LUBRICATING COMPOSITIONS COMPRISING THERMOASSOCIATIVE AND EXCHANGEABLE COPOLYMERS

专利摘要:
The present invention relates to a composition resulting from the mixture of at least one lubricating oil, at least one random copolymer A1, and at least one compound A2 comprising at least two boronic ester functions; the random copolymer A1 results from the copolymerization of at least one first monomer M1 bearing diol functions and at least one second monomer M2 of different chemical structure from that of the monomer M1. The invention also relates to the use of this composition for lubricating a mechanical part. The field of the present invention is that of lubricants.
公开号:FR3016887A1
申请号:FR1450657
申请日:2014-01-27
公开日:2015-07-31
发明作者:Thi Hang Nga Nguyen；Renaud Nicolay；Raphaele Iovine；Ilias Iliopoulos
申请人:Centre National de la Recherche Scientifique CNRS；Ecole Superieure de Physique et Chimie Industrielles de Ville Paris ；Total Marketing Services SA；
IPC主号:

专利说明:

[0001] The present invention relates to a composition resulting from the mixing of at least one lubricating oil, at least one random copolymer Al, and at least one compound A2 comprising at least two boronic ester functional groups; the random copolymer Al results from the copolymerization of at least one first monomer M1 bearing diol functions and at least one second monomer M2 of chemical structure different from that of the monomer M1.
[0002] The invention also relates to the use of this composition for lubricating a mechanical part. The field of the present invention is that of lubricants. BACKGROUND ART Lubricating compositions are compositions applied between the surfaces, in particular metal surfaces, of moving parts. They reduce the friction and wear between two parts in contact and in motion relative to each other. They also serve to dissipate some of the thermal energy generated by this friction. Lubricating compositions form a protective film between the surfaces of the parts to which they are applied. The compositions used for the lubrication of mechanical parts generally consist of a base oil and additives. The base oil, in particular of petroleum or synthetic origin, exhibits variations in viscosity with the temperature being varied. Indeed, when the temperature of a base oil increases, its viscosity decreases and when the temperature of the base oil decreases, its viscosity increases. However, the thickness of the protective film is proportional to the viscosity, so also depends on the temperature. A composition has good lubricating properties if the thickness of the protective film remains substantially constant regardless of the conditions and the duration of use of the lubricant. In an internal combustion engine, a lubricating composition may be subjected to external or internal temperature changes. The external temperature changes are due to changes in ambient air temperature, such as temperature variations between summer and winter, for example. The internal temperature changes result from the implementation of the motor. The temperature of an engine is lower during its start-up phase, especially in cold weather, than during prolonged use. Therefore, the thickness of the protective film may vary in these different situations. There is therefore a need to have a lubricating composition having good lubricating properties and whose viscosity is little subject to temperature variations. It is known to add additives improving the viscosity of a lubricating composition.
[0003] These additives have the function of modifying the rheological behavior of the lubricating composition. They promote a substantially constant viscosity over a temperature range at which the lubricant composition is used. For example, these additives limit the decrease in the viscosity of the lubricant composition when the temperature rises or limit the increase in the viscosity of the lubricating composition as the temperature decreases. The viscosity-improving additives (or viscosity index improvers) currently used are polymers such as polyalpha-olefins, polymethyl methacrylates, copolymers resulting from the polymerization of an ethylenic monomer and an alpha-olefin. . These polymers are of high molecular weight. In general, the contribution of these polymers to the control of the viscosity is all the more important that their molecular weight is high. However, the high molecular weight polymers have the disadvantage of having a low permanent shear strength compared to polymers of the same nature but of smaller size. However, a lubricant composition is subjected to significant shear stresses, particularly in internal combustion engines, where the friction surfaces have a very small gap and the pressures exerted on the parts are high. These shear stresses on the high molecular weight polymers cause cuts in the macromolecular chains. The polymer thus degraded no longer has thickening properties, and the viscosity drops irreversibly. This loss of permanent shear strength therefore leads to a degradation of the lubricating properties of the lubricant composition. The polymers of the prior art, in particular PMMA (polymethylmethacrylates) have a rheo-thickening behavior. At a high shear rate, the PMMA chain breaks. This results in the formation of two molecules having approximately half the molar weight of the initial PMMA. The total hydrodynamic volume of these two small molecules is lower than that of the initial PPMA, which results in a lower viscosity contribution and results in a reduction in viscosity.
[0004] Ethylene-alphaolefin copolymers having a high ethylene content are viscosity improvers and are shear stable. However, these polymers have the disadvantage of aggregating in the compositions containing them and lead to extremely viscous lubricating compositions, such as gels. This aggregation generally occurs at ambient conditions or during cooling.
[0005] Also, the aim of the applicant is to formulate new lubricating compositions whose viscosity is better controlled with respect to the lubricant compositions of the prior art. In particular, it aims to provide new rheological additives, which when introduced into a base oil, have an inverted behavior vis-à-vis a change in temperature with respect to the behavior of the oil base and rheological additives of the polymer type of the prior art. This objective is achieved thanks to new rheological additives that can associate, possibly forming a gel, and exchange in a thermoreversible manner. Unlike the base oil which becomes liquefied as the temperature increases, the additives of the present invention have the advantage of thickening the medium in which they are dispersed as the temperature increases. This characteristic results from the combined use of two particular compounds, a copolymer bearing diol functions and a compound comprising boronic ester functions. It is known from WO2013147795 polymers of which at least one monomer comprises boronic ester functions. These polymers are used for the manufacture of electronic devices, especially for devices which are desired to obtain a flexible user interface. These polymers are also used as synthesis intermediate. They make it possible to functionalize the polymers by coupling with luminescent groups, electron-carrying groups, etc. The coupling of these groups is carried out by conventional organic chemical reactions involving the boron atom, such as, for example, Suzuki coupling. However, no other use of these polymers in the field of lubricating compositions, nor an association with other compounds is contemplated. Unexpectedly, the Applicant has observed that at low temperature, the polydiol copolymer of the invention is not or only slightly crosslinked by the compounds comprising boronic ester functions. As the temperature increases, the diol functions of the copolymer react with the boronic ester functions of the compound comprising them by a transesterification reaction. Polydiol random copolymers and compounds comprising boronic ester functions then bind together and can be exchanged. Depending on the functionality of the polydiols and compounds comprising boronic ester functions, as well as the composition of the mixtures, a gel may form in the base oil. When the temperature decreases again, the boronic ester linkages between the polydiol random copolymers and the compounds comprising them break; the composition loses its gelled character if necessary. The Applicant has also set itself the objective of formulating new rheology additives which are more stable in shear compared to the compounds of the prior art. This objective is achieved thanks to the new rheological additives that can combine and crosslink in a thermoreversible way. In contrast to the polymers of the prior art, it has been found that the molar weight of the copolymers of the invention is not or little changed when a high shear rate is applied. The copolymers of the invention therefore have the advantage of being more stable to shear stresses.
[0006] SUMMARY OF THE INVENTION Thus, the subject of the invention is a new composition resulting from the mixing of: at least one lubricating oil, at least one random copolymer A1 and at least one compound A2 comprising at least two boronic ester functions; the random copolymer A1 resulting from the copolymerization of at least one first monomer M1 of general formula (I) ## STR2 ## in which: R 1 is chosen from the group formed by -H, -CH3 and -CH2-CH3 x is an integer ranging from 2 to 18; y is an integer equal to 0 or 1; X1 and X2, which are identical or different, are chosen from the group formed by hydrogen, tetrahydropyranyl, methyloxymethyl, tert-butyl, benzyl, trimethylsilyl and t-butyl dimethylsilyl; or else X 1 and X 2 form, with the oxygen atoms, a bridge of the following formula R "2 in which: the stars (*) symbolize the bonds to the oxygen atoms, R '2 and R" 2, which are identical or different, are selected from the group consisting of hydrogen and a C1-C11 alkyl, preferably methyl; or else - X1 and X2 form with the oxygen atoms a boronic ester of the following formula RI "2 in which: - the stars (*) symbolize the bonds to the oxygen atoms, - R" '2 is chosen from the group formed by C 6 -C 18 aryl, C 7 -C 18 aralkyl and C 2 -C 18 alkyl, preferably C 6 -C 18 aryl; with at least one second monomer M2 of the general formula (II-A): wherein R 2 is selected from the group consisting of -H, -CH 3 and -CH 2 -CH 3, R 31 is chosen from the group consisting of C6-C18 aryl, C6-C18 aryl substituted with a group R'3, -C (O) -O-R'3 -O-R'3, -S-R'3 and -C (O) -N (H) -R'3 with R'3 is a C1-C30 alkyl group. In a variant, the random copolymer Al results from the copolymerization of at least one monomer M1 with at least two monomers M2 having different R31 groups. Preferably, one of the monomers M2 of the random copolymer Al has the general formula (II-A1): ## STR2 ## in which: R 2 is chosen from the group formed by -H, -CH 3 and CH 2 -CH 3, - R "31 is a C 1 -C 6 alkyl group, and the other monomer M 2 of the random copolymer Al has the general formula (II-A2): ## STR1 ## wherein: R 2 is selected from the group consisting of -H, -CH3et-CH2-CH3, R "'31 is a C15-C30 alkyl group.
[0007] In a variant of the composition, the compound A2 is a compound of formula (III): ## STR1 ## in which: w1 and w2, which are identical or different, are integers chosen from 0 to 1, R4, R5, R6 and R7, which are identical or different, are chosen from the group formed by hydrogen and a hydrocarbon group containing from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 6 to 14 carbon atoms; carbon atoms; L is a divalent linking group and a C6-C18 aryl, a C6-C18 aralkyl and a C2-C24 hydrocarbon chain. In another variant of the composition, the compound A2 is a random copolymer resulting from the copolymerization of at least one monomer M3 of formula (IV): ## STR2 ## (IV) wherein: - 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 may be identical or different, are chosen from the group formed by a C6-C18 aryl, a C7-C24 aralkyl and a C2-C24 alkyl, preferably a C6-C18 aryl, X is a function selected from the group consisting of -O-C (O) -, -C (O) -N (H) -, -N (H) -C (O) -, -S-, -N ( H) -, -N (R'4) - and -O- with R'4 a hydrocarbon chain comprising from 1 to 15 carbon atoms; R9 is selected from the group consisting of -H, -CH3et-CH2-CH3; R 10 and R 11, which are identical or different, chosen from the group formed by hydrogen and a hydrocarbon group containing from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 6 to 14 carbon atoms, at least one second monomer M4 of general formula (V): R12H2CR13 (V) in which: R12 is chosen from the group formed by -H, -CH3 and -CH2-CH3 R13 is chosen from the group formed by an aryl at C6-C18, a C6-C18 aryl substituted with a group R'13, -C (O) -O-R'13, -SR '13 and -C (O) -N (H) -R' 13 with R '13 a C 1 -C 25 alkyl group. Preferably, the compositions described above comprise one or more of the following characteristics, taken separately or in combination: the chain formed by the linking of the groups R10, M, X and (R8) 'with a integer equal to 0 or 1, the monomer of general formula (IV) has a total number of carbon atoms of between 8 and 38, preferably between 10 and 26 carbon atoms; the side chains of the copolymer A2 have an average length greater than 8 carbon atoms, preferably ranging from 11 to 16 carbon atoms; the random copolymer A2 has a molar percentage of monomer of formula (IV) ranging from 0.25 to 20%, preferably from 1 to 10%; the random copolymer A2 has a number-average degree of polymerization ranging from 50 to 1500, preferably from 80 to 800; the side chains of the random copolymer Al have an average length ranging from 8 to 20 carbon atoms, preferably from 9 to 15 carbon atoms; the random copolymer A1 has a molar percentage of monomer M1 of formula (I) ranging from 1 to 30%, preferably ranging from 5 to 25, more preferably ranging from 9 to 21%; the random copolymer Al has a mean degree of polymerization ranging from 100 to 2000, preferably from 150 to 1000; the lubricating oil is chosen from oils of group I, group II, group III, group IV, group V of the API classification and one of their mixtures; the composition further comprises a functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, additional antioxidants, viscosity index improver polymers, pour point improvers, anti-foams, anti-corrosion additives, thickeners, dispersants, friction modifiers and mixtures thereof; the mass ratio in the composition between the random copolymer Al and the compound A2 (ratio Al / A2) ranges from 0.001 to 100, preferably from 0.05 to 20, even more preferably from 0.1 to 10, even more preferably from 0.2 to 5; the sum of the masses of the random copolymer Al and of the compound A2 in the composition is from 0.5 to 20% relative to the total mass of the lubricating composition and the lubricating oil mass ranges from 80% to 99.5% relative to the total mass of the lubricating composition.
[0008] The invention also relates to the use of a composition as described above for lubricating a mechanical part. The subject of the invention is also a parent composition resulting from the mixing of: at least one random copolymer Al; at least A2 compound comprising at least two boronic ester functions; and at least one functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, antioxidants, viscosity index improvers, pour point improvers, anti-wear agents, foam, thickeners, dispersants, friction modifiers and mixtures thereof; the random copolymer Al resulting from the copolymerization of at least a first monomer M1 of general formula (I) ## STR2 ## in which: R 1 is chosen from the group formed by -H, -CH 3 and -CH2-CH3, x is an integer ranging from 2 to 18; y is an integer equal to 0 or 1; X1 and X2, which are identical or different, are chosen from the group formed by hydrogen, tetrahydropyranyl, methyloxymethyl, tert-butyl, benzyl, trimethylsilyl and t-butyl dimethylsilyl; or else X 1 and X 2 together with the oxygen atoms form a bridge of the following formula R "2 in which: - the stars (*) symbolize the bonds to the oxygen atoms, - R '2 and R" 2 , identical or different, are chosen from the group formed by hydrogen and a C1-C11 alkyl, preferably methyl; or else - X1 and X2 form with the oxygen atoms a boronic ester of the following formula RI "2 in which: - the stars (*) symbolize the bonds to the oxygen atoms, - R" '2 is chosen from the group formed by C 6 -C 18 aryl, C 7 -C 18 aralkyl and C 2 -C 18 alkyl, preferably C 6 -C 18 aryl; with at least one second monomer M2 of the general formula (II-A): wherein R 2 is selected from the group consisting of -H, -CH 3 and -CH 2 -CH 3 R 31 is selected from the group formed by a C 6 -C 18 aryl, a C 6 -C 18 aryl substituted with a group R '3, -C (O) -O-W 3 -O-R' 3 -S-R '3 and -C ( 0) -N (H) -R'3 with R'3 is a C1-C30 alkyl group. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 schematically represents a random copolymer (P1), a gradient copolymer (P2) and a block copolymer (P3), each ring represents a monomeric unit. The difference in chemical structure between the monomers is symbolized by a different color (light gray / black). Figure 2 schematically shows a comb copolymer.
[0009] Figure 3 schematically shows a solubility test of the composition according to the invention in tetrahydrofuran (THF). Figure 4 shows schematically the behavior of the composition of the invention as a function of temperature. A random copolymer (2) having diol functions (function A) can associate thermoreversibly with a random copolymer (1) having boronic ester functions (function B) via a transesterification reaction. A chemical bond (3) of the boronic ester type is formed. FIG. 5 represents the variation, for different temperatures between 10 ° C. and 110 ° C., of the viscosity (Pa.s, the ordinate axis) as a function of the shear rate (s-1, the axis of the abscissas) of a 10% by weight solution of a polydiol random copolymer A1-1 and 0.77% by weight of a boronic diester compound A2-1 in the group III base oil. FIG. 6A represents the evolution of the relative viscosity (without unit, the ordinate axis) as a function of the temperature (° C, the abscissa axis) of the compositions A, B-1, C-1 and D- 1. FIG. 6B represents the evolution of the relative viscosity (without unit, the ordinate axis) as a function of the temperature (° C, the abscissa axis) of the compositions A, B-2, C-2 and D- 2. FIG. 6C represents the evolution of the relative viscosity (without unit, the ordinate axis) as a function of the temperature (° C, the abscissa axis) of the compositions A, B-3 and C-3. FIG. 6D represents the evolution of the relative viscosity (without unit, the ordinate axis) as a function of the temperature (° C, the abscissa axis) of the compositions A, B-4, C-4 and D- 4.
[0010] FIG. 7 represents the variation, for different temperatures between 10 ° C. and 110 ° C., of the viscosity (Pa.s, the ordinate axis) as a function of the shear rate (s-1, the axis of the X) shows the evolution of the relative viscosity (without unit, the ordinate axis) as a function of the temperature (° C, the abscissa axis) of the compositions A, B, C Fig. 9 schematically illustrates the boronic ester link exchange reactions between two polydiols random polymers (A1-1 and Al-2) and two boronic ester random polymers (A2-1 and A2-2). .
[0011] DESCRIPTION OF EMBODIMENTS OF THE INVENTION A first subject of the invention is a composition resulting from the mixing of: at least one lubricating oil, at least one random copolymer A1, and at least one compound A2 comprising at least two boronic ester functions; the random copolymer Al resulting from the copolymerization of at least one first monomer M1 bearing diol functions and at least one second monomer M2 of chemical structure different from that of the monomer M1. o Lubricating base oil By "oil" is meant a fatty substance that is liquid at ambient temperature (25 ° C.) and atmospheric pressure (760 mm of Hg at 105 Pa). By "lubricating oil" is meant an oil that reduces the friction between two moving parts to facilitate the operation of these parts. Lubricating oils can be of natural, mineral or synthetic origin. Lubricating oils of natural origin may be oils of vegetable or animal origin, preferably oils of vegetable origin such as rapeseed oil, sunflower oil, palm oil, coconut oil, copra ... Lubricating oils of mineral origin are of petroleum origin and are extracted from petroleum fractions coming from atmospheric and vacuum distillation of crude oil. The distillation can be followed by refining operations such as solvent extraction, désalphatage, solvent dewaxing, hydrotreating, hydrocracking, hydroisomerisation, hydrofinition, etc. As an illustration, mention the paraffinic mineral base oils such as Bright Stock Solvent Oil (BSS), naphthenic mineral base oils, aromatic mineral oils, hydrorefined mineral bases with a viscosity number of about 100, mineral bases hydrocracked products whose viscosity index is between 120 and 130, the hydroisomerized mineral bases whose viscosity index is between 140 and 150. The lubricating oils of synthetic origin (or synthetic base) come as their name indicates chemical synthesis such as the addition of a product to itself or polymerization, or the addition of one product to another such as esterification, alkylation, fluorination, etc., components derived from petrochemistry, carbochemistry, and mineral chemistry such as: olefins, aromatics, alcohols, acids, halogenated compounds, phosphorus compounds, silicones, etc. By way of illustration, mention may be made of: Synthetic oils based on synthetic hydrocarbons such as polyalphaolefins (PAOs), internal polyolefins (IOPs), polybutenes and polyisobutenes (PIBs), dialkylbenenes, alkylated polyphenyls; synthetic oils based on esters such as diacid esters, neopolyol esters; synthetic polyglycol oils such as monoalkylene glycols, polyalkylene glycols and monoethers of polyalkylene glycols; synthetic oils based on ester-phosphates; synthetic oils based on silicon derivatives such as silicone oils or polysiloxanes. Lubricating oils that can be used in the composition of the invention can be selected from any of the I to V oils specified in the API Guidelines (American Petroleum Institute's Base Oil Interchangeability Guidelines). ) (or their equivalents according to the ATIEL classification (Technical Association of the European Lubricants Industry) as summarized below: Content content in Index of saturated compounds * sulfur ** viscosity (VI) ** Group I Mineral oils < 90%> 0.03% 80 VI <120 Group II Oils> 90% 0.03% 80 VI <120 Hydrocracked Group III 90% 0.03%> 120 Hydrocracked or hydro-isomerized oils Group IV (PAO) Polyalphaolefins Group V Esters and other bases not included in bases groups I to IV * measured according to standard ASTM D2007 ** measured according to the standards ASTM D2622, ASTM D4294, ASTM D4927 and ASTM D3120 ** measured according to the standard ASTM D2270 The compositions of the invention can com take one or more lubricating oils. The lubricating oil or the mixture of lubricating oils represents at least 50% by weight relative to the total weight of the composition. Preferably, the lubricating oil or the lubricating oil mixture represents at least 70% by weight relative to the total weight of the composition. In one embodiment of the invention, the lubricating oil is selected from the group consisting of oils of group I, group II, group III, group IV, group V of the API classification and one of their mixture. Preferably, the lubricating oil is chosen from the group consisting of oils of group III, group IV, group V of the API classification and their mixture. Preferably, the lubricating oil is a Group III API oil. The lubricating oil has a kinematic viscosity at 100 ° C measured according to ASTM D445 ranging from 2 to 150 cSt, preferably from 5 to 15 cSt. Lubricating oils can range from SAE grade 15 to SAE grade 250, and most preferably SAE grade 20W to grade SAE 50 (SAE stands for Society of Automotive Engineers). New polydiol random copolymers (random copolymer Al) The composition of the invention comprises at least one novel polydiol random copolymer resulting from the copolymerization of at least one first monomer M1 bearing diol functions and at least one second monomer M2. of different chemical structure from that of the monomer M1. By "copolymer" is meant a linear or branched oligomer or macromolecule having a sequence consisting of several repeating units (or monomeric unit) of which at least two units have a different chemical structure.
[0012] By "monomeric unit" or "monomer" is meant a molecule capable of being converted into an oligomer or a macromolecule by combination with itself or with other molecules of the same type. A monomer refers to the smallest constituent unit whose repetition leads to an oligomer or a macromolecule. The term "random copolymer" is understood to mean an oligomer or a macromolecule in which the sequential distribution of the monomeric units obeys known statistical laws. For example, a copolymer is said to be random when it consists of monomeric units whose distribution is a Markovian distribution. A schematic statistical polymer (P1) is illustrated in FIG. 1. The distribution in the polymer chain of the monomer units depends on the reactivity of the polymerizable functions of the monomers and the relative concentration of the monomers. The polydiol random copolymers of the invention are distinguished from block copolymers and gradient polymers. By "block" is meant a part of a copolymer comprising several identical or different monomer units and which have at least one particular constitution or configuration to distinguish it from its adjacent parts. A schematic block copolymer (P3) is illustrated in FIG. 1. A gradient copolymer designates a copolymer of at least two monomeric units of different structures whose monomer composition gradually changes along the polymer chain, thus changing from progressively from one end of the polymer chain rich in a monomeric unit, to the other end rich in the other comonomer. A schematic gradient polymer (P2) is illustrated in FIG.
[0013] By "copolymerization" is meant a process which makes it possible to convert a mixture of at least two monomeric units of different chemical structures into an oligomer or a copolymer. In the rest of the present application, "B" represents a boron atom. By "Ci-Ci alkyl" is meant a saturated hydrocarbon chain, linear or branched, comprising from 1 to 1 carbon atoms. For example, for "C1-C10 alkyl" is meant a saturated hydrocarbon chain, linear or branched, comprising from 1 to 10 carbon atoms. By "C 6 -C 18 aryl" is meant a functional group derived from an aromatic hydrocarbon compound having from 6 to 18 carbon atoms. This functional group can be monocyclic or polycyclic. By way of illustration, a C 6 -C 18 aryl may be phenyl, naphthalene, anthracene, phenanthrene and tetracene. By "C2-C10 alkenyl" is meant a linear or branched hydrocarbon chain containing at least one unsaturation, preferably a double bond, and from 2 to 10 carbon atoms.
[0014] By "C7-C18 aralkyl" is meant an aromatic hydrocarbon compound preferably monocyclic, substituted by at least one linear or branched alkyl chain and the total number of carbon atoms of the aromatic ring and its substituents ranges from 7 to 18 carbon atoms. By way of illustration, a C 7 -C 18 aralkyl may be selected from the group consisting of benzyl, tolyl and xylyl. By "C 6 -C 18 aryl group substituted by an R '3" group is meant an aromatic hydrocarbon compound preferably monocyclic, comprising from 6 to 18 carbon atoms, at least one carbon atom of the aromatic ring is substituted by a group R'3. By "Hal" or "halogen" is meant a halogen selected from the group consisting of chlorine, bromine, fluorine and iodine. MI monomer The first monomer M1 of the polydiol random copolymer (Al) of the invention has the general formula (I): ## STR2 ## in which: R 1 is chosen from the group formed by -H, -CH 3 and -CH2-CH3, preferably -H and -CH3; x is an integer ranging from 2 to 18; preferably from 3 to 8; more preferably x is 4; y is an integer equal to 0 or 1; preferably y is 0; X1 and X2, which are identical or different, are chosen from the group formed by hydrogen, tetrahydropyranyl, methyloxymethyl, tert-butyl, benzyl, trimethylsilyl and t-butyl dimethylsilyl; or else - X1 and X2 form with the oxygen atoms a bridge of the following formula: in which: the stars (*) symbolize the bonds to the oxygen atoms, - R'2 and R "2, which are identical or different, are chosen from the group formed by hydrogen and a C1-C11 alkyl group or else - X1 and X2 form with the oxygen atoms a boronic ester of the following formula: RI "2 in which: - the stars (*) symbolize the bonds to the oxygen atoms; R "'2 is selected from the group consisting of C 6 -C 18 aryl, C 7 -C 18 aralkyl and C 2 -C 18 alkyl, preferably C 6 -C 18 aryl; more preferably phenyl, Preferably, when R'2 and R "2 is a C1-C11 alkyl group; the hydrocarbon chain is a linear chain. Preferably, the C1-C11 alkyl group is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, octyl, n-nonyl, n-decycling and n-undecyl. More preferably, the C1-C11 alkyl group is methyl. Preferably, when R '"2 is a C 2 -C 18 alkyl group, the hydrocarbon chain is a linear chain.
[0015] Among the monomers of formula (I), the monomers corresponding to formula (IA) are among the preferred ones: ## STR2 ## in which: R 1 is chosen from the group formed by -H, -CH 3 and -CH 2 CH3, preferably -H and -CH3; x is an integer from 2 to 18; preferably from 3 to 8; more preferably x is 4; y is an integer equal to 0 or 1; preferably, y is 0. Among the monomers of formula (I), the monomers corresponding to formula (IB) are among the preferred ones: H 2 C 0 OY 2 (IB) in which: R 1 is chosen from the group formed by -H , -CH3 and -CH2-CH3, preferably -H and -CH3; x is an integer from 2 to 18; preferably from 3 to 8; more preferably x is 4; y is an integer equal to 0 or 1; preferably y is 0; Y1 and Y2, which are identical or different, are chosen from the group formed by tetrahydropyranyl, methyloxymethyl, tert-butyl, benzyl, trimethylsilyl and t-butyl dimethylsilyl; or Y1 and Y2 form, with the oxygen atoms, a bridge of the following formula: in which: the stars (*) symbolize the bonds to the oxygen atoms, R'2 and R "2, which are identical or different, are chosen from the group consisting of hydrogen and a C1-C11 alkyl group or else Y1 and Y2 form with the oxygen atoms a boronic ester of the following formula: R1 "2 in which: - the stars (*) symbolize the to the oxygen atoms, R "'2 is selected from the group consisting of C 6 -C 18 aryl, C 7 -C 18 aralkyl and C 2 -C 18 alkyl, preferably C 6 -C 18 aryl, more preferably phenyl, Preferably, when R'2 and R "2 is a C1-C11 alkyl group; the hydrocarbon chain is a linear chain. Preferably, the C1-C11 alkyl group is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, octyl, n-nonyl, n-decycling and n-undecyl. More preferably, the C1-C11 alkyl group is methyl.
[0016] Preferably, when R '' 2 is a C 2 -C 18 alkyl group, the hydrocarbon chain is a linear chain - Obtaining the MI monomer The M 1 monomer of general formula (IA) is obtained by deprotection of the alcohol functional groups of the monomer general formula (IB) according to reaction scheme 1 below: embedded image wherein R 1, Y 1, Y 2, x and y as defined in general formula (IB) described above; The deprotection reaction of the diol functions of the monomer of general formula (IB) is well known to those skilled in the art.It is able to adapt the deprotection reaction conditions depending on the nature of the protective groups Y 1 and Y 2. of general formula (IB) can be obtained by a reaction of a compound of general formula (Ic) with an alcohol compound of general formula (Ib) according to reaction scheme 2 below: ## STR2 ## ) in which H2C Yi0 (143) OY2 Scheme Y3 is chosen from the group formed by a halogen atom, preferably chlorine, -OH and O-C (O) -R'1 with R'1 chosen from the group formed by -H, -CH3 and -CH2-CH3, preferably -H and -CH3, -Y1, Y2, x and y have the same meaning as given in general formula (IB). These coupling reactions are well known to those skilled in the art. The compound of general formula (I-c) is commercially available from suppliers: Sigma-Aldrich® and Alfa Aesar®. The alcohol compound of general formula (Ib) is obtained from the corresponding polyol of formula (Ia) by protecting the diol functions according to the following reaction scheme 3: HO protection x, y, Y1 and Y2 as defined in the general formula (IB). The protective reaction of the diol functions of the compound of general formula (I-a) is well known to those skilled in the art. It knows how to adapt the reaction protection conditions according to the nature of the protective groups Y1 and Y2 used. The polyol of the general formula (I-a) is commercially available from the suppliers: Sigma-Aldrich® and Alfa Aesar®. Monomer M2 The second monomer of the random copolymer of the invention has the general formula (II): ## STR2 ## wherein R 2 is selected from the group formed by -H, -CH 3 and -CH 2 -CH 3, preferably H or -CH3; R3 is selected from the group consisting of a hydrogen atom, a C1-C10 alkyl group, a C2-C10 alkenyl group, a C6-C18 aryl group, a substituted C6-C18 aryl; by a group R'3, -C (O) -O-R'3 -O-R'3, -S-R'3 and -C (O) -N (H) -R'3 with R'3 C1-C30 alkyl group, preferably R'3 is a C1-C30 alkyl group whose hydrocarbon chain is linear.On the monomers of formula (II), the monomers corresponding to formula (II-A) part of the preferred R2 H2C R31 (II-A) in which: R2 is selected from the group consisting of -H, -CH3 and -CH2-CH3, preferably -H or -CH3; R31 is selected from the group consisting of C6-C18 aryl group, a C6-C18 aryl substituted with a group R'3, -C (O) -O- R'3 -O-R'3, -S-R'3 and -C (O) -N (H) -R'3 with R'3 a C1-C30 alkyl group. Preferably, R'3 is a C1-C30 alkyl group whose hydrocarbon chain is linear.
[0017] Among the monomers of formula (II-A), the monomers corresponding to formula (II-A1) are among the preferred ones: H 2 C (II-A1) in which: R 2 is chosen from the group formed by -H, -CH 3 and -CH2-CH3, preferably -H and -CH3; - R "31 is a C1-C14 alkyl group.
[0018] By "C1-C14 alkyl group" is meant a saturated hydrocarbon chain, linear or branched comprising from 1 to 14 carbon atoms. Preferably, the hydrocarbon chain is linear. Preferably, the hydrocarbon chain comprises from 4 to 12 carbon atoms. Among the monomers of formula (II-A), the monomers corresponding to formula (II-A2) are also among the preferred ones: H2C OO (II-A2) in which: R2 is chosen from the group formed by -H, -CH3 and -CH2-CH3, preferably -H and -CH3; R "'31 is a C 15 -C 30 alkyl group" C 15 -C 30 alkyl "is understood to mean a linear or branched saturated hydrocarbon-based chain comprising from 15 to 30 carbon atoms. Preferably, the hydrocarbon chain comprises from 16 to 24 carbon atoms Among the monomers of formula (II), the monomers corresponding to formula (II-B) are among the preferred ones: R22 H2C R32 (II-B) wherein R22 is selected from the group consisting of H and CH3; R32 is selected from the group consisting of hydrogen, C1-C10 alkyl and C2-C10 alkenyl. Obtaining M2 monomer The monomers of formula (II), (II-A), in particular (II-A1) and (II-A2), (II-B) are well known to those skilled in the art and are marketed by Sigma-Aldrich®. and TCI® Preferred Polydiols Copolymers In one embodiment, a preferred random copolymer results from the copolymerization at least: a first monomer M1 of general formula (I) as previously described; a second monomer M2 of formula (II) as previously described, wherein R2 is -H and R3 is a C6-C18 aryl group; preferably R3 is phenyl. In another embodiment, a preferred random copolymer results from the copolymerization of at least: a first monomer M1 of general formula (I) as previously described; a second monomer M2 of formula (II-A1) as described above; and a third monomer M2 of formula (II-A2) as described above. According to this other embodiment, a preferred random copolymer results from the copolymerization of at least: a first monomer M1 of general formula (I) as described above; a second monomer M2 of formula (II-A1) in which R2 is CH3 and R "31 is a C4-C12 alkyl group, preferably a linear C4-C12 alkyl, a third monomer M2 of formula (II-A2) in wherein R2 is CH3 and R "'31 is a C1-C24 alkyl group, preferably a C1-C24 linear alkyl. According to this embodiment, a preferred random copolymer results from the copolymerization of at least: a first monomer M1 of general formula (I) as described above; a second monomer M2 selected from the group consisting of n-octyl methacrylate, n-decyl methacrylate and n-dodecyl methacrylate; a third monomer M2 selected from the group consisting of palmityl methacrylate, stearyl methacrylate, arachidyl methacrylate and behenyl methacrylate.
[0019] In another embodiment, a preferred random copolymer results from the copolymerization of at least: a first monomer M1 of general formula (I) as defined above; a second monomer M2 of formula (II-B) as defined above, wherein R22 and R32 are a hydrogen atom; a third monomer M2 of formula (II-B) as defined above in which R22 is a hydrogen atom, R32 is a C1-C10 alkyl group, preferably R32 a linear C1-C10 alkyl group, preferably R32 is selected from the group consisting of CH3, CH2-CH3, CH2-CH2-CH3, CH2- (CH2) 2-CH3 and CH2- (CH2) 3-CH3. According to this embodiment, a preferred random copolymer results from the copolymerization of at least: a first monomer M1 of general formula (I) as defined above; a second monomer M2 of formula (II-B) which is ethylene; a third monomer M2 of formula (II-B) which is propylene. In another embodiment, a preferred random copolymer results from a copolymerization step of at least: a first monomer M1 of general formula (I) as defined above; a second monomer M2 of general formula (II-B) as defined above, wherein R22 is a hydrogen atom and R32 is selected from the group consisting of hydrogen and a C1-C10 alkyl group a third monomer M2 of general formula (II-A 1) as defined above. In another embodiment, a preferred random copolymer results from a copolymerization step of at least: a first monomer M1 of general formula (I) as previously described; a second monomer M2 of formula (II) as previously described, wherein R2 is H and R3 is a C6-C18 aryl group; preferably R3 is phenyl; and a third monomer M2 of formula (II-B) as described above, wherein R22 is selected from the group consisting of H or CH3, R32 is a C2-C10 alkenyl group, preferably R32 is -C (H) = CH2; and a hydrogenation step. Hydrogenation can be accomplished by any technique well known to those skilled in the art. Process for Obtaining New Polydiol Copolymers Those skilled in the art are able to synthesize the polydiol random copolymers Al of the invention using their general knowledge. The copolymerization can be initiated in bulk or in solution in an organic solvent with compounds generating free radicals. For example, the copolymers of the invention, in particular those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) ) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), are obtained by the known processes of radical copolymerization, in particular controlled such as the method called radical polymerization controlled by chain transfer reversible addition-fragmentation (in English: Reversible Addition-Fragmentation Chain Transfer (RAFT)) and the so-called atom transfer controlled radical polymerization (Atom Transfer Radical Polymerization (ARTP)) method. Conventional radical polymerization and telomerization can also be employed to prepare the copolymers of the invention (Moad, G .; Solomon, DH, The Chemistry of Radical Polymerization, 2nd ed .; Elsevier Ltd: 2006; p 639; Matyaszewski, K Davis, TP Handbook of Radical Polymerization; Wiley-Interscience: Hoboken, 2002; p 936).
[0020] Thus another object of the present invention is a process for preparing a random copolymer, said process comprising at least one polymerization stage (a) in which at least: i) a first monomer M1 of general formula ( I): wherein: R1 is selected from the group consisting of -H, -CH3et-CH2-CE13; x is an integer from 2 to 18; y is an integer equal to 0 or 1; X1 and X2, which are identical or different, are chosen from the group formed by hydrogen, tetrahydropyranyl, methyloxymethyl, tert-butyl, benzyl, trimethylsilyl and t-butyl dimethylsilyl; or else - X1 and X2 form with the oxygen atoms a bridge of the following formula in which: the stars (*) symbolize the bonds to the oxygen atoms; R'2 and R "2, which are identical or different, are chosen from the group formed by hydrogen and a C1-C11 alkyl, preferably methyl, or else X1 and X2 form, with the oxygen atoms, a boronic ester; of the following formula RI "2 in which: the stars (*) symbolize the bonds to the oxygen atoms; R "'2 is selected from the group consisting of C 6 -C 18 aryl, C 7 -C 18 aralkyl and C 2 -C 18 alkyl, preferably C 6 -C 18 aryl, ii) at least one second M 2 general formula (II-A): H2C R2 (R3) wherein R2 is selected from the group consisting of -H, -CH3 and -CH2-CH3 R3 is selected from the group consisting of C6-C18 aryl, aryl C6-C18 substituted with a group R'3, -C (O) -O-W3, -S-R'3 and -C (O) -N (H) -R'3 with R'3 an alkyl group C1-C30 iii) at least one source of free radicals In one embodiment, the method may further comprise iv) at least one chain transfer agent By "a source of free radicals" is meant a chemical compound or to generate a chemical species having one or more unpaired electrons on its outer layer The person skilled in the art can use any source of free radicals known per se as suitable for polymerization processes, especially polymerization processes. Among the sources of free radicals, benzoyl peroxide, tert-butyl peroxide, disazo compounds such as azobisisobutyronitrile, peroxygen compounds such as persulfates or hydrogen peroxide, redox systems such as the oxidation of Fe2 +, the persulfate / sodium-metabisulphite mixtures, or ascorbic acid / hydrogen peroxide, or the photochemically cleavable compounds or by ionizing radiation, for example the rays. ultraviolet or by beta or gamma radiation.
[0021] By "chain transfer agent" is meant a compound whose purpose is to ensure a homogeneous growth of the macromolecular chains by reversible transfer reactions between growing species, ie polymer chains terminated by a carbon radical, and dormant species, ie polymer chains terminated by a transfer agent. This reversible transfer process makes it possible to control the molecular masses of copolymers thus prepared. Preferably in the process of the invention, the chain transfer agent comprises a thiocarbonylthio group -S-C (= S) -. As an illustration of chain transfer agent, mention may be made of dithioesters, trithiocarbonates, xanthates and dithiocarbamates. A preferred transfer agent is cumyl dithiobenzoate or 2-cyano-2-propyl benzodithioate.
[0022] By "chain transfer agent" is also meant a compound whose purpose is to limit the growth of the macromolecular chains being formed by addition of monomer molecules and to start new chains, which makes it possible to limit the molecular masses final, even to control them. Such a type of transfer agent is used in telomerization. A preferred transfer agent is cysteamine.
[0023] In one embodiment of the invention, the process for preparing a polydiol random copolymer comprises: at least one polymerization step (a) as defined above, in which the monomers M1 and M2 are chosen with X1 and X2 different from hydrogen, and in addition at least one step of deprotection (b) of the diol functions of the copolymer obtained at the end of step (a), so as to obtain a copolymer in which X1 and X2 are identical and are a hydrogen atom. In one embodiment, the polymerization step (a) comprises contacting at least one monomer M1 with at least two monomers M2 having different R31 groups.
[0024] In this embodiment, one of the monomers M2 has the general formula (II-A1) R2 0 0 R "31 (II-A1) in which: R2 is chosen from the group formed by -H, -CH3 and -CH2-CH3, preferably -H and -CH3; -R "31 is a C1-C14 alkyl group and the other monomer M2 has the general formula (II-A2) H2C 27 H2C 0 O (II-A2) wherein: R2 is selected from the group consisting of -H, -CH3 and -CH2-CH3, preferably -H and -CH3; R 31 is a C 15 -C 30 alkyl group The preferences and definitions described for the general formulas (I), (IA), (IB), (II-A), (II-A1) and (II-A) A2) also apply to the processes described above: Properties of the New Polydiols Al Copolymers The polydiols Al random copolymers of the invention are comb copolymers "Comb copolymers" means a copolymer having a main chain The side chains are pendent on both sides of the main chain, the length of each side chain is less than the length of the main chain, and Figure 2 is a schematic representation of a side chain. The copolymers of the invention, in particular those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one forester monomer mule (II-A1) and at least one monomer of formula (II-A2), have a skeleton of polymerizable functions, in particular a skeleton of methacrylate functions, and a mixture of hydrocarbon side chains substituted or not by diol functions. As the monomers of formula (I) and (II-A) have polymerizable functions of identical or substantially identical reactivity, a copolymer is obtained in which the monomers having diol functions are statistically distributed along the backbone of the copolymer relative to the monomers of which the alkyl chains are unsubstituted by diol functions. The polydiol random copolymers of the invention, especially those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), have the advantage of being sensitive to external stimuli, such as temperature, pressure, shear rate ; this sensitivity translates into a change of properties. In response to a stimulus, the conformation in space of the copolymer chains is modified and the diol functions are rendered more or less accessible to the association reactions, which can generate crosslinking, as well as to the exchange reactions. These processes of association and exchange are reversible. The copolymer of the invention A1 is a thermosensitive copolymer, that is to say that it is sensitive to changes in temperature.
[0025] Advantageously, the side chains of the polydiol random copolymer, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I ) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), have an average length ranging from 8 to 20 carbon atoms, preferably from 9 to 15 carbon atoms. By "average side chain length" is meant the average side chain length of each monomer constituting the copolymer. Those skilled in the art can obtain this average length by appropriately selecting the types and ratio of monomers constituting the polydiol random copolymer. The choice of this average chain length makes it possible to obtain a polymer that is soluble in a hydrophobic medium, whatever the temperature at which the copolymer is dissolved. The copolymer is therefore miscible in a hydrophobic medium. By "hydrophobic medium" is meant a medium that has no or a very low affinity for water, that is to say it is not miscible in water or in an aqueous medium. Advantageously, the polydiol random copolymer of the invention, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula ( I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), has a molar percentage of monomer M1 of formula (I) ranging from 1 to 30%, preferably ranging from From 5 to 25%, more preferably from 9 to 21%. In a preferred embodiment of the invention, the copolymer of the invention has a molar percentage of monomer M1 of formula (I) ranging from 1 to 30%, preferably 5 to 25%, more preferably ranging from at 21%, a molar percentage of monomer M2 of formula (II-A1) ranging from 8 to 92% and a molar percentage of monomer M2 of formula (II-A2) ranging from 0.1 to 62%. The molar percentage of monomers in the copolymer results directly from the adjustment of the amounts of monomers used for the synthesis of the copolymer. In a preferred embodiment, the copolymer Al has a molar percentage of monomer M1 of formula (I) ranging from 1 to 30%, a molar percentage of monomer M2 of formula (II-A) ranging from 8 to 62% and a molar percentage of M2 monomer of formula (II-B) ranging from 8 to 91%. The molar percentage of monomers in the copolymer results directly from the adjustment of the amounts of monomers used for the synthesis of the copolymer. Advantageously, the polydiol random copolymer of the invention, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula ( I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), has a number average degree of polymerization ranging from 100 to 2000, preferably from 150 to 1000. As known, the degree of polymerization is controlled using a controlled radical polymerization technique, a telomerization technique or by adjusting the amount of free radical source when the copolymers of the invention are prepared by conventional free radical polymerization. Advantageously, the polydiol random copolymer of the invention, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula ( I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), has a polydispersity index (Ip) ranging from 1.05 to 3.75; preferably from 1.10 to 3.45. The polydispersity index is obtained by measurement of size exclusion chromatography using a polystyrene calibration.
[0026] Advantageously, the polydiol random copolymer of the invention, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula ( I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), has a number-average molar mass ranging from 10,000 to 400,000 g / mol, preferably 25,000 at 150,000 g / mol, the number-average molar mass being obtained by steric exclusion chromatography using a polystyrene calibration. The method for measuring size exclusion chromatography using a polystyrene calibration is described in the book (Fontanille, M. Gnanou, Y., Chemistry and physico-chemistry of polymers, 2nd ed .; Dunod: 2010; p 546 ). Boronic diester A2 compound In one embodiment of the composition of the invention, the compound A2 comprising two boronic ester functions has the general formula (III): ## STR2 ## in which: R 7 w 1 and w2, identical or different, are integers chosen from 0 and 1, R4, R5, R6 and R7, which may be identical or different, are chosen from the group formed by hydrogen and a hydrocarbon group having from 1 to 24 carbon atoms preferably 4 to 18 carbon atoms, preferably 6 to 14 carbon atoms; L is a divalent linking group and selected from the group consisting of C6-C18 aryl, C7-C24 aralkyl and C2-C24 hydrocarbon chain, preferably C6-C18 aryl. By "hydrocarbon group having 1 to 24 carbon atoms" is meant a linear or branched alkyl or alkenyl group having from 1 to 24 carbon atoms. Preferably, the hydrocarbon group comprises from 4 to 18 carbon atoms, preferably from 6 to 14 carbon atoms. Preferably, the hydrocarbon group is a linear alkyl. By "C2-C24 hydrocarbon chain" is meant a linear or branched alkyl or alkenyl group comprising from 2 to 24 carbon atoms. Preferably, the hydrocarbon chain is a linear alkyl group. Preferably the hydrocarbon chain comprises from 6 to 16 carbon atoms. In one embodiment of the invention, the compound A2 is a compound of the general formula (III) above in which: w1 and w2, which are identical or different, are integers chosen from 0 to 1; R4 and R6 are the same and are hydrogen atoms; R5 and R7 are identical and are a hydrocarbon group, preferably a linear alkyl, having 1 to 24 carbon atoms, preferably 4 to 18 carbon atoms, preferably 6 to 16 carbon atoms; L is a divalent linking moiety and is C 6 -C 18 aryl, preferably phenyl. The boronic diester A2 compound of formula (III) as described above is obtained by a condensation reaction between a boronic acid of general formula (III-a) and diol functions of the compounds of general formula (III-b) and (III-c) according to Reaction Scheme 4 below: ## STR3 ## wherein R 1 is OH (III-c) BBII + OH OH Acetone, H 2 O MgSO 4 R 7 OH (III-b) (III) Scheme 4 with w 1, w 2 L, R 4, R 5, R 6 and R 7, as defined above. In fact, by condensation of the boronic acid functions of the compound (III-a) with diol functions of the compounds of formula (III-b) and of formula (III-c), compounds having two boronic ester functions (compound of formula (III)). This step is carried out according to means well known to those skilled in the art. In the context of the present invention, the compound of general formula (III-a) is dissolved, in the presence of water, in a polar solvent such as acetone. The presence of water makes it possible to displace the chemical equilibria between the boronic acid molecules of formula (III-a) and the boroxin molecules obtained from the boronic acids of formula (III-a). Indeed, it is well known that boronic acids can spontaneously form boroxine molecules at room temperature. However, the presence of boroxin molecules is undesirable in the context of the present invention. The condensation reaction is carried out in the presence of a dehydrating agent such as magnesium sulfate. This agent makes it possible to trap the water molecules initially introduced as well as those released by the condensation between the compound of formula (III-a) and the compound of formula (III-b) and between the compound of formula (III- a) and the compound of formula (III-c). In one embodiment, the compound (III-b) and the compound (III-c) are identical. Those skilled in the art can adapt the amounts of reagents of formula (III-b) and / or (III-c) and of formula (III-a) to obtain the product of formula (III). Boronic ester copolymer compound A2 In another embodiment of the composition of the invention, the compound A2 comprising at least two boronic ester functional groups is a boronic ester random copolymer resulting from the copolymerization of at least one monomer M3 of formula ( IV) as described below with at least one monomer M4 of formula (V) as described below. M3 monomer of formula (IV) The monomer M3 of boronic ester random copolymer A2 has the general formula (IV) wherein: IV) 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 may be identical or different, and are chosen from the group formed by a C6-C18 aryl, a C7-C24 aralkyl and a C2-C24 alkyl, preferably a C6-C18 aryl; X is a function selected from the group consisting of -O-C (O) -, -C (O) -O-, -C (O) -N (H) -, -N (H) -C (O) ) -, -S-, -N (H) -, -N (R'4) - and -O- with R'4 a hydrocarbon chain comprising from 1 to 15 carbon atoms; R9 is selected from the group consisting of -H, -CH3 and -CH2-CH3; preferably -H and -CH3; R10 and R11, which are identical or different, are chosen from the group formed by hydrogen and a hydrocarbon chain containing from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 6 to 12 carbon atoms .
[0027] By "C2-C24 alkyl" is meant a saturated hydrocarbon chain, linear or branched, comprising from 2 to 24 carbon atoms. Preferably, the hydrocarbon chain is linear. Preferably the hydrocarbon chain comprises from 6 to 16 carbon atoms. By "hydrocarbon chain comprising 1 to 15 carbon atoms" is meant a linear or branched alkyl or alkenyl group comprising from 1 to 15 carbon atoms. Preferably, the hydrocarbon chain is a linear alkyl group. Preferably, it comprises from 1 to 8 carbon atoms. By "hydrocarbon chain comprising 1 to 24 carbon atoms" is meant a linear or branched alkyl or alkenyl group comprising from 1 to 24 carbon atoms. Preferably, the hydrocarbon chain is a linear alkyl group. Preferably, it comprises from 4 to 18 carbon atoms, preferably from 6 to 12 carbon atoms. In one embodiment of the invention, the monomer M3 has the general formula (IV) wherein: t is an integer equal to 0 or 1; u is an integer equal to 0 or 1; M and R8 are divalent linking groups and are different, M is C6-C18 aryl, preferably phenyl, R8 is C7-C24 aralkyl, preferably benzyl; X is a group selected from the group consisting of -O-C (O) -, -C (O) -O-, -C (O) -N (H) - and -O-, preferably -C (O) ) -O- or -O-C (O) -; R9 is selected from the group consisting of -H, -CH3, preferably -H; R 10 and R 11 are different, one of R 10 or R 11 is H and the other R 10 or R 11 is a hydrocarbon chain, preferably a linear alkyl group having 1 to 24 carbon atoms, preferably 4 to 18 carbon atoms. carbon atoms, preferably between 6 and 12 carbon atoms. / Synthesis of M3 monomer of formula (IV) In all the schemes set out below, unless otherwise indicated, the variables R10, R11, M, u, t, X, R8, R'4 and R9 have the same definition as in formula (IV) above. The monomers M3 of formula (IV) are obtained in particular from a preparation process comprising at least one step of condensation of a boronic acid of general formula (IV-f) with a diol compound of general formula (IV-g ) according to Reaction Scheme 5 below: ## STR2 ## by condensation of the boronic acid functions of the compound of formula (IV-f) with diol functions of the compounds of formula (IV-g), a boronic ester compound of formula (IV) is obtained. This step is carried out according to methods well known to those skilled in the art. In the context of the present invention, the compound of general formula (IV-f) is dissolved, in the presence of water, in a polar solvent such as acetone. The condensation reaction is carried out in the presence of a dehydrating agent, such as magnesium sulfate.
[0028] The compounds of formula (IV-g) are commercially available from the following suppliers: Sigma-Aldrich® and TCI® The compound of formula (IV-f) is obtained directly from the compound of formula (IV-e) by hydrolysis according to Reaction Scheme 6: R12 R9) CH2 (XM B-OH HO (IV-f) Scheme 6 H20 BM / O-X- (R8) u R9 I-12C (IV-e) with z an integer equal to 0 or 1; R12 is selected from the group consisting of -H, -CH3 and -CH2-CH3; u, X, M, R8 and R9 as defined above.
[0029] The compound of formula (IV-e) is obtained by a condensation reaction of a compound of formula (IV-c) with at least one compound of formula (IV-d) according to the following reaction scheme 7: R12 Y9- ( R8) u R9 H2C 0 / 0 y4 (IV-c) (IV-d) R12 0 BM / X- (1:28) u) / '' R9 (IV-e) H2C Scheme 7 with Z, R12, M, R'4, R9 and R8 as defined above; and in this scheme when: - X represents -O-C (O) -, then Y4 represents an alcohol function -OH or a halogen atom, preferably chlorine or bromine and Y5 is a carboxylic acid function -C ( 0) -OH; X represents -C (O) -O-, then Y4 represents a carboxylic acid function -C (O) -OH and Y5 is an alcohol function -OH or a halogen atom, and preferably chlorine or bromine; X represents -C (O) -N (H) -, then Y4 represents a carboxylic acid function -C (O) -OH or a -C (O) -Hal function, and Y5 is an amine NH2 function; X represents -N (H) -C (O) -, then Y4 represents an amine function NH2 and Y5 is a carboxylic acid function -C (O) -OH or a -C (O) -Hal function; X is -S-, then Y4 is a halogen atom and Y5 is a thiol -SH function or Y4 is a thiol -SH function and Y5 is a halogen atom; X represents -N (H) -, then Y4 is a halogen atom and Y5 is an amine function -NH2 or Y4 is an amine function -NH2 and Y5 is a halogen atom; - X represents -N (R'4) -, then Y4 is a halogen atom and Y5 is an amine function -N (H) (R'4) or Y4 is an amine function -N (H) (R 4) and Y5 is a halogen atom; X is -O-, then Y4 is a halogen atom and Y5 is an alcohol function -OH or Y4 is an alcohol function -OH and Y5 is a halogen atom.
[0030] These esterification, etherification, thioetherification, alkylation or condensation reactions between an amine function and a carboxylic acid function are well known to those skilled in the art. Those skilled in the art can therefore choose, depending on the chemical nature of the Y1 and Y2 groups, the reaction conditions to obtain the compound of formula (IV-e).
[0031] The compounds of formula (IV-d) are commercially available from the suppliers: Sigma-Aldrich® and TCI® The compound of formula (IV-c) is obtained by a condensation reaction between a boronic acid of formula (IV-a) with at least one diol compound of formula (IV-b) according to the following reaction scheme 8: Scheme 8 with M, Y4, z and R12 as defined above, Among the compounds of formula (IV-b), it is preferred that in which R12 is methyl and z = 0. The compounds of formula (IV-a) and (IV-b) are commercially available from the following suppliers: Sigma-Aldrich®, Alfa Aesar® and TCI®. M4 monomer of the general formula (V): The monomer M4 of the boronic ester random copolymer A2 has the general formula (V) H 2 C R 13 (V) wherein R 12 is selected from the group consisting of -H, -CH3 and -CH2-CH3, preferably -H and -CH3; R13 is selected from the group consisting of a C6-C18 aryl, a C6-C18 aryl substituted with a group R'13, -C (O) -O-R'13, -O-R'13 -SR ' And -C (O) -N (H) -R '13 with R' 13 is a C1-C25 alkyl group. By "C1-C25 alkyl group" is meant a linear or branched, saturated hydrocarbon chain comprising from 1 to 25 carbon atoms. Preferably, the hydrocarbon chain is linear. By "C16-C18 aryl group substituted by an R13 group" is meant a compound MgSO4 acetone, H2O HO M 4 OH R12 0 le. (IV-b) (IV-c) (aromatic hydrocarbon R12 comprising from 6 to 18 carbon atoms of which at least one carbon atom of the aromatic ring is substituted by an alkyl group C1-C25 as defined above Among the monomers of formula (V), the monomers corresponding to formula (VA) are among the preferred ones: H2C (VA) in which: R2 is chosen from the group formed by: H, -CH3 and -CH2-CH3 preferably -H and -CH3; R'13 a C1-C25 alkyl group, preferably a linear C1-C25 alkyl, even more preferably a linear C5-C15 alkyl Obtaining the monomer M4: The monomers of formulas (V) and (VA) are well known to a person skilled in the art.They are marketed by Sigma-Aldrich® and TCI® / Synthesis of compound A2 random copolymer boronic ester L '. A person skilled in the art is able to synthesize boronic ester random copolymers using his general knowledge. Merification can be initiated in bulk or in solution in an organic solvent by free radical generating compounds. For example, the boronic ester random copolymers are obtained by the known methods of radical copolymerization, in particular controlled such as the method called controlled radical polymerization controlled by reversible addition-fragmentation chain transfer (in English: Reversible Addition-Fragmentation Chain Transfer (RAFT) ) and the method called Atom Transfer Radical Polymerization (ARTP). Conventional radical polymerization and telomerization can also be employed to prepare the copolymers of the invention (Moad, G .; Solomon, DH, The Chemistry of Radical Polymerization, 2nd ed .; Elsevier Ltd: 2006; p 639; Matyaszewski, K Wiley-Interscience: Hoboken, 2002; p 936) Thus another object of the present invention is a process for the preparation of a boronic ester statistical copolymer, said process comprising at least one step of the invention. polymerization (a) in which at least: i) a first monomer M3 of general formula (IV) is contacted: R10 0 B-M / X-OR8, H2C R11 R9 (IV) in which: 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 may be identical or different, and are chosen from the group formed by a C 6 -C 18 aryl, a C 7 -C 24 aralkyl and a C 2 -C 24 alkyl, preferably a C 6 -C 6 aryl; C18 X is a group selected from the group consisting of -O-C (O) -, -C (O) -O-, -C (O) -N (H) -, -N (H) -C (O) ) -, -S-, -N (H) -, -N (R'4) - and -O- with R'4 a hydrocarbon chain comprising from 1 to 15 carbon atoms; R9 is selected from the group consisting of -H, -CH3 and -CH2-CH3; preferably -H and -CH3; R10 and R11, which are identical or different, are chosen from the group formed by hydrogen and a hydrocarbon chain containing from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 6 to 12 carbon atoms ; ii) at least one second monomer M4 of general formula (V): wherein R12 is selected from the group consisting of -H, -CH3 and -CH2-CH3, preferably -H-CH3; R13 is selected from the group consisting of a C6-C18 aryl, a C6-C18 aryl substituted with a group R'13, -C (O) -O-R'13, -S-R'13 and -C (O) -N (H) -R'13 with R'13 a C1-C25 alkyl group. iii) at least one source of free radicals.
[0032] In one embodiment, the method may further comprise iv) at least one chain transfer agent. The preferences and definitions described for general formulas (IV) and (V) also apply to the process.
[0033] Radical sources and transfer agents are those which have been described for the synthesis of polydiol random copolymers. The preferences described for radical sources and transfer agents also apply to this process. Properties of the New Compounds A2 Boron Ester Statistical Copolymers Advantageously, the chain formed by the linking of the groups Rio, M, (R 8) 'with u, an integer equal to 0 or 1, and X of the monomer M 3 of general formula ( IV) has a total number of carbon atoms ranging from 8 to 38, preferably ranging from 10 to 26 carbon atoms.
[0034] Advantageously, the side chains of the boronic ester random copolymer have an average length greater than 8 carbon atoms, preferably ranging from 11 to 16 carbon atoms. This chain length makes it possible to solubilize the boronic ester random copolymer in a hydrophobic medium. By "average side chain length" is meant the average side chain length of each monomer constituting the copolymer.
[0035] The person skilled in the art knows how to obtain this average length by appropriately selecting the types and the ratio of monomers constituting the boronic ester statistical copolymer. Advantageously, the boronic ester statistical copolymer has a molar percentage of monomer of formula (IV) ranging from 0.25 to 20%, preferably from 1 to 10%. Advantageously, the boronic ester statistical copolymer has a molar percentage of monomer of formula (IV) ranging from 0.25 to 20%, preferably from 1 to 10% and a molar percentage of monomer of formula (V) ranging from 80 to 99 , 75%, preferably 90 to 99%. Advantageously, the boronic ester statistical copolymer has a number-average degree of polymerization ranging from 50 to 1500, preferably from 80 to 800. Advantageously, the boronic ester statistical copolymer has a polydispersity index (Ip) ranging from 1.04 to 3 , 54; preferably ranging from 1.10 to 3.10. These values are obtained by size exclusion chromatography using tetrahydrofuran as eluent and a polystyrene calibration. Advantageously, the boronic ester statistical copolymer has a number-average molecular weight ranging from 10,000 to 200,000 g / mol, preferably from 25,000 to 100,000 g / mol.
[0036] These values are obtained by size exclusion chromatography using tetrahydrofuran as eluent and a polystyrene calibration. Characteristics of the New Compositions of the Invention The novel compositions of the invention have the advantage of being thermoreversibly crosslinkable. Polydiols random copolymers Al, in particular those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one a monomer of formula (II-A1) and at least one monomer of formula (II-A2), and the compounds A2 as defined above have the advantage of being associative and of exchanging chemical bonds in a thermoreversible manner , in particular in a hydrophobic medium, in particular an apolar hydrophobic medium Under certain conditions, the polydiol random copolymers Al, in particular those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A ) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and the compounds A2 as defined above can be crosslinked.
[0037] Polydiols random copolymers Al, in particular those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one a monomer of formula (II-A1) and at least one monomer of formula (II-A2), and the compounds A2 also have the advantage of being exchangeable.
[0038] The term "associative" is understood to mean that covalent boronic ester-type chemical bonds are established between the polydiol random copolymers Al, in particular those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and the compounds A2 comprising at least minus two boronic ester functions. Figure 4 illustrates associative polymers. According to the functionality of the Al polydiols, especially those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least minus one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and compounds A2 and according to the composition of the mixtures, the formation of covalent bonds between polydiols A1 and compounds A2 may bring about or no to the formation of a three-dimensional polymeric network. By "chemical bond" is meant a covalent chemical bond of the boronic ester type. By "exchangeable" is meant that the compounds are capable of exchanging chemical bonds between them without the total number of chemical functions being changed. The boronic ester bonds of the compounds A2 as well as the boronic ester bonds formed by the combination of the polydiols Al random copolymers, especially those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A ) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and compounds A2 can be exchanged with diol functions present in the composition to form new boronic esters and new diol functions without the total number of boronic ester functions and diol functions being affected. The chemical exchange reaction (transesterification) is illustrated in the following reaction scheme 9: ## STR2 ## with R a chemical group of the compound A2, the hatched round symbolizes the remainder of the chemical structure of the compound A2, the grid rectangle symbolizes the remainder of the chemical structure of the polydiol Al random polymer, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula ( I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2). The boronic ester bonds of the compounds A2 as well as the boronic ester bonds formed by the combination of the polydiols Al random copolymers, especially those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A ) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and compounds A2 can also be exchanged to form new boronic esters without affecting the total number of boronic ester functions. This other process of exchange of chemical bonds is carried out by metathesis reaction of the boronic ester functions; this process is illustrated in Figure 9.
[0039] The polydiol random copolymer A1-1, which was associated with the polymer A2-1, exchanged a boronic ester bond with the boronic ester random copolymer A2-2. The polydiol random copolymer A1-2, which was in association with the A2-2 polymer, exchanged a boronic ester bond with the boronic ester random copolymer A2-1; the total number of boronic ester bond in the composition being unchanged and is 4. The A1-1 copolymer is then combined with both the A2-1 polymer and the A2-2 copolymer. The copolymer A1-2 is then combined with both the copolymer A2-1 and with the copolymer A2-2. Another chemical link exchange process is illustrated in FIG. 9, in which it can be observed that the polydiol random copolymer A1-1, which was associated with the A2-1 polymer, exchanged two boronic ester bonds with the boronic ester statistical copolymer. A2-2. The polydiol random copolymer Al-2, which was in association with the A2-2 polymer, exchanged two boronic ester bonds with the boronic ester random copolymer A2-1; the total number of boronic ester bond in the composition being unchanged and is equal to 4. The A1-1 copolymer is then combined with the A2-2 polymer. The Al-2 copolymer is then with the A2-1 polymer. The A2-1 copolymer was exchanged with the A2-2 polymer. By "crosslinked" is meant a copolymer in the form of a network obtained by the establishment of bridges between the macromolecular chains of the copolymer. These interconnected chains are for the most part distributed in the three dimensions of space. A crosslinked copolymer forms a three-dimensional network. In practice, the formation of a copolymer network is ensured by a solubility test. It can be ensured that a network of copolymers has been formed by placing the copolymer network in a known solvent to dissolve the uncrosslinked copolymers of the same chemical nature. If the copolymer swells instead of dissolving, the person skilled in the art knows that a network has been formed. Figure 3 illustrates this solubility test. By "crosslinkable" is meant a copolymer capable of being crosslinked. By "reversibly crosslinked" is meant a crosslinked copolymer whose bridges are formed by a reversible chemical reaction. The reversible chemical reaction can move in one direction or another, resulting in a change in structure of the polymer network. The copolymer can pass from an uncrosslinked initial state to a crosslinked state (three-dimensional network of copolymers) and from a crosslinked state to an uncrosslinked initial state. In the context of the present invention, the bridges that form between the copolymer chains are labile. These bridges can form or exchange through a chemical reaction that is reversible. In the context of the present invention, the reversible chemical reaction is a transesterification reaction between diol functions of a random copolymer (Al copolymer, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one a monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2)) and ester functions boronic ester of the compound A2 or a metathesis reaction between the boronic ester functions forming the bridges between the Al copolymers, in particular those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II- A) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and compounds A2. The bridges formed are boronic ester type bonds. These boronic ester bonds are covalent and labile because of the reversibility of the transesterification reaction. By "thermoreversible crosslinked" is meant a copolymer crosslinked by a reversible reaction whose displacement in one direction or the other direction is controlled by the temperature. The thermoreversible crosslinking mechanism of the composition of the invention is shown schematically in FIG. 4. Unexpectedly, the Applicant has observed that at low temperature, the polydiol Al copolymer, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II) -A2) (symbolized by the copolymer bearing functions A in FIG. 4), is not or only slightly crosslinked by the boronic ester compounds A2 (symbolized by the compound carrying functions B in FIG. 4). As the temperature increases, the diol functions of the copolymer react with the boronic ester functions of compound A2 by a transesterification reaction. Polydiols random copolymers Al, in particular those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one a monomer of formula (II-A1) and at least one monomer of formula (II-A2), and the compounds A2 comprising at least two boronic ester functions then bind together and can be exchanged. According to the functionality of the Al polydiols, especially those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least minus one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and compounds A2 and according to the composition of the mixtures, a gel can be formed in the medium, especially when the medium is nonpolar . When the temperature decreases again, the boronic ester bonds between the polydiols random copolymers Al, especially those resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and the A2 compounds are broken, and if necessary, the composition loses its gelled character.
[0040] The amount of boronic ester bonds (or boronic ester bond) that can be established between the polydiols random copolymers Al and the compounds A2 is adjusted by those skilled in the art by means of an appropriate selection of the polydiol Al random copolymer, in particular that resulting of the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and compound A2 and the composition of the mixture. In addition, a person skilled in the art knows how to select the structure of the compound A2 as a function of the structure of the random copolymer Al, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula ( II-A) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2). Preferably, when in the random copolymer Al, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I ) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), comprising at least one monomer M1 in which y = 1, then the compound A2 of general formula (III) or the copolymer A2 comprising at least one monomer M3 of formula (IV) will preferably be chosen with w1 = 1, w2 = 1 and t = 1, respectively.
[0041] Advantageously, the random copolymer content A1, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2) in the composition ranges from 0.25% to 20% by weight relative to the total weight of the final composition, preferably from 1 to 10% by weight relative to the total weight of the final composition. Advantageously, the content of compound A2 in the composition ranges from 0.25% to 20% by weight relative to the total weight of the final composition, preferably preferably from 0.5% to 10% by weight relative to the total weight of the composition. the final composition. Preferably, the mass ratio between the polydiol Al statistical compound, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and the compound A2 (Al / A2 ratio) in the composition ranges from 0.001 to 100, preferably from 0.05 to 20, even more preferably 0.1 to 10, more preferably 0.2 to 5.
[0042] In one embodiment of the invention, the sum of the masses of the random copolymer Al, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and of compound A2 is from 0.5 to 20% with respect to the total mass of the lubricating composition and the lubricating oil mass ranges from 80% to 99.5% relative to the total mass of the lubricating composition. In one embodiment, the composition of the invention may further comprise a functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, antioxidants, viscosity index improving polymers. , pour point improvers, defoamers, thickeners, anticorrosive additives, dispersants, friction modifiers and mixtures thereof. o Functional Additives The functional additive (s) added to the composition of the invention are chosen according to the end use of the lubricant composition. These additives can be introduced in two different ways: either each additive is added separately and sequentially in the composition, or all the additives are added simultaneously in the composition, the additives are in this case generally available in the form of a package, called package of additives. The functional additive or functional additive mixtures, when present, represent from 0.1 to 10% by weight relative to the total weight of the composition. / Detergents: These additives reduce the formation of deposits on the surface of metal parts by dissolving secondary oxidation and combustion products. The detergents that can be used in the lubricant compositions 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 typically anionic compounds having a long lipophilic hydrocarbon chain and a hydrophilic head. The associated cation is typically a metal cation of an alkali or alkaline earth metal. The detergents are preferably chosen from alkali metal or alkaline earth metal salts of carboxylic acids, sulphonates, salicylates and naphthenates, as well as the salts of phenates. The alkali and alkaline earth metals are preferably calcium, magnesium, sodium or barium. These metal salts may contain the metal in an approximately stoichiometric amount or in excess (in an amount greater than the stoichiometric amount). In the latter case, we are dealing with so-called overbased detergents. The excess metal providing the overbased detergent character is in the form of oil insoluble metal salts, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate. / Anti-wear additives and extreme pressure additives: These additives protect friction surfaces by forming a protective film adsorbed on these surfaces. There is a wide variety of anti-wear and extreme pressure additives. By way of illustration, mention may be made of phosphosulfur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or ZnDTPs, amine phosphates and polysulfides, especially sulfur-containing olefins and metal dithiocarbamates. Antioxidants: These additives retard the degradation of the composition. The degradation of the composition may result in the formation of deposits, the presence of sludge, or an increase in the viscosity of the composition. Antioxidants act as free radical inhibitors or destroyers of hydroperoxides. Among the commonly used antioxidants are antioxidants of phenolic or amine type. / Anticorrosions: These additives cover the surface of a film that prevents access of oxygen to the surface of the metal. They can sometimes neutralize acids or certain chemicals to prevent metal corrosion. Illustrative examples include dimercaptothiadiazole (DMTD), benzotriazoles, phosphites (free sulfur capture). / Polymers improving the viscosity index: These additives make it possible to guarantee a good cold behavior and a minimum viscosity at high temperature of the composition. By way of illustration, mention may be made, for example, of polymeric esters, copolymer olefins (OCP), homopolymers or copolymers of styrene, butadiene or isoprene and polymethacrylates (PMA). Pour-point improvers: These additives improve the cold behavior of the compositions by slowing the formation of paraffin crystals. They are, for example, alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes and alkylated polystyrenes. / Antifoams: These additives have the effect of countering the effect of detergents. By way of illustration, mention may be made of polymethylsiloxanes and polyacrylates. Thickeners: Thickeners are additives used mainly for industrial lubrication and make it possible to formulate lubricants of higher viscosity than engine lubricating compositions. By way of illustration, mention may be made of polysiobutenes having a molar mass by weight of 10,000 to 100,000 g / mol. Dispersants These additives ensure the suspension and evacuation of insoluble solid contaminants constituted by the secondary oxidation products which are formed during the use of the composition. By way of illustration, mention may be made, for example, of succinimides, PIBs (polyisobutene) succinimides and Mannich bases / friction modifiers; These additives improve the coefficient of friction of the composition. By way of illustration, mention may be made of molybdenum dithiocarbamate, amines having at least one hydrocarbon chain of at least 16 carbon atoms, esters of fatty acids and polyols such as esters of fatty acids and of glycerol, in particular glycerol monooleate. The novel compositions of the invention are prepared by means well known to those skilled in the art. For example, it suffices for those skilled in the art in particular to: - take a desired quantity of a solution comprising the polydiol random copolymer Al as defined above, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2) ); - Take a desired amount of a solution comprising the compound A2 as defined above; - Mixing the two solutions taken in a lubricating base oil to obtain the composition of the invention. Those skilled in the art can also adjust the various parameters of the composition of the invention to obtain a crosslinkable composition. For example, a person skilled in the art knows how to adjust in particular: the molar percentage of monomer M1 bearing diol functions in the polydiol Al random copolymer, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one a monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2); the molar percentage of M 3 monomer bearing boronic ester functions in the boronic ester random copolymer A2, the average length of the side chains of the polydiol Al random copolymer, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2); the average length of the side chains of the boronic ester random copolymer A2, the length of the monomer M3 of the boronic ester random copolymer A2, the length of the boronic diester compound A2, the average degree of polymerization of the polydiol Al random copolymers, in particular the resulting one. of the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and random copolymers boronic esters A2, - the mass percentage of the polydiols random copolymer Al, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), mass of the diester compound Another object of the present invention is the use of the composition as defined above for lubricating a mechanical part. The compositions of the invention are useful for lubricating the surfaces of parts that are conventionally found in an engine such as the pistons, segments, shirts system. Thus another object of the present invention is a composition for lubricating at least one engine comprising a composition resulting from mixing: 97% to 99.9% by weight of a lubricating oil, and 0.1% to 3% by weight at least one random copolymer Al, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and at least one compound A2 comprising at least two boronic ester functions as defined above; the composition having a kinematic viscosity at 100 ° C measured according to ASTM D445 ranging from 3.8 to 26.1 cSt.
[0043] In a composition for lubricating at least one engine, at least one random copolymer Al, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or from at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and at least one compound A2 comprising at least two boronic ester functions as defined above can associate and exchange in a thermoreversible way; but they do not form three-dimensional networks. They are not crosslinked. In one embodiment, the composition for lubricating at least one engine further comprises at least one functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, additional antioxidants, anti-corrosion additives, viscosity index improvers, pour point improvers, defoamers, thickeners, dispersants, friction modifiers and mixtures thereof.
[0044] In one embodiment of the invention, the composition for lubricating at least one engine consists essentially of a composition resulting from the mixture of: 97% to 99.9% by weight of a lubricating oil, and 0.1% to 3% % by weight of at least one random copolymer Al, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and at least one compound A2 comprising at least two boronic ester functions as defined above; the composition having a kinematic viscosity at 100 ° C measured according to ASTM D445 ranging from 3.8 to 26.1 cSt. In one embodiment of the invention, the composition for lubricating at least one engine consists essentially of a composition resulting from mixing: 82% to 99.8% by weight of a lubricating oil, and 0.1% to 3%. % by weight of at least one random copolymer Al, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and at least one compound A2 comprising at least two boronic ester functions as defined above; 0.1% to 15% by weight of at least one functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, additional antioxidants, anti-corrosion additives, index-improving polymers viscosity, pour point improvers, defoamers, thickeners, dispersants, friction modifiers and mixtures thereof; the composition having a kinematic viscosity at 100 ° C measured according to ASTM D445 ranging from 3.8 to 26.1 cSt. The definitions and preferences relating to lubricating oils, Al random copolymers, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and compounds A2 also apply to compositions for lubricating at least one motor. Another object of the present invention is a composition for lubricating at least one transmission, such as manual or automatic gearboxes.
[0045] In a composition for lubricating at least one transmission, at least one random copolymer Al, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or from at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and at least compound A2 comprising at least two boronic ester functions as defined above can associate and exchange in a thermoreversible way; but they do not form three-dimensional networks. They are not crosslinked. Thus another object of the present invention is a composition for lubricating at least one transmission comprising a composition resulting from the mixing of: 85% to 99.5% by weight of a lubricating oil, and 0.5% to 15% by weight at least one random copolymer Al, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and at least compound A2 comprising at least two boronic ester functions as defined above; the composition having a kinematic viscosity at 100 ° C measured according to ASTM D445 ranging from 4.1 to 41 cSt. In one embodiment, the composition for lubricating at least one transmission further comprises at least one functional additive selected from the group consisting of detergents, antiwear additives, extreme pressure additives, additional antioxidants, anticorrosion additives, viscosity index improver polymers, pour point improvers, defoamers, thickeners, dispersants, friction modifiers and mixtures thereof.
[0046] In one embodiment of the invention, the composition for lubricating at least one transmission consists essentially of a composition resulting from the mixing of: 95% to 99.5% by weight of a lubricating oil, and 0.5% to 15% by weight. % by weight of at least one random copolymer Al, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and at least compound A2 comprising at least two boronic ester functions as defined above; the composition having a kinematic viscosity at 100 ° C measured according to ASTM D445 ranging from 4.1 to 41 cSt. In one embodiment of the invention, the lubricating composition for lubricating at least one transmission consists essentially of a composition resulting from the mixing of: - 70% to 99.4% by weight of a lubricating oil, and 0.5 % to 15% by weight of at least one random copolymer Al, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and at least one compound A2 comprising at least two boronic ester functions as defined above; From 0.1% to 15% by weight of at least one functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, additional antioxidants, anti-corrosion additives, polymers improving the viscosity number, pour point impreners, defoamers, thickeners, dispersants, friction modifiers and mixtures thereof; the composition having a kinematic viscosity at 100 ° C measured according to ASTM D445 ranging from 4.1 to 41 cSt. The definitions and preferences relating to lubricating oils, Al random copolymers, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and compounds A2 also apply to the compositions for lubricating at least one transmission.
[0047] The compositions of the invention can be used for engines or transmissions of light vehicles, trucks but also ships. Another object of the present invention is a method of lubricating at least one mechanical part, in particular at least one motor or at least one transmission, said method comprising a step in which said mechanical part is brought into contact with at least one composition as defined above. The definitions and preferences relating to lubricating oils, Al random copolymers, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), and compounds A2 also apply to the method of lubricating at least one mechanical part. Another subject of the present invention relates to a parent composition resulting from the mixture of at least at least one random copolymer Al as defined above, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) or of at least one monomer of formula (I) with at least one monomer of formula (II-A1) and at least one monomer of formula (II-A2), at least A2 compound comprising at least two boronic ester functions, at least one functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, antioxidants, viscosity index improving polymers, pour point, defoamers, thickeners, dispersants, friction modifiers and their mixtures. By "mother composition" is meant a composition which a person skilled in the art can make daughter solutions by removing a certain amount of mother solution supplemented by the addition of a necessary quantity of diluent (solvent or other) to obtain a desired concentration. A daughter composition is thus obtained by dilution of a parent composition. In one embodiment, the lubricating compositions of the invention can be obtained by diluting in a lubricating oil, especially a Group I, Group II, Group III, Group IV, Group V API classification base oil. or a mixture thereof, the parent composition as defined above. EXAMPLES The following examples illustrate the invention without limiting it. 1 Synthesis of Al Statistical Copolymers of the Invention Bearing Diol Function o 1.1: From a Monomer Bearing a Protected Diol Function in the Ketal Form In one embodiment, the random Al copolymer of the invention is obtained according to the following reaction scheme: OH of the diol OH function 2. Reaction with the MAC 0 OH HO 3. Polyol Protected Copolymers 4. Deprotection Poly (alkyl methacrylate-co-alkyldiol methacrylate) copolymers Scheme 10 1.1.1 Synthesis of the monomer M1 bearing a protected diol function in the form of a ketal The synthesis of a methacrylate monomer carrying a protected diol function in the ketal form is carried out in two steps (steps 1 and 2 of the reaction scheme 10) according to the protocol below: 1 'step: 42.1 g (314 mmol) 1,2,6-hexane triol (1,2,6-HexTri) are introduced into a flask of 1L. 5.88 g of molecular sieves (4 ° A) are added followed by 570 mL of acetone. 5.01 g (26.3 mmol) of para-toluenesulfonic acid (pTSA) are then slowly added. The reaction medium is stirred for 24 hours at room temperature. 4.48 g (53.3 mmol) of NaHCO 3 are then added. The reaction medium is stirred for 3 hours at room temperature before being filtered. The filtrate is then concentrated under vacuum using a rotary evaporator until a suspension of white crystals is obtained. 500 ml of water are then added to this suspension. The solution thus obtained is extracted with 4 x 300 ml of dichloromethane. The organic phases are combined and dried over MgSO4. The solvent is then completely evaporated under vacuum at 25 ° C. by means of a rotary evaporator. 2. The product thus obtained is then introduced into an IL flask surmounted by a dropping funnel. The glassware used was first dried overnight in a thermostatically controlled oven at 100 ° C. 500 ml of anhydrous dichloromethane are then introduced into the flask followed by 36.8 g (364 mmol) of triethylamine. A solution of 39.0 g (373 mmol) of methacryloyl chloride (MAC) in 50 mL of anhydrous dichloromethane is introduced into the dropping funnel. The flask is then placed in an ice bath to lower the temperature of the reaction medium to around 0 ° C. The methacryloyl chloride solution is then added dropwise with vigorous stirring. Once the methacryloyl chloride addition is complete, the reaction medium is left stirring for 1 hour at 0 ° C. and then 23 hours at room temperature. The reaction medium is then transferred into a 3 L Erlenmeyer flask and 1 L of dichloromethane is added. The organic phase is then successively washed with 4 × 300 ml of water, 6 × 300 ml of a 0.5 M aqueous hydrochloric acid solution, 6 × 300 ml of a saturated aqueous solution of NaHCO 3 and again 4 x 300 mL of water. The organic phase is dried over MgSO4, filtered and then concentrated under vacuum using a rotary evaporator to give 64.9 g (85.3% yield) of protected diol monomer in the form of a clear yellow liquid which the characteristics are the following: IF1 NMR (400 MHz, CDCl3) δ: 6.02 (singlet, 1H), 5.47 (singlet, 1H), 4.08 (triplet, J = 6.8 Hz, 2H), 4.05-3.98 (multiplet, 1H), 3.96 (doublet of doublets, J = 6 Hz and J = 7.6 Hz, 1H), 3.43 (doublet of doublet, J = 7.2 Hz and J = 7.2 Hz, 1H), 1.86 (doublet of doublets, J = 1.2 Hz and J = 1.6 Hz, 3H), 1.69-1.33 (multiplet, 6H), 1 , 32 (singlet, 3H), 1.27 (singlet, 3H). 1.1.2 Synthesis of Methacrylate Copolymers According to the Invention with Diol Functions The synthesis of the methacrylate copolymers carrying diol functions according to the invention is carried out in two steps (steps 3 and 4 of the reaction scheme 10): Copolymerization of two methacrylate monomers of alkyl with a methacrylate monomer bearing a protected diol function in the form of ketal Deprotection of the copolymer. More specifically, the synthesis of the copolymer is carried out according to the following protocol: 10.5 g (31.0 mmol) of stearyl methacrylate (StMA), 4.76 g (18.7 mmol) of lauryl methacrylate (LMA) , 3.07 g (12.7 mmol) of methacrylate bearing a protected diol function in the form of a ketal obtained according to the protocol described in paragraph 1.1.1, 68.9 mg (0.253 mmol) of cumyl dithiobenzoate and 19, 5 ml of anisole are introduced into Schlenk tube of 100 ml. The reaction medium is stirred and 8.31 mg (0.0506 mmol) of azobisisobutyronitrile (AIBN) dissolved in 85 μl of anisole are introduced into the Schlenk tube. The reaction medium is then degassed for 30 minutes by bubbling argon before being heated to 65 ° C. for a duration of 16 hours. The Schlenk tube is placed in an ice bath to stop the polymerization, then the polymer is isolated by precipitation in methanol, filtration and drying under vacuum at 30 ° C overnight.
[0048] A copolymer having a number average molar mass (M.) of 41,000 g / mol, a polydispersity index (Ip) of 1.22 and a number-average degree of polymerization (DP) of 16 are thus obtained. values are respectively obtained by size exclusion chromatography using tetrahydrofuran as eluent and polystyrene calibration and by monitoring the conversion to monomers during the copolymerization.
[0049] The deprotection of the copolymer is carried out according to the following protocol: 7.02 g of copolymer containing about 20% protected diol function obtained previously are introduced into a 500 ml Erlenmeyer flask. 180 ml of dioxane are added and the reaction mixture is stirred at 30 ° C. 3 ml of a 1M aqueous solution of hydrochloric acid and then 2.5 ml of an aqueous solution of 35% hydrochloric acid are added dropwise. The reaction medium then becomes slightly opaque and 20 ml of THF are introduced to make the medium completely homogeneous and transparent. The reaction medium is then left stirring at 40 ° C. for 48 hours. The copolymer is recovered by precipitation in methanol, filtration and drying under vacuum at 30 ° C overnight. A poly (alkyl methacrylate-co-alkyldiol methacrylate) copolymer containing about 20 mol% of diol M1 monomer units and having an average length of pendant alkyl chains of 13.8 carbon atoms is obtained. 1.2: From a monomer bearing a protected diol function in the form of a boronic ester In another embodiment, the random copolymer Al of the invention is obtained according to the following reaction scheme 11: Polymeriion Protected Copolymers 4. Deproleetion OH HO OH 1. Protection of the Diol OH Function 2. R: H: with LU "CI 0 0 0 Copolymers Poly (alkyl methacrylate-co-alkyldiol methacrylate) Scheme 11 25 1.2.1 Synthesis of the monomer M1 bearing a protected diol function in the form of a boronic ester The synthesis of a methacrylate monomer carrying a protected diol function in the form of an ester is carried out in two steps (steps 1 and 2 of scheme 11 ) according to the following protocol: the first step: phenylboronic acid (PBA) 6.01 g (49.3 mmol) and 300 mL of acetone are introduced into a 500 mL beaker, followed by 1.5 The reaction medium is stirred and 6.07 g (45.2 mmol) of 1,2,6-hexanetriol are slowly added, an excess of magnesium sulphate is added to the reaction medium in order to trap the water initially introduced as well as the water released by the condensation between phenylboronic acid and 1,2,6-hexanetriol. The reaction mixture is left stirring at room temperature for 30 minutes before being filtered and then concentrated under vacuum using a rotavapor. Stage 2: The light yellow liquid thus obtained in the preceding stage is then introduced into an IL flask surmounted by a dropping funnel. The glassware used having been previously pre-dried overnight in a thermostatically controlled oven at 100 ° C. 90 ml of anhydrous dichloromethane are then introduced into the flask followed by 6.92 g (68.4 mmol) of triethylamine. A solution of 5.82 g (55.7 mmol) of methacryloyl chloride (MAC) in 10 mL of anhydrous dichloromethane is introduced into the dropping funnel. The flask is then placed in an ice bath to lower the temperature of the reaction medium to around 0 ° C. The methacryloyl chloride solution is then added dropwise with vigorous stirring. Once the methacryloyl chloride addition is complete, the reaction mixture is left stirring for 1 hour at 0 ° C. and then 17 hours at room temperature. The reaction medium is then transferred to a 500 ml Erlenmeyer flask and 300 ml of dichloromethane are added. The organic phase is then successively washed with 4 × 100 ml of water, 4 × 100 ml of a 0.1 M aqueous hydrochloric acid solution, 4 × 100 ml of a saturated aqueous solution of NaHCO 3 and again 4 x 100 mL of water. The organic phase is dried over MgSO 4, filtered and then concentrated under vacuum using a rotary evaporator to give 11.6 g (89% yield) of protected diol monomer in the form of a light yellow liquid which the characteristics are the following: IF1 NMR (400 MHz, CDCl3) δ: 7.81 (doublet of doublets, J = 4 Hz and J = 8 Hz, 2H), 7.48 (triplet of triplets, J = 1.2 Hz and J = 7.2 Hz, 1H), 7.38 (triplet triplet, J = 1.2 Hz and J = 6.8 Hz, 1H), 6.10 (singlet, 1H), 5.55 (singlet, 1H), 4.63-4.53 (multiplet, 1H), 4.44 (doublet of doublets, J = 7.6 Hz and J = 8.8 Hz, 1H), 4.18 (triplet, J = 6.8 Hz, 2H), 3.95 (doublet of doublets, J = 6.8 Hz and J = 8.8 Hz, 1H), 1.94 (doublet of doublets, J = 1.2 Hz and J = 1.6 Hz, 3H), 1.81-1.47 (multiplet, 6H) 1.2.2 Synthesis of Methacrylate Copolymers According to the Invention Bearing Diol Functions The Synthesis of Methacrylate Copolymers Bearing Diol Functions According to the Invention is done in two steps (steps 3 and 4 of Scheme 11): Copolymerization of two alkyl methacrylate monomers with a methacrylate monomer bearing a protected diol function as a boronic ester; Deprotection of the copolymer. The following procedures describe the synthesis of a poly (alkyl methacrylate-co-alkyldiol methacrylate) copolymer containing about 10 mol%. of monomeric diol units, and having an average length of pendant alkyl chains of 13.8 carbon atoms.
[0050] The synthesis of the polymer is carried out according to the following protocol: 13.5 g (40 mmol) of stearyl methacrylate (StMA), 12 g (47.2 mmol) of lauryl methacrylate (LMA), 3.12 g (10 , 8 mmol) of methacrylate bearing a protected diol function in the boronic ester form, 92.1 mg (0.416 mmol) of cumyl dithiobenzoate and 34 ml of anisole are introduced into a 100 ml Schlenk tube. The reaction medium is stirred and 13.7 mg (0.0833 mmol) of azobisisobutyronitrile (AIBN) in solution in 135 μl of anisole are introduced into the Schlenk tube. The reaction medium is then degassed for 30 minutes by bubbling argon before being heated to 65 ° C. for a period of 24 hours. The Schlenk tube is placed in an ice bath to stop the polymerization and 30 mL of tetrahydrofuran (THF) is then added to the reaction medium. The polymer is isolated by precipitation in cold methanol, filtration and drying under vacuum at 30 ° C overnight. A copolymer having a number average molecular weight (M.) of 70,400 g / mol, a polydispersity index (Ip) of 3,11 and a number average polymerization degree (DP) of 228 are thus obtained. These values are respectively obtained by steric exclusion chromatography using tetrahydrofuran as eluent and polystyrene calibration and by monitoring the conversion to monomers during the copolymerization. The deprotection of the copolymer is carried out according to the following protocol: 19 g of copolymer obtained in the preceding step and containing about 10% of protected diol function are introduced into an Erlenmeyer flask of L. 1 250 ml of dichloromethane and 30 ml of an aqueous solution of hydrochloric acid are added. The reaction medium is stirred for 24 hours at room temperature before being poured dropwise into 1L of aqueous sodium hydroxide solution (pH = 10) and then stirred again for 24 hours at room temperature. Throughout this stirring period, the reaction medium is composed of two phases. The organic phase is recovered using a separating funnel and the polymer is precipitated in cold methanol. The polymer thus obtained is redissolved in 100 ml of dichloromethane in order to be precipitated again in cold methanol. The polymer is recovered and dried under vacuum at 30 ° C overnight.
[0051] A poly (alkyl methacrylate-co-alkyldiol methacrylate) copolymer containing about 10 mol% of monomer diol units and having an average length of pendant alkyl chains of 13.8 carbon atoms is obtained. 2. Synthesis of the compounds A2 of the invention o 2.1: Synthesis of a boronic diester as crosslinking agent The synthesis of a compound A2 according to the invention is carried out according to the following protocol and according to the reaction scheme 12: HO, OH 0.8.0 1.Acetone, H2O HO 'OH 2.MgSO4, B, O, OH Diagram 12 1,4-Benzenediboronic acid (1,4-BDBA) (1.5 g; 9.05 mmol) is introduced into a 500 ml beaker, followed by 300 ml of acetone. The reaction medium is stirred and 0.300 g (16.7 mmol) of water are introduced dropwise. The reaction medium then becomes transparent and homogeneous and 1,2-dodecanediol (4.02 g, 19.9 mmol) is slowly added. After complete dissolution of the latter, an excess of magnesium sulphate is added in order to trap the water initially introduced as well as the water released by the condensation between 1,4-BDBA and 1,2-dodecanediol. After stirring for 15 minutes, the reaction medium is filtered. The solvent is then removed from the filtrate using a rotary evaporator to give 4.41 g of boronic diester and 1,2-dodecanediol (98% yield) as a white solid. The characteristics are as follows: IF1 NMR (400 MHz, CDCl3) Boronic diester: 8: 7.82 (singlet, 2H), 4.63-4.51 (multiplet, 2H), 4.42 (doublet of doublets, J = 8 Hz and J = 8.8 Hz, 2H), 3.95 (doublet of doublets, J = 7.2 Hz and J = 8.8 Hz, 2H), 1.81-1.31 (multiplet, 36H 0.88 (triplet, J = 7.2 Hz, 6H); 1,2-dodecanediol: 8: 3.85-3.25 (multiplet, about 2.17H), 1.81-1.31 (multiplet, about 13.02H), 0.88 (triplet, J = 7, 2 Hz, about 2.17H) o 2.2: Synthesis of the poly (alkyl methacylate-co-monomer boronic ester) copolymer 2.2.1 Synthesis of the boronic acid monomer The boronic ester monomer of the invention is synthesized according to the following reaction scheme 13: The monomer is obtained according to the two-step protocol: The first step is to synthesize a boronic acid and the second step is to obtain a boronic ester monomer. Step step: The 4-carboxyphenylboronic acid (CPBA) (5.01 g, 30.2 mmol) is introduced into a 1L beaker followed by 350 mL of acetone and the reaction mixture is stirred 7.90 mL (439 mmol) of water are added dropwise until completely dissolved in 4-carboxyphenylboronic acid. The reaction medium is then transparent and homogeneous. The 1,2-propanediol (2.78 g, 36.6 mmol) is then slowly added, followed by an excess of magnesium sulfate to trap the initially introduced water as well as the water released by the condensation between the CPBA and 1,2 propanediol. The reaction medium is stirred for 1 hour at 25 ° C. before being filtered. The solvent is then removed from the filtrate by means of a rotary evaporator. The product thus obtained and 85 ml of DMSO are introduced into a 250 ml flask. The reaction medium is stirred and then after complete homogenization of the reaction medium, 8.33 g (60.3 mmol) of K 2 CO 3 are added. 4- (Chloromethyl) styrene (3.34 g, 21.9 mmol) is then slowly introduced into the flask. The reaction medium is then left stirring at 50 ° C. for 16 hours. The reaction medium is transferred to a 2 L Erlenmeyer flask, then 900 ml of water are added. The aqueous phase is extracted with 8 x 150 mL of ethyl acetate. The organic phases are combined and then extracted with 3 x 250 mL of water. The organic phase is dried over MgSO4 and filtered. The solvent was removed from the filtrate by rotary evaporator to give the boronic acid monomer (5.70 g, 92.2% yield) as a white powder, which had the following characteristics: NMR (400 MHz, CDCl3) δ: 7.98 (doublet, J = 5.6 Hz, 4H), 7.49 (doublet, J = 4 Hz, 4H), 6.77 (doublet of doublets, J = 10) , 8 Hz and J = 17.6 Hz, 1H), 5.83 (doublet of doublet, J = 1.2 Hz and J = 17.6 Hz, 1H), 5.36 (singlet, 2H), 5, 24 (doublet of doublets, J = 1.2 Hz and J = 11.2 Hz, 1H). Step 2: The boronic acid monomer (5.7 g, 20.2 mmol) obtained in the first step and 500 mL of acetone are introduced into a 1L Erlenmeyer flask. The reaction medium is stirred and 2.6 ml (144 mmol) of water are added dropwise until complete dissolution of the boronic acid monomer. The reaction medium is then transparent and homogeneous. A solution of 1,2-dodecanediol (5.32 g, 26.3 mmol) in 50 mL of acetone is slowly added to the reaction medium, followed by an excess of magnesium sulfate to trap the initially introduced water and as the water released by the condensation between the boronic acid monomer and 1,2-dodecanediol. After stirring for 3 hours at ambient temperature, the reaction medium is filtered. The solvent is then removed from the filtrate by means of a rotary evaporator to give 10.2 g of a mixture of boronic ester monomer and 1,2-dodecanediol in the form of a light yellow solid whose characteristics are as follows: NMR (400 MHz, CDCl3): Boronic ester monomer: 8: 8.06 (doublet, J = 8 Hz, 2H), 7.89 (doublet, J = 8 Hz, 2H), 7.51 (doublet, J = 4 Hz, 4H), 6.78 (doublet of doublets, J = 8 Hz and J = 16 Hz, 1H), 5.84 (doublet of doublets, J = 1.2 Hz and J = 17.6 Hz, 1H), 5.38 (singlet, 2H), 5.26 (doublet of doublets, J = 1.2 Hz and J = 11.2 Hz, 1H), 4.69-4.60 (multiplet, 1H), 4.49 (doublet of doublets, J = 8 Hz and J = 9.2 Hz, 1H), 3.99 (doublet of doublets, J = 7.2 Hz and J = 9.2 Hz, 1H), 1, 78-1.34 (multiplet, 18H), 0.87 (triplet, J = 6.4 Hz, 3H); 1,2-dodecanediol: 8: 3.61-3.30 (multiplet, about 1.62H), 1.78-1.34 (multiplet, about 9.72H), 0.87 (triplet, J = 6, 4 Hz, about 1.62 H). 2.2.2 Synthesis of compound A2, random copolymer poly (alkyl methacrylate-co-monomer boronic ester) The random copolymer A2 of the invention is obtained according to the following protocol: 2.09 g of a boronic ester monomer mixture and 1, 2-dodecanediol previously prepared (containing 3.78 mmol of boronic ester monomer), 98.3 mg (0.361 mmol) of cumyl dithiobenzoate, 22.1 g (86.9 mmol) of lauryl methacrylate (LMA) and 26, 5 ml of anisole are introduced into a 100 ml Schlenk tube. The reaction medium is stirred and 11.9 mg (0.0722 mmol) of azobisisobutyronitrile (AIBN) dissolved in 120 of anisole are introduced into the Schlenk tube. The reaction medium is then degassed for 30 minutes by bubbling argon before being heated to 65 ° C. for a duration of 16 hours. The Schlenk tube is placed in an ice bath to stop the polymerization, then the polymer is isolated by precipitation in anhydrous acetone, filtration and drying under vacuum at 30 ° C overnight. A copolymer having the following structure is obtained with m = 0.96 and n = 0.04.
[0052] The boronic ester copolymer obtained has a number average molecular weight (14-) of 37,200 g / mol, a polydispersity index (Ip) equal to 1,24 and a number-average degree of polymerization (DP). These values are respectively obtained by steric exclusion chromatography using tetrahydrofuran as eluent and polystyrene calibration and by monitoring the conversion to monomers during the copolymerization. Proton NMR analysis of the final copolymer gives a composition of 4 mol% boronic ester monomer and 96% lauryl methacrylate. 3. Rheological studies o 3.1 Apparatuses and protocols for viscosity measurement The rheological studies were carried out using a Couette MCR 501 controlled stress rheometer from Anton Paar. The measurements were performed on polymer formulations in solution in a Group III base oil using a DG 26.7 cylindrical reference geometry. The viscosity was measured as a function of the shear rate for a temperature range of 10 ° C to 110 ° C. For each temperature, the viscosity of the system was measured as a function of shear rate from 0.01 to 1000 s-1. Viscosity measurements as a function of shear rate at T = 10 ° C, 20 ° C, 30 ° C, 50 ° C, 70 ° C, 90 ° C and 110 ° C were made (ranging from 10 ° C). C at 110 ° C) followed by further measurements at 10 ° C and / or 20 ° C to assess the reversibility of the systems. An average viscosity was then calculated for each temperature using the measuring points located on the same plate. The relative viscosity of the basic ghelt base solution was also chosen to represent the evolution of the viscosity of the system as a function of temperature, since this quantity directly reflects the compensation for the natural viscosity loss of the Group III base oil. polymer systems studied. o 3.2: Compositions based on random polydiols Al copolymers and A2 diester boronic compounds. Test Compositions Al Copolymers: Four random poly (alkyl methacrylate-co-alkyldiol methacrylate) copolymers of the invention were tested. These are the following copolymers: Copolymer Al-1: This copolymer comprises 20 mol% of monomers having diol functions. The average side chain length is 13.8 carbon atoms. Its average molar mass is 49,600 g / mol. Its polydispersity index is 1.51. Its number-average degree of polymerization (DP) is 167. The number-average molecular weight and the polydispersity index are measured by steric exclusion chromatography using a polystyrene calibration. / Copolymer A1-2: This copolymer comprises 20 mol% of monomers having diol functions. The average side chain length is 10.8 carbon atoms. Its average molecular weight is 59 700 g / mol. Its polydispersity index is 1.6. Its number-average degree of polymerization (DP) was 196. The number average molecular weight and the polydispersity index are measured by steric exclusion chromatography using a polystyrene calibration. Al-3 Copolymer: This copolymer comprises 10 mol% of monomers having diol functions. The average side chain length is 13.8 carbon atoms.
[0053] Its average molar mass is 47,800 g / mol. Its polydispersity index is 1.3. Its number-average degree of polymerization (DP) was 198. The number average molecular weight and the polydispersity index were measured by steric exclusion chromatography using a polystyrene calibration. / Copolymer A1-4: This copolymer comprises 10 mol% of monomers having diol functions. The average side chain length is 13.8 carbon atoms. Its average molar mass is 97 100 g / mol. Its polydispersity index is 3.11. Its number-average degree of polymerization (DP) is 228. The number average molecular weight and the polydispersity index are measured by steric exclusion chromatography using a polystyrene calibration. The copolymers A1-1, Al-2, Al-3 and Al-4 are obtained according to one of the protocols described in paragraph 1.
[0054] Compound A2: Compound A2-1 is the boronic diester obtained according to the protocol described in section 2.1.
[0055] Lubricating base oil The lubricating base oil used in the compositions to be tested is a Group III API oil, marketed by SK under the name Yubase 4. It has the following characteristics: its kinematic viscosity at 40 ° C. measured according to ASTM D445 is 19.57 cSt; its kinematic viscosity, measured at 100 ° C. according to ASTM D445, is 4.23 cSt; its viscosity index, measured according to the ASTM D2270 standard, is 122; its Noack volatility in weight percentage, measured according to DIN 51581, is 14.5; - Its flash point in degrees Celsius measured according to ASTM D92 is 230 ° C; - Its pour point (for point in English) in degrees Celsius measured according to the ASTM D97 standard is -15 ° C. Composition A (outside the invention) is used as a reference. It contains a 4.2% by weight solution of a polymethacrylate polymer in API Group III lubricating base oil. The polymer has a number average molecular weight (M.) of 105,600 g / mol, a polydispersity index (Ip) of 3.06, a number-average degree of polymerization of 466 and the average length of the pendant chains. is 14 carbon atoms. This polymethacrylate is used as a viscosity index improving additive. 4.95 g of this polymethacrylate (pre-dissolved in the base oil group III with a mass concentration of 4.2%) and 44.6 g of base oil group III are introduced into a flask. The solution thus obtained is stirred at 90 ° C. until the polymethacrylate is completely dissolved. A 4.2% by weight solution of this polymethacrylate is obtained.
[0056] Composition B-1 (except the invention) is obtained in the following manner: 4.14 g of polydiol copolymer Al-1 and 37.2 g of base oil group III are introduced into a bottle. The solution thus obtained is stirred at 90 ° C. until the polydiol is completely dissolved.
[0057] A 10% by weight solution of polydiol copolymer A1-1 is obtained.
[0058] Composition C-1 (according to the invention) is obtained in the following manner: 8 g of the 10% by weight solution of polydiol copolymer Al-1 in the Group III base oil previously prepared are introduced into a flask. 55.8 mg of boronic diester A2-1 are added to this solution. The solution thus obtained is stirred at 90 ° C. until complete dissolution of the boronic diester. A 10% by weight solution of polydiol copolymer Al-1 and 20 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer A1-1. Composition D-1 (according to the invention) is obtained in the following manner: 8 g of the 10% by weight solution of polydiol copolymer A1-1 in the Group III base oil previously prepared are introduced into a flask. 223 mg of boronic diester A2-1 are added to this solution. The solution thus obtained is stirred at 90 ° C. until complete dissolution of the boronic diester. A 10% by weight solution of polydiol copolymer A1-1 and 80 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer A1-1. Composition B-2 (except the invention) is obtained in the following manner: 6.52 g of polydiol copolymer Al-2 and 58.7 g of base oil group III are introduced into a flask. The solution thus obtained is stirred at 90 ° C. until the polydiol is completely dissolved. A 10% by weight solution of polydiol copolymer Al-2 is obtained. Composition C-2 (according to the invention) is obtained in the following manner: 8 g of the 10% by weight solution of polydiol copolymer Al-2 in the Group III base oil previously prepared are introduced into a flask. 65.4 mg of boronic diester A2-1 are added to this solution. The solution thus obtained is stirred at 90 ° C. until complete dissolution of the boronic diester. A 10% by weight solution of polydiol copolymer Al-2 and 20 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer Al-2.
[0059] Composition D-2 (according to the invention) is obtained in the following manner: 8 g of the 10% by weight solution of polydiol copolymer Al-2 in the Group III base oil previously prepared are introduced into a flask. 262 mg of boronic diester A2-1 are added to this solution. The solution thus obtained is stirred at 90 ° C. until complete dissolution of the boronic diester. A 10% by weight solution of polydiol copolymer Al-2 and 80 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer Al-2.
[0060] Composition B-3 (except the invention) is obtained in the following manner: 7.24 g of polydiol copolymer Al-3 and 65.2 g of base oil group III are introduced into a flask. The solution thus obtained is stirred at 90 ° C. until the polydiol is completely dissolved.
[0061] A 10% by weight solution of polydiol copolymer Al-3 is obtained. Composition C-3 (according to the invention) is obtained in the following manner: 8 g of the 10% by weight solution of polydiol copolymer Al-3 in the Group III base oil previously prepared are introduced into a flask. 28.2 mg of boronic diester A2-1 are added to this solution. The solution thus obtained is stirred at 90 ° C. until complete dissolution of the boronic diester. A 10% by weight solution of polydiol copolymer Al-3 and 20 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer Al-3.
[0062] Composition B-4 (outside the invention) is obtained in the following manner: 4.99 g of polydiol copolymer Al-4 and 44.4 g of base oil group III are introduced into a flask. The solution thus obtained is stirred at 90 ° C. until the polydiol is completely dissolved. A 10% by weight solution of polydiol copolymer Al-4 is obtained.
[0063] Composition C-4 (according to the invention) is obtained in the following manner: 6.01 g of the 10% by weight solution of polydiol copolymer Al-4 in the Group III base oil previously prepared are introduced into a flask. 18.6 mg of boronic diester A2-1 are added to this solution. The solution thus obtained is stirred at 90 ° C. until complete dissolution of the boronic diester. A 10% by weight solution of polydiol copolymer Al-4 and 20 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer Al-4. Composition D-4 (according to the invention) is obtained in the following manner: 6.03 g of the 10% by weight solution of polydiol copolymer Al-4 in the Group III base oil previously prepared are introduced into a flask. 74.7 mg of boronic diester A2-1 are added to this solution. The solution thus obtained is stirred at 90 ° C. until complete dissolution of the boronic diester. A 10% by weight solution of polydiol copolymer Al-4 and 80 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer Al-4. Results obtained in rheology The rheological behavior of the composition C1-1 was studied for a temperature range from 10 ° C to 110 ° C. The results are shown in FIG. 5. The dynamic viscosity of composition C1-1 varies at low shear rates and at temperatures below 50.degree. Composition C1-1 is deformed under shear stress for temperatures below 50 ° C. For temperatures above 50 ° C., the dynamic viscosity of composition C1-1 varies very slightly or does not vary at low shear rates. The composition C1-1 is no longer deformed under the shear stress at these temperatures. The relative viscosity of compositions A, B-1, C-1, D-1, B-2, C-2, D-2, B-3, C-3, D-3, B4, C-4, D -4 has been studied. The evolution of the relative viscosity of these compositions is illustrated in FIGS. 6A-6D. By comparing the results obtained, it is observed that certain parameters influence the relative viscosity of the compositions. The influence of Lc (pendant side-chain average length) Polydiols copolymers Al-1 and Al-2 have the same percentage of diol monomer (M1) per chain, comparable molar masses, but an average length of the alkyl chains of the monomers different (Le = 13.8 and Le = 10.8 respectively). The evolution of the relative viscosity as a function of temperature for the solutions formulated from these polymers (FIGS. 6A and 6B) indicates that the average length of the alkyl chains of the monomers constituting the polydiol copolymer plays a role in the rheological properties of the formulations. . The influence of the molar percentage of diol monomer (% diol) The polydiols copolymers A1-1 and Al-3 have the same average length of the alkyl chains (Le), comparable molar masses but a percentage of monomer diol (M1) per chain skeletal muscle (20% and 10% respectively). The evolution of the relative viscosity as a function of temperature for the solutions formulated from these polymers (FIGS. 6A and 6C) indicates that the percentage of diol monomer per skeletal chain plays a role on the rheological properties of the formulations.
[0064] The influence of molar masses (DP.) Polydiols Al-3 and Al-4 have the same percentage of diol monomer (M1) per chain, the same average length of alkyl chains (Le) but significantly different molar masses (47). 800 g / mol and 97 100 g / mol respectively) and significantly different number average polymerization degrees (DP of 198 and 228, respectively) .The evolution of the relative viscosity as a function of temperature for the solutions formulated at From these polymers (Figure 6.0 and 6.D) indicates that the molar mass of the polydiol copolymers (Mn) plays a role in the rheological properties of the formulations. 3.2: Compositions based on polydiols random copolymers Al and compounds A2 boronic ester polymer. Tested Compositions Al Copolymers: A random poly (alkyl methacrylate-co-alkyldiol methacrylate) copolymer of the invention is tested This is the following copolymer: / Copolymer Al-1: This copolymer comprises 20 mol% of monomers having functions diol. The average side chain length is 13.8 carbon atoms.
[0065] Its average molar mass is 49,600 g / mol. Its polydispersity index is 1.51. Its number-average degree of polymerization (DP) is 167. The number-average molecular weight and the polydispersity index are measured by steric exclusion chromatography using a polystyrene calibration.
[0066] The copolymer A1-1 is obtained according to one of the protocols described in paragraph 1. Compound A2: The compound A2-2 is the boronic ester polymer obtained according to the protocol described in section 2.2. This copolymer comprises 4 mol% of monomers having boronic ester functions. The average side chain length is greater than 12 carbon atoms. Its average molar mass is 37,200g / mol. Its polydispersity index is 1.24. Its number-average degree of polymerization (DP) is 166. The number average molecular weight and the polydispersity index are measured by steric exclusion chromatography using a polystyrene calibration.
[0067] Lubricating base oil The lubricating base oil used in the compositions to be tested is the Group III oil described above in section 3.1.
[0068] Composition A (outside the invention) is used as a reference and is the same as Composition A used in Section 3.1.
[0069] Composition B (except the invention) is obtained in the following manner: Composition B is the same composition B-1 used in paragraph 3.1. Composition C (according to the invention) is obtained in the following manner: 4 g of the 10% by weight solution of polydiol copolymer Al-1 in the Group III base oil previously prepared are introduced into a flask. 76.8 mg of boronic ester polymer A2-2 and 4 g of the base oil group III are added to this solution. The solution thus obtained is stirred at 90 ° C. until the boronic ester polymer is completely dissolved.
[0070] A 5% by weight solution of polydiol copolymer A1-1 and 1% by weight of boron ester polymer A2-2 is obtained relative to the total mass of the composition. Composition D (according to the invention) is obtained in the following manner: 6 g of the solution of the above composition C (ie the composition with 5% by weight of polydiol copolymer A1-1 and 1% by mass of boron ester polymer A2-2 relative to the total mass of the composition) are introduced into a flask. 61.9 mg of boron ester polymer A2-2 are added to this solution. The solution thus obtained is stirred at 90 ° C. until the boronic ester polymer is completely dissolved. A 5% by weight solution of polydiol copolymer A1-1 and 2% by weight of boron ester polymer A2-2 is obtained relative to the total mass of the composition. Composition E (according to the invention) is obtained in the following manner: 3 g of the 10% by weight solution of polydiol copolymer A1-1 in the Group III base oil previously prepared are introduced into a flask. 176 mg of A2-2 boronic ester polymer and 3 g of the Group III base oil are added to this solution. The solution thus obtained is stirred at 90 ° C. until the boronic ester polymer is completely dissolved. A 5% by weight solution of polydiol copolymer A1-1 and 3% by weight of boron ester polymer A2-2 is obtained relative to the total mass of the composition. Results obtained in rheology The rheological behavior of the composition E was studied for a temperature range from 10 ° C. to 110 ° C. The results are shown in FIG. 7. The dynamic viscosity of composition E varies at low shear rates and at temperatures below 50 ° C. Composition E deforms under shear stress for temperatures below 50 ° C. For temperatures above 50 ° C., the dynamic viscosity of the composition E varies very slightly or does not vary at low shear rates. The composition E no longer deforms under the shear stress at these temperatures. The relative viscosity of compositions A, B, C, D and E was studied. The evolution of the relative viscosity of these compositions is illustrated in FIG. 8. This figure indicates that the polydiols / poly (boronic ester) systems make it possible to very significantly offset the natural viscosity drop of the base oil. temperature function. In addition, the effect obtained can be regulated by varying the mass concentrations of the various polymers in solution in the base oil III.

权利要求:
Claims (18)
[0001]
REVENDICATIONS1. Composition resulting from the mixture: at least one lubricating oil, at least one random copolymer Al and at least one compound A2 comprising at least two boronic ester functions; the random copolymer Al resulting from the copolymerization of at least one first monomer M1 of general formula (I) ## STR2 ## in which: R 1 is chosen from the group formed by -H, -CH3 and -CH2-CH3, x is an integer ranging from 2 to 18; y is an integer equal to 0 or 1; X1 and X2, which are identical or different, are chosen from the group formed by hydrogen, tetrahydropyranyl, methyloxymethyl, tert-butyl, benzyl, trimethylsilyl and t-butyl dimethylsilyl; or else X 1 and X 2 form, with the oxygen atoms, a bridge of the following formula R "2 in which: the stars (*) symbolize the bonds to the oxygen atoms, R '2 and R" 2, which are identical or different, are selected from the group consisting of hydrogen and a C1-C11 alkyl, preferably methyl; or else - X1 and X2 form with the oxygen atoms a boronic ester of the following formula RI "2 in which: - the stars (*) symbolize the bonds to the oxygen atoms, - R" '2 is chosen from the group formed C 6 -C 18 aryl, C 7 -C 18 aralkyl and C 2 -C 18 alkyl, preferably C 6 -C 18 aryl; with at least one second monomer M2 of general formula (II-A): H2C (R2 R31 (II-A) in which: R2 is chosen from the group formed by -H, -CH3 and -CH2-CH3, R31 is chosen from the group formed by a C6-C18 aryl, a C6-C18 aryl substituted with a group R'3, -C (O) -O-R'3 -O-R'3, -S-R ' And -C (O) -N (H) -R'3 with R'3 a C1-C30 alkyl group.
[0002]
2. Composition according to claim 1, in which random copolymer A1 results from the copolymerization of at least one monomer M1 with at least two monomers M2 having different R31 groups.
[0003]
3. Composition according to claim 2, wherein one of the monomers M2 of the random copolymer Al has the general formula (II-A1): H 2 C (II-A1) in which: - R2 is chosen from the group formed by -H, - CH 3 and -CH 2 -CH 3, - R "31 is a C 1 -C 14 alkyl group, and the other monomer M2 of the random copolymer Al has the general formula (II-A2): R 2 H 2 C 0 O (II-A2) in which R2 is selected from the group consisting of -H, -CH3et-CH2-CH3, R "'31 is a C15-C30 alkyl group.
[0004]
4. Composition according to any one of claims 1 to 3, wherein the compound A2 is a compound of formula (III): wherein w1 and w2, identical or different are integers selected from 0 and 1, R4, R5, R6 and R7, which are identical or different, are chosen from the group formed by hydrogen and a hydrocarbon group having from 1 to 24 carbon atoms, preferably from 4 to and 18 carbon atoms, preferably between 6 and 14 carbon atoms; L is a divalent linking group and a C6-C18 aryl, a C6-C18 aralkyl and a C2-C24 hydrocarbon chain.
[0005]
5. Composition according to any one of claims 1 to 3, wherein the compound A2 is a random copolymer resulting from the copolymerization of at least one monomer M3 of formula (IV): ## STR2 ## In which: 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 may be identical or different, are chosen from the group formed by a C6-C18 aryl, a C7-C24 aralkyl and a C2-C24 alkyl, preferably a C6-C18 aryl; X is a function selected from the group consisting of -O-C (O) -, -C (O) -N (H) -, -N (H) -C (O) -, -S-, -N (H) -, -N (R'4) - and -O- with R'4 a hydrocarbon chain comprising from 1 to 15 carbon atoms; R9 is selected from the group consisting of -H, -CH3et-CH2-CH3; R10 and R11, which are identical or different, chosen from the group formed by hydrogen and a hydrocarbon group having 1 to 24 carbon atoms, preferably between 4 and 18 carbon atoms, preferably between 6 and 14 carbon atoms, - with at least one second monomer M4 of general formula (V): H2C / R12 R13 (V) in which: R12 is selected from the group consisting of -H, -CH3 and -CH2-CH3 R13 is selected from the group consisting of C6-C18 aryl, C6-C18 aryl substituted with R'13, -C (O) -O-R'13, -O-R'13, -SR '13 and -C (O) - N (H) -R '13 with R' 13 is a C1-C25 alkyl group.
[0006]
6. Composition according to claim 5, wherein the chain formed by the linking of the groups R10, M, X and (R8) 'with u equal to 0 or 1 of the monomer of general formula (IV) has a total number of carbon atoms of between 8 and 38, preferably between 10 and 26.
[0007]
7. Composition according to one of claims 5 to 6, wherein the side chains ducopolymer A2 have an average length greater than 8 carbon atoms, preferably ranging from 11 to 16 carbon atoms.
[0008]
8. Composition according to one of claims 5 to 7, wherein the random copolymer A2 has a molar percentage of monomer of formula (IV) ranging from 0.25 to 20%, preferably from 1 to 10%.
[0009]
9. Composition according to one of claims 5 to 8, wherein the random copolymer A2 has a number average degree of polymerization ranging from 50 to 1500, preferably from 80 to 800.
[0010]
10. Composition according to one of claims 1 to 9 wherein wherein the side chains of the random copolymer A1 have an average length of 8 to 20 carbon atoms, preferably 9 to 15 carbon atoms.
[0011]
11. Composition according to one of claims 1 to 10 wherein the random copolymer Al has a molar percentage of monomer M1 of formula (I) ranging from 1 to 30%, preferably from 5 to 25%, more preferably ranging from 9 to 21%.
[0012]
12. Composition according to one of claims 1 to 11, wherein the random copolymer Al has a mean degree of polymerization ranging from 100 to 2000, preferably from 150 to 1000.
[0013]
A composition according to any one of claims 1 to 12, wherein the lubricating oil is selected from Group I, Group II, Group III, Group IV, Group V API, and Class I oils. one of their mix.
[0014]
14. Composition according to one of claims 1 to 13, further comprising a functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, additional antioxidants, polymers improving the viscosity, pour point improvers, defoamers, anticorrosive additives, thickeners, dispersants, friction modifiers and mixtures thereof.
[0015]
15. Composition according to one of claims 1 to 14, wherein the mass ratio between the random copolymer Al and the compound A2 (ratio Al / A2) ranges from 0.001 to 100, preferably from 0.05 to 20, so still more preferably from 0.01 to 10, still more preferably from 0.2 to 5.
[0016]
16. Composition according to one of claims 1 to 14, wherein the sum of the masses of random copolymer Al and compound A2 is from 0.5 to 20% relative to the total weight of the lubricant composition and the mass of Lubricating oil ranges from 80% to 99.5% based on the total mass of the lubricant composition.
[0017]
17. Use of a composition according to one of claims 1 to 16 for lubricating a mechanical part.
[0018]
18. Mother composition resulting from the mixture: at least one random copolymer Al; at least A2 compound comprising at least two boronic ester functions; and at least one functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, antioxidants, viscosity index improvers, pour point improvers, anti-wear agents, foam, thickeners, dispersants, friction modifiers and mixtures thereof; the random copolymer Al resulting from the copolymerization of at least one first monomer M1 of general formula (I) ## STR2 ## in which: R 1 is chosen from the group formed by -H, -CH 3 and CH2-CH3; x is an integer from 2 to 18; y is an integer equal to 0 or 1; X1 and X2, which are identical or different, are chosen from the group formed by hydrogen, tetrahydropyranyl, methyloxymethyl, tert-butyl, benzyl, trimethylsilyl and t-butyl dimethylsilyl; or else - X1 and X2 form with the oxygen atoms a bridge of the following formula in which: - the stars (*) symbolize the bonds to the oxygen atoms, - R'2 and R "2, identical or different, are chosen from among the group consisting of hydrogen and a C 1 -C 11 alkyl, preferably methyl, or - X 1 and X 2 form with the oxygen atoms a boronic ester of the following formula R 1 - 2 in which: - the stars (* ) symbolize the bonds to the oxygen atoms; R "'2 is selected from the group consisting of C 6 -C 18 aryl, C 7 -C 18 aralkyl and C 2 -C 18 alkyl, preferably C 6 aryl; -C18; with at least a second monomer M2 of general formula (II-A): R 2 H 2 C R 31 (II-A) in which: R 2 is chosen from the group formed by -H, -CH 3 and -CH 2 -CH 3 R 31 is selected from the group consisting of a C 6 -C 18 aryl, a C 6 -C 18 aryl substituted with a group R '3, -C (O) -O-W 3 -O-R' 3 -S-R '3 and -C (O) -N (H) -R'3 with R'3 a C1-C30 alkyl group;

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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US4401797A|1981-05-20|1983-08-30|Syntex Inc.|Copolymers and hydrogels: process and articles made thereof|

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EP0570073A1|1992-05-15|1993-11-18|Ministero Dell' Universita' E Della Ricerca Scientifica E Tecnologica|Boron-containing additive for lubricating oils, and process for preparing said additive|WO2019224492A1|2018-05-24|2019-11-28|Total Marketing Services|Associative and exchangeable oligomers, composition comprising them|

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WO2019224491A1|2018-05-24|2019-11-28|Total Marketing Services|Associative and exchangeable oligomers, and composition containing same|

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WO2019224493A1|2018-05-24|2019-11-28|Total Marketing Services|Associative and exchangeable oligomers, and composition comprising same|

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WO2019224494A1|2018-05-24|2019-11-28|Total Marketing Services|Associative and exchangeable oligomers, and composition containing same|DE10314776A1|2003-03-31|2004-10-14|Rohmax Additives Gmbh|Lubricating oil composition with good rubbing properties|

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MY136312A|2003-05-21|2008-09-30|Ciba Holding Inc|Borate ester lubricant additives|

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FR2855180B1|2003-05-23|2006-07-14|Rhodia Chimie Sa|AQUEOUS FLUID COMPRISING A BORONATE POLYMER AND A LIGAND POLYMER AND USE IN OPERATING OIL OR GAS STORAGE|

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CN104204009B|2012-03-29|2016-08-17|英派尔科技开发有限公司|Dioxaborinate copolymer and application thereof|

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FR3016885B1|2014-01-27|2017-08-18|Total Marketing Services|THERMOASSOCIATIVE AND EXCHANGEABLE COPOLYMERS, COMPOSITIONS COMPRISING THE SAME|FR3031744B1|2015-01-15|2017-02-10|Total Marketing Services|COMPOSITIONS OF THERMOASSOCIATIVE ADDITIVES WHERE THE ASSOCIATION IS CONTROLLED AND LUBRICATING COMPOSITIONS CONTAINING SAME|

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FR3059005B1|2016-11-23|2018-12-07|Total Marketing Services|THERMOASSOCIATIVE AND EXCHANGEABLE COPOLYMERS, COMPOSITION COMPRISING SAME|

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FR3059006B1|2016-11-23|2020-06-12|Total Marketing Services|THERMOASSOCIATIVE ADDITIVE COMPOSITIONS WHOSE ASSOCIATION IS CONTROLLED AND LUBRICATING COMPOSITIONS CONTAINING THEM|

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CN107298737A|2017-06-20|2017-10-27|西南科技大学|A kind of polyacrylic preparation method of Three-Dimensional Dynamic|

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FR3078706B1|2018-03-07|2020-12-18|Total Marketing Services|THERMOASSOCIATIVE AND EXCHANGEABLE COPOLYMERS, COMPOSITION INCLUDING THEM|

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FR3078710B1|2018-03-07|2020-10-30|Total Marketing Services|COMPOSITION INCLUDING THERMOASSOCIATIVE AND EXCHANGEABLE COPOLYMERS|

法律状态:
2015-01-21| PLFP| Fee payment|Year of fee payment: 2 |

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2015-12-22| PLFP| Fee payment|Year of fee payment: 3 |

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2016-12-21| PLFP| Fee payment|Year of fee payment: 4 |

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2017-12-21| PLFP| Fee payment|Year of fee payment: 5 |

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2019-12-19| PLFP| Fee payment|Year of fee payment: 7 |

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2021-10-08| ST| Notification of lapse|Effective date: 20210905 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1450657A|FR3016887B1|2014-01-27|2014-01-27|LUBRICATING COMPOSITIONS COMPRISING THERMOASSOCIATIVE AND EXCHANGEABLE COPOLYMERS|FR1450657A| FR3016887B1|2014-01-27|2014-01-27|LUBRICATING COMPOSITIONS COMPRISING THERMOASSOCIATIVE AND EXCHANGEABLE COPOLYMERS|

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KR1020167023655A| KR102292997B1|2014-01-27|2015-01-26|Lubricating compositions comprising thermoassociative and exchangeable copolymers|

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MA39196A| MA39196B1|2014-01-27|2015-01-26|Lubricating compositions comprising heat-associative and exchangeable copolymers|

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UAA201609098A| UA119160C2|2014-01-27|2015-01-26|Lubricating compositions comprising thermoassociative and exchangeable copolymers|

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BR112016017393-7A| BR112016017393A2|2014-01-27|2015-01-26|lubricating compositions comprising heat-exchangeable and interchangeable copolymers|

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CA2937928A| CA2937928A1|2014-01-27|2015-01-26|Lubricating compositions comprising thermoassociative and exchangeable copolymers|

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TR2019/05388T| TR201905388T4|2014-01-27|2015-01-26|Lubricant compositions containing thermally coupled and exchangeable copolymers.|

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JP2016565568A| JP6444430B2|2014-01-27|2015-01-26|Lubricant composition comprising a heat-associative and exchangeable copolymer|

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EP15700905.1A| EP3099721B1|2014-01-27|2015-01-26|Lubricating compositions comprising thermoassociative and exchangeable copolymers|

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PCT/EP2015/051518| WO2015110643A1|2014-01-27|2015-01-26|Lubricating compositions comprising thermoassociative and exchangeable copolymers|

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US15/114,157| US10336960B2|2014-01-27|2015-01-26|Lubricating compositions comprising thermoassociative and exchangeable copolymers|

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CN201580006170.3A| CN106164114B|2014-01-27|2015-01-26|Include the lubricating composition of heat association and commutative copolymer|

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ES15700905T| ES2722853T3|2014-01-27|2015-01-26|Lubricating compositions comprising thermo-associative and interchangeable copolymers|