers participating in the constitution of the main chain with at least one "branching" monomer and then grafting the oligomers to the branching functional groups.

[0415] Branching monomers are monomers that contain both a polymerizable functional group (such as a vinyl or acrylic double bond) and at least one reactive functional group that enables:

[0416] - grafted pre-oligomerized side chains, or

[0417] - Initiate polymerization.

[0418] Preferably, the branching monomer is selected from free radical polymerization initiators and transfer agents. The reactive functional groups that initiate the side chain polymerization can be composed of brominated functional groups, as described in detail in the experimental part. Other reactive functional groups well known to those skilled in the art can also be used, such as RAFT agents, free radical polymerization agents in the presence of nitrogen oxides (NMP), sulfhydryls, diazo, peroxides.

[0419] Preferably, the branched monomer M7 corresponds to the following formula (XII):

[0420]

[0421] in:

[0422] G1 represents a group selected from the following: -H, -CH3, -CH2-CH3;

[0423] M represents a hydrocarbon group containing 1 to 40 carbon atoms, optionally with one or more functional groups selected from -O-, -OC(O)-, -OC(O)-O-, -N(H)-, -N=, -N(H)-C(O)-, -N(H)-C(O)-N(H)-, -S-, -SC(O)- or -SC(S)-O-;

[0424] G2 represents a group selected from the following: Cl, Br, I, -C(O)-OH, -G3 or -C(O)-OG3, wherein G3 is C1 to C 12 alkyl.

[0425] As examples of branching monomers, mention may be made of: acrylic acid, methacrylic acid, brominated monomers and xanthate monomers.

[0426]

[0427] · Other monomers

[0428] In addition to the repeating units described in detail above, the comb copolymers A1 according to the invention may comprise in the main chain further repeating units derived from other comonomers, corresponding to the monomers M1, M2, M3 and M6, as in the side chains, in a proportion of up to 20% by weight, preferably up to 10% by weight and more preferably up to 5% by weight, based on the total weight of the repeating units constituting the copolymers A1.

[0429] Structure of Comb-type Polyglycol Copolymer A1

[0430] The comb-type polyglycol copolymer A1 comprises a main chain and at least one side chain.

[0431] Preferably, the comb-type polyglycol copolymer A1 contains two or more oligomer side chains.

[0432] Preferably, the main chain comprises at least repeating units corresponding to the monomer M2 of formula (II).

[0433] Preferably, the main chain further comprises at least a repeating unit corresponding to the monomer M3 of formula (X).

[0434] The main chain advantageously comprises recurring units corresponding to the monomer M1 of formula (I).

[0435] The side chains may in particular be selected from:

[0436] o A Q2 group as defined in formula (IX) above, selected from -Q', -O-Q', -C(O)-O-Q', -OC(O)-Q', -S-Q', -S-(CH2)2-C(O)-O-Q', -N(H)-C(O)-Q' and -C(O)-N(H)-Q', wherein Q' is a polyolefin.

[0437] The Q2 group can be optionally linked to the main chain via a group A selected from: -A1, -O-(A2-O) n' -A1, -C(O)-O-(A2-O) n' -A1, -OC(O)-(A2-O) n' -A1, -S-(A2-O) n' -A1, -N(H)-C(O)-(A2-O) n' -A1 and -C(O)-N(H)-(A2-O) n' -A1, where:

[0438] A1 is C1 to C 30 Alkyl, C6 to C 30 Aryl or C6 to C 30 Aralkyl,

[0439] A2 is a C2 to C4 alkyl group,

[0440] n' is an integer, n' represents 0 or 1,

[0441] o Oligomers consisting of repeating units corresponding to monomer M2 and optionally monomers M1 and / or M3.

[0442] Thus, repeating units corresponding to the monomer M1 and to the monomers M2 and M3 may occur on the main chain and / or on the side chains.

[0443] The different possible distributions of functionality of these copolymers have been described in Fig. 6A , Figure 6B and Figure 6C Indicated in.

[0444] In these figures, diol functional groups (such as those carried by monomers M1 of formula (I)) are indicated as "F".

[0445] exist Fig. 6A In , the main chain (P) comprises diol functional groups, while the side chains (L) do not comprise them. For example, this diagram may correspond to a copolymer based on monomers M1, M2 and optionally M3 and on an olefin macromonomer M6.

[0446] exist Figure 6B In the diagram, the main chain (P) does not contain diol functional groups, while some side chains (Lb) contain them, but the side chains (La) do not. For example, this diagram may correspond to a copolymer based on monomers M2 and M3 and an olefin macromonomer M6 (La), the side chains (Lb) being oligomers of M1 and M2 and optionally M3, which are grafted onto the main chain.

[0447] exist Figure 6C In the diagram, the main chain (P) and some of the side chains (Lb) contain diol functional groups. For example, the diagram may correspond to a copolymer based on monomers M1 and M2 and optionally M3 and based on an olefin macromonomer M6, the macromonomer M6 forming the side chains (La) as side chains of oligomers of M1 and M2 grafted onto the main chain to form the side chains (Lb).

[0448] Preferred polyglycol copolymers

[0449] In one embodiment, the preferred comb copolymer comprises at least:

[0450] - a repeating unit corresponding to the first monomer M1 of the above general formula (I);

[0451] - a repeating unit corresponding to the second monomer M2 of the above formula (II), wherein R2 is -CH3, R3 is a -C(O)-O-R'3 group, and -R'3 represents H or C1 to C30 alkyl;

[0452] - a repeating unit corresponding to the third monomer M3 of the above general formula (X); in particular styrene.

[0453] In another embodiment, the preferred comb copolymer comprises at least:

[0454] - a repeating unit corresponding to the first monomer M1 of the above general formula (I);

[0455] - a repeating unit corresponding to the second monomer M2 of the above formula (II-A), wherein R2 is -CH3, R3 is a -C(O)-O-R'3 group, and -R'3 represents H or a C1 to C8 alkyl group;

[0456] - a repeating unit corresponding to the third monomer M3 of the above general formula (X); in particular styrene,

[0457] - an oligomer side chain O1 comprising at least one polyolefin fragment, in particular corresponding to the side chain of a monomer M6 of the general formula (IX), more preferably Q2 is selected from -Q', -S-(CH2)2-C(O)-O-Q' or -C(O)-O-Q' groups, wherein Q' is a polyolefin.

[0458] In another embodiment, preferred copolymer A1 comprises at least:

[0459] - a repeating unit corresponding to the first monomer M1 of the above general formula (I);

[0460] - a repeating unit corresponding to the second monomer M2 of the above formula (II-A);

[0461] - a repeating unit corresponding to the third monomer M2 of the above formula (II-B), which is different from the first monomer of the above formula (II-A); and

[0462] - repeating units corresponding to the fourth monomer M3 of the above general formula (X); in particular styrene.

[0463] According to this embodiment, preferred copolymers A1 comprise repeating units corresponding at least to the following monomers:

[0464] - the first monomer M1 of the above general formula (I);

[0465] - a second monomer M2 of formula (II-A), wherein R2 is -CH3 and R"3 is a C1 to C8 alkyl group, preferably a linear C1 to C8 alkyl group;

[0466] - a third monomer M2 of formula (II-B), wherein R2 is -CH3 and R"'3 is C9 to C 30 Alkyl, preferably a straight chain C9 to C 30Alkyl, preferably straight chain C 12 To C 24 Alkyl; and

[0467] - a fourth monomer M3 of the abovementioned general formula (X), in particular styrene.

[0468] According to this embodiment, the preferred copolymer A1 is obtained by copolymerizing at least the following substances:

[0469] - the first monomer M1 of the above general formula (I);

[0470] - a second monomer M2 which is n-butyl methacrylate;

[0471] - a third monomer M2 selected from palmityl methacrylate, stearyl methacrylate, eicosanyl methacrylate and behenyl methacrylate,

[0472] - Optionally, a fourth monomer M3 of the abovementioned general formula (X), in particular styrene.

[0473] In one embodiment, the preferred comb copolymer comprises at least:

[0474] - a repeating unit corresponding to the first monomer M1 of the above general formula (I);

[0475] - a repeating unit corresponding to the second monomer M2 of the above formula (II), wherein R2 is -CH3 and R3 is a -C(O)-O-R'3 group, wherein -R'3 represents H or C1 to C 30 alkyl;

[0476] - a repeating unit corresponding to the third monomer M6 of formula (IX) above, advantageously a monomer M6 of formula (IX) in which Q1 represents H, n=0, Q2 is -CO-O-Q' and Q' represents an olefin.

[0477] Preferably, the oligomeric side chains represent 20% to 95% by weight relative to the total weight of copolymer A1.

[0478] According to a first preferred alternative form, the oligomeric side chains O1 comprising polyolefin segments represent from 20% to 70% by weight relative to the total weight of the copolymer A1.

[0479] According to a second preferred alternative, the oligomeric side chains O2 comprising at least repeating units of a monomer M2 corresponding to the general formula (II) and optionally repeating units of a monomer M1 corresponding to the general formula (I) and / or repeating units of a monomer M3 corresponding to the general formula (X) represent 30% to 95% by weight, relative to the total weight of the copolymer A1.

[0480] Preferably, the non-oligomeric side chains represent 5% to 80% by weight relative to the total weight of copolymer A1.

[0481] Preferably, the repeating unit of formula (X) is 2 mol% to 50 mol% relative to the total moles of the monomers constituting copolymer A1.

[0482] Preferably, the repeating unit corresponding to the monomer M2 is 10 mol% to 90 mol%, preferably 30 mol% to 80 mol%, relative to the total moles of the monomers constituting the copolymer A1.

[0483] Preferably, the repeating unit corresponding to the monomer M1 is 1 mol% to 50 mol%, preferably 5 mol% to 30 mol%, relative to the total moles of the monomers constituting the copolymer A1.

[0484] When calculating the mol % of repeating units and / or monomers (e.g. M1, M2 or M3) relative to the total number of moles of monomers constituting copolymer A1, and when copolymer A1 comprises one or more than one side chain comprising a polyolefin type segment, the polyolefin segment is included by treating it as a single monomer (M6).

[0485] Method for obtaining polyglycol copolymer A1

[0486] A person skilled in the art can synthesize the comb-type polyglycol copolymer A1 with the aid of his common knowledge.

[0487] Copolymerization can be initiated by a free radical generating compound in bulk or in a solution in an organic solvent. For example, the copolymers of the present invention are obtained by known free radical copolymerization methods, particularly controlled radical copolymerization methods, such as the method known as reversible addition-fragmentation chain transfer (RAFT) free radical polymerization and the method known as atom transfer radical polymerization (ARTP). Telomerization and conventional free radical polymerization can also be used to prepare the copolymers of the present invention (Moad, G. and Solomon, DH, The Chemistry of Radical Polymerization, 2nd Ed., Elsevier Ltd, 2006, p. 639; Matyaszewski, K. and Davis, TP, Handbook of Radical Polymerization, Wiley-Interscience, Hoboken, 2002, p. 936).

[0488] According to a preferred embodiment, the copolymerization is carried out by conventional free radical synthesis in the absence of a RAFT chain transfer agent.

[0489] According to a preferred embodiment, the copolymerization is carried out by free-radical synthesis in the presence of chain transfer agents of the mercaptan or halogenated derivative type.

[0490] The comb-type polyglycol copolymer A1 is prepared according to a process comprising at least one polymerization step (a) in which the following substances are contacted:

[0491] i) a monomer selected from the monomer M1 of the general formula (I), the monomer M2 of the general formula (II), the monomer M3 of the general formula (X), the monomer M7 of the general formula (XII), and the monomer M6 of the general formula (IX) as described above;

[0492] ii) at least one source of free radicals.

[0493] In one embodiment, the process may additionally comprise iii) at least one chain transfer agent.

[0494] A "free radical source" is understood to mean a compound which can generate a chemical entity with one or more unpaired outermost electrons. The person skilled in the art can use any known free radical source which is suitable for the polymerization process, in particular the controlled free radical polymerization process. Among the free radical sources, benzoyl peroxide, tert-butyl peroxide, diazo compounds, such as azobisisobutyronitrile, peroxidic compounds, such as persulfates or hydrogen peroxide, redox systems, such as Fe 2+ Oxidative systems, persulfate / sodium metabisulfite mixtures, or ascorbic acid / hydrogen peroxide or compounds which can be cleaved photochemically or by ionizing radiation (eg UV) or by beta or gamma radiation.

[0495] "Chain transfer agent" is understood to mean a compound whose purpose is to provide uniform growth of macromolecular chains by reversible transfer reactions between growing entities (i.e. polymer chains terminated by carbonyl free radicals) and dormant entities (i.e. polymer chains terminated by transfer agents). This reversible transfer process makes it possible to control the molecular weight of the copolymers thus prepared. Preferably, in the process of the invention, the chain transfer agent comprises a thiocarbonylthio-SC(=S)-group. Examples of chain transfer agents may include dithioesters, trithiocarbonates, xanthates and dithiocarbamates. Preferred transfer agents are cumyl dithiobenzoate or 2-cyano-2-propyl dithiobenzoate.

[0496] A "chain transfer agent" is also understood to be a compound whose purpose is to limit the growth of macromolecular chains during their formation by adding monomer molecules and to initiate new chains, which makes it possible to limit the final molecular weights or even control them. Transfer agents of this type are used in telomerization reactions. A preferred transfer agent is cysteamine.

[0497] In one embodiment, the process for preparing a comb-type polyglycol copolymer comprises at least one polymerization stage (a) as described above, wherein the monomers M1 and M2 are selected and X1 and X2 represent hydrogen.

[0498] In one embodiment, the process for preparing a comb-type polyglycol copolymer comprises at least one polymerization stage (a) as described above, wherein at least one branching monomer M7 has the general formula (XII), which polymerization stage is followed by:

[0499] (b) Optional functionalization of branching monomer M7

[0500] (c) at least one oligomerization stage starting from a branching monomer M7 (or a functional group derived from M7), or

[0501] (d) at least one stage of grafting oligomers starting from branching monomers M7 (or functional groups derived from M7).

[0502] According to one embodiment (when free-radical polymerization is carried out using a RAFT chain transfer agent), after direct synthesis of the polymer comprising diol functional groups, the process comprises a stage of removal of the RAFT chain ends by aminolysis followed by Michael addition.

[0503] The preferences and definitions described for the general formulae (I), (Ia), (IA), (IB), (Ia-A), (Ia-B), (II-A), (II-B), (IX), (X) and (XII) also apply to the above processes.

[0504] Those skilled in the art can use various synthesis schemes to introduce side chains into the polyglycol copolymer A1.

[0505] Graft synthesis Figure 7 shown.

[0506] In stage E1 , the monomers M1 , M2 and optionally M3 are copolymerized with the branching comonomers M7 to form the main chain (P).

[0507] The monomer M1 forms a repeating unit comprising a diol functional group represented by the letter F.

[0508] The monomer M7 forms a repeating unit comprising a branching functional group represented by the letter F' (a plurality of different functional groups F' may be present).

[0509] In stage E2, the main chain (P) is grafted with side chains (La), for example polyolefin chains, via partial functional groups F'.

[0510] In stage E3, the main chain (P) is grafted with side chains (Lb) via the remaining functional groups F', for example oligomeric chains resulting from the copolymerization of monomers M1 and M2 and optionally M3, these side chains carrying the diol functional groups denoted F belonging to monomer M1.

[0511] Figure 8The synthesis is shown by a process involving the polymerization of macromonomers and the grafting of oligomers, both techniques allowing the incorporation of side chains.

[0512] In stage E1 , various monomers are reacted: olefin macromonomer M6, monomer M1 comprising diol functional group F, monomer M7 comprising branching functional group F′ and methacrylate or acrylate monomer M2.

[0513] In stage E2 , a comb copolymer is obtained having a main chain (P) with olefin side chains (La), diol functions F, branching functions F′ and acrylate functions (not shown).

[0514] The branched functional groups F' of the copolymer react with the methacrylate or acrylate monomers M2 and the diol monomers M1 to produce, in stage E3, a comb copolymer having a main chain (P) with:

[0515] -Methacrylate or acrylate moieties (not shown)

[0516] - olefin side chain (La),

[0517] - diol functional group (F),

[0518] - side chains (Lb) comprising diol functional groups (F) and acrylate functional groups (not shown).

[0519] Properties of Comb-type Polyglycol Copolymer A1

[0520] The polyglycol copolymer A1 is a comb-type copolymer. "Comb-type copolymer" is understood to mean a copolymer having an available main chain (also referred to as backbone) and oligomeric side chains. The side chains extend from both sides of the main chain. Figure 2 Schematic representation of a comb polymer.

[0521] Copolymer A1 exhibits a main chain derived from polymerizable functional groups, in particular methacrylate functional groups, preferably styrene functional groups, and a mixture of hydrocarbon side chains, substituted or unsubstituted by diol functional groups, some of which are oligomeric and others of which are monomeric side chains, which are non-oligomeric.

[0522] The side chains of copolymer A1 may be:

[0523] - chains produced from monomers of formula (I), (II) and (X),

[0524] - polyolefins, in particular macromonomers M6 corresponding to formula (IX),

[0525] - Oligomers obtained by polymerization of monomers of formula (I) and (II) and optionally monomers of (X).

[0526] The monomers of formula (I), (II) and (X) have polymerizable functional groups whose reactivity can lead to the formation of copolymers, and the monomers with diol functional groups are distributed statistically or in a gradient manner or mixedly along the main chain of the copolymer or on the side chains.

[0527] The comb-type polydiol copolymer A1 has the advantage of being sensitive to external stimuli such as temperature, pressure or shear rate; this sensitivity is reflected in the change of properties. In response to the stimulus, the spatial conformation of the copolymer chain is changed and the diol functional groups become more or less susceptible to association reactions, thereby generating crosslinking and exchange reactions. These association and exchange processes are reversible. The comb-type copolymer A1 is a thermosensitive copolymer, that is, it is sensitive to temperature changes.

[0528] Advantageously, the side chains of the comb-type polyglycol copolymers A1 of oligomeric type corresponding to the monomers M1, M2 and M3 of formulae (I), (II) and (X), respectively, have a number average molar mass of 400 to 50 000, obtained by size exclusion chromatography measurement calibrated with poly(methyl methacrylate).

[0529] The person skilled in the art knows how to obtain this average length by appropriate choice of the types and proportions of the monomers constituting the polyglycol copolymer A1. The choice of this average chain length makes it possible to obtain a polymer that is compatible with hydrophobic media, regardless of the temperature at which the copolymer is dispersed, and to adjust the viscosity of the medium. "Hydrophobic medium" is understood to mean a medium that has no or very little affinity for water, that is to say, it is immiscible in water or in an aqueous medium.

[0530] Advantageously, the polyglycol copolymer A1 has a molar percentage of recurring units corresponding to the monomer M1 of formula (I) in the copolymer ranging from 1% to 50%, preferably from 5% to 30%.

[0531] Advantageously, the polyglycol copolymer A1 has a molar percentage of recurring units corresponding to the monomer M2 of formula (II) in the copolymer ranging from 10% to 90%, preferably from 30% to 80%.

[0532] The mole percentage of the repeating unit in the copolymer results directly from the adjustment of the amounts of monomers used to synthesize the copolymer.

[0533] Advantageously, the number average degree of polymerization of the main chain of the comb-type polyglycol copolymer A1 is from 40 to 2000, preferably from 40 to 1000. The degree of polymerization is controlled in a known manner when the copolymers of the invention are prepared by conventional free radical polymerization, by using controlled free radical polymerization techniques, free radical polymerization techniques in the presence of transfer agents (also referred to as telomerization in some cases) or by adjusting the amount of free radical source.

[0534] Advantageously, the comb-type polyglycol copolymer A1 has a number-average molar mass of 5000 to 400000 g / mol, preferably 10000 to 200000 g / mol, as determined by size exclusion chromatography calibrated with poly(methyl methacrylate).

[0535] The measurement method of size exclusion chromatography is described in Fontanille, M. and Gnanou, Y., Chimie et physico-chimie des polymères [Chemistry and Physical Chemistry of Polymers], 2nd edition, Dunod, 2010, p. 546.

[0536] Advantageously, the degree of branching of the comb-type polyglycol copolymer A1 is from 0.1 to 10 mol %, preferably from 0.5 to 5 mol %.

[0537] The degree of branching is measured by proton NMR and / or by gel permeation chromatography (GPC) equipped with quadruple detection, ie, concentration detector, light scattering detector, UV / visible detector and viscometer.

[0538] ο Compound A2

[0539] Boric acid diester compound A2

[0540] In one embodiment, compound A2 comprising two boronate functional groups has the general formula (III):

[0541]

[0542] in:

[0543] - w1 and w2 are the same or different and are integers equal to 0 or 1;

[0544] - R4, R5, R6 and R7 are identical or different and are chosen from a hydrogen atom or a hydrocarbon radical containing 1 to 30 carbon atoms, preferably 4 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, the hydrocarbon radical being optionally substituted by one or more than one radical chosen from: a hydroxyl radical or an -OJ or -C(O)-OJ radical, wherein J is a hydrocarbon radical containing 1 to 24 carbon atoms;

[0545] -L is selected from C6 to C 18 Aryl, C7 to C 24 Arylalkyl and C2 to C 24 A divalent hydrocarbon chain linking group, preferably C6 to C 18Aryl. “Hydrocarbon radical containing 1 to 30 carbon atoms” is understood to mean a linear, branched or cyclic alkyl radical containing 1 to 30 carbon atoms, a linear, branched or cyclic alkenyl radical containing 2 to 30 carbon atoms, an aryl radical containing 6 to 30 carbon atoms or an aralkyl radical containing 7 to 30 carbon atoms.

[0546] "Hydrocarbon radical containing 1 to 24 carbon atoms" is understood to mean a linear or branched alkyl radical containing 1 to 24 carbon atoms, a linear or branched alkenyl radical containing 2 to 24 carbon atoms, an aryl radical containing 6 to 24 carbon atoms or an aralkyl radical containing 7 to 24 carbon atoms. Preferably, J contains 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms.

[0547] "C2 to C 24 The term "hydrocarbon chain" is understood to mean a straight-chain or branched alkyl or alkenyl group containing from 2 to 24 carbon atoms. Preferably, the hydrocarbon chain L is a straight-chain alkyl group. Preferably, the hydrocarbon chain L contains from 6 to 16 carbon atoms.

[0548] In one embodiment of the present invention, compound A2 is a compound of the above general formula (III), wherein:

[0549] - w1 and w2 are the same or different and are integers equal to 0 or 1;

[0550] - R4 and R6 are the same and are hydrogen atoms;

[0551] - R5 and R7 are identical and are hydrocarbon groups, preferably straight-chain alkyl groups, having 1 to 24 carbon atoms, preferably 4 to 18 carbon atoms, preferably 6 to 16 carbon atoms;

[0552] -L is a divalent linking group and is C6 to C 18 Aryl, preferably phenyl.

[0553] The boronic acid diester compound A2 of formula (III) as described above is obtained according to the method described in WO2015 / 110642 or WO2015 / 110643.

[0554] Polyboric acid ester copolymer compound A2

[0555] In another embodiment, compound A2 comprising at least two borate functional groups is a poly(borate) copolymer obtained by copolymerizing at least one monomer M4 of formula (IV) as described below and at least one monomer M5 of formula (V) as described below.

[0556] In the remainder of this patent application, the expressions "borate copolymer" or "poly(borate) copolymer" are equivalent and refer to the same copolymer.

[0557] Monomer M4 of formula (IV)

[0558] Monomer M4 of borate copolymer compound A2 has the general formula (IV):

[0559]

[0560] in:

[0561] -t is an integer equal to 0 or 1;

[0562] -u is an integer equal to 0 or 1;

[0563] -M and R8 are divalent linking groups, which are the same or different and are selected from C6 to C 18 Aryl, C7 to C 24 Arylalkyl and C1 to C 24 Preferably, M is C6 to C 18 Aryl, R8 is C7 to C 24 Aralkyl;

[0564] -X is a functional group selected from -OC(O)-, -C(O)-O-, -C(O)-N(H)-, -N(H)-C(O)-, -S-, -N(H)-, -N(R'4)- and -O-, wherein R'4 is a hydrocarbon chain containing 1 to 15 carbon atoms;

[0565] -R9 is selected from -H, -CH3 and -CH2-CH3, preferably -H and -CH3;

[0566] -R 10 and R 11 The same or different, which are selected from a hydrogen atom or a hydrocarbon group containing 1 to 30 carbon atoms, preferably 4 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, the hydrocarbon group is optionally substituted by one or more than one group selected from the following: hydroxyl or -OJ or -C(O)-OJ groups, wherein J is a hydrocarbon group containing 1 to 24 carbon atoms.

[0567] "C1 to C 24 "Alkyl" is understood to mean a saturated, linear or branched hydrocarbon chain containing from 1 to 24 carbon atoms. Preferably, the hydrocarbon chain is linear. Preferably, the hydrocarbon chain contains from 6 to 16 carbon atoms.

[0568] "Hydrocarbon chain containing 1 to 15 carbon atoms" is understood to mean a straight-chain or branched alkyl or alkenyl group containing 1 to 15 carbon atoms. Preferably, the hydrocarbon chain is a straight-chain alkyl group. Preferably, it contains 1 to 8 carbon atoms.

[0569] “Hydrocarbon radical containing 1 to 30 carbon atoms” is understood to mean a linear, branched or cyclic alkyl radical containing 1 to 30 carbon atoms, a linear, branched or cyclic alkenyl radical containing 2 to 30 carbon atoms, an aryl radical containing 6 to 30 carbon atoms or an aralkyl radical containing 7 to 30 carbon atoms.

[0570] "Hydrocarbon radical containing 1 to 24 carbon atoms" is understood to mean a linear or branched alkyl radical containing 1 to 24 carbon atoms, a linear or branched alkenyl radical containing 2 to 24 carbon atoms, an aryl radical containing 6 to 24 carbon atoms or an aralkyl radical containing 7 to 24 carbon atoms. Preferably, J contains 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms.

[0571] In one embodiment, monomer M4 has the general formula (IV), wherein:

[0572] -t is an integer equal to 0 or 1;

[0573] -u is an integer equal to 0 or 1;

[0574] -M and R8 are divalent linking groups and are different; M is C6 to C 18 Aryl, preferably phenyl, R8 is C7 to C 24 Aralkyl, preferably benzyl;

[0575] -X is a functional group selected from -OC(O)-, -C(O)-O-, -C(O)-N(H)- and -O-, preferably -C(O)-O- or -OC(O)-;

[0576] -R9 is selected from -H and -CH3, preferably -H;

[0577] -R 10 and R 11 Different; R 10 or R 11 One of the groups is H, R 10 or R 11 Another of the groups is a hydrocarbon chain, preferably a straight chain alkyl, having 1 to 24 carbon atoms, preferably 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms.

[0578] In one embodiment, monomer M4 is a styrene monomer. In this case, in formula (IV): u=1, R9 is H, R8 represents C6 to C 18 Aryl or C7 to C 24 The double bond of the monomer M4 of formula (IV) is directly connected to the aryl group.

[0579] Synthesis of monomer M4 of formula (IV)

[0580] The monomer M4 of formula (IV) as described above is obtained according to the method described in WO2015 / 110642 or WO2015 / 110643.

[0581] Monomer M5 of general formula (V) :

[0582] Monomer M5 of borate copolymer compound A2 has the general formula (V):

[0583]

[0584] in:

[0585] -R 12 Selected from -H, -CH3 and -CH2-CH3, preferably -H and -CH3;

[0586] -R 13 Choose from C6 to C 18 Aryl and R' 13 、-C(O)-OR' 13 、-OR' 13 、-SR' 13 and -C(O)-N(H)-R' 13 C6 to C 18 Aryl, where R' 13 Indicates H or C1 to C 25 alkyl.

[0587] "C1 to C 25 "Alkyl" is understood to mean a saturated, straight-chain or branched hydrocarbon chain containing from 1 to 25 carbon atoms. Preferably, the hydrocarbon chain is straight-chain.

[0588] "Being R' 13 C6 to C 18 The term "aryl" is understood to mean an aromatic hydrocarbon compound containing 6 to 18 carbon atoms, at least one carbon atom of the aromatic ring of which is replaced by a C1 to C 25 Alkyl substitution.

[0589] Among the monomers of formula (V), the monomers corresponding to formula (VA) are part of the preferred monomers:

[0590]

[0591] in:

[0592] -R2 is selected from -H, -CH3 and -CH2-CH3, preferably -H and -CH3;

[0593] -R' 13 Indicates H or C1 to C 25Alkyl, preferably H or a straight chain C1 to C 25 Alkyl, more preferably H or straight chain C3 to C 15 Alkyl, more preferably H or straight chain C5 to C 15 alkyl.

[0594] According to another embodiment, the monomer M5 is a styrene monomer. In this case, in formula (V): R 12 Indicates H, R 13 Selected from C6 to C 18 Aryl and R' 13 C6 to C 18 Aryl, R' 13 Indicates H or C1 to C 25 Alkyl, the double bond of the monomer M5 of formula (V) is directly connected to the aryl group.

[0595] Advantageously, according to this embodiment, monomer M5 is styrene.

[0596] Obtaining Monomer M5:

[0597] The monomers of formula (V) and (VA) are well known to those skilled in the art. and sell.

[0598] Styrene Monomer :

[0599] Advantageously, copolymer A2 comprises at least one monomer of styrenic nature, ie styrene or a styrene derivative, for example styrene substituted on the aromatic ring by another group.

[0600] The monomer M4 may be the following styrene monomer: wherein: u=1, R9 is H, and R8 represents C6 to C 18 Aryl or C7 to C 24 The double bond of the monomer M4 of formula (IV) is directly connected to the aryl group.

[0601] Monomer M5 may also be the following styrene monomer: When in formula (V): R 12 Indicates H, R 13 Selected from C6 to C 18 Aryl and R' 13 C6 to C 18 Aryl, R' 13 Indicates H or C1 to C 25 Alkyl, the double bond of the monomer M5 of formula (V) is directly connected to the aryl group.

[0602] When both M4 and M5 are not styrenic, copolymer A2 advantageously comprises at least one third monomer M3 of formula (X):

[0603]

[0604] in:

[0605] - Z1, Z2 and Z3 are the same or different and represent a hydrogen atom, a C1 to C 12 alkyl or -OZ' or -C(O)-O-Z' group, wherein Z' is C1 to C 12 alkyl.

[0606] M3 has already been described in detail above for the preparation of copolymer A1. Preferred monomers M3 and their preferred amounts are the same in A2 as in A1.

[0607] Advantageously, when A2 comprises a third monomer M3 of formula (X), this monomer M3 is styrene.

[0608] Olefin Monomers :

[0609] According to an alternative form, copolymer A2 comprises repeating units corresponding to at least one monomer with olefinic properties, i.e. a monomer with an olefin chain and optionally one or more than one other functional groups. In particular, according to this alternative form, copolymer A2 comprises repeating units corresponding to at least one monomer M6 of general formula (IX) as described above.

[0610] The preferred alternatives of the monomers M6 of the general formula (IX) for copolymer A1 also apply to copolymer A2.

[0611] · Other monomers

[0612] In addition to the repeating units described in detail above, copolymer A2 comprises further repeating units derived from other comonomers in a proportion of up to 20% by weight, preferably up to 10% by weight, more preferably up to 5% by weight, based on the total weight of the repeating units constituting copolymer A2.

[0613] · Structure of poly(borate) copolymers

[0614] Copolymer A2 may be a linear copolymer or a comb copolymer, ie a copolymer comprising oligomeric side chains.

[0615] In the case of comb copolymers, the oligomeric side chains may in particular correspond to polyolefin monomers M6 of the formula (IX) or to chains of oligomers comprising structural units corresponding to monomers M2 of the formula (II) and optionally monomers M3 of the formula (X).

[0616] In one embodiment, the preferred comb copolymer comprises at least:

[0617] - a repeating unit corresponding to the first monomer M4 of the above general formula (IV);

[0618] - a repeating unit corresponding to the second monomer M5 of the above formula (V), preferably formula (VA);

[0619] - a repeating unit corresponding to the third monomer M6 of formula (IX) above, advantageously a monomer M6 of formula (IX) in which Q1 represents H, n=0, Q2 is -CO-O-Q' and Q' represents an olefin.

[0620] Synthesis of Poly(Borate) Copolymer Compound A2

[0621] Copolymer A2 is obtained according to the process described in WO 2015 / 110642 or WO 2015 / 110643.

[0622] In case copolymer A2 is a comb copolymer, the skilled person will apply the same derivatization or copolymerization techniques as described above for A1.

[0623] Properties of poly(borate) copolymer compound A2

[0624] Advantageously, by R 10 , M, (R8) u (u is an integer equal to 0 or 1) and the X groups of the monomer M4 of the general formula (IV) are connected to form a chain, showing a total number of carbon atoms of 8 to 38, preferably 10 to 26.

[0625] Advantageously, the average length of the non-oligomeric side chains of the borate copolymer A2 is greater than 8 carbon atoms, preferably from 11 to 16 carbon atoms. This chain length makes it possible to disperse the borate copolymer in a hydrophobic medium.

[0626] Advantageously, when copolymer A2 comprises polyolefin side chains, the average length of the non-oligomeric side chains of copolymer A2 is between 1 and 8 carbon atoms.

[0627] The "average length of the side chains" is understood to mean the average length of the side chains of each monomer constituting the copolymer. When calculating the average length of the side chains, the side chains resulting from styrene monomers are not taken into account. A person skilled in the art knows how to obtain this average length by appropriately selecting the types and proportions of the monomers constituting the borate copolymer.

[0628] Advantageously, the borate copolymer A2 has a molar percentage of monomers of formula (IV) in the copolymer of 0.25% to 30%, preferably 1% to 25%, more preferably 5% to 20%.

[0629] Advantageously, the borate copolymer A2 has a molar percentage of monomers of formula (IV) in the copolymer of 0.25% to 30%, preferably 1% to 25%, and a molar percentage of monomers of formula (V) in the copolymer of 70% to 99.75%, preferably 75% to 99%.

[0630] Advantageously, the borate copolymer A2 has a molar percentage of styrene monomers of formula (IV), (V) and / or (X) in the copolymer of 2 to 50 mol %, preferably 3 to 40 mol %, more preferably 5 to 35 mol %.

[0631] The "molar percentage of styrene monomers" is understood to mean the sum of the contents of each styrene monomer in the borate copolymer A2, and the styrene monomers may be:

[0632] · having formula (IV), wherein: u=1, R9 is H, and R8 represents C6 to C 18 Aryl or C7 to C 24 The double bond of the monomer M4 of formula (IV) is directly connected to the aryl group.

[0633] · having the formula (V), wherein: R 12 Indicates H, R 13 Selected from C6 to C 18 Aryl and R' 13 C6 to C 18 Aryl, R' 13 Indicates H or C1 to C 25 Alkyl, the double bond of the monomer M5 of formula (V) is directly connected to the aromatic group;

[0634] and / or

[0635] • having formula (X), as described above.

[0636] Advantageously, the poly(borate) copolymer has a number average degree of polymerization of 50 to 1500, preferably 50 to 800.

[0637] Advantageously, the poly(borate) copolymers have a polydispersity index (PI) ranging from 1.04 to 3.54, preferably from 1.10 to 3.10. These values ​​are obtained by size exclusion chromatography using tetrahydrofuran as eluent and poly(methyl methacrylate) calibration.

[0638] Advantageously, the poly(borate) copolymer has a number average molar mass of 10000 to 200000 g / mol, preferably 25000 to 100000 g / mol. These values ​​are obtained by size exclusion chromatography using tetrahydrofuran as eluent and poly(methyl methacrylate) calibration.

[0639] Compound A2, in particular poly(boric acid ester) copolymers, exhibits the property of being able to react with compounds with diol functional groups in hydrophobic media, in particular non-polar media, by transesterification. The transesterification reaction can be represented according to the following Scheme 9:

[0640]

[0641] Therefore, during the transesterification reaction, a boric acid ester having a chemical structure different from that of the starting boric acid ester is formed by exchanging the hydrocarbon groups represented by the following formula.

[0642]

[0643] ο Exogenous compound A4

[0644] According to one embodiment, the additive composition is mixed with at least the following substances:

[0645] - Comb-type polyglycol copolymer A1,

[0646] a copolymer A2 comprising at least two borate functional groups and capable of associating with the polyglycol copolymer A1 by at least one transesterification reaction,

[0647] - Exogenous polyol compound A4.

[0648] Advantageously, according to this embodiment of the invention, the molar percentage of exogenous compound A4 in the additive composition relative to the borate functional groups of copolymer A2 is from 0.025% to 5000%, preferably from 0.1% to 1000%, more preferably from 0.5% to 500%, more preferably from 1% to 150%.

[0649] The exogenous compound A4 is selected from polyols, in particular 1,2-diols and 1,3-diols, and glycerol derivatives. Within the meaning of the present invention, "exogenous compound" is understood to mean a compound which is added to the additive composition by mixing at least one comb-type polyglycol copolymer A1 and at least one compound A2, in particular a poly(borate) copolymer.

[0650] Compound A4 is chosen from organic compounds comprising at least one diol group and capable of use in a lubricating composition. Preferably, compound A4 is chosen from hydrocarbon compounds comprising from 2 to 30 carbon atoms.

[0651] Preferably, the exogenous compound A4 is chosen from lubricant additives, such as compounds known to have the function of friction modifier, thickener, dispersant or detergent in lubricating compositions.

[0652] It is worth noting that the exogenous compound A4 can be selected from 1,2-diols and 1,3-diols and glycerol derivatives.

[0653] According to a preferred embodiment, the exogenous compound A4 may have the general formula (VI):

[0654]

[0655] in:

[0656] w3 is an integer equal to 0 or 1,

[0657] R 14 and R 15 Identical or different, they are chosen from hydrogen and hydrocarbon chains having 1 to 24 carbon atoms, preferably 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms.

[0658] "Hydrocarbon chain containing 1 to 24 carbon atoms" is understood to mean a straight-chain or branched alkyl or alkenyl group containing 1 to 24 carbon atoms. Preferably, the hydrocarbon chain is a straight-chain alkyl group. Preferably, it contains 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms.

[0659] In one embodiment, the exogenous compound A4 has the general formula (VI), wherein:

[0660] w3 is an integer equal to 0 or 1;

[0661] R 14 and R 15 The same or different, which are selected from -T, -CH2-OT and -CH2-OC(O)-T, T is selected from hydrogen or a hydrocarbon chain, preferably a linear alkyl chain having 1 to 24 carbon atoms, preferably 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms.

[0662] In one embodiment, the exogenous compound A4 has the general formula (VI), wherein:

[0663] w3 is an integer equal to 0 or 1;

[0664] R 14 and R 15 Different; R 14 or R 15 One of the groups is H, R 14 or R 15 Another of the groups is a hydrocarbon chain, preferably a straight chain alkyl, having 1 to 24 carbon atoms, preferably 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms.

[0665] In another preferred embodiment, the exogenous compound is selected from sugars and sugar derivatives.

[0666] A person skilled in the art is able to select sugars and sugar derivatives among sugars and sugar derivatives that are compatible with lubricating oils by virtue of his general knowledge.

[0667] The compound of formula (VI) is commercially available from the following suppliers: and

[0668] ο Exogenous compound A5

[0669] According to one embodiment, the additive composition is mixed with at least the following substances:

[0670] - Comb-type polyglycol copolymer A1,

[0671] a copolymer A2 comprising at least two borate functional groups and being able to associate with the comb-type polyglycol copolymer A1 by at least one transesterification reaction,

[0672] - selected from exogenous compounds A5 corresponding to formula (XI):

[0673]

[0674] in:

[0675] -Q represents a group chosen from hydrocarbon radicals containing 1 to 30 carbon atoms, optionally substituted by one or more than one group chosen from: hydroxyl or -OJ or -C(O)-OJ radicals, wherein J is a hydrocarbon radical containing 1 to 24 carbon atoms,

[0676] -G4 and G5 are the same or different and represent a group selected from a hydrogen atom, a hydrocarbon group containing 1 to 24 carbon atoms, a hydroxyl group or -OJ or -C(O)-OJ, wherein J is a hydrocarbon group containing 1 to 24 carbon atoms,

[0677] -g means 0 or 1.

[0678] Advantageously, the exogenous compound A5 corresponds to formula (XIIA):

[0679]

[0680] in:

[0681] - G1, G2, G3, G4 and G5 are the same or different and represent a group selected from a hydrogen atom, a hydrocarbon chain containing 1 to 24 carbon atoms, a hydroxyl group or -OJ or -C(O)-OJ, wherein J is a hydrocarbon group containing 1 to 24 carbon atoms,

[0682] -g means 0 or 1.

[0683] According to a preferred embodiment, the molar percentage of exogenous compound A5 relative to the diol functional groups of comb copolymer A1 is 0.025% to 5000%, preferably 0.1% to 1000%, more preferably 0.5% to 500%, more preferably 1% to 150%.

[0684] According to a preferred embodiment, the exogenous compound A5 is chosen from those corresponding to formula (XII B):

[0685]

[0686] According to yet another preferred embodiment, the exogenous compound A5 is selected from those corresponding to formula (XII B), wherein g=0, G4=H, and G5 represents C1 to C 24 alkyl.

[0687] Through transesterification, the exogenous compound A5 releases in situ the diol fragment A6 of formula (XIII):

[0688]

[0689] Features of the novel additive composition of the present invention

[0690] Depending on the temperature and on the ratio of compounds A1, A2 and optionally A4 and / or A5 used, the additive compositions according to the invention exhibit very different rheological properties.

[0691] The comb-type polyglycol copolymer A1 and compound A2 above show the advantage of associating and exchanging chemical bonds in a thermoreversible manner, especially in a hydrophobic medium, especially in a non-polar hydrophobic medium.

[0692] Under certain conditions, the comb-type polyglycol copolymer A1 and the compound A2 may be cross-linked.

[0693] The comb-type polyglycol copolymer A1 and the compound A2 also show the advantage of being interchangeable.

[0694] "Associated" is understood to mean the establishment of covalent chemical bonds of the borate type between the comb-type polyglycol copolymer A1 and the compound A2 comprising at least two borate functional groups, in particular with the poly(borate) copolymer. Depending on the functionality of the comb-type polyglycol A1 and the compound A2 and on the composition of the mixture, the formation of covalent bonds between the comb-type polyglycol A1 and the compound A2 may or may not lead to the formation of a three-dimensional polymer network.

[0695] "Chemical bond" is understood to mean a covalent chemical bond of the borate ester type.

[0696] "Interchangeable" is understood to mean that the compounds are able to exchange chemical bonds with each other without changing the total number and type of chemical functional groups. The following reaction scheme 10 illustrates the exchange (ester exchange) chemical reaction:

[0697]

[0698] in

[0699] -R is a chemical group of compound A2,

[0700] - the hatched lines represent the remainder of the chemical structure of compound A2,

[0701] - The square rectangle represents the remainder of the chemical structure of the polydiol comb polymer A1.

[0702] The boronate bonds of compound A2 (optionally formed by transesterification reaction between the boronate of compound A2 and exogenous compounds A4 and / or A5, and boronate bonds formed by association of comb-type polyglycol copolymer A1 and compound A2) can be exchanged with diol functional groups carried by compound A3 released in situ, optionally with diol functional groups carried by exogenous compounds A4 and / or A5, to form new boronate and new diol functional groups without affecting the total number of boronate functional groups and diol functional groups. Another process of chemical bond exchange is by continuous exchange of boronate functional groups in the presence of diols through metathesis reaction. Another process of chemical bond exchange is as follows Figure 3 As shown, it can be observed that the polyglycol copolymer A1-1 associated with polymer A2-1 has exchanged two borate bonds with borate copolymer A2-2. The polyglycol copolymer A1-2 associated with polymer A2-2 has exchanged two borate bonds with borate copolymer A2-1; the total number of borate bonds in the composition remains unchanged and is equal to 4. Copolymer A1-1 is then associated with polymer A2-2. Copolymer A1-2 is then associated with polymer A2-1. Copolymer A2-1 has exchanged with polymer A2-2.

[0703] "Crosslinking" is understood to mean a copolymer in the form of a network obtained by building bridges between the macromolecular chains of the copolymer. These interconnected chains are mostly distributed in three dimensions in space. Crosslinked copolymers form a three-dimensional network. In practice, the formation of a copolymer network is ensured by solubility tests. The formation of a copolymer network can be determined by placing the copolymer network in a solvent known to dissolve non-crosslinked copolymers of the same chemical substance. If the copolymer swells instead of dissolving, the person skilled in the art knows that a network has been formed. Figure 4 Such a solubility test is described.

[0704] "Crosslinkable" is understood to mean a copolymer that is capable of crosslinking.

[0705] "Reversible crosslinking" is understood to refer to a crosslinked copolymer whose bridge is formed by a reversible chemical reaction. The reversible chemical reaction can be transferred in one direction or another, thereby causing a change in the polymer network structure. The copolymer can change from an initial non-crosslinked state to a crosslinked state (three-dimensional network of the copolymer), and can change from a crosslinked state to an initial non-crosslinked state. In the context of the present invention, the bridge formed between the chains of the copolymer is unstable. These bridges can be formed or exchanged by a reversible chemical reaction. In the context of the present invention, the reversible chemical reaction is an ester exchange reaction between the diol functional group of the copolymer (copolymer A1) and the borate functional group of the crosslinking agent (compound A2). The bridge formed is a bond of a borate type. Due to the reversibility of the ester exchange reaction, these borate bonds are covalent and unstable.

[0706] "Crosslinking in a thermoreversible manner" is understood to mean a copolymer that is crosslinked by means of a reversible reaction, the transfer of which in one direction or the other is controlled by temperature. Figure 5 At low temperature, the polyglycol copolymer A1 (composed of Figure 5 The copolymer with functional group A in the above is not crosslinked by borate compound A2 or is only crosslinked by borate compound A2 (represented by Figure 5 The polyglycol copolymer A1 and the compound A2 containing at least two borate functional groups are then combined and can be exchanged. Depending on the functionality of the polyglycol A1 and the compound A2 and on the composition of the mixture, a gel can be formed in the medium, in particular when the medium is non-polar. When the temperature is lowered again, the borate bond between the polyglycol copolymer A1 and the compound A2 breaks and, if applicable, the composition loses its gelling properties.

[0707] A person skilled in the art can adjust the amount of borate ester bonds that can be formed between the comb-type polyglycol copolymer A1 and the compound A2 by appropriately selecting the polyglycol copolymer A1, the compound A2 and the composition of the mixture.

[0708] In addition, a person skilled in the art knows how to select the structure of compound A2 according to the structure of copolymer A1. Preferably, when copolymer A1 contains at least one monomer M1 with y=1, compound A2 of general formula (III) or copolymer A2 containing at least one monomer M4 of formula (IV), wherein w1=1, w2=1 and t=1, is preferred.

[0709] By controlling the degree of association of the polyglycol copolymer A1 and the compound A2, in particular the static polyboric ester copolymer, the viscosity and rheological behavior of the composition can be adjusted. When exogenous compounds A4 and / or A5 are present, the viscosity of the composition can be adjusted according to the temperature and the desired use.

[0710] In a preferred embodiment of the invention, the chemical substance of the exogenous compound A4 is identical to the chemical substance of the diol compound A3 released in situ by the transesterification reaction between the comb-type polydiol copolymer A1 and the compound A2, in particular a polyboric acid ester copolymer. According to this embodiment, the total amount of free diols present in the composition is strictly greater than the amount of diol compounds released in situ. "Free diols" are understood to mean diol functional groups that are capable of forming borate-type chemical bonds by transesterification. Within the meaning of the present patent application, the "total amount of free diols" are understood to mean the total number of diol functional groups that are capable of forming borate-type chemical bonds by transesterification.

[0711] According to this embodiment, the total amount of free diols is always equal to the sum of the number of moles of exogenous polyol compound A4 and the number of diol functional groups (expressed in moles) of the polyglycol copolymer A1. In other words, if in the additive composition there are:

[0712] -i moles of exogenous polyol compound A4 and

[0713] -j moles of polyglycol copolymer A1,

[0714] (Thus, regardless of the degree of association between polyglycol copolymer A1 and compound A2, in particular poly(boric ester) copolymer A2) the total amount of free glycols will always be = i + j * average number of glycols per comb polymer chain A1 (in mol).

[0715] The amount of diol released in situ in the case of the transesterification reaction between A1 and A2 is equal to the number of borate functions linking copolymers A1 and A2.

[0716] A person skilled in the art knows how to select the chemical structure and amount of exogenous compounds A4 and / or A5 added to the additive composition, depending on compound A2, in particular on the molar percentage of borate functional groups of the poly(borate) copolymer, in order to adjust the rheological behavior of the composition.

[0717] Advantageously, the content of copolymer A1 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, more preferably from 1% to 30% by weight relative to the total weight of the final composition.

[0718] Advantageously, the content of compound A2 in the composition is 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, more preferably from 0.5% to 30% by weight relative to the total weight of the final composition.

[0719] In one embodiment, the content of copolymer A1 in the composition is 0.5 wt % to 50.0 wt % relative to the total weight of the composition, and the content of compound A2, especially borate copolymer, in the composition is 0.5 wt % to 50.0 wt % relative to the total weight of the composition.

[0720] Preferably, the weight ratio of the polyglycol compound A1 to the compound A2 (A1 / A2 ratio) in the composition is 0.005 to 200, preferably 0.05 to 20, and more preferably 0.1 to 10.

[0721] In one embodiment, the composition of the present invention is provided in the form of a parent composition. "Parent composition" is understood to mean a composition that a person skilled in the art can make into a daughter solution by extracting a certain amount of a mother solution and supplementing it with a necessary amount of a diluent (solvent or other) to obtain a desired concentration. Thus, a daughter composition is obtained by diluting the parent composition.

[0722] The hydrophobic medium can be a solvent, mineral oil, natural oil or synthetic oil.

[0723] In one embodiment, the composition of the present invention may further comprise at least one additive selected from thermoplastics, elastomers, thermoplastic elastomers, thermosetting polymers, pigments, dyes, fillers, plasticizers, fibers, antioxidants, lubricant additives, compatibilizers, defoamers, dispersant additives, tackifiers and stabilizers.

[0724] Preparation method of the novel additive composition of the present invention

[0725] The novel additive composition of the present invention is prepared by methods well known to those skilled in the art. For example, it is sufficient, in particular for those skilled in the art, to carry out the following operations:

[0726] - taking out a desired amount of a solution containing the comb-type polyglycol copolymer A1;

[0727] - taking out a desired amount of a solution comprising the above compound A2; in particular a desired amount of a solution comprising the above defined poly(borate) copolymer; and

[0728] - optionally taking out a desired amount of a solution containing the above exogenous compound A4 and / or A5;

[0729] - Mixing the withdrawn solutions simultaneously or sequentially to obtain the composition of the invention.

[0730] The order of addition of the compounds has no influence on the performance of the process for the preparation of the additive composition.

[0731] A person skilled in the art also knows how to adjust the various parameters of the composition of the invention to obtain a composition in which the comb-type polyglycol copolymer A1 and the compound A2 (especially the borate copolymer) are associated or a composition in which the comb-type polyglycol copolymer A1 and the compound A2, especially the borate copolymer, are crosslinked, so as to adjust the degree of association or crosslinking at a given use temperature. For example, a person skilled in the art knows how to adjust in particular, in a non-exhaustive manner:

[0732] - the molar percentage of monomers M1 carrying diol functions in the comb-type polyglycol copolymer A1;

[0733] - the content of styrene monomer M3 in the comb-type polyglycol copolymer A1;

[0734] - molar percentage of olefinic macromonomer M6 in comb-type polyglycol copolymer A1;

[0735] - the molar percentage of oligomeric side chains comprising repeating units corresponding to the monomers M2 and optionally M1 and M3 in the comb-type polyglycol copolymer A1;

[0736] - the molar percentage of monomers M4 carrying borate functional groups in the borate copolymer A2;

[0737] - the average length of the oligomer side chains of the polyglycol copolymer A1;

[0738] - the average length of the non-oligomeric side chains of the polyglycol copolymer A1;

[0739] - the average length of the side chains of the borate copolymer A2;

[0740] - the length of the monomer M4 of the borate copolymer A2;

[0741] - the content of styrene monomer M4 of formula (IV) or M5 of formula (V) or M3 of formula (X) in the borate copolymer A2;

[0742] - the length of the boronic acid diester compound A2;

[0743] - the number average degree of polymerization of the main chains of the polyglycol copolymer A1 and the borate copolymer A2;

[0744] - the number average degree of polymerization of the side chains of the polyglycol copolymer A1 and optionally the borate ester copolymer A2;

[0745] - weight percentage of polyglycol copolymer A1;

[0746] - weight percentage of the boric acid diester compound A2;

[0747] - weight percentage of borate copolymer A2;

[0748] and, if applicable:

[0749] - the molar amount of exogenous compound A4 relative to compound A2, in particular the borate functional groups of the poly(borate) copolymer;

[0750] - Chemical substances of exogenous compound A4;

[0751] - molar percentage of exogenous compound A4;

[0752] - the molar amount of the exogenous compound A5 relative to the diol functional groups of the diol copolymer A1;

[0753] - Chemical substance of exogenous compound A5;

[0754] - Mole percentage of exogenous compound A5.

[0755] Use of the novel composition of the present invention

[0756] The composition of the invention can be used in all media whose viscosity varies with temperature. The composition of the invention makes it possible to thicken fluids and to adjust the viscosity according to the temperature of use. The additive composition according to the invention can be used for improvements in the field of oil production, paper industry, paints, food additives or cosmetic or pharmaceutical preparations.

[0757] The lubricating composition according to the invention

[0758] Another subject of the present invention relates to a lubricating composition obtained by mixing at least the following substances:

[0759] - Lubricating oil, and

[0760] - the above-mentioned comb-type polyglycol copolymer A1,

[0761] a compound A2, in particular a copolymer A2 as defined above, which comprises at least two borate functional groups and is capable of associating with the comb-type polyglycol copolymer A1 by at least one transesterification reaction,

[0762] - Optionally, an exogenous compound A4, in particular as defined above,

[0763] - Optionally, an exogenous compound A5 as defined above.

[0764] The preferences and definitions described in the general formulae (I), (IA), (IB), (Ia), (Ia-A), (Ia-B), (II-A), (II-B), (IX), (X) and (XII) also apply to the comb-type polyglycol copolymer A1 used in the lubricating composition of the present invention.

[0765] The preferences and definitions described for the general formulae (III), (IV), (V), (IX) and (X) also apply to the borate compound A2 used in the lubricating composition of the present invention.

[0766] Compared to the behavior of base oils and rheological additives of the polymer type of the prior art, the lubricating composition according to the invention has an opposite behavior with respect to temperature changes and exhibits the advantage that the rheological behavior can be adjusted according to the use temperature. Unlike base oils that become thinner when the temperature rises, the composition of the invention exhibits the advantage of becoming thicker when the temperature rises. The formation of reversible covalent bonds makes it possible to (reversibly) increase the molar mass of the polymer, thereby limiting the decrease in the viscosity of the base oil at high temperatures. The supplementary addition of the diol compound makes it possible to control the rate of formation of these reversible bonds. Advantageously, the viscosity of the lubricating composition is thereby controlled and less dependent on temperature fluctuations. In addition, for a given use temperature, the viscosity of the lubricating composition and its rheological behavior can be adjusted by adjusting the amount of diol compound added to the lubricating composition. Finally, the lubricating composition of the invention has improved thermal stability, improved oxidation stability, improved viscosity index, improved cycle resistance and better reproducibility of performance qualities over time.

[0767] lubricating oil

[0768] "Oil" is understood to mean oil at ambient temperature (25°C) and atmospheric pressure (760 mm Hg, i.e. 10 5 Pa) is a fatty substance that is liquid below 4000 Pa.

[0769] "Lubricating oil" is understood to mean an oil that reduces friction between two moving parts to facilitate the operation of these parts. The lubricating oil may be of natural, mineral or synthetic origin.

[0770] The lubricating oil of natural origin may be oil of plant or animal origin, preferably oil of plant origin, such as rapeseed oil, sunflower oil, palm oil, coconut oil and the like.

[0771] Lubricating oils of mineral origin are of petroleum origin and are extracted from the petroleum fractions of atmospheric and vacuum distillation of crude oil. The distillation may be followed by refining operations such as solvent extraction, deasphalting, solvent dewaxing, hydrotreating, hydrocracking, hydroisomerization, hydrofining, etc. By way of example, mention may be made of paraffinic mineral base oils, such as bright solvent (BSS) oils, naphthenic mineral base oils, aromatic mineral oils, hydrofined mineral base oils having a viscosity index of about 100, hydrocracked mineral base oils having a viscosity index of 120 to 130 or hydroisomerized mineral base oils having a viscosity index of 140 to 150.

[0772] As the name implies, lubricating oils of synthetic origin (or based on synthetic) come from chemical synthesis, such as the addition of a product to itself or to polymerization, or the addition of a product to another product, such as esterification, alkylation, fluorination, etc., products derived from components of petrochemicals, carbon chemistry and inorganic chemistry, such as: olefins, aromatic compounds, alcohols, acids, halogenated compounds, phosphorus compounds, silicon compounds, etc. By way of example, mention may be made of:

[0773] - synthetic oils based on synthetic hydrocarbons, for example poly(alpha-olefins) (PAOs), poly(internal olefins) (PIOs), polybutenes and polyisobutylenes (PIBs), alkylbenzenes or alkylated polyphenylenes;

[0774] - synthetic oils based on esters, for example esters of diacids or of neopolyols;

[0775] - synthetic oils based on polyethylene glycols, for example monoalkylene glycols, polyalkylene glycols and polyalkylene glycol monoethers;

[0776] - synthetic oils based on phosphate esters;

[0777] - Synthetic oils based on silicon derivatives, for example silicone oils or polysiloxanes.

[0778] The lubricating oil that can be used in the composition of the present invention can be selected from any oil of Group I to Group V specified in the API classification guide (Base Oil Interchangeability Guide of the American Petroleum Institute (API)) or equivalent standards according to ATIEL (European Technical Association of the Lubricant Industry)), which are summarized as follows:

[0779]

[0780] *Measured according to standard ASTM D2007

[0781] **Measured according to standards ASTM D2622, ASTM D4294, ASTM D4927 and ASTM D3120

[0782] ***Measured according to standard ASTM D2270

[0783] The composition of the present invention may contain one or more than one lubricating oil. The lubricating oil or lubricating oil mixture is the main component in the lubricating oil composition. The description then used is lubricating base oil. Main component is understood to mean that the lubricating oil or lubricating oil mixture accounts for at least 51% by weight of the total weight of the composition.

[0784] Preferably, the lubricating oil or lubricating oil mixture comprises at least 70 wt % of the total weight of the composition.

[0785] In one embodiment of the present invention, the lubricating oil is selected from one of the oils of Group I, Group II, Group III, Group IV or Group V of the API classification and mixtures thereof. Preferably, the lubricating oil is selected from the oils of Group III, Group IV or Group V of the API classification and mixtures thereof. Preferably, the lubricating oil is an oil of Group III of the API classification.

[0786] The lubricating oil has a kinematic viscosity at 100° C. measured according to standard ASTM D445, ranging from 2 cSt to 150 cSt, preferably from 2 cSt to 15 cSt.

[0787] Functional additives

[0788] In one embodiment, the composition of the present invention may further comprise one or more functional additives selected from the group consisting of detergents, anti-wear additives, load-bearing additives, antioxidants, polymers for improving viscosity index, pour point improvers, defoamers, thickeners, anti-corrosion additives, dispersants, friction modifiers, and mixtures thereof.

[0789] The functional additives added to the composition of the present invention are selected according to the final use of the lubricating composition. These additives can be introduced in two different ways:

[0790] - each additive is added to the composition individually and sequentially,

[0791] - or all additives are added to the composition simultaneously; in this case, the additives are usually obtained in the form of a package, called an additive package.

[0792] When a functional additive or a mixture of functional additives is present, it is present in an amount ranging from 0.1% to 10% by weight relative to the total weight of the composition.

[0793] Detergent:

[0794] These additives reduce the formation of deposits on the surface of metal parts by dissolving oxidation by-products and combustion by-products. Detergents that can be used in the lubricating composition according to the present invention are well known to those skilled in the art. The detergents commonly used in the formulation of lubricating compositions are generally anionic compounds containing long lipophilic hydrocarbon chains and hydrophilic heads. The associated cations are generally metal cations of alkali metals or alkaline earth metals. The detergent is preferably selected from alkali metal or alkaline earth metal salts of carboxylic acids, sulfonic acids, salicylic acids, cyclohexane acids and phenols. Alkali metals and alkaline earth metals are preferably calcium, magnesium, sodium or barium. These metal salts may contain approximately stoichiometric amounts or excess (greater than stoichiometric amounts) of metal. In the latter case, "high alkalinity" detergents must be treated. The excess metal that makes the detergent high alkalinity is provided in the form of an oil-insoluble metal salt, such as a carbonate, hydroxide, oxalate, acetate or glutamate, preferably a carbonate.

[0795] Anti-wear additives and load-carrying additives:

[0796] These additives protect surfaces from friction by forming a protective film adsorbed on these surfaces. There are a wide variety of anti-wear additives and supported additives. Mention may be made, by way of example, of phosphorus / sulfur additives, such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, more particularly zinc dialkyldithiophosphates or ZnDTP, amine phosphates, polysulfides, in particular sulfur-based olefins and metal dithiocarbamates.

[0797] Antioxidants:

[0798] These additives slow down the degradation of the composition. The degradation of the composition can be reflected by the formation of deposits, the presence of scale or an increase in the viscosity of the composition. Antioxidants act as free radical inhibitors or destroyers of hydroperoxides. Commonly used antioxidants include phenolic or aminic antioxidants.

[0799] Anti-corrosion additives:

[0800] 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. For example, mention can be made of dithiothiadiazole (DMTD), benzotriazole or phosphites (which capture free sulfur).

[0801] Viscosity Index Improving Polymers:

[0802] These additives can ensure good cold resistance and a minimum viscosity of the composition at high temperatures. Mention may be made, by way of example, of polymer esters, olefin copolymers (OCP) or polymethacrylates (PMA).

[0803] Pour point improvers:

[0804] These additives improve the cold properties of the composition by slowing down the formation of paraffin crystals. These are, for example, polyalkyl methacrylates, polyacrylates, polyarylamide, polyalkylphenols, polyalkylnaphthalenes and alkylated polystyrenes.

[0805] Defoaming agent:

[0806] These additives have the effect of counteracting the action of the detergents. By way of example, mention may be made of polydimethylsiloxanes and polyacrylates.

[0807] Thickener:

[0808] Thickeners are additives used in particular in industrial lubrication and make it possible to formulate lubricants of higher viscosity than engine lubricating compositions. By way of example, mention may be made of polyisobutylenes having a weight-average molar mass of 10 000 to 100 000 g / mol.

[0809] Dispersants:

[0810] These additives ensure the maintenance in suspension and the removal of insoluble solid contaminants consisting of oxidation by-products formed during use of the composition. Mention may be made, by way of example, of succinimide, PIB (polyisobutylene) succinimide and Mannich bases.

[0811] Friction modifiers:

[0812] These additives improve the friction coefficient of the composition. Mention may be made, by way of example, of molybdenum dithiocarbamates, amines having at least one hydrocarbon chain of at least 16 carbon atoms, esters of fatty acids and of polyols, for example esters of fatty acids and of glycerol, in particular glycerol monooleate.

[0813] o Content of the compound of the lubricating composition

[0814] Advantageously, the content of comb copolymer A1 in the lubricating composition is from 0.05% to 20% by weight relative to the total weight of the lubricating composition, preferably from 0.5% to 10% by weight relative to the total weight of the lubricating composition.

[0815] Advantageously, the content of compound A2, in particular the poly(borate) copolymer, is from 0.05% to 20% by weight relative to the total weight of the lubricating composition, preferably from 0.25% to 10% by weight relative to the total weight of the lubricating composition.

[0816] Preferably, the weight ratio of polyglycol compound A1 to compound A2, in particular poly(borate) copolymer (A1 / A2 ratio) is from 0.001 to 100, preferably from 0.05 to 20, more preferably from 0.1 to 10, more preferably from 0.2 to 5.

[0817] In one embodiment, the sum of the weights of comb copolymer A1 and compound A2 is from 0.01% to 40% relative to the total weight of the lubricating composition, advantageously from 0.75% to 20%, preferably from 2% to 15% relative to the total weight of the lubricating composition, and the weight of lubricating oil is from 60% to 99.9% relative to the total weight of the lubricating composition.

[0818] When applied to an engine, advantageously, the sum of the weight of the comb copolymer A1 and the compound A2 is between 0.1% and 15% relative to the total weight of the lubricating composition.

[0819] When applied to a transmission, advantageously, the sum of the weight of the comb copolymer A1 and the compound A2 is between 0.5% and 40% relative to the total weight of the lubricating composition.

[0820] In one embodiment, the molar percentage of exogenous compound A4 in the lubricating composition is 0.05% to 5000%, preferably 0.1% to 1000%, more preferably 0.5% to 500%, more preferably 1% to 150%, relative to compound A2, especially the borate functional group of the poly(borate) copolymer.

[0821] In one embodiment, the lubricating composition of the present invention is obtained by mixing:

[0822] - 0.05% to 20% by weight of at least one of the above-mentioned comb-type polyglycol copolymers A1, relative to the total weight of the lubricating composition;

[0823] - 0.05% to 20% by weight, relative to the total weight of the lubricating composition, of at least one of the abovementioned compounds A2, in particular poly(borate) copolymers; and

[0824] - Optionally, 0.001% to 0.5% by weight of at least one exogenous compound A4 described above, relative to the total weight of the lubricating composition;

[0825] - optionally, 0.001% to 0.5% by weight of at least one exogenous compound A5 as defined above, relative to the total weight of the lubricating composition; and

[0826] - 60% to 99.9% by weight of at least one lubricating oil as defined above, relative to the total weight of the lubricating composition;

[0827] In another embodiment, the lubricating composition of the present invention is obtained by mixing:

[0828] - 0.5 to 20% by weight, relative to the total weight of the lubricating composition, of at least one of the above-mentioned comb-type polyglycol copolymers A1;

[0829] - 0.25% to 20% by weight, relative to the total weight of the lubricating composition, of at least one of the abovementioned compounds A2, in particular poly(borate) copolymers; and

[0830] - Optionally, 0.001% to 0.5% by weight of at least one exogenous compound A4 described above, relative to the total weight of the lubricating composition;

[0831] - Optionally, 0.001% to 0.5% by weight of at least one exogenous compound A5 described above, relative to the total weight of the lubricating composition;

[0832] - 0.5% to 15% by weight of at least one functional additive as defined above, relative to the total weight of the lubricating composition; and

[0833] - 60% to 99.25% by weight of at least one lubricating oil as defined above, relative to the total weight of the lubricating composition.

[0834] Preparation method of the lubricating composition of the present invention

[0835] The lubricating composition of the invention is prepared by methods well known to those skilled in the art. For example, it is sufficient, in particular for those skilled in the art, to carry out the following operations:

[0836] - taking out a desired amount of a solution containing the comb-type polyglycol copolymer A1;

[0837] - taking out the desired amount of a solution comprising the above compound A2, in particular a poly(borate) copolymer A2;

[0838] -optionally taking out a desired amount of a solution containing the exogenous compound A4;

[0839] - The withdrawn solution is mixed simultaneously or sequentially in a lubricating base oil to obtain the lubricating composition of the present invention.

[0840] The order of addition of the compounds has no influence on the performance of the process for the preparation of the lubricating composition.

[0841] Properties of the lubricating composition according to the invention

[0842] The lubricating compositions of the invention result from the mixing of associative polymers which exhibit the property of increasing the viscosity of the lubricating oil by association. The lubricating compositions according to the invention have the advantage that these associations or crosslinks are thermally reversible and, optionally, the extent of association or crosslinking can be controlled by adding supplementary diol compounds. In addition, they exhibit improved thermal stability, improved viscosity index, improved oxidation stability, improved cycling performance and better reproducibility of performance qualities over time.

[0843] A person skilled in the art knows how to adjust the different parameters of the different components of the composition in order to obtain a lubricating composition whose viscosity increases when the temperature rises and to adjust its viscosity and rheological behavior.

[0844] Method for adjusting the viscosity of lubricating compositions

[0845] Another subject of the present invention is a method for adjusting the viscosity of a lubricating composition, comprising at least:

[0846] - providing a lubricating composition obtained by mixing at least one lubricating oil, at least one comb-type polyglycol copolymer A1 and at least one compound A2, wherein the compound A2 comprises at least two borate functional groups and can associate with the polyglycol copolymer A1 by at least one transesterification reaction,

[0847] - Optionally, adding at least one exogenous compound A4 to the lubricating composition,

[0848] Optionally, at least one exogenous compound A5 selected from boric acid diesters and boric acid triesters is added to the lubricating composition.

[0849] Within the meaning of the present invention, "adjusting the viscosity of the lubricating composition" is understood to mean adapting the viscosity at a given temperature according to the use of the lubricating composition. This can be obtained by adding the above-mentioned exogenous compounds A4 and / or A5. These compounds make it possible to control the degree of association and crosslinking of the copolymer of the two polyglycols A1 and poly(boric ester) A2. This method is described in detail in WO2016 / 113229.

[0850] Other subjects according to the invention:

[0851] Another subject of the present invention is the use of the lubricating composition described above for lubricating machine parts.

[0852] In the remainder of the description, percentages are expressed by weight relative to the total weight of the lubricating composition.

[0853] The composition of the present invention can be used to lubricate the surfaces of parts typically present in an engine, such as the surfaces of pistons, rings, and bushing systems.

[0854] Therefore, another subject of the present invention is a composition for lubricating at least an engine, said composition comprising, in particular consisting essentially of, a composition obtained by mixing:

[0855] - 85% to 99.9% by weight, advantageously 92% to 99% by weight, of lubricating oil, and

[0856] - 0.1% to 15% by weight, advantageously 1% to 8% by weight, of a mixture of at least one of the above-mentioned comb copolymers A1 and at least one of the above-mentioned borate copolymers A2; and

[0857] - Optionally, 0.001% to 0.1% by weight of at least one exogenous compound A4 as described above;

[0858] - Optionally, 0.001% to 0.1% by weight of at least one exogenous compound A5 as described above;

[0859] The kinematic viscosity of the composition at 100° C., measured according to standard ASTM D445, is between 3.8 cSt and 26.1 cSt; expressed as a weight percentage relative to the total weight of the composition.

[0860] In one embodiment, a subject of the present invention is a composition for lubricating at least an engine, comprising, in particular consisting essentially of, a composition obtained by mixing:

[0861] - 80% to 99% by weight of lubricating oil, and

[0862] - 0.1 to 15% by weight of a mixture of at least one of the abovementioned copolymers A1 and at least one of the abovementioned borate copolymers A2; and

[0863] - Optionally, 0.001% to 0.1% by weight of at least one exogenous compound A4 as described above;

[0864] - 0.5 wt % to 15 wt % of at least one functional additive selected from detergents, antiwear additives, load-bearing additives, other antioxidants, anticorrosive additives, polymers that increase viscosity index, pour point improvers, defoamers, thickeners, dispersants, friction modifiers and mixtures thereof;

[0865] The kinematic viscosity of the composition at 100° C., measured according to standard ASTM D445, is between 3.8 cSt and 26.1 cSt; expressed as a weight percentage relative to the total weight of the composition.

[0866] The definitions and preferences concerning lubricating oil, comb copolymer A1, borate compound A2 and exogenous compound A4 and / or A5 also apply at least to the composition for lubricating an engine.

[0867] Another subject of the invention is a composition for lubricating at least a transmission, for example a manual transmission or an automatic transmission.

[0868] Therefore, another subject of the present invention is a composition at least for lubricating a transmission, said composition comprising, in particular consisting essentially of, a composition obtained by mixing:

[0869] - 50% to 99.5% by weight of lubricating oil, and

[0870] - 0.5 to 50% by weight of a mixture of at least one of the abovementioned copolymers A1 and at least one of the abovementioned borate copolymers A2; and

[0871] - Optionally, 0.001% to 0.5% by weight of at least one exogenous compound A4 as described above;

[0872] - Optionally, 0.001% to 0.5% by weight of at least one exogenous compound A5 as described above;

[0873] The kinematic viscosity of the composition at 100° C., measured according to standard ASTM D445, is between 4.1 cSt and 41 cSt, expressed as a weight percentage relative to the total weight of the composition.

[0874] In one embodiment of the present invention, at least the composition for lubricating a transmission comprises, in particular essentially consists of, a composition obtained by mixing:

[0875] - 45% to 99.39% by weight of lubricating oil, and

[0876] - 0.5 to 50% by weight of a mixture of at least one of the above-mentioned comb copolymers A1 and at least one of the above-mentioned borate copolymers A2; and

[0877] - Optionally, 0.001% to 0.5% by weight of at least one exogenous compound A4 as described above;

[0878] - Optionally, 0.001% to 0.5% by weight of at least one exogenous compound A5 as described above;

[0879] - 0.1 wt % to 15 wt % of at least one functional additive selected from detergents, antiwear additives, load-bearing additives, other antioxidants, anticorrosive additives, polymers that increase viscosity index, pour point improvers, defoamers, thickeners, dispersants, friction modifiers and mixtures thereof;

[0880] The kinematic viscosity of the composition at 100° C., measured according to standard ASTM D445, is between 4.1 cSt and 41 cSt, expressed as a weight percentage relative to the total weight of the composition.

[0881] The definitions and preferences with regard to lubricating oil, copolymer A1, borate copolymer A2 and exogenous compounds A4 and A5 also apply at least to the composition for lubricating a transmission.

[0882] The composition of the present invention can be used in engines or transmissions of light vehicles, heavy vehicles and ships.

[0883] Another subject of the invention is a method for lubricating at least one machine component, in particular at least one engine or at least one transmission, comprising a phase in which the machine component is brought into contact with at least one lubricating composition as described above.

[0884] The definitions and preferences with respect to the lubricating oil, copolymer A1, borate copolymer A2 and, if applicable, exogenous compounds A4 and A5 also apply to the method for lubricating at least machine parts. BRIEF DESCRIPTION OF THE DRAWINGS

[0885] Figure 1 The diagram shows a random copolymer (P1), a gradient copolymer (P2) and a block copolymer (P3); each circle represents a monomer unit. The differences in chemical structure between monomers are represented by different colors (light grey / black).

[0886] Figure 2 Schematic representation of a comb copolymer.

[0887] Figure 3 Schematic representation of the boronate ester bond exchange reaction between two polydiol polymers (A1-1 and A1-2) and two boronate ester polymers (A2-1 and A2-2) in the presence of diols.

[0888] Figure 4 The crosslinking of a composition according to the present invention in tetrahydrofuran (THF) is schematically illustrated and represented.

[0889] Figure 5 The diagram shows the behavior of the composition of the invention as a function of temperature. The copolymer (2) with diol functional groups (functional group A) can be associated with the copolymer (1) with borate functional groups (functional group B) in a thermoreversible manner by transesterification. The organic radical of the borate functional group (functional group B) exchanged during the transesterification reaction is the diol represented by the black crescent symbol. A borate-type chemical bond (3) is formed, releasing the diol compound.

[0890] Fig. 6A , Figure 6B and Figure 6C Different comb copolymers A1 are shown.

[0891] Figure 7 The scheme for the synthesis of comb copolymer A1 is shown.

[0892] Figure 8 The scheme for the synthesis of comb copolymer A1 is shown.

[0893] Fig. 9It is a graph showing the relative viscosity (ordinate) of compositions B, C and D as a function of temperature (abscissa) from 10°C to 90°C.

[0894] Fig.10 It is a graph showing the relative viscosity (ordinate) of compositions F and G as a function of temperature (abscissa) from 10°C to 90°C over three cycles.

[0895] Fig.11 It is a graph showing the relative viscosity (ordinate) of compositions H, I and J as a function of temperature (abscissa) from 10°C to 150°C.

[0896] Fig.12 Represents a graph reporting the relative viscosity (ordinate) of compositions I and Id (obtained from composition I by diluting composition I to 2.10% by weight of the copolymer) as a function of temperature (abscissa) between 10°C and 150°C.

[0897] Fig.13 is a graph showing the relative viscosity (ordinate) of composition Id as a function of temperature (abscissa) from 10°C to 150°C during three consecutive heating-cooling cycles (Id-1, Id-2 and Id-3).

[0898] Fig.14 is a graph showing the relative viscosity (ordinate) of composition J as a function of temperature (abscissa) from 10°C to 150°C during five consecutive heating-cooling cycles (J-1, J-2, J-3, J-4 and J-5).

[0899] Experimental part:

[0900] The following examples illustrate the invention without limiting it.

[0901] 1 Synthesis of comb-type copolymer A1 with diol functional groups

[0902] ο1.1: Synthesis of monomers

[0903] 1.1.1 Synthesis of monomer M1 with diol functional group

[0904] The synthesis of the methacrylate monomer with diol functionality was carried out in three stages (stages 1, 2 and 3) according to the following scheme:

[0905] Phase 1 :

[0906] 42.1 g (314 mmol) of 1,2,6-hexanetriol (1,2,6-HexTri) was introduced into a 1-liter round-bottom flask. 5.88 g of molecular sieves were added. Then add 570ml of acetone. Then slowly add 5.01g (26.3mmol) of p-toluenesulfonic acid (pTSA). The reaction medium is stirred at ambient temperature for 24 hours. Then add 4.48g (53.3mmol) of NaHCO3. The reaction medium is stirred at ambient temperature for 3 hours and then filtered. The filtrate is then concentrated under vacuum using a rotary evaporator until a suspension of white crystals is obtained. Then 500ml of water is added to the suspension. The solution thus obtained is extracted with 4×300ml of dichloromethane. Combine the organic phases and dry with MgSO4. Then use a rotary evaporator to completely evaporate the solvent under vacuum at 25°C.

[0907] Phase 2:

[0908] 5.01 g (28.8 mmol) of the product thus obtained was introduced into a 1 liter round-bottom flask. Subsequently, 4.13 g (31.9 mmol) of DIPEA and 37.9 mg (0.31 mmol) of DMAP were introduced into the round-bottom flask, followed by 5.34 g (34.6 mmol) of methacrylic anhydride. The round-bottom flask was then stirred at ambient temperature for 24 hours. Subsequently, 0.95 g of methanol (29.7 mmol) was added to the solution, and the round-bottom flask was stirred for another hour. The product was then dissolved in 40 ml of hexane. The organic phase was then washed with 25 ml of water, 3×25 ml of 0.5 M hydrochloric acid aqueous solution, 3×25 ml of 0.5 M NaOH aqueous solution, and then with 25 ml of water. The organic phase was dried over MgSO4, filtered, and then concentrated under vacuum using a rotary evaporator to obtain a light yellow liquid.

[0909] Phase 3:

[0910] 17.23 g (71.2 mmol) of the product thus obtained were introduced into a 1 liter round-bottom flask. Subsequently, 90 ml of water and 90 ml of acetonitrile were introduced into the round-bottom flask, and then 59.1 ml (159 mmol) of acetic acid were added. The round-bottom flask was then stirred at 30° C. for 24 hours while a slow stream of nitrogen was allowed to bubble through to facilitate the removal of acetone. The solution thus obtained was extracted with 6×30 ml of ethyl acetate. The organic phase was then washed with 5×30 ml of a 0.5 M NaOH aqueous solution and 3×30 ml of water in sequence. The organic phase was then dried with MgSO4, filtered, and then concentrated under vacuum using a rotary evaporator to obtain a light yellow liquid characterized as follows:

[0911] 1H NMR (400 MHz, CDCl3) δ: 6.02 (singlet, 1H), 5.49 (singlet, 1H), 4.08 (triplet, J = 6.4 Hz, 1H), 3.65-3.58 (multiplet, 1H), 3.57-3.50 (multiplet, 3H), 3.35 (fragmentation doublet, J = 7.6 Hz and J = 11.2 Hz, 1H), 1.86 (fragmentation doublet, J = 1.2 Hz and J = 1.6 Hz, 3H), 1.69-1.31 (multiplet, 6H).

[0912] 1.1.2 Synthesis of brominated monomers (branched monomers):

[0913]

[0914] 7ml of hydroxyethyl methacrylate (58mmol), 5.4ml of pyridine (66mmol) and 75ml of dichloromethane were introduced into a 250ml round-bottom flask. The round-bottom flask was then closed using a septum, degassed by bubbling with N2 for 30 minutes, and then placed in an ice-cold water bath. 7.7ml of 2-bromo-2-methylpropionyl bromide (64mmol) was subsequently added dropwise to the reaction mixture over approximately 15 minutes. The round-bottom flask was kept stirring for 6 hours. A white precipitate was formed during the reaction. The solution was then filtered to remove the solid. The solid was rinsed with dichloromethane (2×10ml). The organic phase was then washed twice with 100ml of distilled water, washed twice with 100ml of 10% NaHCO3 solution, and then washed twice with 100ml of saturated NaCl solution. The organic phase was then dried with MgSO4, and a rotary evaporator was used to remove the solvent. 11.6g of bright yellow liquid (yield = 72%) was obtained.

[0915] 1 H NMR (CDCl3): δ: 6.05ppm (m, 1H), 5.52ppm (m, 1H), 4.35ppm (m, 4H), 1.87ppm (m, 3H), 1.85ppm (s, 6H).

[0916] 1.1.3 Synthesis of methacrylic acid olefin macromonomer (monomer M6-A):

[0917]

[0918] 58.8 g (11.6 mmol) of Krasol HLBH 5000M (provided by Cray Valley) was dissolved in 150 g of dichloromethane (DCM). Subsequently, 11.9 g of methacrylic anhydride (77.3 mmol), 56.2 mg of 4-dimethylaminopyridine (0.47 mmol) and 7.37 g of trimethylamine (76 mmol) were added. The solution was stirred at ambient temperature for 24 hours. The solution was then washed twice with a 0.5 M aqueous sodium hydroxide solution, then twice with a 0.5 M aqueous hydrochloric acid solution, and finally twice with distilled water. The organic phase was dried over MgSO4, and the solvent was evaporated using a rotary evaporator. The product was then dissolved in tetrahydrofuran (THF) and then precipitated three times from acetone in succession (dissolved in THF before each precipitation). The product was dried at 50°C under vacuum for 18 hours. A colorless, transparent, viscous liquid was thus obtained. By 1 1H NMR confirmed the quantitative functionalization of Krasol (alcohol used to generate the methacrylate) by the complete disappearance of the peak between 3.8 ppm and 4.1 ppm, which is characteristic of protons in the alpha position relative to the Krasol alcohol functionality.

[0919] 1 H NMR (CDCl3): δ: 6.05 ppm (m, 1H), 5.52 ppm (m, 1H), 5.1-4.9 ppm (m, 1H), 1.94 ppm (s, 3H), 2.05-0.48 ppm (1020H), traces of DCM (5.29 ppm), THF (3.75 ppm; 1,84 ppm) and acetone (2.17 ppm).

[0920] 1.1.4 Synthesis of olefin macromonomer with terminal styrene functional group (monomer M6-B-OLF1500-St)

[0921] The synthesis of olefin macromonomers with terminal styrene functional groups (OLF1500-St) was carried out in two stages according to the following scheme (Schemes 13 and 14):

[0922] Phase 1

[0923] 4.0 g (27 mmol) of 4-vinylbenzoic acid (4-VBA) was dissolved in 110 ml of anhydrous dichloromethane (DCM), and a catalytic amount (15 drops) of anhydrous dimethylformamide (DMF) was added. Subsequently, 5.8 ml (67 mmol) of oxalyl chloride was added to the solution. The reaction mixture was stirred at ambient temperature for 2 hours. After the solvent was evaporated under reduced pressure, the yellow liquid obtained was dried under vacuum for 2 hours.

[0924] Phase 2:

[0925] 2.64 g (1.76 mmol) of an olefin copolymer OLF1500-OH with a number average molar mass Mn of 1500 g / mol and a terminal primary alcohol functional group and 3.8 ml (27.5 mmol) of NEt3 were dissolved in 50 ml of anhydrous DCM, and the mixture was cooled to about 0 ° C using an ice bath. The solution of 4-vinylbenzoyl chloride (27 mmol) obtained in the first stage in 30 ml of DCM was then added dropwise to the reaction mixture over about 25 minutes. The mixture was stirred in an ice bath for 1 hour, and then stirred at ambient temperature for 24 hours. Excess 4-vinylbenzoyl chloride was neutralized by adding 10 ml of water and stirring the reaction mixture for 1 hour. The reaction mixture was then washed with 3 × 100 ml of 1M HCl solution, 2 × 100 ml of 1M NaOH solution and 1 × 100 ml of sodium chloride aqueous solution in sequence. After drying the organic phase with MgSO4, the transparent yellow solution obtained was filtered through a basic alumina column. Evaporation of DCM and drying in vacuo gave 2.80 g (97.6%) of a light yellow oil with the following characteristics:

[0926] 1 H NMR (400 MHz, CDCl3) δ: 8.00 (multiplet, 2H), 7.46 (fragmentation doublet, J = 1.5 Hz and J = 8.3 Hz, 2H), 6.75 (fragmentation doublet, J = 12.0 Hz and J = 17.5 Hz, 1H), 5.86 (fragmentation doublet, J = 0.8 Hz and J = 17.7 Hz, 1H), 5.38 (doublet, J = 11.0 Hz, 1H), 4.41-4.28 (multiplet, 2H), 1.83-0.52 (multiplet, 961H).

[0927] 1.1.5. Synthesis of 1,2-dodecanediol monomer (mEB-C 12 )Condensed boric acid ester

[0928] This monomer was obtained according to the protocol described in application WO 2016 / 113229 (experimental part §2.1).

[0929] ο 1.2: Synthesis of copolymers - methods

[0930] The inventive comb copolymers A1 are obtained by the synthesis methods described in applications WO 2015 / 110642, WO 2015 / 110643 and WO 2016 / 113229, supplemented, if appropriate, by the methods described in the present patent application.

[0931] Number average molar masses and distribution coefficients were obtained by size exclusion chromatography using poly(methyl methacrylate) calibration and THF as eluent.

[0932] 1.2.1 Synthesis of brominated backbone (brominated backbone 1) :

[0933]

[0934] 0.50 g (1.8 mmol) of the brominated monomer obtained according to the scheme described in step 1.1.2 (Scheme 11) above, 8.52 g (59.9 mmol) of butyl methacrylate, 1.14 g (11.0 mmol) of styrene, 35.8 mg (0.13 mmol) of cumyl dithiobenzoate, 6.3 mg (0.04 mmol) of azobisisobutyronitrile (AIBN) and 5 g of anisole were introduced into a 50 ml Schlenk tube. The reaction medium was stirred and degassed by bubbling nitrogen for 30 minutes and then brought to 65° C. for 16 hours. The polymer was subsequently isolated by three consecutive precipitations from methanol and then dried under vacuum at 50° C. for 16 hours. The number average molar mass (M n ) is 38000 g / mol, and the distribution coefficient The number average degree of polymerization (DP n ) is about 300. The polymer thus obtained contains about 2.3 mol % (about 5 wt %) of bromomethylacrylate monomer. These values ​​were obtained by size exclusion chromatography, using THF as eluent and polymethyl methacrylate (PMMA) calibration and by monitoring the conversion of the monomers during the copolymerization.

[0935] 1.2.2 Synthesis of brominated backbone (brominated backbone 2) :

[0936]

[0937] 0.50 g (1.8 mmol) of the brominated monomer obtained according to the protocol described in step 1.1.2 above (Scheme 11), 7.45 g (52.4 mmol) of butyl methacrylate, 1.46 g (7.2 mmol) of 5,6-dihydroxyhexyl methacrylate obtained according to the protocol described in section 1.1.1 above, 1.13 g (10.8 mmol) of styrene, 35.8 mg (0.13 mmol) of cumyl dithiobenzoate, 6.3 mg (0.04 mmol) of AIBN and 5 g of anisole are introduced into a 50 ml Schlenk tube. The reaction medium is stirred and degassed by bubbling nitrogen for 30 minutes and then brought to 65° C. for 16 hours. The polymer is subsequently isolated by three consecutive precipitations from methanol and then dried under vacuum at 50° C. for 16 hours. M is obtained. n is 46000g / mol, and the distribution coefficient The number average degree of polymerization (DP n) is about 300. The polymer thus obtained contains about 2.3 mol % (about 5 wt %) of bromomethylacrylate monomer. These values ​​were obtained by size exclusion chromatography, using THF as eluent and PMMA calibration and by monitoring the conversion of the monomers during the copolymerization.

[0938] 1.2.3 Synthesis of comb-shaped polydiol copolymer CPDiol-1 by ATRP

[0939]

[0940] 520 mg (87 μmol of brominated monomer and about 12 μmol of dithiobenzoate) of brominated backbone 1 obtained according to the above protocol, 13.4 g (39.5 mmol) of octadecyl methacrylate, 0.91 g (4.5 mmol) of 5,6-dihydroxyhexyl methacrylate obtained according to the protocol described in Section 1.1.1 above, 3 g of N,N-dimethylformamide (DMF) and 10 g of anisole were introduced into a 50 ml Schlenk round-bottom flask. In parallel, in a sample tube, 52 mg (333 μmol) of 2,2'-bipyridine, 5 mg (20 μmol) of copper (II) dibromide (CuBr2) and 21 mg (147 μmol) of CuBr were dissolved in 2 g of DMF, which was then sealed with a septum. The flask and sample tube were degassed by bubbling nitrogen through the solution for 30 minutes. The solution contained in the sample tube was then taken out and then injected into the round-bottom flask using a syringe. The round-bottom flask was then placed in an oil bath thermostatically controlled at 60°C for 7 hours. The solution was subsequently filtered through a basic alumina column to remove copper. Finally, the polymer was isolated by three consecutive precipitations from methanol and then dried in vacuo at 50°C for 20 hours. The number average molar mass M was obtained. n is 105000 g / mol and the distribution coefficient These values ​​were obtained using size exclusion chromatography using THF as eluent and PMMA calibration. 1 The monomer conversion determined by H NMR and the number average degree of polymerization (DP) of the side chains n About 40.

[0941] 1.2.4 Synthesis of comb-type polydiol BB by ATRP:

[0942]

[0943] 522 mg (84 μmol of brominated monomer and about 12 μmol of dithiobenzoate) of brominated backbone 2 obtained according to the above protocol, 9.22 g (27.2 mmol) of octadecyl methacrylate, 0.80 g (3.1 mmol) of lauryl methacrylate and 6.8 g of anisole were introduced into a 50 ml Schlenk round-bottom flask. In parallel, in a sample tube, 48 mg (308 μmol) of 2,2'-bipyridine, 4 mg (18 μmol) of CuBr2 and 19 mg (133 μmol) of CuBr were dissolved in 3.3 g of DMF, which was then sealed with a septum. The flask and sample tube were degassed by bubbling nitrogen through the solution for 30 minutes. The solution contained in the sample tube was then taken out and then injected into the round-bottom flask using a syringe. The round-bottom flask was then placed in an oil bath thermostatically controlled at 60 ° C for 6.3 hours. The solution was then filtered through a basic alumina column to remove copper. Finally, the polymer was isolated by three consecutive precipitations from methanol and then dried under vacuum at 50 °C for 20 h. The number average molar mass M n is 210000 g / mol and the distribution coefficient These values ​​were obtained using size exclusion chromatography using THF as eluent and PMMA calibration. 1 The monomer conversion determined by H NMR and the number average degree of polymerization (DP) of the side chains n About 30.

[0944] 1.2.5 Synthesis of butyl methacrylate, methacrylate with diol functional group and olefin macromonomer Comb copolymer of OLF1500-St (CPDiol-2)

[0945]

[0946] The synthesis of comb copolymers carrying diol functional groups in the main chain CPDiol-2 was carried out according to the following scheme (Scheme 13 above).

[0947] 2.50 g (17.5 mmol) of butyl methacrylate (BMA), 0.18 g (0.89 mmol) of a methacrylate monomer with a diol function, 0.89 g (0.93 mmol) of the olefin macromonomer M6-B-OLF1500-St obtained according to the protocol described in section 1.1.4 above, 9.3 mg (0.04 mmol) of the RAFT transfer agent 2-cyano-2-propyldithiobenzoate (CPBD), 2.8 mg (0.02 mmol) of azobisisobutyronitrile (AIBN) and 3.6 ml of anisole are introduced into a 25 ml Schlenk tube. The reaction medium is stirred and degassed by bubbling nitrogen for 30 minutes and then brought to 65° C. for 19 hours.

[0948] After 19 hours of polymerization, the Schlenk tube was placed in an ice bath to stop the polymerization. The polymer was then separated by two consecutive precipitations from ice-cooled methanol, filtered and dried overnight at 50° C. under vacuum. The number average molar mass (M) of the copolymer thus obtained was n ) is 65500 g / mol, and the distribution coefficient The number average degree of polymerization (DP n ) is 350. The first two values ​​were obtained by size exclusion chromatography using THF as eluent and poly(methyl methacrylate) calibration, DP n pass 1 The conversion of monomers during the polymerization process was monitored by H NMR.

[0949] A poly(butyl methacrylate-co-alkyl methacrylate-co-M6-B-OLF1500-St) copolymer CPDiol-2 containing 4.5 mol% of diol repeating units (4.6 wt%) and 6.8 mol% of OLF1500-OCP side chains (32 wt%) was obtained. The average length of the side chains was 10.9 carbon atoms.

[0950] 1.2.6 Synthesis of butyl methacrylate, olefin macromonomer M6-B-OLF1500-St and polyglycol polymer Chain comb copolymer (CPDiol-3)

[0951] The synthesis of the comb copolymer (CPDiol-3) containing the olefin macromonomer M6-B-OLF1500-St and the polydiol polymer side chains was carried out according to the following scheme (Scheme 14 below):

[0952]

[0953] 1.2.6.1 Synthesis of olefin macromonomer M6-B-OLF1500-St and ethyl methacrylate 2-xanthate Ester backbone (M6-B-OLF1500-St-co-xanthate backbone)

[0954] 4.00 g (28.1 mmol) of butyl methacrylate, 1.30 g (1.36 mmol) of olefin macromonomer M6-B-OLF1500-St, 1.06 g (4.52 mmol) of ethyl methacrylate 2-xanthate (XEMA; according to "Synthesis of Well-Defined Polythiol Copolymers by RAFT Polymerization", 2012, 45, 821-827), 16.4 mg (0.074 mmol) of RAFT transfer agent 2-cyano-2-propyl dithiobenzoate (CPBD), 4.8 mg (0.030 mmol) of azobisisobutyronitrile (AIBN) and 6.4 ml of anisole were introduced into a 50 ml Schlenk tube. The reaction medium was stirred and degassed by bubbling nitrogen for 30 minutes and then brought to 65° C. for 20.5 hours.

[0955] After 20.5 hours of polymerization, the Schlenk tube was placed in an ice bath to stop the polymerization. The polymer was then separated by two consecutive precipitations from ice-cooled methanol, filtered and dried overnight at 50° C. under vacuum. The number average molar mass (M) of the copolymer thus obtained was n ) is 80600 g / mol, and the distribution coefficient The number average degree of polymerization (DP n ) is 350. The first two values ​​were obtained by size exclusion chromatography using THF as eluent and poly(methyl methacrylate) calibration, DP n pass 1 The conversion of monomers during the polymerization process was monitored by H NMR.

[0956] A poly(butyl methacrylate-co-ethyl methacrylate 2-xanthate-co-M6-B-OLF1500-St) copolymer, "M6-B-OLF1500-St-xanthate backbone", was obtained containing 7.9 mol% of ethyl methacrylate 2-xanthate repeating units (9.5 wt%) and 5.6 mol% of OLF1500-OCP side chains (27 wt%).

[0957] 1.2.6.2 Synthesis of the main monomer containing olefin macromonomer M6-B-OLF1500-St and acrylate functional side chains Chain (M6-B-OLF1500-St-Acrylate Main Chain)

[0958] The xanthate functionality of the "M6-B-OLF1500-St-co-xanthate backbone" copolymer was subsequently converted to acrylate via a Michael addition reaction with 1,6-hexanediol diacrylate according to the following scheme:

[0959] 3.70 g (1.50 mmol XEMA functional groups) of "M6-B-OLF1500-St-co-xanthate backbone" were introduced into a 250 ml Schlenk tube and dissolved in 35 ml of a mixture of THF:DMF=1:1 (volume ratio). 0.44 g (6.00 mmol) of n-butylamine and three drops of tributylphosphine were introduced into the Schlenk tube. The reaction medium was degassed for 10 minutes by bubbling nitrogen and then stirred at ambient temperature for 2 hours. Subsequently, a solution of 6.79 g (30.0 mmol) of 1,6-hexanediol diacrylate in 3 ml THF was introduced, and the reaction medium was stirred at ambient temperature for 48 hours.

[0960] The reaction medium is subsequently concentrated under vacuum and the polymer is isolated by three consecutive precipitations using methanol cooled in an ice bath, filtered and dried overnight under vacuum at 50° C. The number-average molar mass (M n ) is 60100 g / mol, and the distribution coefficient is 1.65, which was obtained by size exclusion chromatography using THF as eluent and poly(methyl methacrylate) calibration.

[0961] pass 1 H NMR analysis revealed a "M6-B-OLF1500-St-acrylate backbone" copolymer containing 5.1 mol % repeating units with pendant acrylate functional groups (9.4 wt %) and 5.6 mol % OLF1500-OCP side chains (27 wt %).

[0962] 1.2.6.3 Lauryl methacrylate, styrene and methacrylate with diol functional groups (polydimethylsiloxane) Copolymerization of alcohol side chains to synthesize side chain precursors

[0963] The polydiol polymer side chains of the comb copolymer containing the olefin macromonomer M6-B-OLF1500-St and the polydiol polymer side chains (CPDiol-3) were prepared according to the following scheme (Scheme 14 above).

[0964] 8.00 g (31.4 mmol) of lauryl methacrylate (LMA), 0.54 g (5.24 mmol) of styrene, 1.86 g (9.17 mmol) of a methacrylate monomer with a diol function, 290 mg (1.31 mmol) of the RAFT transfer agent PPBD, 10.8 mg (0.066 mmol) of AIBN and 3.6 ml of anisole were introduced into a 50 ml Schlenk tube. The reaction medium was stirred and degassed by bubbling nitrogen for 30 minutes and then brought to 65° C. for 24 hours.

[0965] After 24 hours of polymerization, the Schlenk tube was placed in an ice bath to stop the polymerization. The polymer was then isolated by precipitation from methanol cooled using an ice bath, separated by sedimentation of the supernatant, and dried overnight at 50° C. under vacuum. The number average molar mass (M) of the copolymer thus obtained was n ) is 9850 g / mol, and the distribution coefficient The number average degree of polymerization (DP n ) is 27. The first two values ​​were obtained by size exclusion chromatography using THF as eluent and poly(methyl methacrylate) calibration, DP n pass 1 The conversion of monomers during the polymerization process was monitored by H NMR.

[0966] This resulted in a poly(lauryl methacrylate-methacrylate comonomer with glycol functionality-co-styrene) "polyglycol side chains" copolymer comprising 20 mol % of glycol repeating units (18 wt %), 67 mol % of lauryl methacrylate repeating units (76 wt %) and 13 mol % of styrene repeating units (6.0 wt %).

[0967] 1.2.6.4 Synthesis of Comb-type Polymers Comprising Olefin Macromonomer M6-B-OLF1500-St and Polyglycol Polymer Side Chains Copolymer (CPDiol-3)

[0968] 1.07 g (0.12 mmol) of the "polyglycol side chain" copolymer prepared according to the scheme described in 1.2.6.3 was introduced into a 100 ml Schlenk tube and dissolved in 10 ml of a mixture of THF:DMF=2:1 (volume ratio). 65 mg (0.88 mmol) of n-butylamine and three drops of tributylphosphine were added to the solution. The reaction medium was degassed for 5 minutes by bubbling nitrogen and stirred at ambient temperature for 2 hours. Subsequently, under a nitrogen atmosphere, a solution of 1.70 g (0.43 mmol of acrylate functional groups) of the "M6-B-OLF1500-St-co-acrylate main chain" copolymer prepared according to the scheme described in 1.2.6.2 in a mixture of THF:DMF=2:1 (volume ratio) was added to the reaction mixture. The reaction mixture was then kept at 40°C for 40 hours.

[0969] After 40 hours of reaction, 125 mg (2.03 mmol) of ethanethiol are added to the reaction medium, which is kept stirring at ambient temperature for 4 hours.

[0970] The comb copolymer (CPDiol-3) comprising the olefin macromonomer M6-B-OLF1500-St and the polydiol polymer side chains was then isolated by two consecutive precipitations with methanol cooled in an ice bath, separated by settling the supernatant and dried in vacuo at 50°C overnight.

[0971] ο 1.3: Synthesis of comparative copolymers - Methods

[0972] 1.3.1 Linear Polydiol-1 (Compared to LPDiol-1):

[0973] The linear polyglycol-1 was synthesized according to the protocol described in application FR1661400 or WO2018096252A1 (experimental part §1.2.). The polyglycol comprises about 10 mol% of a monomer with a diol functional group (8.6 wt%), 37 mol% of lauryl methacrylate (39.8 wt%), 28 mol% of octadecyl methacrylate (40.1 wt%) and 26 mol% of styrene (11.5 wt%). The M of the copolymer n is 53000 g / mol, The value is 1.3, DP n is 250. These values ​​were obtained by size exclusion chromatography using THF as eluent and PMMA calibration and by monitoring the conversion of the monomers during the copolymerization.

[0974] 1.3.2 Linear Polydiol-2 (Compared to LPDiol-2):

[0975] The linear polyglycol-2 was synthesized according to the protocol described in the application FR1661400 or WO2018096252A1 (experimental part §1.2.). The copolymer contains 7.0 mol% of monomers with diol functional groups (6.0 wt%). The average side chain length is 10.3 carbon atoms. Its number average molar mass is 40000 g / mol. Its distribution coefficient is 1.46. Its number average degree of polymerization (DP n ) was 170. The number average molar mass and distribution coefficient were obtained by size exclusion chromatography calibrated with poly(methyl methacrylate).

[0976] ο 1.4: Synthesis of borate copolymers - Methods

[0977] 1.4.1 Linear Polyboric Acid-1 (LPB1) :

[0978] The linear polyborate was synthesized according to the protocol described in the application WO2016 / 113229 (experimental part §2.). The polyborate contained about 4 mol % of a monomer with a borate functional group (8.1 wt %), 61 mol % of lauryl methacrylate (69.6 wt %) and 35 mol % of butyl methacrylate (22.3 wt %). The M of the copolymer n is 41000 g / mol, The value is 1.3, DP n is 210. These values ​​were obtained by size exclusion chromatography using THF as eluent and PMMA calibration and by monitoring the conversion of the monomers during the copolymerization.

[0979] 1.4.2 Random linear poly(borate) copolymer (LPB2):

[0980] The copolymer contains 6.0 mol% BC 12 E repeating unit (10 wt%). The average side chain length is 12 carbon atoms. Its number average molar mass is 45700 g / mol. Its distribution coefficient is 1.39. Its number average degree of polymerization (DP n ) is 175. The number average molar mass and distribution coefficient were obtained by size exclusion chromatography using poly(methyl methacrylate) calibration and THF as eluent. The copolymer was obtained according to the protocol described in part 2 of the experimental part of application WO2016 / 113229.

[0981] 1.4.3 Synthesis of butyl methacrylate, boron-C 12 Ester-functional styrene and olefin macromonomers M6- Comb copolymer of B-OLF1500-St (PBB2)

[0982]

[0983] The synthesis of the comb copolymer PBB2 with borate functional groups in the main chain was carried out according to the following scheme:

[0984] 2.50 g (17.5 mmol) of butyl methacrylate (BMA), 0.39 g (0.87 mmol) of 1,2-dodecanediol monomer (BCMA) obtained according to the protocol described in application WO 2016 / 113229 (experimental part §2.1) were added. 12 Em) condensed boric acid ester, 0.89 g (0.93 mmol) of olefin macromonomer M6-B-OLF1500-St obtained according to the protocol described in Section 1.1.4 above, 9.3 mg (0.04 mmol) of RAFT transfer agent 2-cyano-2-propyl dithiobenzoate (CPBD), 2.8 mg (0.02 mmol) of AIBN and 3.8 ml of anisole were introduced into a 25 ml Schlenk tube. The reaction medium was stirred and degassed by bubbling nitrogen for 30 minutes and then allowed to rise to 65° C. for 19 hours.

[0985] After 19 hours of polymerization, the Schlenk tube was placed in an ice bath to stop the polymerization. The polymer was then isolated by precipitation from acetone cooled in an ice bath, separation was performed by settling the supernatant, and the pasty polymer phase was dried overnight at 50° C. in a vacuum. The number average molar mass (M) of the copolymer thus obtained was n ) is 54800 g / mol, and the distribution coefficient The number average degree of polymerization (DP n ) is 280. The first two values ​​were obtained by size exclusion chromatography using THF as eluent and poly(methyl methacrylate) calibration, DP n pass1 The conversion of monomers during the polymerization process was monitored by H NMR.

[0986] Obtain poly(butyl methacrylate-co-BC 12 Em-co-M6-B-OLF1500-St) copolymer PBB2, which contains 5.7 mol% BC 12 Em repeat units (12 wt%) and 6.8 mol % of M6-B-OLF1500-St repeat units (30 wt%).

[0987] 2. Preparation of Composition

[0988] Each polymer was dissolved in a Group III base oil to obtain a 10 wt% polymer solution. Once the polymer was completely dissolved in the oil, these solutions served as stock solutions for the preparation of formulations for rheological studies.

[0989] ο 2.1 Ingredients for preparing the composition

[0990] Lubricating base oil

[0991] The lubricating base oil used in the compositions to be tested is an oil of group III of the API classification, sold by SK under the trade name Yubase 4. It has the following characteristics:

[0992] - Kinematic viscosity at 40°C measured according to standard ASTM D445 is 19.57 cSt;

[0993] - Kinematic viscosity at 100°C measured according to standard ASTM D445 is 4.23 cSt;

[0994] - Viscosity index measured according to standard ASTM D2270 is 122;

[0995] - Noack volatility measured according to standard DIN 51581 is 15% by weight;

[0996] - a flash point of 230° C. (degrees Celsius) measured according to standard ASTM D92;

[0997] - The pour point measured according to standard ASTM D97 is -15°C (degrees Celsius).

[0998] ο 2.2 Composition preparation

[0999] Preparation of Composition B

[1000] 1.60 g of a base oil of group III and 0.40 g of a 10 wt % stock solution of comb polydiol CPDiol-1 were introduced into a sample tube and mixed vigorously for 30 seconds using a vortex mixer. Thus, the formulation contained 2 wt % of comb polydiol CPDiol-1.

[1001] Preparation of Composition C

[1002] 1.60 g of a base oil of Group III and 0.40 g of a 10 wt% comb polyglycol BB stock solution were introduced into a sample tube and mixed vigorously for 30 seconds using a vortex mixer. Thus, the formulation contained 2 wt% comb polyglycol BB.

[1003] Preparation of Composition D (Comparative)

[1004] 1.60 g of a group III base oil and 0.40 g of a 10 wt % linear polydiol-1 (LPDiol-1) stock solution were introduced into a sample tube and mixed vigorously for 30 seconds using a vortex mixer. Thus, the formulation contained 2 wt % linear polydiol-1 (LPDiol-1).

[1005] Preparation of Composition F (according to the invention)

[1006] 1.20 g of the base oil of Group III, 0.40 g of a 10 wt % comb polydiol CPDiol-1 mother solution and 0.40 g of a 10 wt % linear polyborate-1 (LPB1) mother solution were introduced into a sample tube and vigorously mixed for 30 seconds using a vortex mixer. Thus, the formulation contained 2 wt % comb polydiol CPDiol-1, TD 4-37 and 2 wt % linear poly(borate)-1 (LPB1).

[1007] Preparation of Composition G (according to the invention)

[1008] 1.20 g of a base oil of Group III, 0.40 g of a 10 wt % comb polyglycol BB stock solution, and 0.40 g of a 10 wt % linear polyborate-1 (LPB1) stock solution were introduced into a sample tube and mixed vigorously for 30 seconds using a vortex mixer. Thus, the formulation contained 2 wt % comb polyglycol BB and 2 wt % linear poly(borate)-1 (LPB1).

[1009] Preparation of Composition H (Comparative)

[1010] 0.53 g of a 39.2 wt % solution of LPB2 in a base oil of Group III was mixed with 6.76 g of the same base oil. The mixture was stirred in a vortex mixer at ambient temperature for 1 minute. The solution of LPB2 thus obtained was subsequently mixed with 0.71 g of a 25.4 wt % solution of LPDiol-2 in a base oil of Group III. The mixture thus obtained was stirred in a vortex mixer at ambient temperature for 2 minutes. A solution containing 2.60 wt % of the linear copolymer LPB2 and 2.25 wt % of the linear copolymer LPDiol-2 was obtained.

[1011] Preparation of composition I (according to the invention)

[1012] 0.60 g of the comb-type polyglycol copolymer CPDiol-2 and 5.40 g of a base oil of group III were introduced into a flask. The mixture thus obtained was kept stirred at 100° C. until the comb-type polyglycol copolymer CPDiol-2 was completely dissolved. A 10% by weight solution of the comb-type polyglycol copolymer CPDiol-2 was thus obtained.

[1013] 0.60 g of a comb-type poly(borate) copolymer PBB2 and 5.40 g of a base oil of group III are introduced into a flask. The mixture thus obtained is kept stirred at 100° C. until the polyborate PBB2 is completely dissolved. A 10% by weight solution of the comb-type polyborate PBB2 is thus obtained.

[1014] The solution of 10 % by weight of the polyglycol CPDiol-2 of 1.47g in the base oil of Group III was mixed with the same base oil of 2.94g. The mixture was stirred at ambient temperature for 1 minute in a vortex mixer. Subsequently, the solution of the CPDiol-2 thus obtained was mixed with a solution of 10 % by weight of the poly (boric ester) PBB2 of 1.47g in the base oil of Group III, and kept stirring for 2 minutes at ambient temperature in a vortex mixer. Thus obtained composition I, it comprises 2.50 % by weight of the comb-type polyglycol copolymer CPDiol-2 and 2.50 % by weight of the comb-type poly (boric ester) copolymer PBB2.

[1015] Preparation of Composition J (according to the invention)

[1016] The solution of 10 wt % of the comb-type polydiol CPDiol-2 prepared above was mixed with 4.03 g of the base oil of Group III. The mixture was stirred at ambient temperature for 1 minute in a vortex mixer. The solution of the CPDiol-2 thus obtained was subsequently mixed with a 39.2 wt % solution of 0.38 g of LPB2 in the base oil of Group III, and stirred for 2 minutes at ambient temperature in a vortex mixer. Thus obtained was a solution of 2.50 wt % of the comb-type polydiol copolymer CPDiol-2 and 2.50 wt % of the linear poly (boric ester) copolymer LPB2.

[1017] 3. Rheological properties of polymer solutions

[1018] Select the relative viscosity calculated according to the following formula,

[1019]

[1020] The change in system viscosity with temperature is expressed as V / V since this quantity directly reflects the compensation for the natural viscosity loss of the Group III base oil of the polymer system under investigation.

[1021] 3.1 Equipment and Protocol for Measuring Viscosity of (Compositions A to G)

[1022] Rheological studies were performed using a Lovis 2000 rolling ball viscometer from Anton Paar.

[1023] For polymer formulations that do not form gels in group III base oils within the temperature range studied, rheological measurements were performed using reference cylinder geometry DG 26.7. The viscosity was measured as a function of shear rate in the temperature range from 10°C to 90°C. For each temperature, the viscosity of the system was measured as a function of shear rate (from 1 s -1 Up to 100s -1 ). The viscosity variation with shear rate was measured at T = 10°C, 50°C and 90°C. The average viscosity at each temperature was then calculated using the measurement points located on the same plate.

[1024] 3.2 Rheological results

[1025] The relative viscosities of compositions B, C and D were measured at 90°C, 50°C and 10°C. Fig. 9). All compositions contained 2% by weight of polymer. Although the two comb-type polyglycols exhibited similar structures, the relative viscosity of composition B (with diol functional groups on the side chains) was significantly lower than the relative viscosity of composition C (with functional groups on the main chain). Composition D was formed from a polyglycol exhibiting an average degree of polymerization of about 250 monomer units. Therefore, the polymer was significantly shorter than the polymer of composition B (with an average degree of polymerization of the main chain of about 300). However, over the entire temperature range, the relative viscosity of composition D was significantly greater than that of composition B. This means that, compared with linear diol polymers, comb-type diol polymers have less effect on the viscosity of the oil, especially when the comb-type side chains contain diol functional groups. In addition, the relative viscosity of composition B at this temperature was greater than that of compositions C and D.

[1026] The relative viscosities of compositions F and G were measured at 90°C, 50°C and 10°C. Fig.10 ). The two compositions were studied in 3 cycles of cooling from 90°C to 10°C and then heating. The relative viscosities were very close at each temperature between the cycles, regardless of the composition. This means that the rheological behavior of the formulations is reproducible after at least 3 cycles. The relative viscosity of the two compositions increases significantly when the temperature is increased. Compositions F and G show approximately the same relative viscosity at 50°C. On the other hand, composition F has a lower viscosity at 10°C and a higher viscosity at 90°C. This means that formulations formed in particular with comb polydiol CPDiol-1 are able to obtain stronger viscosities of non-polar oils than formulations formed in particular with comb polydiol BB.

[1027] 3.3 Equipment and protocol for measuring viscosity (compositions H, I and J)

[1028] Rheological studies were performed using a stress-controlled Couette MCR 501 rheometer from Anton Paar.

[1029] Rheological measurements were performed using the cylindrical geometry of the DG 26.7 reference. The viscosity was measured as a function of shear rate in the temperature range from 10°C to 150°C. For each temperature, the viscosity of the system was measured as a function of shear rate (from 1s -1 Up to 100s -1 ). The viscosity was measured at T = 10°C, 40°C, 70°C, 100°C, 130°C and 150°C (10°C to 150°C). Then, the measurement point (15s -1 Up to 100s -1 ) Calculate the average viscosity at each temperature.

[1030] Table 1 below shows the absolute viscosity of compositions H to J as a function of temperature.

[1031] 3.4 Rheological results (compositions H, I and J)

[1032] The relative viscosities of compositions I and J were studied over the temperature range of 10°C to 150°C and compared with the relative viscosity of composition H. -1 Up to 100s -1 The viscosity of the solution is calculated by taking the average of the absolute viscosities obtained at the shear rate of Fig.11 shown.

[1033] Table 1

[1034]

[1035] When the linear polydiol LPDiol-2 and the linear polyborate LPB2 are present together in the same lubricating composition (Composition H), it is observed that the natural viscosity loss of the base oil of Group III is significantly compensated over the entire temperature range studied. This is reflected in a practically linear increase in relative viscosity from 10°C to 150°C ( Fig.11 , dotted line-open square). However, composition H also affects the cold viscosity of the formulation, with a relative viscosity of 1.58 at 10°C.

[1036] In the same lubricating composition (Composition I), the presence of comb-type polydiol copolymer CPDiol-2 and comb-type poly(boric acid ester) copolymer PBB2 can significantly reduce the relative viscosity at low temperature, as low as η at 10°C. 相对 =1.30. At the same time, with preparation H ( Fig.11 , dashed / solid asterisks), the formulation has a lower compensation for the natural viscosity loss of Group III base oils at high temperatures.

[1037] Composition I was diluted to 2.10 wt% of comb-type polydiol copolymer CPDiol-2 and 2.10 wt% of comb-type poly(boric acid ester) copolymer PBB2, so that the relative viscosity could be further reduced to η at 10°C. 相对 =1.21( Fig.12 However, unlike the composition containing the linear copolymer, composition Id can be used at high temperature (η at 150°C) even with a relatively low relative viscosity under cold conditions. 相对 =1.43) maintains its viscosity increasing performance. It represents the relative viscosity values ​​of three consecutive heating and cooling cycles (Id-1, Id-2 and Id-3) from 10℃ to 150℃. In the 3 cycles, these changes are negligible and the relative viscosity ( Fig.13 ).

[1038] When the comb-type polydiol copolymer CPDiol-2 and the linear poly(borate) copolymer LPB2 are present together in the same lubricating composition (Composition J), the advantages of both systems are combined. Based on this combination of associative copolymer structure types, a significant compensation of the natural viscosity loss of the base oil is observed in the temperature range of 100°C to 150°C compared to formulations containing only linear copolymers ( Fig.11 , continuous solid circles), which occurs with a significant decrease in relative viscosity at low temperatures.

[1039] The relative viscosity values ​​are also shown for five consecutive heating and cooling cycles (J-1, J-2, J-3, J-4 and J-5) from 10°C to 150°C. They vary very little over the five cycles and always increase the relative viscosity by about 0.65 from 10°C to 150°C, reflecting good compensation for the natural viscosity loss of Group III base oils in this temperature range ( Fig.14 ).

Claims

1. A composition comprising: o 0.1 to 50 wt. % of a random or gradient comb polyglycol copolymer A1, and o 0.1 to 50% by weight of a compound A2 comprising at least two borate functional groups, The comb-type polyglycol copolymer A1 comprises a main chain and side chains, at least a part of the side chains of the copolymer A1 is constituted by oligomers comprising more than 30 carbon atoms, and exhibits a degree of polymerization of 5 to 1000, At least part of the side chains of the copolymer A1 consist of oligomers O1 comprising polyolefin segments in the form of repeating units corresponding to one or more than one monomer M6 of the general formula (IX): in: Q1 is selected from -H, -CH3 and -CH2-CH3; Q2 is selected from the group consisting of -Q', -O-Q', -C(O)-O-Q', -OC(O)-Q', -S-(CH2)2-C(O)-O-Q', -S-Q', -N(H)-C(O)-Q' and -C(O)-N(H)-Q', wherein Q' is a polyolefin, n represents an integer from 0 to 1, A represents a group selected from -A1-, -O-(-A2-O-) n' -A1-, -C(O)-O-(-A2-O-) n' -A1-、-OC(O)-(-A2-O-) n' -A1-、-S-(-A2-O-) n' -A1-, -N(H)-C(O)-(-A2-O-) n' -A1- and -C(O)-N(H)-(-A2-O-) n' -A1- divalent group, wherein A1 is selected from C1 to C 30 Alkyl, C6 to C 30 Aryl or C6 to C 30 A divalent aralkyl group, A2 is a divalent group selected from C2 to C4 alkyl groups, n' is an integer, n' represents 0 or 1, and Compound A2 is selected from: ○Compounds of formula (III): in: - w1 and w2 are the same or different and are integers from 0 to 1; -R4, R5, R6 and R7 are identical or different and represent a group selected from a hydrogen atom or a hydrocarbon group containing 1 to 30 carbon atoms, optionally substituted by one or more than one group selected from: hydroxyl or -OJ or -C(O)-OJ group, wherein J is a hydrocarbon group containing 1 to 24 carbon atoms; -L is selected from C6 to C 18 Aryl, C6 to C 18 Arylalkyl and C2 to C 24 A divalent linking group of a hydrocarbon chain; ○ A copolymer comprising at least the following repeating units; The repeating unit corresponding to the monomer M4 of formula (IV): in: -t is an integer equal to 0 or 1; -u is an integer equal to 0 or 1; -M and R8 are divalent linking groups, which are the same or different and are selected from C6 to C 18 Aryl, C7 to C 24 Arylalkyl and C2 to C 24 alkyl; -X is a functional group selected from -OC(O)-, -C(O)-O-, -C(O)-N(H)-, -N(H)-C(O)-, -S-, -N(H)-, -N(R'4)- and -O-, wherein R'4 is a hydrocarbon chain containing 1 to 15 carbon atoms; -R9 is selected from -H, -CH3 and -CH2-CH3; -R 10 and R 11 identical or different, it represents a group chosen from a hydrogen atom or a hydrocarbon radical containing 1 to 30 carbon atoms, optionally substituted by one or more than one group chosen from: a hydroxyl group or an -OJ or -C(O)-OJ group, in which J is a hydrocarbon radical containing 1 to 24 carbon atoms; The repeating unit corresponding to the monomer M5 of formula (V): in: -R 12 is selected from -H, -CH3 and -CH2-CH3, -R 13 Choose from C6 to C 18 Aryl and R' 13 、-C(O)-OR' 13 、-OR' 13 、-SR' 13 and -C(O)-N(H)-R' 13 C6 to C 18 Aryl, where R' 13 For C1 to C 30 alkyl. 2 . The composition according to claim 1 , wherein at least a portion of the side chains of copolymer A1 are composed of oligomers comprising at least 50 carbon atoms. 3 . The composition according to claim 1 , wherein at least a part of the side chains of the copolymer A1 is composed of an oligomer having a degree of polymerization of 5 to 500. The composition according to claim 1 , wherein the side chains consisting of oligomers are 3% to 95% by weight relative to the total weight of the copolymer A1. The composition according to claim 1 , wherein the side chains comprising polyolefin segments are 3% to 85% by weight relative to the total weight of the copolymer A1.

6. The composition according to claim 1, wherein the degree of branching of copolymer A1 is from 0.1 mol% to 10 mol%. 7 . The composition according to claim 1 , wherein the comb copolymer A1 comprises non-oligomeric side chains whose average length is from 1 to 10 carbon atoms. 8 . The composition according to claim 1 , wherein the number average degree of polymerization of the main chain of the comb copolymer A1 is from 40 to 2000. 9 . The composition according to claim 1 , wherein the number average degree of polymerization of the oligomeric side chains of the comb copolymer A1 is from 8 to 1000.

10. A lubricating composition, which is obtained by mixing at least the following substances: - Lubricating oil; and - A composition according to claim 1.

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