COMPOSITIONS OF THERMOASSOCIATIVE ADDITIVES WHERE THE ASSOCIATION IS CONTROLLED AND LUBRICATING COMP

专利摘要:
The present invention relates to novel additive compositions which result from the mixture of at least two thermoassociative and exchangeable copolymers and at least one compound for controlling the combination of these two copolymers. The invention also relates to a lubricant composition which results from the mixture of at least one lubricating base oil, at least two thermoassociative and exchangeable copolymers and at least one compound making it possible to control the combination of these two copolymers. The present invention also relates to a method for modulating the viscosity of a lubricating composition which results from mixing at least one lubricating base oil with at least two thermoassociative and exchangeable copolymers; and the use of a diol compound for modulating the viscosity of a lubricating composition.
公开号:FR3031744A1
申请号:FR1550328
申请日:2015-01-15
公开日:2016-07-22
发明作者:Renaud Nicolay；Thi Hang Nga Nguyen；Raphaele Iovine；Gregory Descroix
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] FIELD OF THE INVENTION The present invention relates to novel additive compositions which result from the blending of at least two heat-associative and exchangeable copolymers and at least one compound for controlling the combination of these two copolymers. The invention also relates to a lubricating composition which results from mixing at least one lubricating base oil, at least two thermoassociative and exchangeable copolymers and at least one compound for controlling the combination of these two copolymers. The present invention also relates to a method for modulating the viscosity of a lubricating composition which results from mixing at least one lubricating base oil with at least two thermoassociative and exchangeable copolymers; and the use of a diol compound for modulating the viscosity of a lubricating composition. BACKGROUND OF THE INVENTION High molecular weight polymers are widely used to increase the viscosity of solutions in many fields, such as the oil, paper, water treatment, mining, cosmetics industry. , textile and generally in all industrial techniques using thickened solutions. However, these high molecular weight polymers have the disadvantage of having a low permanent shear strength compared to the same polymers of smaller sizes. These shear stresses on high molecular weight polymers cause cleavages in the macromolecular chains. The polymer thus degraded has diminished thickening properties, and the viscosity of the solutions containing it drops irreversibly. In addition, these polymers do not make it possible to modulate the thickening of the composition in which they are added as a function of the use temperature of the composition. It has been the object of the Applicant to formulate new additive compositions which are more shear stable than the compounds of the prior art and whose rheological behavior can be adapted according to the use of the composition in the art. which additives are added. This objective is achieved by the combination of associative and thermoreversibly exchangeable additives and an agent which makes it possible to control the association and dissociation of these additives. The associated (potentially crosslinked) and exchangeable copolymers have the advantage of being more stable to shear stresses. This characteristic results from the combined use of two particular compounds, a random copolymer bearing diol functions and a compound comprising at least two 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, in particular for the devices of which it is 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 or an association with other compounds is contemplated. The additive composition according to the invention has many advantages. It makes it possible to increase the viscosity of solutions, in particular of hydrophobic solutions, comprising them with respect to the additive compositions of the prior art. The additives of the composition of the invention have an inverted behavior vis-à-vis a temperature change with respect to the behavior of the solution and rheological additives of the polymer type of the prior art. It also makes it possible to adapt the increase in viscosity and the rheological behavior of these solutions as a function of their temperature of use. The Applicant has also set itself the objective of formulating new lubricating compositions which make it possible to reduce the friction between two mechanical parts during cold use and during hot use. 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 when the temperature is varied. Indeed, as the temperature of a base oil increases, its viscosity decreases and as 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 can 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. A lubricating composition that is too viscous at the starting temperature can interfere with the movement of the moving parts and thus prevent the motor from rotating fast enough. A lubricating composition must also be on the one hand sufficiently fluid to reach the bearings quickly and prevent wear thereof and on the other sufficiently thick to ensure good protection of the engine when the latter reaches its operating temperature . There is therefore a need for a lubricating composition having both good lubricating properties for the starting phases of an engine and for the operating phases of the engine at its operating temperature. It is known to add additives improving the viscosity of a lubricating composition. 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, high molecular weight polymers have the disadvantage of having a low permanent shear strength over polymers of the same nature but of smaller sizes. In addition, they thicken the lubricating compositions whatever the operating temperature of the lubricating composition, and especially at low temperature. Lubricating compositions of the prior art comprising viscosity improving additives may exhibit poor lubricating properties during engine start-up phases. The lubricant composition according to the invention makes it possible to overcome the aforementioned drawbacks by virtue of the combined use of a mixture of two thermoassociative and exchangeable compounds (a copolymer bearing diol functions and a compound comprising boronic ester functions) and a diol compound in a basic lubricating oil. Unexpectedly, the Applicant has observed that the addition of a diol compound makes it possible to control the association between a copolymer carrying diol functions and a compound comprising boronic ester functions. At low temperature, the polydiol copolymer is not or poorly associated with compounds comprising boronic ester functions; the latter reacts with the added diol compound. 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 polydiols random copolymers and the compounds comprising them break; the composition loses its gelled character if necessary. The boronic ester functions of the compound comprising them react with the added diol compound. It is possible to modulate the kinetics and the temperature window of formation of these associations, thus to modulate the rheological behavior of the lubricant composition according to the desired use.
[0002] It is possible, by virtue of the compositions of the invention, to provide lubricating compositions which have good lubricating properties during the engine starting phases (cold phase) and good lubricating properties when the engine is operating at its temperature. service (hot phase).
[0003] SUMMARY OF THE INVENTION Thus, the subject of the invention is an additive composition resulting from the mixture of at least: a random polydiol Al copolymer, a random copolymer A2 comprising at least two boronic ester functions and capable of associating with said polydiol random copolymer Al by at least one transesterification reaction, an exogenous compound A4 selected from 1,2-diols and 1,3-diols. According to one embodiment of the invention, the molar percentage of exogenous compound A4 in the additive composition relative to the boronic ester functions of the random copolymer A2 is from 0.025 to 5000%, preferably from 0.1 from 1% to 1000%, more preferably from 0.5% to 500%, even more preferably from 1% to 150%. According to one embodiment of the invention, the random copolymer Al results from the copolymerization of: at least one first monomer M1 of general formula (I): ## STR2 ## in which: selected from the group consisting of -H, -CH3, and -CH2-CH3; x is an integer ranging from 1 to 18; preferably from 2 to 18; y is an integer equal to 0 or 1; X1 and X2, which are identical or different, are selected from the group consisting of 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 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: B / 2 in which: - the stars ( *) symbolize the bonds to the oxygen atoms, - R "2 is selected from the group consisting of a C6-C18 aryl, a C7-C18 aralkyl and C2-C18 alkyl, preferably a C6-C18 aryl with at least one second monomer M2 of general formula (II): wherein R 2 is selected from the group consisting of -H, -CH 3 and -CH 2 -CH 3 -R 3 is selected from the group consisting of C6-C18 aryl, C6-C18 aryl substituted with R'3, -C (O) -O-R'3 -O-R'3, -S-W3 and -C (O) -N (H) -R'3 with R'3 a C1-C30 alkyl group. According to one embodiment of the invention, the random copolymer Al results from the copolymerization of at least one monomer M1 with at least two monomers M2 having different R3 groups. According to one embodiment of the invention, one of the monomers M2 of the random copolymer Al has the general formula (II-A): H 2 C 0 (II-A) in which: R 2 is chosen from the group formed by -H, -CH3 and -CH2-CH3, -R "3 is a C1-C14 alkyl group, and the other monomer M2 of the random copolymer Al has general formula (II-B): H2C 0 (II-B wherein: R2 is selected from the group consisting of -H, -CH3 and -CH2-CH3; -R "3 is a C15-C30 alkyl group.
[0004] According to one embodiment of the invention, 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. According to one embodiment of the invention, the random copolymer A1 has a molar percentage of monomer M1 of formula (I) in said copolymer ranging from 1 to 30%, preferably from 5 to 25%, more preferably ranging from from 9 to 21%. According to one embodiment of the invention, the random copolymer A2 results from the copolymerization of: at least one monomer M3 of formula (IV): ## STR2 ## H2C R11 R9 (IV) wherein: - t is an integer of 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, 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 18 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; R10 and R11, 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 18 carbon atoms, preferably from 6 to 14 carbon atoms; with at least one second monomer M4 of general formula (V): R 12 (R 13 H 2 C (y) in which: R 12 is chosen from the group formed by -H, -CH 3 and -CH 2 -CH 3 R 13 is chosen from the group formed by a C6-C18 aryl, a C6-C18 aryl substituted with a group R'13, -C (O) -O-R'13, -O-R'13, _S_ R'13 and -C (O) -N (H) -R '13 with R'13 a C1-C25 alkyl group According to one embodiment of the invention, the chain formed by the linking of the groups R10, M, X and (R8) 6 with u equal to 0 or 1 of the monomer of the general formula (IV) of the random copolymer A2 has a total number of carbon atoms ranging from 8 to 38, preferably from 10 to 26. According to one embodiment of the invention, the side chains of the random copolymer A2 have an average length greater than or equal to 8 carbon atoms, preferably ranging from 11 to 16 carbon atoms, According to one embodiment of the invention, the statistical copolymer A2 has a percentage 30 mola monomer of formula (IV) in said copolymer ranging from 0.25 to 20%, preferably from 1 to 10%. According to one embodiment of the invention, the exogenous compound A4 has the general formula (VI): ## STR3 ## where: w is an integer equal to 0 or 1; R14 and R15 identical or different selected from the group consisting of hydrogen and a hydrocarbon group having 1 to 24 carbon atoms.
[0005] According to one embodiment, the substituents R10, R11 and the value of the index (t) of the monomer of formula (IV) of the random copolymer A2 are identical, respectively, to the substituents R14, R15 and to the value of the index w3, exogenous compound A4 of formula (VI). According to one embodiment of the invention, at least one of the substituents R10, R11 or the value of the index (t) of the monomer of formula (IV) of the random copolymer A2 is different from the substituents R14, R15 or the value of the index w3, of the exogenous compound A4 of formula (VI). According to one embodiment of the invention, the mass ratio between the polydiol random copolymer Al and the statistical copolymer A2 (ratio A 1 / A2) ranges from 0.005 to 200, preferably from 0.05 to 20, and even more so. preferred from 0.1 to 10, still more preferably from 0.2 to 5. The present invention also relates to a lubricant composition resulting from mixing at least: - a lubricating oil; and an additive composition defined above. According to one embodiment of the invention, 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 mixture. . According to one embodiment of the invention, the mass ratio between the random copolymer Al and the statistical copolymer A2 (ratio A 1 / A2) ranges from 0.001 to 100, preferably from 0.05 to 20, even more preferably from 0.1 to 10, still more preferably from 0.2 to 5. According to one embodiment of the invention, the molar percentage of exogenous compound A4 relative to the boronic ester functions of the random copolymer A2 ranges from 0.05 to 5000%, preferably 0.1 to 1000%, more preferably 0.5 to 500%, still more preferably 1 to 150%. According to one embodiment of the invention, the lubricant composition of the invention results from the addition of 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, defoamers, anticorrosive additives, thickeners, dispersants, friction modifiers, and mixtures thereof. The present invention also relates to a method for modulating the viscosity of a lubricating composition, the method comprising at least: providing a lubricating composition resulting from mixing at least one lubricating oil, at least one polydiol random copolymer Al and at least one random copolymer A2 comprising at least two boronic ester functional groups and capable of associating with said polydiol Al random copolymer by at least one transesterification reaction, adding to said lubricating composition at least one exogenous compound A4 selected from 1,2-diols and 1,3-diols. The invention also proposes the use of at least one compound selected from 1,2 diols or 1,3 diols for modulating the viscosity of a lubricating composition, said lubricating composition resulting from the mixture of at least one lubricating oil, at least one polydiol random copolymer Al and at least one random copolymer A2 comprising at least two boronic ester functional groups and capable of associating with said polydiol Al random copolymer by at least one transesterification reaction.
[0006] BRIEF DESCRIPTION OF THE FIGURES FIG. 1 schematically represents a random copolymer (P1), a gradient copolymer (P2) and a block copolymer (P3), each round represents a monomeric unit. The difference in chemical structure between the monomers is symbolized by a different color (light gray / black).
[0007] Figure 2 schematically shows a comb copolymer. FIG. 3 schematically illustrates the crosslinking of the composition according to the invention in tetrahydrofuran (THF) in the presence of exogenous diol A4 compounds. Figure 4 shows schematically the behavior of the composition of the invention as a function of temperature. A random copolymer having diol functions (function A) can associate thermoreversibly with a random copolymer having boronic ester functions (function B) via a reversible transesterification reaction. A boronic ester chemical bond is formed between the two polymers. The free diol compounds (function C) present in the medium in the form of small organic molecules make it possible to adjust the level of association between the copolymers bearing the functions diol A and the copolymers carrying the boronic ester functions B. FIG. evolution of the relative viscosity (without unit, the ordinate axis) as a function of the temperature (° C, the abscissa axis) of the compositions A, C, D and E. FIG. 6 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 and F.
[0008] FIG. 7 represents the evolution of the elastic modulus (G ') and the viscous modulus (G ") (Pa, the ordinate axis) as a function of the temperature (° C, the abscissa axis) of the composition G FIG. 8 represents the evolution of the elastic modulus (G ') and the viscous modulus (G ") (Pa, the ordinate axis) as a function of the temperature (° C, the abscissa axis) of the composition Figure 9 schematically illustrates the boronic ester link exchange reactions between two polydiols random polymers (A1-1 and A1-2) and two boronic ester random polymers (A2-1 and A2-2) in the presence exogenous diol compounds (A4) and diol compounds released in situ (A3). DESCRIPTION OF EMBODIMENTS OF THE INVENTION Additive Composition According to the Invention A first object of the present invention is an associative additive composition that is thermoreversibly exchangeable and whose association rate is controlled by the the presence of a so-called exogenous compound, the composition resulting from the mixture of at least one random polydiol Al copolymer, a compound A2, in particular a random copolymer A2, comprising at least two boronic ester functional groups and capable of associating with said copolymer polydiol Al by a transesterification reaction, an exogenous compound A4 selected from 1,2-diols and 1,3-diols. This additive composition makes it possible to modulate the rheological behavior of a medium in which it is added. The medium may be a hydrophobic medium, especially apolar, such as a solvent, a mineral oil, a natural oil, a synthetic oil. Polydiol Al Statistical Copolymers The polydiol Al random copolymer results from the copolymerization of at least one first monomer M1 carrying diol functions and at least one second monomer M2, of chemical structure different from that of the monomer M1. The term "copolymer" is intended to mean 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. 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. By "random copolymer" is meant 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 copolymers. 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 Figure 1. A gradient copolymer refers to a copolymer of at least two monomeric units of different structures whose monomer composition changes gradually along the polymer chain, passing thus 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. 1. 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 "C1 -C1 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, linear or branched hydrocarbon chain 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 comprising at least one unsaturation, preferably a carbon-carbon double bond, and comprising from 2 to 10 carbon atoms. "C7-C18 aralkyl" means an aromatic hydrocarbon compound, preferably monocyclic, substituted by at least one linear or branched alkyl chain and in which the total number of carbon atoms of the aromatic ring and its substituents ranges from to 18 carbon atoms. Illustratively, a C7-C18 aralkyl may be selected from the group consisting of benzyl, tolyl and xylyl. By "C 6 -C 18 aryl group substituted with an R '3" group is meant an aromatic hydrocarbon compound, preferably monocyclic, comprising from 6 to 18 carbon atoms of which at least one carbon atom of the aromatic ring is substituted by a group R'3. By "Hal" or "halogen" is meant a halogen atom 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 1 to 18, preferably ranging from 2 to 18; more preferably from 3 to 8; even 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, - W2 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: ## STR1 ## in which: (*) symbolize the bonds to the oxygen atoms, - R "2 is selected from the group consisting of a C6-C18 aryl, a C7-C18 aralkyl and a C2-C18 alkyl, preferably a C6 aryl -C18, more preferably phenyl.
[0009] Preferably, when W 2 and R "2 is a C 1 -C 11 alkyl group, the hydrocarbon chain is a linear chain, Preferably the C 1 -C 11 alkyl group is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decycling and n-undecyl. C1-C11 alkyl is methyl.
[0010] Preferably, when R "2 is a C 2 -C 18 alkyl group, the hydrocarbon chain is a linear chain Among the monomers of formula (I), the monomers corresponding to formula (IA) are among the preferred ones: H 2 C 0 HO Wherein R1 is selected from the group consisting of -H, -CH3 and -CH2-CH3, preferably -H and 25-x is an integer ranging from 1 to 18, preferably from 2 to 18, more preferably from 3 to 8, even more preferably x is equal to 4, y is an integer equal to 0 or 1, and preferably y is 0.
[0011] Among the monomers of formula (I), the monomers corresponding to formula (IB) are among the preferred ones: ## STR2 ## in which: R 1 is chosen from the group formed by -H, -CH 3 and CH 2 -CH 3, preferably -H and -CH 3; x is an integer from 1 to 18, preferably from 2 to 18; more preferably from 3 to 8; even more preferably x is 4; y is an integer equal to 0 or 1; preferably y is 0; Y 1 and Y 2, 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 among the group formed by hydrogen and a C1-C11 alkyl group or else Y1 and Y2 form with the oxygen atoms a boronic ester of the following formula: B./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, so more preferred is phenyl. Preferably, when W 2 and R "2 is a C 1 -C 11 alkyl group, the hydrocarbon chain is a linear chain, Preferably the C 1 -C 11 alkyl group is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decycling and n-undecyl. C1-C11alkyl is methyl Preferably, when R "2 is C2-C18alkyl; the hydrocarbon chain is a linear chain. Obtaining MI monomer The monomer M1 of general formula (IA) is obtained by deprotection of the alcohol functions of the monomer of general formula (IB) according to reaction scheme 1 below: ## STR1 ## with R1, Y1, Y2, x and y as defined in the general formula (IB) described above. The deprotection reaction of the diol functions of the monomer of general formula (I-B) is well known to those skilled in the art. It knows how to adapt the reaction conditions of deprotection according to the nature of the protective groups Yi and Y2. The monomer M1 of general formula (IB) can be obtained by reacting a compound of general formula (Ic) with an alcohol compound of general formula (Ib) according to reaction scheme 2 below: ## STR2 ## Wherein Y3 is selected from the group consisting of a halogen atom, preferably chlorine, -OH and 0-C (O) -R'1 with R'1 chosen from the group formed by -H, -CH3 and -CH2-CH3, preferably -H and -CH3, -R1, Y1, Y2, X and y have the same meaning as that given in general formula (IB). Coupling reactions are well known to those skilled in the art The compound of the general formula (Ic) is commercially available from the suppliers Sigma-Aldrich® and Alfa Aesar®.
[0012] 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 HO OH (la) HO protection Y10 0Y2 Scheme 3 with 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.
[0013] 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): H 2 C in which: R 2 is chosen from the group formed by -H, -CH 3 and -CH 2 -CH 3, preferably -H and - CH3; R3 is selected from the group consisting of a 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 with R'3 a C1-C30 alkyl group. Preferably, R'3 is a C1-C30 alkyl group whose hydrocarbon chain is linear.
[0014] Among the monomers of formula (II), the monomers corresponding to formula (II-A) are among the preferred ones: H 2 C (II-A) in which: R 2 is chosen from the group formed by -H, -CH 3 and CH 2 -CH 3, preferably -H and -CH 3; - R "3 is a C1-C14 alkyl group" C1-C14 alkyl group "means a linear or branched saturated hydrocarbon-based chain containing from 1 to 14 carbon atoms, preferably the hydrocarbon-based chain is linear Preferably, the hydrocarbon chain comprises from 4 to 12 carbon atoms. Among the monomers of formula (II), the monomers corresponding to formula (II-B) are also among the preferred ones: H2C 0 o (II-B) wherein: R2 is selected from the group consisting of -H, -CH3 and -CH2-CH3, preferably -H and -R '"3 is a C15-C30 alkyl group. By "C15-C30 alkyl group" is meant a saturated hydrocarbon chain, linear or branched comprising from 15 to 30 carbon atoms. Preferably, the hydrocarbon chain is linear. Preferably, the hydrocarbon chain comprises from 16 to 24 carbon atoms. Obtaining the M2 Monomer The monomers of formula (II), (II-A) and (II-B) are well known to those skilled in the art. They are marketed by Sigma-Aldrich® and TCIO. Preferred Polydiols Copolymers In one embodiment, a preferred random copolymer results from the copolymerization of at least: a first monomer M1 of general formula (I) as previously described; In particular of general formula (I-A) as described above; a second monomer M2 of formula (II) as described above, in which 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; in particular of general formula (I-A) as described above; a second monomer M2 of formula (II-A) as described above; and a third monomer M2 of formula (II-B) as previously described. 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; in particular of general formula (I-A) as described above; A second monomer M2 of formula (II-A) in which R2 is -CH3 and R "3 is a C4-C12 alkyl group, preferably a linear C4-C12 alkyl, a third monomer M2 of formula (II- B) wherein R2 is -CH3 and R '"3 is a C16-C24 alkyl group, preferably a C16-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 previously described; in particular of general formula (I-A) 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. Process for Obtaining Polydiol Copolymers Those skilled in the art are able to synthesize the polydiol Al random copolymers 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 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 Davis, TP Handbook of Radical Polymerization; Wiley-Interscience: Hoboken, 2002; p 936).
[0015] The polydiol random copolymer Al is prepared according to a preparation process which comprises at least one polymerization step (a) in which at least: i) a first monomer M1 of general formula (I) as described above is contacted: ii ) at least one second monomer M2 of general formula (II): iii) at least one source of free radicals.
[0016] 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 for generating a chemical species having one or more unpaired electrons on its surface. outer layer. Those skilled in the art can use any source of free radicals known per se and adapted to polymerization processes, especially controlled radical polymerization. Among the sources of free radicals, benzoyl peroxide, tert-butyl peroxide, diazo compounds such as azobisisobutyronitrile, peroxygen compounds such as persulfates or hydrogen peroxide, the systems are preferably exemplified. redox such as oxidation of Fe2 +, persulfate / sodium-metabisulphite mixtures, or ascorbic acid / hydrogen peroxide or photochemically cleavable compounds or ionizing radiation, for example ultraviolet or by beta or gamma radiation. 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. 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. In one embodiment, the method 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 the hydrogen, and further 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 X 1 and X 2 are identical and are an atom hydrogen. In one embodiment, the polymerization step (a) comprises contacting at least one monomer M1 with at least two monomers M2 having different R3 groups. In this embodiment, one of the monomers M2 has the general formula (II-A) as defined above and the other monomer M2 has the general formula (II-B) as defined above. The preferences and definitions described for the general formulas (I), (I-A), (I-B), (II-A), (II-B) also apply to the processes described above. Properties of Polydiols Al Copolymers The polydiol Al random copolymers are comb copolymers. "Comb copolymers" means a copolymer having a main chain (also called backbone) and side chains. The side chains are hanging on both sides of the main chain. The length of each side chain is less than the length of the main chain. Figure 2 schematically shows a comb polymer.
[0017] The Al copolymers have a skeleton of polymerizable functions, in particular a skeleton of methacrylate functions or styrene functions, and a mixture of hydrocarbon side chains which may or may not be substituted by diol functions. As the monomers of formula (I) and (II) have polymerizable functions of identical or substantially identical reactivity, a copolymer is obtained whose monomers having diol functions are statistically distributed along the backbone of the copolymer relative to the monomers whose chains alkyls are unsubstituted by diol functions. The polydiol Al random copolymers 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 random copolymer Al is a thermosensitive copolymer, that is to say that it is sensitive to changes in temperature. Advantageously, the side chains of the polydiol Al random copolymer 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 polydiol random copolymer Al 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 Al has a molar percentage of monomer M1 of formula (I) in said copolymer ranging from 1 to 30%, preferably 5 to 25%, more preferably ranging from 9 to 21%. In a preferred embodiment, the polydiol random copolymer Al has a molar percentage of monomer M1 of formula (I) in said copolymer ranging from 1 to 30%, preferably 5 to 25%, more preferably ranging from 9 to 21. %, a molar percentage of M2 monomer of formula (II-A) in said copolymer ranging from 8 to 92% and a molar percentage of monomer M2 of formula (II-B) in said copolymer 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 polydiol random copolymer Al has a molar percentage of monomer M1 of formula (I) in said copolymer ranging from 1 to 30%, a molar percentage of monomer M2 of formula (II-A) in said copolymer ranging from 8 to 62% and a molar percentage of M2 monomer of formula (II-B) in said copolymer ranging from 8 to 91%.
[0018] 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 Al statistical copolymer has a number-average degree of polymerization ranging from 100 to 2000, preferably from 150 to 1000. In known manner, the degree of polymerization is controlled using a controlled radical polymerization technique, a technique of telomerization or by adjusting the amount of free radical source when the copolymers of the invention are prepared by conventional radical polymerization. Advantageously, the polydiol random copolymer Al 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. Advantageously, the polydiol random copolymer Al has a number-average molar mass ranging from 10,000 to 400,000 g / mol, preferably from 25,000 to 150,000 g / mol, the number-average molar mass being obtained by chromatography measurement. Steric exclusion 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 ). Compound A2 - Boronic Diester Compound A2 In one embodiment, Compound A2 comprising two boronic ester functions has the general formula (III): ## STR3 ## in which: w 1 and W 2, identical or different, are numbers 0 or 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 from 4 to 18 carbon atoms, carbon, preferably from 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, compound A2 is a compound of general formula (III) above wherein: w 1 and w 2, the same or different, are integers equal to 0 or 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 group and is C6-C18 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: (III-c) Acetone, H20 R6 O R7 MgSO, OH (III-b) Scheme 4 with w1, w2 , L, R4, R5, R6 and R7 as defined above. In fact, by condensation of the boronic acid functional groups 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.
[0019] 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).
[0020] 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). In another embodiment, the compound A2 comprising at least two boronic ester functional groups is a poly (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. In the remainder of the application, the terms "boronic ester random copolymer" or "poly (boronic ester) random copolymer" are equivalent and denote the same copolymer. M3 Monomer of Formula (IV) The monomer M3 of boronic ester random copolymer compound A2 has the general formula (IV) wherein: ## STR1 ## wherein: t is an integer equal to 0 or 1; u is an integer equal to 0 or 1; M and R 8 are divalent, identical or different linking groups, and are selected from the group consisting of C 6 -C 18 aryl, C 7 -C 24 aralkyl and C 2 -C 24 alkyl, preferably C 6 -C 6 aryl; C18, X is a function selected from the group consisting of -O-C (O) -, -C (O) -O-, -C (O) -N (H) -, -N (H) -C ( 0) -, -S-, -N (M-, -N (R'4) - and -O- with R'4 a hydrocarbon chain comprising from 1 to 15 carbon atoms; R9 is selected from the group formed by -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, "C2-C24 alkyl" means a linear or branched saturated hydrocarbon chain comprising from 2 to 24 carbon atoms Preferably, the hydrocarbon chain is linear. 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, the monomer M3 has the general formula (IV) wherein: t is an integer of 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) Wherein R 9 is selected from the group consisting of -H, -CH 3, preferably -H; R10 and R11 are different, one of R10 or R11 is H and the other R10 or R11 is a hydrocarbon chain, preferably a linear alkyl group, having 1 to 24 carbon atoms, preferably 4 and 18 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 RE), 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 ## ## STR2 ## ## STR2 ## In fact, 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. The compounds of formula (IV-g) are commercially available from the following suppliers: Sigma-Aldrich®, Alfa Aesar® and TCIO. The compound of formula (IV-f) is obtained directly from the compound of formula (IV-e) by hydrolysis according to the following reaction scheme 6: R 1 2 0 H 2 O 1 /. ## STR2 ## wherein Z is an integer of 0 or 1; R 12 is selected from the group consisting of: ## STR5 ## wherein: the group formed by -H, -CH3 and -CH2-CH3; u, X, M, R8 and R9 as defined above R12 0 BM o Y4 (IV-e) Y5- (R8) u H2C (IV ## STR2 ## The compound of formula (IV-e) is obtained by reaction of a compound of formula (IV-c) with a compound of formula (IV-d) according to the following reaction scheme 7: R12 Scheme 7 with u, 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 (O) -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 funct carboxylic acid ion -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 represents -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. 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). The compounds of formula (IV-d) are commercially available from the suppliers: Sigma-Aldrich®, TCIO and Acros Organics®.
[0021] 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: R12 (IV -b) (IV-c) OH OH Acetone, H 2 O (/ / BM M MgSO 4, yO HO MB, Y 4 OH OH (IV-a) Scheme 8 with M, Y 4, Z and R 12 as defined above Among the compounds of formula (IV-b), the one in which R12 is methyl and z = 0 is preferred. The compounds of formula (IV-a) and (IV-b) are commercially available from the following Sigma-based suppliers. Aldrich®, Alfa Aesar® and TCIO 7 M4 Monomer of General Formula (V): The monomer M4 of the boronic ester random copolymer A2 has the general formula (V) R 12 H 2 C R 13 (y) in which: R 12 is selected from the group consisting of group formed by -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 an R'13 group , -C (O) -O-R'13, OR 13, -S-R'13 and -C (O) -N (H) -R '13 with R'13 a C1-C25 alkyl group. By "C1-C25 alkyl group" is meant a saturated hydrocarbon chain, linear or branched, comprising from 1 to 25 carbon atoms. Preferably, the hydrocarbon chain is linear.
[0022] By "C16-C18 aryl group substituted with an R13 group" is meant an aromatic hydrocarbon compound comprising from 6 to 18 carbon atoms, at least one carbon atom of the aromatic ring is substituted by a C 1 -C 25 alkyl group such as defined above.
[0023] Among the monomers of formula (V), the monomers corresponding to formula (VA) are among the preferred ones: H 2 C (VA) in which: R 2 is chosen from the group formed by -H, -CH 3 and -CH 2 -CH 3, preferably - H and -CH3; R'13 is a C1-C25 alkyl group, preferably a C1-C25 linear alkyl, even more preferably a linear C5-C15 alkyl.
[0024] Obtaining M4 Monomer: The monomers of formulas (V) and (V-A) are well known to those skilled in the art. They are marketed by Sigma-Aldrich® and TCIO. Synthesis of Compound A2 Statistical Compound Poly (Boronic Ester) One skilled in the art is able to synthesize the boronic ester random copolymers using his general knowledge. The copolymerization can be initiated in bulk or in solution in an organic solvent with compounds generating free radicals. 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 Davis, TP Handbook of Radical Polymerization; Wiley-Interscience: Hoboken, 2002; p 936)). The boronic ester statistical copolymer is prepared according to a process which comprises at least one polymerization step (a) in which at least: i) a first monomer M3 of general formula (IV) as defined above; ii) at least one second monomer M4 of general formula (V) as defined above: iii) at least one source of free radicals. 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. 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 Compounds A2 Statistical Copolymers Poly (Boronic Ester) Advantageously, the chain formed by the linking of the groups R 10, M, (R 8) 'with u, an integer equal to 0 or 1, and X of the monomer M 3 of formula general (IV) has a total number of carbon atoms ranging from 8 to 38, preferably ranging from 10 to 26. 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. 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. 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) in said copolymer 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) in said copolymer ranging from 0.25 to 20%, preferably from 1 to 10% and a molar percentage of monomer of formula (V) in said copolymer ranging from 80 to 99.75%, preferably from 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 polystyrene calibration. Advantageously, the boronic ester statistical copolymer has a number-average molar mass ranging from 10,000 to 200,000 g / mol, preferably from 25,000 to 100,000 g / mol. These values are obtained by size exclusion chromatography using tetrahydrofuran as eluent and a polystyrene calibration. The compound A2, in particular the boronic ester random copolymer, has the property of being able to react in a hydrophobic medium, in particular apolar medium, with a compound carrying a diol function (s) by a transesterification reaction. This transesterification reaction can be represented according to the following scheme 9: Scheme 9 Thus, during a transesterification reaction, a boronic ester of chemical structure different from the starting boronic ester is formed by exchange of the hydrocarbon groups 10 symbolized by And exogenous compound A4 The exogenous compound A4 is chosen from 1,2 diols and 1,3 diols. "Exogenous compound" is understood to mean, within the meaning of the present invention, a compound which is added to the composition of the additives resulting from the mixing of at least one random polydiol Al copolymer and at least one A2 compound, especially the poly (boronic ester) random copolymer The exogenous compound A4 may have the general formula (VI): R14 R15 In which: w3 is an integer equal to 0 or 1, R14 and R15, which are identical or different, are chosen from the group formed by hydrogen and a hydrocarbon chain having from 1 to 24 a carbon atoms, preferably between 4 and 18 carbon atoms, preferably between 6 and 12 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, the exogenous compound A4 has the general formula (VI) wherein: - w3 is an integer of 0 or 1; R14 and R15 are different, one of the groups R14 OR R15 is H and the other group R14 OR R15 is a hydrocarbon chain, preferably a linear alkyl group, having 1 to 24 carbon atoms, preferably 4 and 18 carbon atoms, preferably between 6 and 12 carbon atoms. In one embodiment, the exogenous compound A4 has a different chemical structure of the diol compound A3 released in situ by transesterification reaction. In this embodiment, at least one of the substituents R14, R15 or the value of the index w3 of the exogenous compound A4 of formula (VI) is different respectively from the substituents R4 and R5 or from the value of the index w1 or substituents R5 and R7 or the value of the index w2 of the compound A2 diester boronic of formula (III) or is different respectively from the substituents R10, R11 or from the value of the index t of the monomer (IV) of the random copolymer poly (boronic ester) A2. In another embodiment, the exogenous compound A4 has a chemical structure identical to the diol compound A3 released in situ by transesterification reaction. In this embodiment, the substituents R14, R15 and the value of the index w3 of the exogenous compound A4 of formula (VI) are identical respectively to the substituents R4 and R5 and to the value of the index w1 or to the R5 and R7 and the value of the index w2 of the compound A2 diester boronic of formula (III) or is identical respectively to the substituents R10, R11 and the value of the index t of the monomer (IV) of the random copolymer poly (boronic ester A2. Depending on its temperature of use, the additive composition results from the mixture of at least one polydiol random copolymer Al, at least one compound A2, in particular a random copolymer A2, comprising at least two boronic ester functions and which can be associate with said polydiol Al random copolymer by a transesterification reaction, and an addition of at least one exogenous compound A4 as defined above, may further comprise a compound A3 diol released in situ, identical to the exogenous compound A4 added in the composition. For the purpose of the present invention, the term "diol released in situ" is understood to mean the compound carrying a diol function, this compound being produced in the additive composition during the exchange of the hydrocarbon groups of the boronic ester compound A2, in particular the poly (boronic ester) random copolymer, during the transesterification reaction. The random polymer Al polydiol is not a diol released in situ within the meaning of the present invention. The compounds of formula (VI) are commercially available from the following suppliers: Sigma-Aldrich®, Alfa Aesar® and TCIO. Characteristic of the novel additive compositions of the invention The additive compositions of the invention resulting from the mixture of at least one polydiol random copolymer Al as defined above, of at least one compound A2 as defined previously, in particular at least one poly (boronic ester) random copolymer as defined above, and at least one exogenous compound A4 as defined above have very varied rheological properties as a function of the temperature and according to the proportion of the compounds Al, A2 and A4 used.
[0025] The polydiols random copolymers Al 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.
[0026] Under certain conditions, the polydiols random copolymers Al and the compounds A2 as defined above can be crosslinked. The polydiols random copolymers Al and the compounds A2 also have the advantage of being exchangeable. The term "associative" is understood to mean that covalent boronic ester-type chemical bonds are established between the polydiol random copolymers Al and the compounds A2 comprising at least two boronic ester functional groups, in particular with the poly (boronic ester) random copolymer. Depending on the functionality of the Al polydiols and the A2 compounds and depending on the composition of the mixtures, the formation of covalent bonds between the Al polydiols and the A2 compounds may or may not lead to the formation of a three-dimensional polymeric network.
[0027] By "chemical bond" is meant a covalent chemical bond of the boronic ester type. By "exchangeable" is meant that the compounds are able to exchange chemical bonds between them without the total number and nature of chemical functions being changed. The boronic ester bonds of the A2 compounds, the boronic ester bonds formed by transesterification reaction between the boronic esters of the A2 compounds and the exogenous compounds A4, as well as the boronic ester bonds formed by the combination of the polydiols Al random copolymers and the A2 compounds can be exchange with diol functions carried by the exogenous compounds A4 or carried by the released compounds A3 in situ to form new boronic esters and new diol functions without the total number of boronic ester functions and diol functions being affected.
[0028] In the presence of exogenous compounds A4, the boronic ester bonds of the compounds A2 as well as the boronic ester bonds formed by the combination of the polydiols random copolymers Al and the compounds A2 can also be exchanged to form new boronic esters without the total number of functions boronic esters is affected. This other process of exchange of chemical bonds is carried out by metathesis reaction, via successive exchanges of boronic ester functions in the presence of diol compounds (compounds released in situ A3 and exogenous compounds A4); this process is illustrated in FIG. 9. The polydiol random copolymer A1-1, which was associated with the A2-1 polymer, 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.
[0029] Another chemical link exchange process is illustrated in FIG. 9, in which it can be seen 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 A1-2, 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 copolymer A1-2 is then associated with the polymer A2-1. 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) and boronic ester functions of a crosslinking agent (compound A2). The bridges formed are boronic ester type bonds. These boronic ester bonds are covalent and labile because of the reversibility of the stereotransformation reaction.
[0030] 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. Unexpectedly, the Applicant has observed that the presence of exogenous compounds A4 in this additive composition makes it possible to control the rate of association and dissociation between the polydiol Al statistical copolymer and the A2 compound, in particular the poly ( boronic ester). The thermoreversible crosslinking mechanism of the additive composition of the invention in the presence of exogenous compounds A4 is shown schematically in FIG. 4.
[0031] Unexpectedly, the Applicant has observed that at low temperature, the polydiol copolymer Al (symbolized by the copolymer bearing functions A in FIG. 4) is not or very little crosslinked by the boronic ester compounds A2 (symbolized by the compound carrying functions B in Figure 4). The boronic ester compounds A2 establish boronic ester bonds with the exogenous compound A4 (symbolized by the compound C in Figure 4) by transesterification reaction. The polydiol random copolymer Al is a thermosensitive copolymer. When the temperature increases, the conformation in the space of the chains of this copolymer is modified; diol functions are made more accessible to association reactions. Thus, when the temperature increases, the diol functions of the copolymer Al react with the boronic ester functions of the compound A2 by a transesterification reaction and release in situ an A3 diol. The polydiols random copolymers Al and the compounds A2 comprising at least two boronic ester functions then bind together and can be exchanged. Depending on the functionality of Al polydiols and A2 compounds and depending on the composition of the mixtures, a gel may form in the medium, especially when the medium is apolar. When the temperature decreases again, the boronic ester bonds between the polydiols random copolymers A1 and the A2 compounds are broken, and if necessary, the composition loses its gel character. The compounds A2, in particular the random poly (boronic ester) copolymer, then establish boronic ester bonds by transesterification reaction with the exogenous compound A4 or with the diol compound A3 released in situ. By controlling the degree of association of the polydiol Al random copolymer and of the compound A2, in particular the poly (boronic ester) static copolymer, the viscosity and the rheological behavior of this composition are modulated. The exogenous compound A4 makes it possible to modulate the viscosity of this composition as a function of the temperature and according to the desired use.
[0032] In a preferred embodiment of the invention, the exogenous compound A4 is of the same chemical nature as the diol compound A3 released in situ by transesterification reaction between the polydiol random copolymer Al and the compound A2, in particular the poly (ester) random copolymer. boronic acid). The total amount of free diols present in said composition is strictly greater than the amount of diol compounds released in situ. By "free diols" is meant diol functions which are capable of forming a chemical bond of boronic ester type by transesterification reaction. By "total amount of free diols" is meant in the sense of the present application, the total number of diol functions capable of forming a boronic ester chemical bond by transesterification. The total amount of free diols is always equal to the sum of the number of moles of exogenous diol compounds A4 and the number (expressed in moles) of diol functions of the polydiol copolymer Al. In other words, if in the composition of In the additives, there are: - 1 moles of exogenous diol compounds A4 and - mole of polydiol Al random copolymers, the total amount of free diol will be at any time (therefore regardless of the degree of association between the polydiol random copolymer Al and the compound A2, in particular the random copolymer poly (boronic ester) A2) = i + j * the average number of diols per random polymer chain Al (unit: mol).
[0033] The amount of diols released in situ in the context of the transesterification reactions between Al and A2 is equal to the number of boronic ester functions linking the copolymers Al and A2. The person skilled in the art knows how to select the chemical structure and the quantity of exogenous compounds A4 that he adds to the additive composition as a function of the molar percentage of boronic ester function of compound A2, in particular as a function of the random poly (ester) copolymer boronic), to modulate the rheological behaviors of the composition. The amount of boronic ester bonds (or boronic ester link) which can be established between the polydiols random copolymers Al and the compounds A2, in particular the random copolymers poly (boronic ester), is adjusted by those skilled in the art by means of a appropriate selection of the polydiol Al random copolymer, the compound A2 and the composition of the mixture. Furthermore, one skilled in the art knows how to select the structure of the compound A2, in particular of the random poly (boronic ester) random copolymer, as a function of the structure of the random copolymer Al. Preferably, when in the random copolymer Al 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 be chosen preferably with w1 = 1, 20 w2 = 1 and t = 1 , respectively. Advantageously, the content of random copolymer Al in the composition ranges from 0.1% to 99.5% by weight relative to the total weight of the additive composition, preferably from 0.25% to 80% by weight relative to relative to the total weight of the additive composition, more preferably from 1% to 50% by weight based on the total weight of the additive composition. Advantageously, the content of compound A2, in particular of poly (boronic ester) random copolymer, in the composition ranges from 0.1% to 99.5% by weight relative to the total weight of the additive composition, preferably from 0.25% to 80% by weight relative to the total weight of the additive composition, more preferably from 0.5% to 50% by weight relative to the total weight of the additive composition. In one embodiment, the mole percentage of exogenous compound A4 in the additive composition is from 0.025% to 5000%, preferably from 0.1% to 1000%, more preferably from 0.5 to 500%. %, even more preferably 1% to 150% relative to the boronic ester functions of the compound A2, especially the poly (boronic ester) random copolymer. The molar percentage of exogenous compound A4 relative to the number of boronic ester functions of compound A2 is the ratio of the number of moles of exogenous compound A4 to the number of moles of boronic ester function of compound A2 multiplied by one hundred. The number of moles of boronic ester function of the compound A2 can be determined by those skilled in the art by NMR analysis of the proton of the compound A2, or by following the conversion to monomers during the synthesis of the copolymer A2, when the compound A2 is a poly (boronic ester) random copolymer. Preferably, the mass ratio (A 1 / A2 ratio) between the polydiol Al statistical compound and the A2 compound, in particular the poly (boronic ester) random copolymer, in the additive composition ranges from 0.005 to 200, preferably from 0.degree. , 05 to 20, even more preferably from 0.1 to 10, even more preferably from 0.2 to 5. In one embodiment, the composition of the invention may further comprise at least one additive selected among the group formed by thermoplastics, elastomers, thermoplastic elastomers, thermosetting polymers, pigments, dyes, fillers, plasticizers, fibers, antioxidants, lubricant additives, compatibilizers, agents and the like. anti-foams, dispersant additives, adhesion promoters and stabilizers. Process for the Preparation of the New Additive Compositions of the Invention The novel additive 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; withdrawing a desired quantity of a solution comprising compound A2 as defined above; in particular a desired amount of a solution comprising the poly (boronic ester) random copolymer as defined above; and - withdrawing a desired amount of a solution comprising the exogenous compound A4 as defined above - mixing the three solutions taken, either simultaneously or sequentially, to obtain the composition of the invention. The order of addition of the compounds has no influence in the implementation of the process for preparing the additive composition. The person skilled in the art also knows how to adjust the various parameters of the composition of the invention to obtain either a composition in which the polydiol random copolymer Al and the compound A2, in particular the boronic ester statistical copolymer, are combined either with a composition in which the polydiol Al random copolymer and the compound A2, in particular the boronic ester random copolymer, are crosslinked and to modulate the degree of association or the degree of crosslinking for a given use temperature. For example, those skilled in the art can adjust, in particular: the molar percentage of monomer M1 carrying diol functions in the polydiol random copolymer Ai; the molar percentage of monomer M3 bearing boronic ester functions in the boronic ester random copolymer A2; the average length of the side chains of the polydiol random copolymer Ai; 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 number-average degree of polymerization of the polydiol Al random copolymers and of the boronic ester random copolymers A2; the mass percentage of the polydiol random copolymer Ai; the mass percentage of the boronic diester compound A2; the weight percentage of the boronic ester random copolymer A2; the molar quantity of the exogenous compound A4 relative to the boronic ester functions of the compound A2, in particular the random poly (boronic ester) copolymer, the chemical nature of the exogenous compound A4; the molar percentage of exogenous compound A4; Use of the New Compositions of the Invention The compositions of the invention can be used in all media whose viscosity varies as a function of temperature. The compositions of the invention make it possible to thicken a fluid and to modulate the viscosity as a function of the temperature of use. The additive composition according to the invention can be used in fields as varied as the improved recovery of oil, the paper industry, paints, food additives, cosmetic or pharmaceutical formulation. Another object of the present invention relates to a lubricant composition resulting from the mixture of at least one lubricating oil and a random polydiol Al copolymer as defined above, a random copolymer A2, as defined above, comprising at least two boronic ester functional groups which can associate with said polydiol Al random copolymer by at least one transesterification reaction, an exogenous compound A4 chosen from 1,2-diols and 1,3-diols, and especially as defined previously. The preferences and definitions described for the general formulas (I), (IA), (IB), (II-A), (II-B) also apply to the random polydiol Al copolymer used in the lubricating compositions of the invention. . The preferences and definitions described for general formulas (IV) and (V) also apply to the boronic ester random copolymer A2 used in the lubricant compositions of the invention.
[0034] The lubricating compositions according to the invention have an inverted behavior with respect to a modification of the temperature with respect to the behavior of the base oil and the polymer type rheological additives of the prior art and have the advantage that this rheological behavior can be modulated according to the temperature of use. Unlike the base oil which becomes liquefied as the temperature increases, the compositions of the present invention have the advantage of thickening as the temperature increases. The formation of reversible covalent bonds makes it possible to increase (reversibly) the molar mass of the polymers and thus limits the drop in the viscosity of the base oil at high temperatures. The additional addition of diol compounds makes it possible to control the rate of formation of these reversible bonds. Advantageously, the viscosity of the lubricating composition is thus controlled and depends less on temperature fluctuations. In addition, for a given temperature of use, it is possible to modulate the viscosity of the lubricating composition and its rheological behavior by varying the amount of diol compounds added to the lubricating composition. o Lubricating oil By "oil" is meant a liquid fatty substance at room temperature (25 ° C) and atmospheric pressure (760 mmm Hg evening 105 Pa). By "lubricating oil" is meant an oil that attenuates the friction between two parts in 25 movements 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 ... 30 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 of 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, bases hydrocracked minerals 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 n, etc., components derived from petrochemicals, 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 Basic 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 H 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 base groups I to IV * measured according to ASTM D2007 ** measured according to ASTM D2622, ASTM D4294, ASTM D4927 and ASTM D3120 *** measured according to ASTM D2270. The compositions of the invention can be make one or more lubricating oils. The lubricating oil or the lubricating oil mixture is the major ingredient in the lubricating composition. This is called lubricating base oil. By major ingredient is meant that the lubricating oil or the lubricating oil mixture represents at least 51% 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.
[0035] 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.
[0036] 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 preferably from grade SAE 20W to grade SAE 50 (SAE means Society of Automotive Engineers or Functional Additives In one embodiment, the composition of the invention can further comprising a functional additive selected from the group consisting of detergents, antiwear additives, extreme pressure additives, antioxidants, viscosity index improvers, pour point improvers, defoamers thickeners, anti-corrosion additives, dispersants, friction modifiers and mixtures thereof Functional additive (s) added to the composition of the invention are chosen according to the end use of the lubricating composition. can be introduced in two different ways: either each additive is added individually and sequentially in the composition, or the whole of 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.
[0037] Detergents: These additives reduce the formation of deposits on the surface of metal parts by dissolving secondary products of oxidation and combustion. 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.
[0038] Anti-wear additives and extreme pressure additives: These additives protect the 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 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.
[0039] 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).
[0040] The 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, slowing down the formation of paraffin crystals. They are, for example, alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes and alkylated polystyrenes. - Defoamers: 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. Process for the Preparation of the Lubricating Compositions of the Invention The lubricating compositions of the invention are prepared by means well known to those skilled in the art. For example, it suffices for a person skilled in the art, in particular: to take a desired quantity of a solution comprising the polydiol 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) and at least one monomer of formula (II-B); - Take a desired amount of a solution comprising the random copolymer A2 poly (boronic ester) as defined above; - Take a desired amount of a solution comprising the exogenous compound A4 as defined above - Mix either simultaneously or sequentially the three solutions taken from a lubricating base oil, to obtain the lubricant composition of the invention. The order of addition of the compounds has no influence in the implementation of the process for preparing the lubricant composition. Properties of the lubricant compositions according to the invention The lubricant compositions of the invention result from the mixture of associative polymers which have the property of increasing the viscosity of the lubricating oil by combinations, and in particular in some cases by crosslinking. The lubricating compositions according to the invention have the advantage that these combinations or crosslinking are thermoreversible and that the level of association or crosslinking can be controlled by the addition of an additional diol compound. Those skilled in the art can adjust the various parameters of the various constituents of the composition to obtain a lubricant composition whose viscosity increases when the temperature increases and to modulate its viscosity and rheological behavior. The amount of boronic ester bonds (or boronic ester bond) which can be established between the polydiols random copolymers Al and the compounds A2, in particular the boronic ester random copolymer 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 from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) and at least one monomer of formula (II-B), of the compound A2, in particular the boronic ester random copolymer A2, of the exogenous compound A4, and in particular the molar percentage of exogenous compound A4. In addition, the person skilled in the art knows how to select the structure of the compound A2, in particular of the boronic ester statistical copolymer, 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) and at least one monomer of formula (11-B). 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) and at least one monomer of formula (II-B ), 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. Moreover, one 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) and at least one monomer of formula (II-B) - the molar percentage of monomer M3 carrying boronic ester functions in the boronic ester random copolymer A2, - the average length of the side chains of the copolymer polydiol 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) and at least one monomer of formula (II-B) - the average length of side chains of the boronic ester random copolymer A2, - the length of the M3 monomer of the boronic ester random copolymer A2, - the average degree of polymerization of the polydiol Al random copolymers, in particular ent that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) and at least one monomer of formula (II-B), and random copolymers boronic esters A2, the weight 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 one monomer of formula (II-A) and at least one monomer of formula (II-B) the mass percentage of the boronic ester random copolymer A2, the molar percentage of exogenous compound A4 relative to the boronic ester functions of the compound A2, in particular of the poly (boronic ester) random copolymer, Advantageously, the content 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) and at least one monomer of formula (II-B) in the lubricating composition is 0.25 % to 20% by weight relative to the total weight of the lubricating composition, preferably from 1% to 10% by weight relative to the total weight of the lubricant composition.
[0041] Advantageously, the content of compound A2, in particular the content of random boronic ester copolymer, ranges from 0.25% to 20% by weight relative to the total weight of the lubricating composition, preferably preferably from 0.5 to 10% by weight. weight relative to the total weight of the lubricating composition. Preferably, the mass ratio (ratio Ai / A2) between the polydiol Al statistical compound, in particular that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) and at least one a monomer of formula (II-B), and the compound A2, in particular the boronic ester statistical copolymer, ranges from 0.001 to 100, preferably from 0.05 to 20, even more preferably from 0.1 to 10, of more preferably from 0.2 to 5.
[0042] In one embodiment, the sum of the masses of 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) and at least one monomer of formula (II-A2), and of the compound A2, in particular of the boronic ester random copolymer, is from 0.5 to 20% relative to the total mass of the lubricating composition, preferably from 4% to 15% relative to the total mass of the lubricating composition and the lubricating oil mass is from 60% to 99% relative to the total mass of the lubricating composition. In one embodiment, the mole percentage of exogenous compound A4 in the lubricating composition is from 0.05% to 5000%, preferably from 0.1% to 1000%, more preferably from 0.5% to 500%, even more preferably from 1% to 150% relative to the boronic ester functions of compound A2, in particular the poly (boronic ester) random copolymer. In one embodiment, the lubricant composition of the invention results from the mixture of: - 0.5% to 20% by weight of at least one polydiol random copolymer Al 15 as defined above, relative to the total weight of the lubricating composition; - 0.5% to 20% by weight of at least one compound A2 as defined above, in particular boronic ester random copolymer; relative to the total weight of the lubricating composition; and from 0.001% to 0.5% by weight of at least one exogenous compound A4 as defined above, relative to the total weight of the lubricating composition, and from 60% to 99% by weight of at least one oil lubricant as defined above, relative to the total weight of the lubricant composition. In another embodiment, the lubricating composition of the invention results from the mixture of: from 0.5% to 20% by weight of at least one random polydiol Al copolymer as defined above, relative to the total weight of the lubricating composition; From 0.5% to 20% by weight of at least one compound A2 as defined above, in particular of boronic ester random copolymer; relative to the total weight of the lubricating composition; and - 0.001% to 0.5% by weight of at least one exogenous compound A4 as defined above, relative to the total weight of the lubricating composition, and 35 - 0.5% to 15% by weight of at least a functional additive as defined above, relative to the total weight of the lubricating composition, and - 60% to 99% by weight of at least one lubricating oil as defined above, relative to the total weight of the lubricating composition.
[0043] Process for modulating the viscosity of a lubricating composition Another object of the present invention is a method for modulating the viscosity of a lubricating composition, the process comprising at least: providing a lubricating composition resulting from mixing at least one lubricating oil, at least one polydiol random copolymer A1 and at least one random copolymer A2 comprising at least two boronic ester functions and capable of associating with said polydiol random copolymer Al by at least one transesterification reaction, the addition in said lubricant composition of at least one minus an exogenous compound A4 selected from 1,2-diols and 1,3-diols. By "modulating the viscosity of a lubricating composition" is meant within the meaning of the present invention, an adaptation of the viscosity at a given temperature depending on the use of the lubricating composition. This is achieved by adding an exogenous compound A4 as defined above. This compound makes it possible to control the degree of association and crosslinking of the two copolymers polydiol Al and poly (boronic ester) A2. Preferably, these 1,2-diol or 1,3 diols have the general formula (VI): ## STR3 ## with an integer of 0 or 1; R14 and R15 identical or different selected from the group consisting of hydrogen and a hydrocarbon group having 1 to 24 carbon atoms. In one embodiment, these 1,2-diol or 1,3-diols have the general formula (VI) wherein: w is an integer of 0 or 1; R14 and R15 are different, one of the groups R14 OR R15 is H and the other group R14 OR R15 is a hydrocarbon chain, preferably a linear alkyl group, having 1 to 24 carbon atoms, preferably 4 and 18 carbon atoms, preferably between 6 and 12 carbon atoms. The definitions and preferences relating to lubricating oils, random copolymers A1, especially that resulting from the copolymerization of at least one monomer of formula (I) with at least one monomer of formula (II-A) and at least one monomer of Formula (II-B), boronic ester random copolymer A2 and exogenous compound A4 also apply to processes for modulating the viscosity of a lubricating composition. Other objects are the inventi on. Another object of the present invention is the use of the lubricant composition as defined above for lubricating a mechanical part. In the remainder of the description, the percentages are expressed by weight relative to the total weight of the lubricating composition. 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, said composition comprising, in particular, essentially consisting of a composition resulting from the mixing of: 97% to 99.98% by weight of a lubricating oil, and 0.1% to 3% by weight of at least 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) and at least one monomer of formula (II-B), at least one random boronic ester copolymer A2 as defined above; and 0.001% to 0.1% by weight of at least one exogenous compound A4 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; the percentages by weight being expressed relative to the total weight of said composition. In a composition for lubricating at least one engine as defined above, the random copolymers 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 ) and at least one monomer of formula (II-B), and the boronic ester random copolymers A2 as defined above can associate and exchange thermoreversibly in the presence of the exogenous compound A4; 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. In one embodiment of the invention, the composition for lubricating at least one engine, said composition comprising, in particular, essentially consists of a composition resulting from the mixing of: 82% to 99% by weight of a lubricating oil, and 0.1% to 3% by weight of at least 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 ) and at least one monomer of formula (II-B), at least one random boronic ester copolymer A2 as defined above; and 0.001% to 0.1% by weight of at least one exogenous compound A4 as defined above; 0.5 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, anticorrosion additives, polymers improving the 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 percentages by weight being expressed relative to the total weight of said composition.
[0044] The definitions and preferences relating to lubricating oils, to statistical copolymers 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) and at least one monomer of formula (II-B), the boronic ester random copolymer A2 and the exogenous compound A4 also apply to the compositions for lubricating at least one motor.
[0045] Another object of the present invention is a composition for lubricating at least one transmission, such as manual or automatic gearboxes. Thus another object of the present invention is a composition for lubricating at least one transmission, said composition comprising, in particular, essentially consisting of a composition resulting from the mixing of: 85% to 99.49% by weight of a lubricating oil, and 0.5% to 15% by weight of at least 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 ) and at least one monomer of formula (II-B), at least one boronic ester random copolymer A2 as defined above; and 0.001% to 0.5% by weight of at least one exogenous compound A4 as defined above; the composition having a kinematic viscosity at 100 ° C measured according to ASTM D445 ranging from 4.1 to 41 cSt, the percentages by weight being expressed relative to the total weight of said composition. In a composition for lubricating at least one transmission as defined above, the random copolymers 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) and at least one monomer of formula (II-B), and the boronic ester random copolymers A2 as defined above can associate and exchange thermoreversibly in the presence of the exogenous compound A4; but they do not form three-dimensional networks. They are not crosslinked. In one embodiment the composition for lubricating at least one transmission 5 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. In one embodiment of the invention, the lubricating composition for lubricating at least one transmission, said composition comprising, in particular, essentially consists of a composition resulting from the mixing of: 70% to 99.39% by weight of a lubricating oil, and 0.5% to 15% by weight of at least 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) and at least one monomer of formula (II-B), at least one random boronic ester copolymer A2 as defined above; and 0.001% to 0.5% by weight of at least one exogenous compound A4 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 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 percentages by weight being expressed relative to the total weight of said composition. The definitions and preferences relating to lubricating oils, to random copolymers 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) and at least one monomer of Formula (II-B), boronic ester random copolymer A2 and exogenous compound A4 also apply to the compositions for lubricating at least one transmission. 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 lubricant composition as defined above.
[0046] The definitions and preferences relating to lubricating oils, to random copolymers 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) and at least one monomer of formula (II-B), boronic ester random copolymers A2 and exogenous compound A4 also apply to the method of lubricating at least one mechanical part. Another subject of the present invention relates to the use of at least one compound chosen from 1,2-diols or 1,3 diols for modulating the viscosity of a lubricating composition, said lubricating composition resulting from the mixing of at least one lubricating oil, at least one polydiol random copolymer Al and at least one random copolymer A2 comprising at least two boronic ester functions and capable of associating with said polydiol Al random copolymer by at least one transesterification reaction. Preferably, these 1,2-diol or 1,3 diols have for general formula (VI): ## STR2 ## with: w an integer equal to 0 or 1; R14 and R15 identical or different selected from the group consisting of hydrogen and a hydrocarbon group having 1 to 24 carbon atoms. In one embodiment, these 1,2-diol or 1,3 diols have the general formula (VI) wherein: w3 is an integer of 0 or 1; R14 and R15 are different, one of R14 OR R15 is H and the other R14 OR R15 is a hydrocarbon chain, preferably a linear alkyl group having 1 to 24 carbon atoms, preferably 4 to 18 carbon atoms, preferably between 6 and 12 carbon atoms.
[0047] EXAMPLES The following examples illustrate the invention without limiting it. Synthesis of random copolymers A1 bearing diol function O / ./: From a monomer carrying a protected diol function in the form of ketol In one embodiment, the random copolymer Al of the invention is obtained according to FIG. The following reaction scheme is as follows: ## STR1 ## wherein the reaction is carried out in a controlled manner.
[0048] Protected Copolymers Y Copolymers poly (alkyl methacrylamidol) -alkyl dialkyl methacrylate Scheme 10 1.1.1 Synthesis of monomer M1 bearing a protected diol function in ketol form Synthesis of a methacrylate monomer carrying a diol function The ketal protected form is carried out in two steps (steps 1 and 2 of Reaction Scheme 10) according to the protocol below: Vele step: 42.1 g (314 mmol) 1,2,6-hexane triol (1,2,6-HexTri) are introduced into an IL flask 5.88 g of molecular sieve (4A) are added followed by 570 mL of acetone 5.01 g (26.3 mmol) para-toluenesulfonic acid (pTSA) are then slowly added The reaction medium is left stirring for 24 hours at room temperature 4.48 g (53.3 mmol) of NaHCO 3 are then added. stirring for 3 hours at room temperature before being filtered, the filtrate is then concentrated in vacuo using a Rotating aporator until a suspension of white crystals. 500 ml of water are then added to this suspension. The solution thus obtained is extracted with 4 × 300 ml of dichloromethane. The organic phases are combined and dried over MgSO.sub.4. 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 MgSO 4, 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 liquid. light yellow with the following characteristics: NMR (400 MHz, CDCl3): 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 Bearing Diol Functions The synthesis of methacrylate copolymers carrying diol functions is carried out in two steps (steps 3 and 4 of reaction scheme 10): Copolymerization of two monomers alkyl methacrylate with a carrier methacrylate monomer of 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.
[0049] A copolymer having a number average molecular weight (M11) of 51,400 g / mol, a polydispersity index (Ip) of 1.20 and a number-average degree of polymerization (D1311) of 184. These values are thus obtained. 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: 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.
[0050] 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. 2. Synthesis of the poly (alkyl methacrylate-co-monomer boronic ester copolymer o 2.1: Synthesis of the boronic acid monomer The boronic ester monomer is synthesized according to the following reaction scheme 11: The monomer is obtained according to the protocol in two steps: The first step is to synthesize a boronic acid and the second step is to obtain a boronic ester monomer. "Step 4-carboxyphenylboronic acid (CPBA) (5.01 g, 30.2 mmol) is introduced into a beaker of IL followed by 350 mL of acetone and the reaction mixture is stirred 7.90 mL (439 mmol) of water are added dropwise until complete dissolution of the 4-carboxyphenylboronic acid. The reaction medium is then transparent and homogeneous, 1,2-propanediol (2.78 g, 36.6 mmol) is then slowly added, followed by an excess of sodium sulphate (CH.sub.2 O.sub.3). 25 magnesium in order to trap the water initially introduced 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.
[0051] 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 using a rotary evaporator to give the boronic acid monomer (5.70 g, 92.2% yield) as a white powder, which had the following characteristics: 1H NMR (400MHz, CDCl3): 7.98 (doublet, J = 5.6Hz, 4H), 7.49 (doublet, J = 4Hz, 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 21: The boronic acid monomer (5.7 g, 20.2 mmol) obtained in the first step and 500 mL of acetone are introduced into an 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. as well 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 using a rotary evaporator to give 10.2 g of a mixture of boronic ester monomer and 1,2-dodecanediol as a light yellow solid. The characteristics are as follows: 1H NMR (400 MHz, CDCl3): Boronic ester monomer: 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 35 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:: 3.61-3.30 (multiplet, about 1.62H), 1.78-1.34 (multiplet, about 9.72H), 0.87 (triplet, J = 6.4 Hz, about 1.62H) o 2.2 Polymeric copolymer synthesis A2 poly (alkyl methacrylate-co-monomer boronic ester) The random copolymer A2 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 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 anhydrous acetone, filtration and drying under vacuum at 30 ° C overnight. A copolymer having the following structure is thus obtained: m = 0.96 and n = 0.04. The resulting boronic ester copolymer has a number average molecular weight (M.) of 37,200 g / mol, a polydispersity index (Ip) of 1.24 and a number average degree of polymerization (DP11) equal to 166. These 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. Proton NMR analysis of the final copolymer gives a composition of 4 mol% boronic ester monomer and 96% lauryl methacrylate. 3. Rheological studies 3.1 Ingredients for the formulation of compositions A to H 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 the ASTM D445 standard is 19.57 cSt; - Its kinematic viscosity measured at 100 ° C according to ASTM D445 is 4.23 cSt; Its viscosity number measured according to ASTM standard D2270 is 122; - Its Noack volatility in weight percentage, measured according to the DIN 51581 standard is 14.5; - Are point flash (flash point in English) 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. Polydiol A-1 Polymeric Copolymer 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 51,400 g / mol. Its polydispersity index is 1.20. Its number-average degree of polymerization (DPn) is 184. The number average molecular weight and the polydispersity index are measured by steric exclusion chromatography using a polystyrene calibration. This copolymer is obtained according to the implementation of the protocol described in the paragraph above. Statistical Copolymer A-2 Boronic Ester: This copolymer comprises 4 mol% of monomers having boronic functional groups.
[0052] The average side chain length is greater than 12 carbon atoms. Its average molar mass is 37,200 g / mol. Its polydispersity index is 1.24. Its number-average degree of polymerization (DPn) is 166. Its number-average molecular weight and the polydispersity index are measured by size exclusion chromatography using a polystyrene calibration. This copolymer is obtained by the implementation of the protocol described in paragraph 2 above. Compound A-4: 1,2-Docecanediol from the TCIO supplier. 3.2 Formulation of Compositions for the Study of Viscosity Composition A (comparative) is obtained in the following manner: It contains a 4.2% by weight solution of a polymethacrylate polymer in a lubricating base oil of group III of API classification. The polymer has a number average molecular weight (Mn) equal to 10600 g / mol, a polydispersity index (Ip) equal to 3.06, a number average polymerization degree of 466 and the average length of the pendant chains is of 14 carbon atoms.
[0053] This polymethacrylate is used as a viscosity index improving additive. 4.95 g of a formulation having a mass concentration of 42% of this polymethacrylate in a Group III base oil and 44.6 g of Group III base oil are introduced into a flask. The solution thus obtained is stirred at 90 ° C. until the polymethacrylate is completely dissolved.
[0054] A 4.2% by weight solution of this polymethacrylate is obtained. This composition is used as a reference for the study of viscosity. It represents the rheological behavior of the lubricating compositions marketed.
[0055] Composition B (comparative) is obtained in the following manner: 6.75 g of polydiol copolymer A-1 and 60.7 g of a base oil group III are introduced into a flask. The solution thus obtained is stirred at 90 ° C until complete dissolution of the polydiol A-1. A 10% by weight solution of polydiol copolymer A-1 is obtained.
[0056] Composition C (comparative) is obtained in the following manner: 6 g of the 10% by weight solution of polydiol copolymer A-1 in a Group III base oil previously prepared are introduced into a flask. 0.596 g of A-2 poly (boronic ester) and 9.01 g of Group III base oil are added to this solution. The solution thus obtained is stirred at 90 ° C. until complete dissolution of the poly (boronic ester) A-2. A solution at 3.8% by weight of polydiol copolymer A-1 and 3.8% by weight of poly (boronic ester) copolymer A-2 is obtained. The composition D (according to the invention) is obtained in the following manner: 7.95 g of the composition C previously prepared are introduced into a flask. 19.2 mg of a 5% by weight solution of 1,2-dodecanediol (compound A-4) in a base oil group III are added to this solution. The solution thus obtained is stirred at 90 ° C. for two hours.
[0057] A solution at 3.8 mass% of polydiol copolymer A-1, 3.8% by weight of poly (boronic ester) copolymer A-2 and 10 mol% of free 1,2-dodecanediol (compound A-4) is obtained. relative to the boronic ester functions of the poly (boronic ester) copolymer A-2.
[0058] The composition E (according to the invention) is obtained in the following manner: 4.04 g of the composition C previously prepared are introduced into a flask. 97.6 mg of a 5% by weight solution of 1,2-dodecanediol (compound A-4) in a Group III base oil are added to this solution. The solution thus obtained is stirred at 90 ° C. for two hours.
[0059] A solution at 3.8 mass% of polydiol copolymer A-1, 3.8% by weight of poly (boronic ester) copolymer A-2 and 100 mol% of free 1,2-dodecanediol (compound A-4) is obtained. relative to the boronic ester functions of the poly (boronic ester) copolymer A-2. Composition F (comparative) is obtained in the following manner: 0.80 g of poly (boronic ester) copolymer A-2 and 7.21 g of a Group III base oil are introduced into a flask. The solution thus obtained is stirred at 90 ° C. until complete dissolution of the polymer. A 10% by weight solution of poly (boronic ester) copolymer A-2 is obtained. 3.2 Formulation of compositions for the study of their elastic modulus and of their viscous modulus Composition G (comparative) is obtained in the following manner: 0.416 g of polydiol-Al copolymer and 0.46 g of poly (boronic ester) copolymer A -2, then 8.01 g of Group III base oil are introduced into a flask. The solution thus obtained is stirred at 90 ° C. until complete dissolution of the polymers. A solution containing 4.7% by weight of polydiol copolymer A-1 and 5.2% by weight of poly (boronic ester) copolymer A-2 is obtained. Composition H (according to the invention) is obtained in the following manner: 2.00 g of solution G are introduced into a flask. 40.5 mg of the 5% by weight solution of 1,2-dodecanediol (compound A-4) are added. The solution thus obtained is stirred at 90 ° C. for 2 hours. A solution containing 4.7% by weight of polydiol copolymer A-1, 5.2% by weight of poly (boronic ester) copolymer A-2 and 66% by mole of 1,2-dodecanediol relative to boronic ester functions is obtained. poly (boronic ester) copolymer A-2. o 3.3 Apparatuses and Protocols for Measuring Viscosity The rheological studies were carried out using a Couette MCR 501 controlled stress rheometer from Anton Paar.
[0060] In the case of polymer formulations that do not form gels in a Group III base oil over the temperature range of the study (compositions A to F), the rheology measurements were performed using a cylindrical geometry of reference DG 26.7 Viscosity was measured as a function of 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 the shear rate of 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.
[0061] The relative viscosity calculated according to the following formula was 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 loss of natural viscosity of a group base oil. III of the polymer systems studied.
[0062] In the case of the polymer formulations that form gels in a Group III base oil over the temperature range of the study (compositions G and H), the rheology measurements were made using a cone-plane geometry of reference CP50 (diameter = 50 mm, angle 2 °). The elastic modulus and the viscous modulus were measured as a function of temperature over a temperature range of 10 ° C to 110 ° C. The heating (and cooling) speed was set at 0.003 ° C / s, the angular frequency was chosen at 1 rad / s with the deformation rate of 1%. 3.4 Results obtained in rheology The viscosity of the compositions A to F was studied for a temperature range of between 10 ° and 110 ° C. The relative viscosity of these compositions is illustrated in FIGS. 5 and 6. The polydiol random copolymer A-1, alone in composition B, does not allow compensation for the natural viscosity loss of the Group III base oil. The same is true for the poly (boronic ester) copolymer A-2 when this copolymer is used alone in the composition F. When the polydiol random copolymer A-1 and the poly (boronic ester) copolymer A-2 are present together in With the same lubricating composition (composition C), the natural viscosity loss of the Group III base oil is greater than that resulting from the addition of the polymethacrylate polymer in the Group III base oil. (composition A). When the composition (composition C) further comprises 10 mol% of free 1,2-dodecanediol (compound A-4) relative to the boronic ester functions of the poly (boronic ester) copolymer A-2 (composition D); a slight decrease in relative viscosity is observed at low temperatures (temperatures below 45 ° C.) while the compensation for the loss of hot viscosity is slightly greater than that of composition C which comprises the polydiol random copolymer A-1 and the poly (boronic ester) copolymer A-2. When the composition (composition C) additionally comprises 100 mol% of free 1,2-dodecanediol (compound A-4) relative to the boronic ester functions of the poly (boronic ester) copolymer A-2 (composition E), observed a decrease in relative viscosity at low temperatures (temperatures below 45 ° C). At higher temperatures, the composition resulting from mixing the random copolymer polydiols A-1, poly (boronic ester) copolymer A-2 and 1,2-dodecanediol (compound A-4) compensates for the loss of viscosity of the oil. Group III base in a manner comparable to that obtained with the polymethacrylate polymer in the Group III base oil (Composition A). Thus, in the presence of 1,2-dodecanediol, the cold properties of the composition E have been improved compared with those of the composition C. In addition, the composition E still retains the property of compensating for the loss of viscosity of the Group III base oil for high temperatures. 1,2-Dodecanediol therefore makes it possible to modify, as a function of temperature, the viscosity of a lubricant composition resulting from the mixing of at least one random polydiol copolymer A-1 and at least one random copolymer A-2 poly (ester boronic) by controlling the level of association of the chains of these two copolymers.
[0063] The rheological behavior of compositions G and H was studied as a function of temperature (hysteresis curve of FIGS. 7 and 8). These two compositions result from the mixture in a Group III base oil of the polydiol random copolymer A-1 and the statistical copolymer A-2 poly (boronic ester). The composition H further comprises 1,2-dodecanediol (compound A-4).
[0064] The intersection of the curves G 'and G "illustrates the change of state of the compositions, that is to say the transition from a liquid state to a gelled state when the temperature increases and the transition from a gelled state to A liquid state when the temperature decreases For the composition G (Figure No. 7), it is observed that the temperature at which the composition changes from a liquid state to a gelled state is between 95 ° C and 100 ° C. At this temperature, the chains of copolymers A-1 and A-2 combine, exchange and form a three-dimensional crosslinked network.When the temperature is decreased, a new change of state is observed for a temperature of between 65.degree. ° and 70 ° C. The composition changes from a gelled state to a liquid state in which the copolymer chains no longer associate with each other.For the composition H (FIG. the temperature at which the composition changes state. H is gelled for a temperature of between 105 and 110 ° C and goes to a liquid state for a temperature of between 70 ° C and 75 ° C. 1,2-dodecanediol (compound A-4) makes it possible to modulate the rheological behavior of the composition H.

权利要求:
Claims (22)
[0001]
REVENDICATIONS1. Additive composition resulting from the mixture of at least one polydiol random copolymer Ai, a random copolymer A2 comprising at least two boronic ester functional groups and capable of associating with said polydiol random copolymer Ai by at least one transesterification reaction, a compound exogenous A4 selected from 1,2-diols and 1,3-diols.
[0002]
An additive composition according to claim 1, wherein the mole percentage of exogenous compound A4 with respect to the boronic ester functions of the random copolymer A2 is from 0.025 to 5000%, preferably from 0.1% to 1000%, of even more preferably from 0.5% to 500%, even more preferably from 1% to 150%.
[0003]
3. additive composition according to any one of claims 1 to 2 wherein the random copolymer Ai results from the copolymerization of: - at least a first monomer M1 of general formula (I): 0 Xi 0 OX2 (I) wherein: R1 is selected from the group consisting of -H, -CH3, and -CH2-CH3; x is an integer from I to 18; preferably from 2 to 18; y is an integer equal to 0 or 1; X1 and X2, which may be identical or different, are chosen from the group formed by hydrogen, tetrahydropyranyl, methyloxymethyl, tert-butyl, benzyl, trimethylsilyl and t-butyl dimethylsilyl, or -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 the group formed by the hydrogen and a C1-C11 alkyl, preferably methyl, or - X1 and X2 form with the oxygen atoms a boronic ester of the following formula: in which: - the stars (*) symbolize the bonds to the atoms of oxygen, 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, with at least one second monomer M2 of general formula (II): (II) in which: R2 is chosen from the group formed by -H, -CH3 and -CH2-CH3 R3 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'3 and -C (O) -N (H) -R'3 with R'3 a C1-C30 alkyl group.
[0004]
An additive composition according to claim 3, wherein the random copolymer Al results from the copolymerization of at least one monomer M1 with at least two monomers M2 having different R3 groups.
[0005]
An additive composition according to claim 4, wherein one of the monomers M2 of the random copolymer Al has the general formula (II-A): (II-A) wherein: R2 is selected from the group consisting of -H, -CH3 and -CH2-CH3, -R "3 is a C1-C14 alkyl group, and the other monomer M2 of the random copolymer Al has general formula (II-B): H2C (II-B) wherein: R2 is selected from the group consisting of -H, -CH3 and -CH2-CH3, -R "3 is a C15-C30 alkyl group.
[0006]
An additive composition according to any one of claims 3 to 5, 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.
[0007]
An additive composition according to any one of claims 3 to 6, wherein the random copolymer A1 has a molar percentage of monomer M1 of formula (I) in said copolymer ranging from 1 to 30%, preferably from at 25%, more preferably from 9 to 21%.
[0008]
8. Additive composition according to any one of claims 1 to 7, wherein the random copolymer A2 results from the copolymerization of at least one monomer M3 of formula (IV): BM, / x wherein R is an integer of 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, 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 18 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; R10 and R11, 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 18 carbon atoms, preferably from 6 to 14 carbon atoms; with at least one second monomer M4 of general formula (V): R 12 H 2 C R 13 (V) in which: R 12 is chosen from the group formed by -H, -CH 3 and -CH 2 -CH 3 R 13 is chosen from the group formed with a C 6 -C 18 aryl, a C 6 -C 18 aryl substituted with a group R '13, -C (O) -O-R' 13 OR '13, -SR' 13 and -C (O) -N ( H) -R'13 with R'13 a C1-C25 alkyl group.
[0009]
9. Additive composition according to claim 8, wherein the chain formed by the linking of the groups R10, M, X and (R8) u with u equal to 0 or 1 of the monomer of general formula (IV) of the statistical copolymer. A2 has a total number of carbon atoms ranging from 8 to 38, preferably from 10 to 26.
[0010]
10. Additive composition according to any one of claims 8 to 9, wherein the side chains of the random copolymer A2 have an average length greater than or equal to 8 carbon atoms, preferably ranging from 11 to 16 carbon atoms.
[0011]
An additive composition according to any one of claims 8 to 10, wherein the random copolymer A2 has a molar percentage of monomer of formula (IV) in said copolymer ranging from 0.25 to 20%, preferably from 1 to at 10%.
[0012]
12. Additive composition according to any one of claims 1 to 11, wherein the exogenous compound A4 has the general formula (VI): R14 R15 OH (VI) with: w3 an integer equal to 0 or 1; R14 and R15 are the same or different selected from the group consisting of hydrogen and a hydrocarbon group having 1 to 24 carbon atoms.
[0013]
13. Additive composition according to any one of claims 8 to 12 wherein the substituents R10, R1 and the value of the index (t) of the monomer of formula (IV) of the random copolymer A2 are identical to the substituents, respectively. R14, R15 and the value of the index w3, the exogenous compound A4 of formula (VI).
[0014]
14. Additive composition according to any one of claims 8 to 12 wherein at least one of the substituents R10, Rn or the value of the index (t) of the monomer of formula (IV) of the random copolymer A2 is different. respectively substituents R14, R15 or the value of the index w3, of the exogenous compound A4 of formula (VI).
[0015]
15. Additive composition according to any one of claims 1 to 14, wherein the mass ratio between the polydiol random copolymer Al and the statistical copolymer A2 (ratio A 1 / A2) ranges from 0.005 to 200, preferably from 0.05 to 20, even more preferably 0.1 to 10, still more preferably 0.2 to 5.15
[0016]
16. Lubricating composition resulting from the mixing of at least: - a lubricating oil; and - an additive composition defined according to any one of claims 1 to 15.
[0017]
17. Lubricating composition according to claim 16, wherein 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 mixture. .
[0018]
18. Lubricating composition according to any one of claims 16 to 17, wherein the mass ratio between the random copolymer Al and the statistical copolymer A2 (ratio A 1 / A2) ranges from 0.001 to 100, preferably from 0.05 to Even more preferably from 0.1 to 10, still more preferably from 0.2 to 5.
[0019]
19. Lubricating composition according to any one of claims 16 to 18, wherein the mole percentage of exogenous compound A4 with respect to the boronic ester functions of the random copolymer A2 ranges from 0.05 to 5000%, preferably from 0 to From 1% to 1000%, more preferably from 0.5% to 500%, even more preferably from 1% to 150%. 20
[0020]
20. A lubricating composition according to any one of claims 16 to 19 resulting from the further mixing of a functional additive selected from the group consisting of detergents, anti-wear additives, extreme pressure additives, additional antioxidants, viscosity index improvers, pour point improvers, antifoams, anti-corrosion additives, thickeners, dispersants, friction modifiers and mixtures thereof.
[0021]
21. A process for modulating the viscosity of a lubricating composition, the process comprising at least: providing a lubricating composition resulting from mixing at least one lubricating oil, at least one polydiol random copolymer Al and at least one random copolymer A2 comprising at least two boronic ester functional groups and capable of associating with said polydiol Al random copolymer by at least one transesterification reaction, adding to said lubricating composition at least one exogenous compound A4 chosen from 1,2-diols and 1,3-diols.
[0022]
22. Use of at least one compound selected from 1,2-diols or 1,3 diols to modulate the viscosity of a lubricating composition, wherein said lubricating composition resulting from mixing at least one lubricating oil, at least one polydiol random copolymer Al and at least one random copolymer A2 comprising at least two boronic ester functional groups and capable of associating with said polydiol Al random copolymer by at least one transesterification reaction.

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同族专利:

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公开号 | 公开日

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EP3245276B1|2021-09-08|

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CN107109285A|2017-08-29|

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JP2018506620A|2018-03-08|

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CA2971690A1|2016-07-21|

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BR112017015040A2|2019-11-19|

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WO2016113229A1|2016-07-21|

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优先权:

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申请号 | 申请日 | 专利标题

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FR1550328A|FR3031744B1|2015-01-15|2015-01-15|COMPOSITIONS OF THERMOASSOCIATIVE ADDITIVES WHERE THE ASSOCIATION IS CONTROLLED AND LUBRICATING COMPOSITIONS CONTAINING SAME|FR1550328A| FR3031744B1|2015-01-15|2015-01-15|COMPOSITIONS OF THERMOASSOCIATIVE ADDITIVES WHERE THE ASSOCIATION IS CONTROLLED AND LUBRICATING COMPOSITIONS CONTAINING SAME|

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CA2971690A| CA2971690A1|2015-01-15|2016-01-11|Compositions of thermoassociative additives, the association of which is controlled, and lubricating compositions containing same|

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MA40661A| MA40661B1|2015-01-15|2016-01-11|Thermoassociative additive compositions whose combination is controlled and lubricating compositions containing them|

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PCT/EP2016/050400| WO2016113229A1|2015-01-15|2016-01-11|Compositions of thermoassociative additives, the association of which is controlled, and lubricating compositions containing same|

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JP2017537494A| JP6778685B2|2015-01-15|2016-01-11|A thermally associative additive composition having controlled associativity, and a lubricant composition containing the same.|

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CN201680005777.4A| CN107109285B|2015-01-15|2016-01-11|Controlled association thermal association additive composition and lubricant composition comprising same|

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KR1020177021655A| KR20170128221A|2015-01-15|2016-01-11|Heat-bonding additive compositions, controlled binders, and lubricating oil compositions comprising same|

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US15/543,100| US10508250B2|2015-01-15|2016-01-11|Compositions of thermoassociative additives with controlled association and lubricant compositions containing them|

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BR112017015040-9A| BR112017015040A2|2015-01-15|2016-01-11|controlled association thermo-associative additive compositions and lubricating compositions containing them|

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EP16700342.5A| EP3245276B1|2015-01-15|2016-01-11|Compositions of thermoassociative additives, the association of which is controlled, and lubricating compositions containing same|