THERMOASSOCIATIVE AND EXCHANGEABLE COPOLYMERS, COMPOSITIONS COMPRISING THE SAME

专利摘要:
The present invention relates to a random copolymer resulting from the copolymerization of at least one monomer functionalized with diol functions. The invention also relates to a process for preparing said copolymer. The invention also relates to a composition resulting from the mixing of at least one copolymer resulting from the copolymerization of at least one monomer functionalized with diol functions and at least one compound comprising at least two boronic ester functions. The random copolymers resulting from the copolymerization of at least one monomer functionalized with diol functions and the compound comprising at least two boronic ester functions are used to thicken fluids and control their viscosities.
公开号:FR3016885A1
申请号:FR1450654
申请日:2014-01-27
公开日:2015-07-31
发明作者:Thi Hang Nga Nguyen；Renaud Nicolay；Lise Deves
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] TECHNICAL FIELD The present invention relates to a random copolymer resulting from the copolymerization of at least one monomer functionalized with diol functions. The invention also relates to a process for preparing said copolymer. The invention also relates to a composition resulting from the mixing of at least one copolymer resulting from the copolymerization of at least one functionalized monomer with diol functions and at least one compound comprising at least two boronic ester functional groups. The invention also relates to a compound comprising at least two boronic ester functions. The present invention also relates to a process for preparing random copolymers resulting from the copolymerization of at least one functionalized monomer with boronic ester functions. The field of the invention is that of associative and exchangeable polymers. BACKGROUND OF THE INVENTION High molecular weight polymers are widely used to increase the viscosity of solutions in many fields, such as the petroleum, paper, water treatment, mining and cosmetics industries. , 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 over the same smaller size polymers. These shear stresses on the high molecular weight polymers cause cuts in the macromolecular chains. The polymer thus degraded no longer has thickening properties, and the viscosity of the solutions containing it drops irreversibly. This loss of permanent shear strength leads to a degradation of the properties of the high molecular weight polymer solutions. The Applicant has set itself the objective of formulating new additives which are more stable in shear compared with the compounds of the prior art. This objective is achieved thanks to new associative additives and exchangeable thermoreversibly. The associated (potentially cross-linked) and exchangeable copolymers of the invention 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.
[0002] It is known from WO2013147795 polymers of which at least one monomer comprises boronic ester functions. These polymers are used for the manufacture of electronic devices, especially for devices which are desired to obtain a flexible user interface. These polymers are also used as synthesis intermediate. They make it possible to functionalize the polymers by coupling with luminescent groups, electron-carrying groups, etc. The coupling of these groups is carried out by conventional organic chemical reactions involving the boron atom, such as, for example, Suzuki coupling. However, no other use of these polymers or an association with other compounds is contemplated.
[0003] The Applicant has also set itself the objective of synthesizing new polymers for increasing the viscosity of solutions comprising them with respect to the polymers of the prior art. In particular, it aims to provide novel rheological additives which, when introduced into a solution, especially in a hydrophobic solution, have an inverted behavior vis-à-vis a change in temperature with respect to behavior of the solution and the rheological additives of polymer type of the prior art. This objective is achieved thanks to new rheological additives that can associate, to possibly form a gel, and exchange chemical bonds thermoreversibly. The additives of the present invention have the advantage of increasing the viscosity of the solution comprising them when the temperature increases.
[0004] Initially, the Applicant has attempted to synthesize copolymers carrying diol functions from commercial compounds such as solketal methacrylate marketed by Sigma-Aldrich®. However, the use of this monomer has several disadvantages: - its cost to purchase is high; the polarity of the solketal methacrylate and 2,3-dihydroxypropyl methacrylate units (resulting from the deprotection of the solketal function) limits the solubility of the copolymers in apolar media; the pendant diol function is hardly accessible on the copolymers; depending on the nature of the copolymer, the deprotection of the monomer once polymerized may be difficult and / or lead to the formation of gels. Thus, the Applicant has also set itself the objective of synthesizing new statistical copolymers carrying diol functions that overcome the aforementioned drawbacks. This objective is achieved thanks to novel polydiol random copolymers Al comprising at least one monomer M1 of general formula (I) as described below.
[0005] The polydiols Al random copolymers of the invention have the following advantages in particular: the deprotection of the protected diol functions once polymerized is simpler because of their greater accessibility; - they are better soluble in an apolar environment; these polymers are adaptive, that is to say that they are capable of responding to an external stimulus by a change of properties; they can associate and exchange thermoreversibly with compounds having at least two boronic ester functions, especially in an apolar medium, for example. In a second step, the Applicant has attempted to synthesize compounds carrying at least two boronic ester functions from commercial compounds such as 4-vinylphenylboronic acid sold by Sigma-Aldrich®.
[0006] However, the use of this compound has several disadvantages: the polymerization of these monomers in a hydrophobic medium leads to the formation of gels which are not compatible with the desired use; copolymers containing 4-vinylphenylboronic acid functions are not stable in temperature in a hydrophobic medium and lead to the formation of gels. Thus, the Applicant has also set itself the objective of synthesizing new compounds carrying at least two boronic ester functions which overcome the aforementioned drawbacks. This objective is achieved by the novel compounds having at least two boronic ester functions of general formula (III), or comprising at least one M3 monomer of general formula (IV), as described below. The compounds of the invention having at least two boronic ester functions have the following advantages in particular: their syntheses are simple and inexpensive; they are soluble in a hydrophobic medium, especially in an apolar hydrophobic medium; they do not form a gel during the polymerization; they are stable in temperature in a hydrophobic medium and do not lead to the formation of gels. SUMMARY OF THE INVENTION Thus, the subject of the invention is a random copolymer Al resulting from the copolymerization of at least one first monomer M1 of general formula (I): ## STR2 ## in which: R1 is selected from the group consisting of -H, -CH3, and -CH2-CH3; x is an integer from 2 to 18; y is an integer equal to 0 or 1; X1 and X2, which are identical or different, are chosen from the group formed by hydrogen, tetrahydropyranyl, methyloxymethyl, tert-butyl, benzyl, trimethylsilyl and t-butyl dimethylsilyl; or else X1 and X2 form with the oxygen atoms a bridge of the following formula R "2 in which: the stars (*) symbolize the bonds to the oxygen atoms, R'2 and R" 2, identical or different, are selected from the group consisting of hydrogen and a C1-C11 alkyl, preferably methyl; or else - X1 and X2 form with the oxygen atoms a boronic ester of the following formula RI "2 in which: - the stars (*) symbolize the bonds to the oxygen atoms, - R" '2 is chosen from the group formed by C 6 -C 18 aryl, C 7 -C 18 aralkyl and C 2 -C 18 alkyl, preferably C 6 -C 18 aryl; with at least one second monomer M2 of general formula (II): wherein R2 is selected from the group consisting of -H, -CH3 and -CH2-CH3 R3 is selected from the group consisting of aryl; C6-C18, a C6-C18 aryl substituted with a group R'3, -C (O) -O-R'3, -S-R'3 and -C (O) -N (H) -R With R'3 is a C1-C30 alkyl group. In one variant, the random copolymer results from the copolymerization of at least one monomer M1 with at least two monomers M2 having different R3 groups. Preferably, one of the monomers M2 has the general formula (II-A): ## STR2 ## wherein: R2 is selected from the group consisting of -H, -CH3 and -CH2-CH3; R 3 is a C 1 -C 14 alkyl group and the other monomer M2 has the general formula (II-B): wherein R 2 is selected from the group consisting of the group formed by -H, -CH3 and -CH2-CH3; R "'3 is a C5-C30 alkyl group. Preferably, the random copolymer described above comprises one or more of the following characteristics, taken separately or in combination: the side chains of the copolymer have an average length ranging from 8 to 20 carbon atoms, preferably from 9 to 15 carbon atoms; the molar percentage of monomer M1 of formula (I) ranging from 1 to 30%, preferably from 5 to 25%, more preferably ranging from 9 to 21%; its number-average degree of polymerization ranges from 100 to 2000, preferably from 150 to 1000; its polydispersity index (Ip) ranges from 1.05 to 3.75; preferably ranging from 1.10 to 3.45; The invention also relates to a method for preparing a random copolymer as defined above, the process comprising at least one polymerization step (a) in which at least: i) a first monomer is brought into contact with each other; M1 of the general formula (I): wherein: R1 is selected from the group consisting of -H, -CH3, -CH2-CE13 x is an integer ranging from 2 to 18; y is an integer equal to 0 or 1; X1 and X2, which are identical or different, are chosen from the group formed by hydrogen, tetrahydropyranyl, methyloxymethyl, tert-butyl, benzyl, trimethylsilyl and t-butyl dimethylsilyl; or else X 1 and X 2 form, with the oxygen atoms, a bridge of the following formula R "2 in which: the stars (*) symbolize the bonds to the oxygen atoms; R'2 and R" 2 , identical or different, are chosen from the group formed by hydrogen and a C1-C11 alkyl, preferably methyl; or else - X1 and X2 form with the oxygen atoms a boronic ester of the following formula RI "2 in which: - the stars (*) symbolize the bonds to the oxygen atoms; - R" '2 is chosen from the group formed by C 6 -C 18 aryl, C 7 -C 18 aralkyl and C 2 -C 18 alkyl, preferably C 6 -C 18 aryl; ii) 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 aryl C6-C18, 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 iii) at least one source of free radicals.
[0007] Alternatively, the process may further comprise iv) at least one chain transfer agent. Preferably, the process for preparing a random copolymer as described above, comprising - at least one polymerization step (a) as described above, in which the monomers M1 and M2 are chosen with X1 and X2 different from hydrogen, and in addition at least one step of deprotection (b) of the diol functions of the copolymer obtained at the end of the step (a), so as to obtain a copolymer in which X1 and X2 are identical and are a hydrogen atom.
[0008] The subject of the invention is also a composition resulting from the mixing of at least: a random copolymer Al as defined above or obtainable by one of the processes described above; and a compound A2 comprising at least two boronic ester functions. Alternatively, compound A2 is a compound of formula (III): wherein: w1 and w2, the same or different, are integers selected from 0 to 1; R4, R5, R6 and R7, which are identical or different, are chosen from the group formed by hydrogen and a hydrocarbon group containing from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 6 to 14 carbon atoms; carbon atoms; L is a divalent linking group and selected from C6-C18 aryl, C6-C18 aralkyl and C2-C24 hydrocarbon chain. In another variant, the compound A2 is a random copolymer resulting from the copolymerization of: at least one monomer M3 of formula (IV): ## STR2 ## IV) wherein: t is an integer equal to 0 or 1; u is an integer equal to 0 or 1; M and R 8 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, -CH3et-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, -O-R '13 -SR' 13 and -C (O) -N (H) -R '13 with R' 13 a C1-C25 alkyl group. Preferably, the composition described above comprises one or more of the following characteristics, taken separately or in combination: the chain formed by the linking of the groups R10, M, X and (R8) 'with u equal to 0 or 1 of the monomer of general formula (IV) has a total number of carbon atoms ranging from 8 to 38, preferably from 10 to 26; the side chains of the copolymer A2 have an average length greater than or equal to 8 carbon atoms, preferably ranging from 11 to 16 carbon atoms; the copolymer A2 has a molar percentage of monomer of formula (IV) ranging from 0.25; at 20%, preferably from 1 to 10%; the copolymer A2 has a number-average degree of polymerization ranging from 50 to 1500, preferably from 80 to 800; copolymer A2 has a polydispersity index (Ip) ranging from 1.04 to 3.54; preferably ranging from 1.10 to 3.10; the content of copolymer Al in the composition ranges from 0.1% to 50% by weight relative to the total weight of the composition; the content of compound A2 in the composition ranges from 0.1% to 50% by weight relative to the total weight of the composition; the mass ratio between the copolymer Al and the compound A2 (ratio Al / A2) ranges from 0.005 to 200, preferably from 0.05 to 20, even more preferably from 0.1 to 10; the composition further comprises at least one additive chosen from the group formed by polymers, pigments, dyes, fillers, plasticizers, fibers, antioxidants, lubricant additives, compatibilizers, anti-corrosive agents, foam, dispersant additives, adhesion promoters and stabilizers.
[0009] 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). Figure 2 schematically shows a comb copolymer. Figure 3 illustrates and shows schematically the crosslinking of the composition according to the invention in tetrahydrofuran (THF). Figure 4 shows schematically the behavior of the composition of the invention as a function of temperature. A random copolymer (2) having diol functions (function A) can associate thermoreversibly with a random copolymer (1) having boronic ester functions (function B) via a transesterification reaction. A chemical bond (3) of the boronic ester type is formed. FIG. 5 represents the variation, for different temperatures between 10 ° C. and 110 ° C., of the viscosity (Pa.s, the ordinate axis) as a function of the shear rate (s-1, the axis of the abscissas) of a 10% by weight solution of a polydiol random copolymer A1-1 and 0.77% by weight of a boronic diester compound A2-1 in the group III base oil. FIG. 6A represents the evolution of the relative viscosity (without unit, the ordinate axis) as a function of the temperature (° C, the abscissa axis) of the compositions A, B-1, C-1 and D- 1.
[0010] FIG. 6B represents the evolution of the relative viscosity (without unit, the ordinate axis) as a function of the temperature (° C, the abscissa axis) of the compositions A, B-2, C-2 and D- 2. FIG. 6C represents the evolution of the relative viscosity (without unit, the ordinate axis) as a function of the temperature (° C, the abscissa axis) of the compositions A, B-3 and C-3. FIG. 6D shows the evolution of the relative viscosity (without unit, the ordinate axis) as a function of the temperature (° C, the abscissa axis) of the compositions A, B-4, C-4 and D -4. FIG. 7 represents the variation, for different temperatures between 10 ° C. and 110 ° C., of the viscosity (Pa.s, the ordinate axis) as a function of the shear rate (s-1, the axis of the X) shows the evolution of the relative viscosity (without unit, the ordinate axis) as a function of the temperature (° C, the abscissa axis) of the compositions A, B, C, D and E. FIG. 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). ). DESCRIPTION OF EMBODIMENTS OF THE INVENTION New polydiols random copolymers (Al random copolymers) A first object of the present invention is a polydiol (Al) random copolymer resulting from the copolymerization of at least one first M1 monomer bearing diols functions and at least a second monomer M2, of different chemical structure from that of the monomer M1. By "copolymer" is meant a linear or branched oligomer or macromolecule having a sequence consisting of several repeating units (or monomeric unit) of which at least two units have a different chemical structure. 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 monomeric units is dependent 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 FIG. 1. A gradient copolymer designates a copolymer of at least two monomeric units of different structures whose monomer composition gradually changes along the polymer chain, thus passing 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. "Copolymerization" means a process which makes it possible to convert a mixture of at least two monomeric units of different chemical structures into an oligomer or a copolymer. In the rest of the present application, "B" represents a boron atom. By "Ci-Ci alkyl" is meant a linear or branched saturated hydrocarbon chain comprising from 1 to 1 carbon atoms. For example, for "C 1 -C 10 alkyl" is meant a saturated hydrocarbon chain, linear or branched, comprising from 1 to 10 carbon atoms. By "C 6 -C 18 aryl" is meant a functional group derived from an aromatic hydrocarbon compound having from 6 to 18 carbon atoms. This functional group can be monocyclic or polycyclic. By way of illustration, a C 6 -C 18 aryl may be phenyl, naphthalene, anthracene, phenanthrene and tetracene. By "C2-C10 alkenyl" is meant a linear or branched hydrocarbon chain containing at least one unsaturation, preferably a carbon-carbon double bond, and 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 at 18 carbon atoms. By way of illustration, a C 7 -C 18 aralkyl may be selected from the group consisting of benzyl, tolyl and xylyl. By "C 6 -C 18 aryl group substituted 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 R'3 group. By "Hal" or "halogen" is meant a halogen selected from the group consisting of chlorine, bromine, fluorine and iodine. Monomer MI 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 , -CH3 and -CH2-CH3, preferably -H and -CH3; x is an integer ranging from 2 to 18; preferably from 3 to 8; more preferably, x 35 is 4; y is an integer equal to 0 or 1; preferably y is 0; X1 and X2, which are identical or different, are chosen from the group formed by hydrogen, tetrahydropyranyl, methyloxymethyl, tert-butyl, benzyl, trimethylsilyl and t-butyl dimethylsilyl; or else - X1 and X2 form with the oxygen atoms a bridge of the following formula: in which: the stars (*) symbolize the bonds to the oxygen atoms, - R'2 and R "2, which are identical or different, are chosen from the group formed by hydrogen and a C1-C11 alkyl group or else X1 and X2 form with the oxygen atoms a boronic ester of the following formula: RI "2 in which: the stars (*) symbolize the to the oxygen atoms, R "'2 is selected from the group consisting of C 6 -C 18 aryl, C 7 -C 18 aralkyl and C 2 -C 18 alkyl, preferably C 6 -C 18 aryl, more preferably phenyl, Preferably, when R'2 and R "2 is a C1-C11 alkyl group; the hydrocarbon chain is a linear chain. Preferably, the C1-C11 alkyl group is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, octyl, n-nonyl, n-decycling and n-undecyl. More preferably, the C1-C11 alkyl group is methyl. Preferably, when R "'2 is a C 2 -C 18 alkyl group, the hydrocarbon chain is a linear chain. Among the monomers of formula (I), the monomers corresponding to formula (IA) are among the preferred ones: H 2 C Wherein: R1 is selected from the group consisting of -H, -CH3 and -CH2-CH3, preferably -H and -CH3; x is an integer ranging from 2 to 18; 3 to 8, more preferably x is equal to 4, y is an integer equal to 0 or 1, and preferably y is 0. Among the monomers of formula (I), the monomers corresponding to formula (IB are among the preferred ones: wherein R 1 is selected from the group consisting of -H, -CH 3 and -CH 2 -CH 3, preferably -H and -CH 3, x is an integer ranging from from 2 to 18, preferably from 3 to 8, more preferably x is equal to 4, y is an integer equal to 0 or 1, preferably y is 0, Y 1 and Y 2, identi or different are selected from the group consisting of 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: R1 "2 B in which: the stars (*) symbolize the bonds at the oxygen atoms, R "'2 is selected from the group consisting of C 6 -C 18 aryl, C 7 -C 18 aralkyl and C 2 -C 18 alkyl, preferably C 6 -C 18 aryl, more preferably preferred is phenyl, Preferably, when R'2 and R "2 is a C1-C11 alkyl group; the hydrocarbon chain is a linear chain. Preferably, the C1-C11 alkyl group is selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, octyl, n-nonyl, n-decycling and n-undecyl. More preferably, the C1-C11 alkyl group is methyl. Preferably, when R "'2 is a C 2 -C 18 alkyl group, the hydrocarbon chain is a linear chain - Obtaining the MI monomer The M 1 monomer of the general formula (IA) is obtained by deprotection of the alcohol functions of the monomer of general formula (IB) according to reaction scheme 1 below: embedded image wherein R 1, Y 1, Y 2, x and y as defined in general formula (IB) described herein The deprotection reaction of the diol functions of the monomer of the general formula (IB) is well known to a person skilled in the art, and it can adapt the deprotection reaction conditions according to the nature of the protecting groups Y 1 and Y 2. M1 of general formula (IB) can be obtained by a reaction of a compound of general formula (Ic) with an alcohol compound of general formula (Ib) according to reaction scheme 2 below: HO H2C 25 Y10 H2C OO Y10 0Y2 (IB 0Y2 Scheme 2 in wherein: Y 3 is selected from the group consisting of a halogen atom, preferably chlorine, -OH and O-C (O) -R '1 with R' 1 selected from the group consisting of -H, - CH 3 and -CH 2 -CH 3, preferably -H and -CH 3, -R 1, Y 1, Y 2, x and y have the same meaning as given in general formula (IB). These coupling reactions are well known to those skilled in the art.
[0011] The compound of general formula (I-c) is commercially available from suppliers: Sigma-Aldrich® and Alfa Aesar®. The alcohol compound of general formula (Ib) is obtained from the corresponding polyol of formula (Ia) by protecting the diol functions according to the following reaction scheme 3: HO HO OH (Ia) 10 HO protection Y10 0Y2 Scheme 3 with x, y , 1 and Y2 as defined in the general formula (IB). The protective reaction of the diol functions of the compound of general formula (I-a) is well known to those skilled in the art. It knows how to adapt the reaction protection conditions according to the nature of the protective groups Y1 and Y2 used. The polyol of general formula (I-a) is commercially available from suppliers: Sigma-Aldrich® and Alfa Aesar®. Monomer M2 The second monomer of the random copolymer of the invention has the general formula (II): wherein R 2 is selected from the group consisting of -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 -C (O) -N (H) -R'3 with R'3 a C1-C30 alkyl group. Preferably, R'3 is a C1-C30 alkyl group whose hydrocarbon chain is linear.
[0012] 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 comprising from 4 to 12 carbon atoms.
[0013] Among the monomers of formula (II), the monomers corresponding to formula (II-B) are also among the preferred ones: H 2 C (II-B) in which: R 2 is chosen from the group formed by -H, -CH 3 and -CH2-CH3, preferably -H and -CH3; R "'3 is a C 15 -C 30 alkyl group" C 15 -C 30 alkyl "is understood to mean a linear or branched saturated hydrocarbon-based chain comprising from 15 to 30 carbon atoms. Preferably, the hydrocarbon chain comprises from 16 to 24 carbon atoms - Obtaining the monomer M2 The monomers of formulas (II), (II-A) and (II-B) are well known to the human being They are marketed by Sigma-Aldrich® and TCI® 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) such that previously described, a second monomer M2 of formula (II) as previously described, wherein R2 is -H and R3 is a C6-C18 aryl group, preferably R3 is phenyl.
[0014] In another embodiment, a preferred random copolymer results from the copolymerization of at least: a first monomer M1 of general formula (I) as previously described; a second monomer M2 of formula (II-A) as described above; and a third monomer M2 of formula (II-B) as described above.
[0015] According to this other embodiment, a preferred random copolymer results from the copolymerization of at least: a first monomer M1 of general formula (I) as described above; a second monomer M2 of formula (II-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 ) in which 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 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 the New Polydiol Copolymers Those skilled in the art are able to synthesize the polydiol random copolymers Al 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). Thus another object of the present invention is a process for preparing a random copolymer, said process comprising at least one polymerization stage (a) in which at least: i) a first monomer M1 of general formula ( Wherein: R1 is selected from the group consisting of -H, -CH3, and -CH2-CH3 x is an integer ranging from 2 to 18; y is an integer equal to 0 or 1; X1 and X2, which are identical or different, are chosen from the group formed by hydrogen, tetrahydropyranyl, methyloxymethyl, tert-butyl, benzyl, trimethylsilyl and t-butyl dimethylsilyl; or else - X1 and X2 form with the oxygen atoms a bridge of the following formula R "2 in which: - the stars (*) symbolize the bonds to the oxygen atoms; - R'2 and R" 2, identical or different, are selected from the group consisting of hydrogen and a C1-C11 alkyl, preferably methyl; or else - X1 and X2 form with the oxygen atoms a boronic ester of the following formula RI "2 in which: - the stars (*) symbolize the bonds to the oxygen atoms; - R" '2 is chosen from a group consisting of C6-C18 aryl, C7-C18 aralkyl and C2-C18 alkyl, preferably C6-C18 aryl; ii) at least one second monomer M2 of general formula (II): H 2 C (R 2 R 3 (II) in which: R 2 is chosen from the group formed by -H, -CH 3 and -CH 2 -CH 3; R 3 is chosen from the group formed by a C6-C18 aryl, a C6-C18 aryl substituted with a group R'3, -C (O) -O-W3, -S-R'3 and -C (O) -N (H) -R'3 with R'3 a C1-C30 alkyl group; iii) at least one source of free radicals. In one embodiment, the method may further comprise iv) at least one chain transfer agent. By "a source of free radicals" is meant a chemical compound 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 of the invention, the process for preparing a polydiol random copolymer comprises: at least one polymerization step (a) as defined above, in which the monomers M1 and M2 are chosen with Xi and X2 different from hydrogen, and furthermore at least one deprotection step (b) of the diol functions of the copolymer obtained at the end of step (a), so as to obtain a copolymer in which X1 and X2 are identical and are a hydrogen atom. In one embodiment, the polymerization step (a) comprises contacting at least one monomer M1 with at least two monomers M2 having different R3 groups. In this embodiment, one of the monomers M2 has the general formula (II-A): ## STR2 ## wherein: R2 is selected from the group consisting of -H, -CH3et-CH2-CH3; R "3 is a C1-C14 alkyl group; and the other monomer M2 has the general formula (II-B): wherein: R2 is selected from the group consisting of -H, -CH3et-CH2-CE13; - R "'3 is a C15-C30 alkyl group The preferences and definitions described for the general formulas (I), (IA), (IB), (II-A), (II-B) also apply The properties of the novel polydiol A copolymers The polydiol random copolymers Al are comb copolymers The term "comb copolymers" is intended to mean a copolymer having a main chain (also called a backbone) and side chains. The side chains are pendent on either side of the main chain The length of each side chain is less than the length of the main chain Figure 2 schematically represents a comb polymer The Al copolymers have a skeleton polymerizable functions, in particular a skeleton of methacrylate functions, and a mixture of hydrocarbon side chains which may or may not be substituted by diol functions, such as the monomers of formula (I) and (II) exhibit polymerizable functions of identical or substantially identical reactivity, a copolymer is obtained in which the monomers having diol functions are statistically distributed along the backbone of the copolymer relative to the monomers whose alkyl chains are not substituted by diol functions . The polydiols Al statistical 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 made 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 Al copolymer is a thermosensitive copolymer, i.e. 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 Al copolymer is therefore miscible in a hydrophobic medium. By "hydrophobic medium" is meant a medium that has no or a very low affinity for water, that is to say it is not miscible in water or in an aqueous medium. Advantageously, the polydiol random copolymer Al has a molar percentage of monomer M1 of formula (I) ranging from 1 to 30%, preferably 5 to 25%, more preferably ranging from 9 to 21%. In a preferred embodiment, the copolymer Al has a molar percentage of monomer M1 of formula (I) ranging from 1 to 30%, preferably 5 to 25%, more preferably ranging from 9 to 21%, a molar percentage. monomer M2 of formula (II-A) ranging from 8 to 92% and a molar percentage of monomer M2 of formula (II-B) ranging from 0.1 to 62%. The molar percentage of monomers in the copolymer results directly from the adjustment of the amounts of monomers used for the synthesis of the copolymer. In a preferred embodiment, the copolymer Al has a molar percentage of monomer M1 of formula (I) ranging from 1 to 30%, a molar percentage of monomer M2 of formula (II-A) ranging from 8 to 62% and a molar percentage of M2 monomer of formula (II-B) ranging from 8 to 91%. The molar percentage of monomers in the copolymer results directly from the adjustment of the amounts of monomers used for the synthesis of the copolymer. Advantageously, the polydiol Al random 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 or by adjusting the amount of free radical source when the copolymers of the invention are prepared by conventional free radical polymerization. Advantageously, the polydiol random copolymer 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 ). New associative and exchangeable compositions Another object of the present invention is a composition of associative and thermoreversibly exchangeable compounds, the composition resulting from the mixture of at least one random polydiol Al copolymer as described above or in particular capable of be obtained by one of the methods described above; A compound A2 comprising at least two boronic ester functions. In one embodiment of the composition of the invention, the compound A2 comprising two boronic ester functions has the general formula (III): , identical or different, are integers chosen between 0 and 1, R4, R5, R6 and R7, which are identical or different, are chosen from the group formed by hydrogen and a hydrocarbon group having from 1 to 24 carbon atoms, from preferably from 4 to 18 carbon atoms, 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, the compound A2 is a compound of the general formula (III) above in which: w1 and w2, which are identical or different, are integers chosen from 0 to 1; R4 and R6 are the same and are hydrogen atoms; R5 and R7 are identical and are a hydrocarbon group, preferably a linear alkyl, having 1 to 24 carbon atoms, preferably 4 to 18 carbon atoms, preferably 6 to 16 carbon atoms; L is a divalent linking moiety and is C 6 -C 18 aryl, preferably phenyl. The boronic diester A2 compound of formula (III) as described above is obtained by a condensation reaction between a boronic acid of general formula (III-a) and diol functions of the compounds of general formula (III-b) and (III-c) according to Reaction Scheme 4 below: ## STR5 ## wherein R 6 is selected from the group consisting of: ## STR5 ## ## STR2 ## 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. The condensation reaction is carried out in the presence of a dehydrating agent such as magnesium sulfate. This agent makes it possible to trap the water molecules initially introduced as well as those released by the condensation between the compound of formula (III-a) and the compound of formula (III-b) and between the compound of formula (III- a) and the compound of formula (III-c). In one embodiment, the compound (III-b) and the compound (III-c) are identical. Those skilled in the art can adapt the amounts of reagents of formula (III-b) and / or (III-c) and of formula (III-a) to obtain the product of formula (III). Boronic ester copolymer compound A2 In another embodiment of the composition of the invention, the compound A2 comprising at least two boronic ester functional groups is a boronic ester random copolymer resulting from the copolymerization of at least one monomer M3 of formula (IV) as described below with at least one M4 monomer of formula (V) as described below. M3 monomer of formula (IV) The monomer M3 of the boronic ester random copolymer compound A2 has the general formula (IV) in which: ## STR1 ## in which which: t is an integer equal to 0 or 1; u is an integer equal to 0 or 1; M and R8 are divalent linking groups, which may be identical or different, and are chosen from the group formed by a C 6 -C 18 aryl, a C 7 -C 24 aralkyl and a C 2 -C 24 alkyl, preferably a C 6 -C 6 aryl; C18, X is a function selected from the group consisting of -O-C (O) -, -C (O) -O-, -C (O) -N (H) -, -N (H) -C ( 0) -, -S-, -N (H) -, -N (R'4) - and -O- with R'4 a hydrocarbon chain comprising from 1 to 15 carbon atoms; R9 is selected from the group consisting of -H, -CH3 and -CH2-CH3; preferably -H and -CH3; R10 and R11, which are identical or different, are chosen from the group formed by hydrogen and a hydrocarbon chain containing from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 6 to 12 carbon atoms ; By "C2-C24 alkyl" is meant a saturated hydrocarbon chain, linear or branched, comprising from 2 to 24 carbon atoms. Preferably, the hydrocarbon chain is linear. Preferably the hydrocarbon chain comprises from 6 to 16 carbon atoms. By "hydrocarbon chain comprising from 1 to 15 carbon atoms" is meant a linear or branched alkyl or alkenyl group comprising from 1 to 15 carbon atoms. Preferably, the hydrocarbon chain is a linear alkyl group. Preferably, it comprises from 1 to 8 carbon atoms. By "hydrocarbon chain comprising 1 to 24 carbon atoms" is meant a linear or branched alkyl or alkenyl group comprising from 1 to 24 carbon atoms. Preferably, the hydrocarbon chain is a linear alkyl group. Preferably, it comprises from 4 to 18 carbon atoms, preferably from 6 to 12 carbon atoms. In one embodiment of the invention, the monomer M3 has the general formula (IV) wherein: t is an integer equal to 0 or 1; U is an integer equal to 0 or 1; M and R8 are divalent linking groups and are different, M is C6-C18 aryl, preferably phenyl, R8 is C7-C24 aralkyl, preferably benzyl; X is a group selected from the group consisting of -O-C (O) -, -C (O) -O-, -C (O) -N (H) - and -O-, preferably -C ( 0) -O- or -O-C (O) -; R9 is selected from the group consisting of -H, -CH3, preferably -H; R 10 and R 11 are different, one of R 10 or R 11 is H and the other R 10 or R 11 is a hydrocarbon chain, preferably a linear alkyl group having 1 to 24 carbon atoms, preferably 4 to 18 carbon atoms. carbon atoms, preferably between 6 and 12 carbon atoms. / Synthesis of M3 monomer of formula (IV) In all the schemes set out below, unless otherwise indicated, the variables R10, R11, M, u, t, X, R8, R'4 and R9 have the same definition as in formula (IV) above. The monomers M3 of formula (IV) are especially obtained 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: R10cl-12 1) Acetone, H2O OH OH 2) MgSO4 R11 (R8) X -OH HO O / BM X- (R0 H2C (IV-f) ( IV-g) (IV) Diagram 5 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) 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 sulphate The compounds of formula (IV-g) are commercially available from the following suppliers: Sigma-Aldrich®, Alfa Aesar® and TCI®. 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: ## STR2 ## ## STR2 ## Scheme 6 with 35 z an integer equal to 0 or 1; R12 is selected from the group consisting of -H, -CH3 and -CH2-CH3; u, X, M, R8 and R9 as defined above. The compound of formula (IV-e) is obtained by reaction of a compound of formula (IV-c) with 29 a compound of formula (IV-d) according to the following reaction scheme 7: R12 R12 0 BM O / ' X-R y R (IV-e) H2C 0 Y5- (R8) u Rg) z / BM / H2C 0 Y4 (IV-d) (IV-c) Scheme 7 with 10 z, 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 ( 0) -OH; X represents -C (O) -O-, then Y4 represents a carboxylic acid function -C (O) -OH and Y5 is an alcohol function -OH or a halogen atom, and preferably chlorine or bromine; ; X represents -C (O) -N (H) -, then Y4 represents a carboxylic acid function -C (O) -OH or a -C (O) -Hal function, and Y5 is an amine NH2 function; X represents -N (H) -C (O) -, then Y4 represents an amine function NH2 and Y5 is a carboxylic acid function -C (O) -OH or a -C (O) -Hal function; X is -S-, then Y4 is a halogen atom and Y5 is a thiol -SH function or Y4 is a thiol -SH function and Y5 is a halogen atom; X is -N (H) -, then Y4 is a halogen atom and Y5 is an amine -NH2 function or Y4 is an amine -NH2 function 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 groups Y 1 and Y 2, 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®, TCI® and Acros Organics®. 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: MgSO 4 Acetone, ## STR5 ## wherein R, M, Y, Z and R are as defined above, among the compounds of formula (IV-b), the one in which R12 is methyl and z = 0. The compounds of formula (IV-a) and (IV-b) are commercially available from the following suppliers Sigma-Aldrich®, Alfa Aesar® and TCI® 7 M4 Monomer of General Formula (V): The monomer M4 of the boronic ester random copolymer A2 has the general formula (V) H 2 C R 13 (V) in which: R 12 is selected from the 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 a group R'13, -C (0) -0-R'13, -O-R'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. By "C16-C18 aryl group substituted with an R13 group" is meant an aromatic hydrocarbon compound comprising from 6 to 18 carbon atoms of which at least one carbon atom of the aromatic ring is substituted by a C 1 -C 25 alkyl group. as defined above. (R12 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 a C1-C25 alkyl group, preferably a C1-C25 linear alkyl, even more preferably a linear C5-C15 alkyl. / Obtaining the M4 monomer: Monomers of formulas (V) and (VA) are well known to those skilled in the art.They are marketed by Sigma-Aldrich® and TCI® / Synthesis of compound A2 random copolymer boronic ester The skilled person is able to synthesizing the boronic ester random copolymers using its general knowledge The copolymerization can be initiated in bulk or in solution in an organic solvent by compounds generating free radicals.For example, the boronic ester random copolymers are obtained by known methods. of radical copolymerization, in particular controlled such as the method called controlled radical polymerization controlled by reversible addition-fragmentation chain transfer (Reversible Addition-Fragmentation Chain Transfer (RAFT)) and the so-called method controlled radical polymerization by atom transfer ( in English 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)).
[0016] Thus another object of the present invention is a process for preparing a boronic ester statistical copolymer, said process comprising at least one polymerization step (a) in which at least: i) a first monomer M3 of formula general (IV): ## STR1 ## 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, and are chosen from the group formed by a C 6 -C 18 aryl, a C 7 -C 24 aralkyl and a C 2 -C 24 alkyl, preferably a C 6 -C 6 aryl; C18 X is a group selected from the group consisting of -O-C (O) -, -C (O) -O-, -C (O) -N (H) -, -N (H) -C (O) ) -, -S-, -N (H) -, -N (R'4) - and -O- with R'4 a hydrocarbon chain comprising from 1 to 15 carbon atoms; R9 is selected from the group consisting of -H, -CH3 and -CH2-CH3; preferably -H; R10 and R11, which are identical or different, are chosen from the group formed by hydrogen and a hydrocarbon chain containing from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 6 to 12 carbon atoms ; ii) at least one second monomer M4 of general formula (V): R12H2CR13 (V) in which: R12 is chosen from the group formed by -H, -CH3 and -CH2-CH3, preferably -H or -CH3 ; R13 is selected from the group consisting of a C6-C18 aryl, a C6-C18 aryl substituted with a group R'13, -C (O) -O-R'13, -O-R'13 -S- R'13 and -C (O) -N (H) -R'13 with R'13 a C1-C25 alkyl group. iii) at least one source of free radicals.
[0017] 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.
[0018] Radical sources and transfer agents are those which have been described for the synthesis of polydiol random copolymers. The preferences described for radical sources and transfer agents also apply to this process. Properties of the New Compounds A2 Boron Ester Statistical Copolymers Advantageously, the chain formed by the linking of the groups R10, M, (R8) 'with u, an integer equal to 0 or 1, and X of the monomer M3 of general formula ( IV) has a total number of carbon atoms ranging from 8 to 38, preferably 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 statistical 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.
[0019] Advantageously, the boronic ester statistical copolymer has a molar percentage of monomer of formula (IV) ranging from 0.25 to 20%, preferably from 1 to 10%. Advantageously, the boronic ester statistical copolymer has a molar percentage of monomer of formula (IV) ranging from 0.25 to 20%, preferably from 1 to 10% and a molar percentage of monomer of formula (V) ranging from 80 to 99 , 75%, preferably 90 to 99%.
[0020] 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 molecular weight 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. Characteristics of the New Compositions of the Invention The compositions of the invention resulting from the mixture of at least one polydiol random copolymer Al as defined above and at least one compound A2 as defined above have rheological properties. very varied according to the proportion of the compounds Al and A2 used. 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.
[0021] 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 chemical bonds are established between the polydiols random copolymers Al and the compounds A2 comprising at least two boronic ester functions. Figure 4 illustrates associative polymers. 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.
[0022] By "chemical bond" is meant a covalent chemical bond of the boronic ester type. By "exchangeable" is meant that the compounds are capable of exchanging chemical bonds between them without the total number of chemical functions being changed. The boronic ester bonds of the compounds A2 as well as the boronic ester bonds formed by the combination of the polydiol random copolymers Al and the compounds A2 can be exchanged with diol functions present in the composition to form new boronic esters and new diol functions without the total number of boronic ester functions and diol functions is affected. The chemical exchange reaction (transesterification) is illustrated in the following reaction scheme 9: ## STR1 ## with: - R a chemical group of the compound A2, - the hatched circle symbolizes the rest of the the chemical structure of the compound A2, the grid rectangle symbolizes the rest of the chemical structure of the polydiol Al random polymer. The boronic ester bonds of the compounds A2 as well as the boronic ester bonds formed by the combination of the polydiols Al random copolymers and the A2 compounds can also exchange to form new boronic esters without the total number of boronic ester functions being affected. This other process of exchange of chemical bonds is carried out by metathesis reaction of the boronic ester functions; 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 Al-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 Al-2 copolymer is then combined with both the A2-1 copolymer and the A2-2 copolymer. Another chemical link exchange process is illustrated in FIG. 9, in which it can be observed that the polydiol random copolymer A1-1, which was associated with the A2-1 polymer, exchanged two boronic ester bonds with the boronic ester statistical copolymer. A2-2. The polydiol random copolymer Al-2, which was in association with the A2-2 polymer, exchanged two boronic ester bonds with the boronic ester random copolymer A2-1; the total number of boronic ester bond in the composition being unchanged and is equal to 4. The A1-1 copolymer is then combined with the A2-2 polymer. The Al-2 copolymer is then with the A2-1 polymer. The A2-1 copolymer was exchanged with the A2-2 polymer. By "crosslinked" is meant a copolymer in the form of a network obtained by the establishment of bridges between the macromolecular chains of the copolymer. These interconnected chains are for the most part distributed in the three dimensions of space. A crosslinked copolymer forms a three-dimensional network. In practice, the formation of a copolymer network is ensured by a solubility test. It can be ensured that a network of copolymers has been formed by placing the copolymer network in a known solvent to dissolve the uncrosslinked copolymers of the same chemical nature. If the copolymer swells instead of dissolving, the person skilled in the art knows that a network has been formed. Figure 3 illustrates this solubility test.
[0023] 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) or a reaction. of metathesis between the boronic ester functions forming the bridges between the Al copolymers and the A2 compounds. The bridges formed are boronic ester type bonds. These boronic ester bonds are covalent and labile because of the reversibility of the transesterification reaction. By "thermoreversible crosslinked" is meant a copolymer crosslinked by a reversible reaction whose displacement in one direction or the other direction is controlled by the temperature. The thermoreversible crosslinking mechanism of the composition of the invention is shown schematically in FIG. 4. Unexpectedly, the Applicant has observed that at low temperature, the polydiol copolymer Al (symbolized by the copolymer bearing functions A in FIG. 4) is not or only slightly crosslinked by the boronic ester compounds A2 (symbolized by the compound bearing functions B in FIG. 4). As the temperature increases, the diol functions of copolymer Al react with the boronic ester functions of compound A2 by a transesterification reaction. The polydiol random copolymers A1 and A2 compounds 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 linkages between the polydiol random copolymers A1 and the A2 compounds break, and if necessary, the composition loses its gel character. The amount of boronic ester linkages (or boronic ester linkage) which can be established between the polydiols random copolymers A1 and the A2 compounds is adjusted by those skilled in the art by means of an appropriate selection of the polydiol Al random copolymer of the A2 compound. and the composition of the mixture. Furthermore, those skilled in the art know how to select the structure of the compound A2 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, w2 = 1 and t = 1, respectively. Advantageously, the content of statistical copolymer Al in the composition ranges from 0.1% to 99.5% by weight relative to the total weight of the composition, preferably from 0.25% to 80% by weight relative to total weight of the final composition, more preferably from 1% to 50% by weight relative to the total weight of the final composition.
[0024] Advantageously, the content of compound A2 in the composition ranges from 0.1% to 99.5% by weight relative to the total weight of the composition, preferably from 0.25% to 80% by weight relative to the total weight. of the final composition, more preferably from 0.5% to 50% by weight relative to the total weight of the final composition.
[0025] In one embodiment, the content of random copolymer Al in the composition ranges from 0.5 to 99.5% by weight relative to the total weight of the composition and the content of compound A2, in particular boronic ester random copolymer in the composition. composition ranges from 0.5% to 99.5% by weight relative to the total weight of the composition. Preferably, the mass ratio between the statistical compound polydiol Al and compound A2 (ratio Al / A2) in the composition ranges from 0.005 to 200, preferably from 0.05 to 20, even more preferably from 0.1 to 10. In one embodiment, the composition of the invention comprises: 0.5% to 40% by weight of a mixture of at least one random polydiol Al copolymer as defined above and at least one compound A2 as defined above, preferably the mixture comprising from 0.5% to 99.5% by weight of the random copolymer Al relative to the total weight of the mixture and from 0.5% to 99.5% by weight of the compound A2 , in particular boronic ester random copolymer, relative to the total weight of the mixture; 20 - 60% to 99.5% by weight of a hydrophobic medium. In one embodiment, the composition of the invention consists essentially of: 0.5% to 40% by weight of a mixture of at least one random polydiol Al copolymer as defined above and at least one compound A2 as defined above, preferably the mixture comprising from 0.5% to 99.5% by weight of the random copolymer Al relative to the total weight of the mixture and from 0.5% to 99.5% by weight of the compound A2, in particular boronic ester random copolymer, relative to the total weight of the mixture; 60% to 99.5% by weight of a hydrophobic medium. In one embodiment, the composition of the invention is in the form of a parent composition. By "mother composition" is meant a composition which a person skilled in the art can make daughter solutions by removing a certain amount of mother solution supplemented by the addition of a necessary quantity of diluent (solvent or other) to obtain a desired concentration. A daughter composition is thus obtained by dilution of a parent composition. A hydrophobic medium may be a solvent, a mineral oil, a natural oil, a synthetic oil. In one embodiment, the composition of the invention may also comprise at least one additive chosen from the group formed by thermoplastics, elastomers, thermoplastic elastomers, thermosetting polymers, pigments, dyes, fillers, plasticizers, fibers, antioxidants, lubricant additives, compatibilizers, antifoam agents, dispersant additives, adhesion promoters and stabilizers. The novel compositions of the invention are prepared by means well known to those skilled in the art. For example, it suffices for those skilled in the art in particular to: - take a desired quantity of a solution comprising the polydiol random copolymer Al as defined above; - Take a desired amount of a solution comprising the compound A2 as defined above; - Mixing the two solutions taken to obtain the composition of the invention.
[0026] 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 random copolymer, are associated either with a composition in which the polydiol Al random copolymer and the compound A2, especially the boronic ester random copolymer, are crosslinked. 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 Al; 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 Al; 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 Al; the mass percentage of the boronic diester compound A2; the weight percentage of the boronic ester random copolymer A2; Use of the New Compositions of the Invention The compositions of the invention can be used in all solutions whose viscosity varies as a function of temperature. The compositions of the invention make it possible to thicken a fluid and to control its viscosity. The polydiols Al random copolymers, the A2 compounds and the compositions can be used in fields as varied as the improved recovery of petroleum, the paper industry, paints, food additives, cosmetic or pharmaceutical formulation. For example, the compositions of the invention can be added to compositions for lubricating mechanical parts. Indeed, the new compositions of the invention when introduced into a base oil have an inverted behavior vis-à-vis a change in temperature with respect to the behavior of the base oil and rheological additives of the polymer type of the prior art. 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. Advantageously, the viscosity of the lubricating composition is thus controlled and depends less on temperature fluctuations. EXAMPLES The following examples illustrate the invention without limiting it. 1 Synthesis of Al Statistical Copolymers of the Invention Bearing Diol Function o 1.1: From a Monomer Bearing a Protected Diol Function in the Ketal Form In one embodiment, the random Al copolymer of the invention is obtained according to the following reaction scheme 10: Protection of the OH Diol Function 2. Reaction with MAC Cl HO Polymerisa Protected Copolymers 4. © eproteetion Poly (alkyl methacrylate-co-alkyldiol methacrylate) Copolymers Scheme 10 1.1.1 Synthesis of the monomer M1 bearing a protected diol function in the ketal form The synthesis of a methacrylate monomer carrying a protected diol function in the ketal form is carried out in two stages (steps 1 and 2 of the scheme). Reaction 10) according to the protocol below: Step: 42.1 g (314 mmol) of 1,2,6-hexane triol (1,2,6-HexTri) are introduced into an IL flask. . 5.88 g of molecular sieves (4 ° A) are added followed by 570 mL of acetone. 5.01 g (26.3 mmol) of para-toluenesulfonic acid (pTSA) are then slowly added. The reaction medium is stirred for 24 hours at room temperature. 4.48 g (53.3 mmol) of NaHCO 3 are then added. The reaction medium is stirred for 3 hours at room temperature before being filtered. The filtrate is then concentrated under vacuum using a rotary evaporator until a suspension of white crystals is obtained. 500 ml of water are then added to this suspension. The solution thus obtained is extracted with 4 × 300 ml of dichloromethane. The organic phases are combined and dried over MgSO 4. The solvent is then completely evaporated under vacuum at 25 ° C. by means of a rotary evaporator. Stage 2: The product thus obtained is then introduced into an IL flask surmounted by a dropping funnel. The glassware used was first dried overnight in a thermostatically controlled oven at 100 ° C. 500 ml of anhydrous dichloromethane are then introduced into the flask followed by 36.8 g (364 mmol) of triethylamine. A solution of 39.0 g (373 mmol) of methacryloyl chloride (MAC) in 50 mL of anhydrous dichloromethane is introduced into the dropping funnel. The flask is then placed in an ice bath to lower the temperature of the reaction medium to around 0 ° C. The methacryloyl chloride solution is then added dropwise with vigorous stirring. Once the methacryloyl chloride addition is complete, the reaction medium is left stirring for 1 hour at 0 ° C. and then 23 hours at room temperature. The reaction medium is then transferred into a 3 L Erlenmeyer flask and 1 L of dichloromethane is added. The organic phase is then successively washed with 4 × 300 ml of water, 6 × 300 ml of a 0.5 M aqueous hydrochloric acid solution, 6 × 300 ml of a saturated aqueous solution of NaHCO 3 and again 4 x 300 mL of water. The organic phase is dried over MgSO4, filtered and then concentrated under vacuum using a rotary evaporator to give 64.9 g (85.3% yield) of protected diol monomer in the form of a clear yellow liquid which the characteristics are as follows: 1 H NMR (400 MHz, CDCl 3) δ: 6.02 (singlet, 1H), 5.47 (singlet, 1H), 4.08 (triplet, J = 6.8 Hz, 2H), 4.05-3.98 (multiplet, 1H), 3.96 (doublet of doublets, J = 6 Hz and J = 7.6 Hz, 1H), 3.43 (doublet of doublet, J = 7.2 Hz and J = 7.2 Hz, 1H), 1.86 (doublet of doublets, J = 1.2 Hz and J = 1.6 Hz, 3H), 1.69-1.33 (multiplet, 6H), 1.32 (singlet, 3H), 1.27 (singlet, 3H). 1.1.2 Synthesis of methacrylate copolymers according to the invention bearing diol functions The synthesis of the methacrylate copolymers bearing diol functions according to the invention is carried out in two stages (steps 3 and 4 of reaction scheme 10): Copolymerization of two monomers alkyl methacrylate with a methacrylate monomer bearing a protected diol function in the form of a ketal Deprotection of the copolymer. More precisely, 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 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) in solution 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. A copolymer having a number average molar mass (M.) of 41,000 g / mol, a polydispersity index (Ip) of 1.22 and a number-average degree of polymerization (DP) of 16 are thus obtained. values are respectively obtained by size exclusion chromatography using tetrahydrofuran as eluent and polystyrene calibration and by monitoring the conversion to monomers during the copolymerization. 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 above are introduced into a 500 ml Erlenmeyer flask. 180 ml of dioxane are added and the reaction mixture is stirred at 30 ° C. 3 ml of a 1M aqueous solution of hydrochloric acid and then 2.5 ml of an aqueous solution of 35% hydrochloric acid are added dropwise. The reaction medium then becomes slightly opaque and 20 ml of THF are introduced to make the medium completely homogeneous and transparent. The reaction medium is then left stirring at 40 ° C. for 48 hours. The copolymer is recovered by precipitation in methanol, filtration and drying under vacuum at 30 ° C overnight. A poly (alkyl methacrylate-co-alkyldiol methacrylate) copolymer containing about 20 mol% of diol M1 monomer units and having an average length of pendant alkyl chains of 13.8 carbon atoms is obtained. 1.2: From a monomer bearing a protected diol function in the form of a boronic ester In another embodiment, the random copolymer Al of the invention is obtained according to the following reaction scheme 11: 3. Polymerization HO OH 1. Protection of the OH Diol Function 2. Reaction to the IAC Cl 0 35 Protected Copolymers 4. Deprotection Poly (alkyl methacrylate-co-aikyldiol methacrylate) Copolymers Scheme 11 1.2.1 Synthesis of the M1 monomer carrying a protected diol function in the form of a boronic ester The synthesis of a methacrylate monomer carrying a protected diol function in the form of an ester is carried out in two stages (steps 1 and 2 of Scheme 11) according to the following protocol: Step father: 6.01 g (49.3 mmol) of phenylboronic acid (PBA) and 300 mL of acetone are introduced into a 500 mL beaker, followed by 1.5 mL of water . The reaction medium is stirred and 6.07 g (45.2 mmol) of 1,2,6-hexanetriol are slowly added. An excess of magnesium sulphate is added to the reaction medium in order to trap the water initially introduced as well as the water released by the condensation between phenylboronic acid and 1,2,6-hexanetriol. The reaction medium is left stirring at ambient temperature for 30 minutes before being filtered and then concentrated under vacuum using a rotavapor. Step 21: The light yellow liquid thus obtained in the previous step is then introduced into an IL flask surmounted by a dropping funnel. The glassware used having been previously pre-dried overnight in a thermostatically controlled oven at 100 ° C. 90 ml of anhydrous dichloromethane are then introduced into the flask followed by 6.92 g (68.4 mmol) of triethylamine. A solution of 5.82 g (55.7 mmol) of methacryloyl chloride (MAC) in 10 mL of anhydrous dichloromethane is added to the dropping funnel. The flask is then placed in an ice bath to lower the temperature of the reaction medium to around 0 ° C. The methacryloyl chloride solution is then added dropwise with vigorous stirring. Once the methacryloyl chloride addition is complete, the reaction mixture is left stirring for 1 hour at 0 ° C. and then 17 hours at room temperature. The reaction medium is then transferred to a 500 ml Erlenmeyer flask and 300 ml of dichloromethane are added. The organic phase is then successively washed with 4 × 100 ml of water, 4 × 100 ml of a 0.1 M aqueous hydrochloric acid solution, 4 × 100 ml of a saturated aqueous solution of NaHCO 3 and again 4 X 100 mL of water. The organic phase is dried over MgSO 4, filtered and then concentrated under vacuum using a rotary evaporator to give 11.6 g (89% yield) of protected diol monomer as a light yellow liquid. whose characteristics are the following: 1 H NMR (400 MHz, CDCl 3) δ: 7.81 (doublet of doublets, J = 4 Hz and J = 8 Hz, 2H), 7.48 (triplet of triplets, J = 1, 2 Hz and J = 7.2 Hz, 1H), 7.38 (triplet triplet, J = 1.2 Hz and J = 6.8 Hz, 1H), 6.10 (singlet, 1H), 5, 55 (singlet, 1H), 4.63-4.53 (multiplet, 1H), 4.44 (doublet of doublets, J = 7.6 Hz and J = 8.8 Hz, 1H), 4.18 (triplet , J = 6.8 Hz, 2H), 3.95 (doublet of doublets, J = 6.8 Hz and J = 35.8.8 Hz, 1H), 1.94 (doublet of doublets, J = 1.2 Hz and J = 1.6 Hz, 3H), 1.81-1.47 (multiplet, 6H) 1.2.2 Synthesis of methacrylate copolymers according to the invention bearing diol functions The synthesis of methacrylate copolymers carrying diol functions according to the invention invention is carried out in two steps (step 3 and 4 of Scheme 11): Copolymerization of two alkyl methacrylate monomers with a methacrylate monomer bearing a protected diol function as a boronic ester; Deprotection of the copolymer. The following procedures describe the synthesis of a poly (alkyl methacrylate-co-alkyldiol methacrylate) copolymer containing about 10 mol%. of monomeric units diol, and having an average length of pendant alkyl chains of 13.8 carbon atoms. The synthesis of the polymer is carried out according to the following protocol: 13.5 g (40 mmol) of stearyl methacrylate (StMA), 12 g (47.2 mmol) of lauryl methacrylate (LMA), 3.12 g ( 10.8 mmol) of methacrylate bearing a protected diol function in the boronic ester form, 92.1 mg (0.416 mmol) of cumyl dithiobenzoate and 34 ml of anisole are introduced into a 100 ml Schlenk tube. The reaction medium is stirred and 13.7 mg (0.0833 mmol) of azobisisobutyronitrile (AIBN) dissolved in 135 μl of anisole are introduced into the Schlenk tube. The reaction medium is then degassed for 30 minutes by bubbling argon before being heated to 65 ° C. for a period of 24 hours. The Schlenk tube is placed in an ice bath to stop the polymerization and 30 mL of tetrahydrofuran (THF) is then added to the reaction medium. The polymer is isolated by precipitation in cold methanol, filtration and drying under vacuum at 30 ° C overnight. A copolymer having a number average molecular weight (M.) of 70 70 g / mol, a polydispersity index (Ip) of 3.11 and a number average polymerization degree (DP) of 228 are thus obtained. These values are respectively obtained by steric exclusion chromatography using tetrahydrofuran as eluent and a polystyrene calibration and by monitoring the conversion to monomers during the copolymerization. The deprotection of the copolymer is carried out according to the following protocol: 19 g of copolymer obtained in the preceding step and containing about 10% protected diol function are introduced into an Erlenmeyer flask of L. 1 250 ml of dichloromethane and 30 ml of an aqueous solution of hydrochloric acid are added. The reaction medium is stirred for 24 hours at room temperature before being poured dropwise into 1L of aqueous sodium hydroxide solution (pH = 10) and then stirred again for 24 hours at room temperature. Throughout this stirring period, the reaction medium is composed of two phases. The organic phase is recovered using a separating funnel and the polymer is precipitated in cold methanol. The polymer thus obtained is redissolved in 100 ml of dichloromethane in order to be precipitated again in cold methanol. The polymer is recovered and dried under vacuum at 30 ° C overnight. A poly (alkyl methacrylate-co-alkyldiol methacrylate) copolymer containing about 10 mol% of monomer diol units and having an average length of pendant alkyl chains of 13.8 carbon atoms is obtained. 2. Synthesis of the compounds A2 of the invention o 2.1: Synthesis of a boronic diester as crosslinking agent The synthesis of a compound A2 according to the invention is carried out according to the following protocol and according to the reaction scheme 12: HO ## STR1 ## 1,4-Benzenediboronic acid (1,4-BDBA) (1.5 g, 9.05 mmol) is introduced into a 500 beaker. ml, followed by 300 ml of acetone, the reaction mixture is stirred and 0.300 g (16.7 mmol) of water are introduced dropwise, the reaction medium then becomes transparent and homogeneous, and the dodecanediol (4.02 g, 19.9 mmol) is slowly added After complete dissolution of the latter, an excess of magnesium sulphate is added in order to trap the water introduced initially and the water released by the condensation between 1,4-BDBA and 1'1,2-dodecanediol After stirring for 15 minutes, the reaction medium is filtered and the solvent is then eluted. filtered from the filtrate using a rotary evaporator to give 4.41 g of boronic diester and 1,2-dodecanediol (98% yield) as a white solid. The characteristics are as follows: 1 H NMR (400 MHz, CDCl 3) Diester boronic: 8: 7.82 (singlet, 2H), 4.63-4.51 (multiplet, 2H), 4.42 (doublet of doublets, J = 8 Hz and J = 8.8 Hz, 2H), 3.95 (doublet of doublets, J = 7.2 Hz and J = 8.8 Hz, 2H), 1.81-1.31 (multiplet, 36H 0.88 (triplet, J = 7.2 Hz, 6H); 1,2-dodecanediol: 8: 3.85-3.25 (multiplet, about 2.17H), 1.81-1.31 (multiplet, about 13.02H), 0.88 (triplet, J = 7) , 2 Hz, about 2.17H) o 2.2: Synthesis of the poly (alkyl methacylate-co-monomer boronic ester) copolymer 2.2.1 Synthesis of the boronic acid monomer The boronic ester monomer of the invention is synthesized according to the following reaction scheme 13 The monomer is obtained according to the two-step protocol: The first step consists in synthesizing a boronic acid and the second step consists in obtaining a boronic ester monomer. step: 4-carboxyphenylboronic acid (CPBA) (5.01 g, 30.2 mmol) is introduced into a 1L beaker followed by 350 mL of acetone and the reaction mixture is stirred 7.90 mL (439 mmol) of water are added dropwise until dissolution is complete ± 4-carboxyphenylboronic acid The reaction medium is then transparent and homogeneous The 1,2-propanediol (2.78 g, 36.6 mmol) is then slowly added, followed by an excess of magnesium sulfate to trap the initially introduced water and the water released from the condensation between the CPBA and 1,2 propanediol. The reaction medium is stirred for 1 hour at 25 ° C before being filtered. The solvent is then removed from the filtrate by means of a rotary evaporator. The product thus obtained and 85 ml of DMSO are introduced into a 250 ml flask. The reaction medium is stirred and then after complete homogenization of the reaction medium, 8.33 g (60.3 mmol) of K 2 CO 3 are added. 4- (Chloromethyl) styrene (3.34 g, 21.9 mmol) is then slowly introduced into the flask. The reaction medium is then left stirring at 50 ° C. for 16 hours. The reaction medium is transferred to a 2 L Erlenmeyer flask, then 900 ml of water are added. The aqueous phase is extracted with 8 x 150 mL of ethyl acetate. The organic phases are combined and then extracted with 3 x 250 mL of water. The organic phase is dried over MgSO4 and filtered. The solvent was removed from the filtrate 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 (400 MHz, CDCl3) δ: 7.98 (doublet, J = 5.6 Hz, 4H), 7.49 (doublet, J = 4 Hz, 4H), 6.77 (doublet of doublets, J = 10, 8 Hz and J = 17.6 Hz, 1H), 5.83 (doublet of doublet, J = 1.2 Hz and J = 17.6 Hz, 1H), 5.36 (singlet, 2H), 5.24 (doublet of doublets, J = 1,2 Hz and J = 11,2 Hz, 1H). Step 2: The boronic acid monomer (5.7 g, 20.2 mmol) obtained in the first step and 500 mL of acetone are introduced into a 1L Erlenmeyer flask. The reaction medium is stirred and 2.6 ml (144 mmol) of water are added dropwise until complete dissolution of the boronic acid monomer. The reaction medium is then transparent and homogeneous. A solution of 1,2-dodecanediol (5.32 g, 26.3 mmol) in 50 mL of acetone is slowly added to the reaction medium, followed by an excess of magnesium sulfate to trap the initially introduced water and as the water released by the condensation between the boronic acid monomer and 1,2-dodecanediol. After stirring for 3 hours at ambient temperature, the reaction medium is filtered. The solvent is then removed from the filtrate 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.
[0027] The characteristics are as follows: NMR (400 MHz, CDCl3): Boronic ester monomer: 8: 8.06 (doublet, J = 8 Hz, 2H), 7.89 (doublet, J = 8 Hz, 2H), 7, 51 (doublet, J = 4 Hz, 4H), 6.78 (doublet of doublets, J = 8 Hz and J = 16 Hz, 1H), 5.84 (doublet of doublets, J = 1.2 Hz and J = 17.6 Hz, 1H), 5.38 (singlet, 2H), 5.26 (doublet of doublets, J = 1.2 Hz and J = 11.2 Hz, 1H), 4.69-4.60 ( multiplet, 1H), 4.49 (doublet of doublets, J = 8 Hz and J = 9.2 Hz, 1H), 3.99 (doublet of doublets, J = 7.2 Hz and J = 9.2 Hz, 1H), 1.78-1.34 (multiplet, 18H), 0.87 (triplet, J = 6.4 Hz, 3H); 1,2-dodecanediol:: 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) 2.2.2 Synthesis of compound A2, random copolymer poly (alkyl methacrylate-co-monomer boronic ester) The random copolymer A2 of the invention is obtained according to the following protocol: 2.09 g of a boronic ester monomer mixture and 1,2-dodecanediol previously prepared (containing 3.78 mmol of boronic ester monomer), 98.3 mg (0.361 mmol) of cumyl dithiobenzoate, 22.1 g (86.9 mmol) of methacrylate of lauryl (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. There is thus obtained a copolymer having the following structure: with m = 0.96 and n = 0.04.
[0028] The boronic ester copolymer obtained has a number-average molar mass (M.) of 37,200 g / mol, a polydispersity index (Ip) equal to 1.24 and a number-average degree of polymerization (DP) 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 o 3.1 Apparatuses and protocols for viscosity measurement The rheological studies were carried out using a Couette MCR 501 controlled stress rheometer from Anton Paar. The measurements were performed on polymer formulations in solution in a Group III base oil using a DG 26.7 cylindrical reference geometry. The viscosity was measured as a function of the shear rate for a temperature range of 10 ° C to 110 ° C. For each temperature, the viscosity of the system was measured as a function of shear rate from 0.01 to 1000 s-1. Viscosity measurements as a function of shear rate at T = 10 ° C, 20 ° C, 30 ° C, 50 ° C, 70 ° C, 90 ° C and 110 ° C were made (ranging from 10 ° C). C at 110 ° C) followed by further measurements at 10 ° C and / or 20 ° C to assess the reversibility of the systems. An average viscosity was then calculated for each temperature using the measuring points located on the same plate. The relative viscosity, solution, base oil, was also chosen to represent the evolution of the system viscosity as a function of temperature, since this quantity directly reflects the compensation for the loss of natural viscosity of the system. the Group III base oil of the polymer systems studied. o 3.2: Compositions based on random polydiols Al copolymers and A2 diester boronic compounds. Test Compositions Al Copolymers: Four random poly (alkyl methacrylate-co-alkyldiol methacrylate) copolymers of the invention were tested. These are the following copolymers: Copolymer Al-1: This copolymer comprises 20 mol% of monomers having diol functions. The average side chain length is 13.8 carbon atoms.
[0029] Its average molar mass is 49,600 g / mol. Its polydispersity index is 1.51. Its number-average degree of polymerization (DP) is 167. The number-average molecular weight and the polydispersity index are measured by steric exclusion chromatography using a polystyrene calibration. / Copolymer A1-2: This copolymer comprises 20 mol% of monomers having diol functions. The average side chain length is 10.8 carbon atoms. Its average molecular weight is 59 700 g / mol. Its polydispersity index is 1.6. Its number-average degree of polymerization (DP) was 196. The number average molecular weight and the polydispersity index are measured by steric exclusion chromatography using a polystyrene calibration. Al-3 Copolymer: This copolymer comprises 10 mol% of monomers having diol functions. The average side chain length is 13.8 carbon atoms. Its average molar mass is 47,800 g / mol. Its polydispersity index is 1.3. Its number-average degree of polymerization (DP) was 198. The number average molecular weight and the polydispersity index were measured by steric exclusion chromatography using a polystyrene calibration. / Copolymer A1-4: This copolymer comprises 10 mol% of monomers having diol functions. The average side chain length is 13.8 carbon atoms. Its average molar mass is 97 100 g / mol. Its polydispersity index is 3.11. Its number-average degree of polymerization (DP) is 228. The number average molecular weight and the polydispersity index are measured by steric exclusion chromatography using a polystyrene calibration. The copolymers A1-1, Al-2, Al-3 and Al-4 are obtained according to one of the protocols described in paragraph 1.
[0030] Compound A2: Compound A2-1 is the boronic diester obtained according to the protocol described in section 2.1.
[0031] Lubricating base oil The lubricating base oil used in the compositions to be tested is a Group III API oil, marketed by SK under the name Yubase 4. It has the following characteristics: its kinematic viscosity at 40 ° C. measured according to ASTM D445 is 19.57 cSt; its kinematic viscosity, measured at 100 ° C. according to ASTM D445, is 4.23 cSt; its viscosity index, measured according to the ASTM D2270 standard, is 122; its Noack volatility in weight percentage, measured according to DIN 51581, is 14.5; - Its flash point in degrees Celsius measured according to ASTM D92 is 230 ° C; - Its pour point (for point in English) in degrees Celsius measured according to the ASTM D97 standard is -15 ° C. Composition A (outside the invention) is used as a reference.
[0032] It contains a 4.2% by weight solution of a polymethacrylate polymer in API Group III lubricating base oil. The polymer has a number average molecular weight (M.) of 105,600 g / mol, a polydispersity index (Ip) of 3.06, a number-average degree of polymerization of 466 and the average length of the pendant chains. is 14 carbon atoms.
[0033] This polymethacrylate is used as a viscosity index improving additive. 4.95 g of this polymethacrylate (pre-dissolved in the base oil group III with a mass concentration of 4.2%) and 44.6 g of base oil group III are introduced into a flask. The solution thus obtained is stirred at 90 ° C. until the polymethacrylate is completely dissolved.
[0034] A 4.2% by weight solution of this polymethacrylate is obtained. Composition B-1 (except the invention) is obtained in the following manner: 4.14 g of polydiol copolymer Al-1 and 37.2 g of base oil group III are introduced into a bottle. The solution thus obtained is stirred at 90 ° C. until the polydiol is completely dissolved. A 10% by weight solution of polydiol copolymer A1-1 is obtained. Composition C-1 (according to the invention) is obtained in the following manner: 8 g of the 10% by weight solution of polydiol copolymer Al-1 in the previously prepared Group III base oil are introduced into a flask. 55.8 mg of boronic diester A2-1 are added to this solution. The solution thus obtained is stirred at 90 ° C. until complete dissolution of the boronic diester.
[0035] A 10% by weight solution of polydiol copolymer Al-1 and 20 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer A1-1. Composition D-1 (according to the invention) is obtained in the following manner: 8 g of the 10% by weight solution of polydiol copolymer A1-1 in the Group III base oil previously prepared are introduced into a flask. 223 mg of boronic diester A21 are added to this solution. The solution thus obtained is stirred at 90 ° C. until complete dissolution of the boronic diester. A 10% by weight solution of polydiol copolymer A1-1 and 80 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer A1-1. Composition B-2 (except the invention) is obtained in the following manner: 6.52 g of polydiol copolymer Al-2 and 58.7 g of base oil group III are introduced into a flask. The solution thus obtained is stirred at 90 ° C. until the polydiol has completely dissolved. A 10% by weight solution of polydiol copolymer Al-2 is obtained. Composition C-2 (according to the invention) is obtained in the following manner: 8 g of the 10% by weight solution of polydiol copolymer Al-2 in the Group III base oil prepared previously are introduced into a flask. 65.4 mg of boronic diester A2-1 are added to this solution. The solution thus obtained is stirred at 90 ° C. until complete dissolution of the boronic diester. A 10% by weight solution of polydiol copolymer Al-2 and 20 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer Al-2. Composition D-2 (according to the invention) is obtained in the following manner: 8 g of the 10% by weight solution of polydiol copolymer Al-2 in the Group III base oil previously prepared are introduced into a flask. 262 mg of boronic diester A21 are added to this solution. The solution thus obtained is stirred at 90 ° C. until complete dissolution of the boronic diester. A 10% by weight solution of polydiol copolymer Al-2 and 80 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer Al-2. Composition B-3 (except for the invention) is obtained in the following manner: 7.24 g of polydiol copolymer Al-3 and 65.2 g of base oil group III are introduced into a flask. The solution thus obtained is stirred at 90 ° C. until the polydiol is completely dissolved. A 10% by weight solution of polydiol copolymer Al-3 is obtained.
[0036] Composition C-3 (according to the invention) is obtained in the following manner: 8 g of the 10% by weight solution of polydiol copolymer Al-3 in the Group III base oil previously prepared are introduced into a flask. 28.2 mg of boronic diester A2-1 are added to this solution. The solution thus obtained is stirred at 90 ° C. until complete dissolution of the boronic diester. A 10% by weight solution of polydiol copolymer Al-3 and 20 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer Al-3. Composition B-4 (except for the invention) is obtained in the following manner: 4.99 g of polydiol copolymer Al-4 and 44.4 g of base oil group III are introduced into a flask. The solution thus obtained is stirred at 90 ° C. until the polydiol is completely dissolved. A 10% by weight solution of polydiol copolymer Al-4 is obtained. Composition C-4 (according to the invention) is obtained in the following manner: 6.01 g of the 10% by weight solution of polydiol copolymer Al-4 in the Group III base oil previously prepared are introduced into a flask. . 18.6 mg of boronic diester A2-1 are added to this solution. The solution thus obtained is stirred at 90 ° C. until complete dissolution of the boronic diester. A 10% by weight solution of polydiol copolymer Al-4 and 20 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer Al-4. Composition D-4 (according to the invention) is obtained in the following manner: 6.03 g of the 10% by weight solution of polydiol copolymer Al-4 in the Group III base oil previously prepared are introduced into a flask. . 74.7 mg of boronic diester A2-1 are added to this solution. The solution thus obtained is stirred at 90 ° C. until complete dissolution of the boronic diester. A 10% by weight solution of polydiol copolymer Al-4 and 80 mol% of boronic diester A2-1 is obtained relative to the diol functions of the polydiol copolymer Al-4. Results obtained in rheology The rheological behavior of the composition C1-1 was studied for a temperature range of 10 ° C to 110 ° C. The results are shown in FIG. 5. The dynamic viscosity of composition C1-1 varies at low shear rates and at temperatures below 50.degree. Composition C1-1 is deformed under shear stress for temperatures below 50 ° C.
[0037] For temperatures above 50 ° C., the dynamic viscosity of composition C1-1 varies very slightly or does not vary at low shear rates. The composition C1-1 is no longer deformed under the shear stress at these temperatures.
[0038] The relative viscosity of compositions A, B-1, C-1, D-1, B-2, C-2, D-2, B-3, C-3, D-3, B-4, C-4 , D-4 has been studied. The evolution of the relative viscosity of these compositions is illustrated in FIGS. 6A-6D. By comparing the results obtained, it is observed that certain parameters influence the relative viscosity of the compositions.
[0039] The influence of Lc (mean pendant side chain length) The polydiols copolymers Al-1 and Al-2 have the same percentage of M1 diol monomer per chain, comparable molar masses, but an average length of the alkyl chains of the different monomers ( Le = 13.8 and Le = 10.8 respectively). The evolution of the relative viscosity as a function of temperature for the solutions formulated from these polymers (FIGS. 6A and 6B) indicates that the average length of the alkyl chains of the monomers constituting the polydiol copolymer plays a role in the rheological properties of the polymers. formulations. The influence of the molar percentage of diol monomer (% diol) The polydiols copolymers A1-1 and Al-3 have the same average length of the alkyl chains (Le), comparable molar masses but a percentage of monomer diol M1 per skeletal chain different (20% and 10% respectively). The evolution of the relative viscosity as a function of temperature for the solutions formulated from these polymers (FIGS. 6A and 6C) indicates that the percentage of diol monomer per skeletal chain plays a role in the rheological properties of the formulations. The influence of the molar masses and the degree of polymerization (DP) The polydiols Al-3 and Al-4 have the same percentage of M1 diol monomer per chain, the same average length of the alkyl chains (Le) but molar masses ( 47,800 g / mol and 97,100 g / mol respectively) and significantly different number average polymerization degrees (DP of 198 and 228, respectively). The evolution of the relative viscosity as a function of temperature for the solutions formulated from these polymers (FIGS. 6.0 and 6.D) indicates that the molar mass of the polydiol copolymers (Mn) plays a role in the rheological properties of the formulations. 3.2: Compositions based on polydiol random copolymers Al and compounds A2 boronic ester polymer. Tested Copolymer Al Composites: A random poly (alkyl methacrylate-co-alkyldiol methacrylate) copolymer of the invention was tested. This is the following copolymer: / Copolymer Al-1: This copolymer comprises 20 mol% of monomers having diol functions. The average side chain length is 13.8 carbon atoms. Its average molar mass is 49,600 g / mol. Its polydispersity index is 1.51. Its number-average degree of polymerization (DP) is 167. The number-average molecular weight and the polydispersity index are measured by steric exclusion chromatography using a polystyrene calibration.
[0040] The Al-1 copolymer is obtained according to one of the protocols described in paragraph 1. Compound A2: The compound A2-2 is the boronic ester polymer obtained according to the protocol described in paragraph 2.2. This copolymer comprises 4 mol% of monomers having boronic ester functions. The average side chain length is greater than 12 carbon atoms. Its average molar mass is 37,200g / mol. Its polydispersity index is 1.24. Its number-average degree of polymerization (DP) is 166. The number average molecular weight and the polydispersity index are measured by steric exclusion chromatography using a polystyrene calibration.
[0041] Lubricating base oil The lubricating base oil used in the compositions to be tested is the Group III oil described above in section 3.1.
[0042] Composition A (outside the invention) is used as a reference and is the same as Composition A used in Section 3.1. Composition B (except the invention) is obtained in the following manner: Composition B is the same composition B-1 used in paragraph 3.1.
[0043] Composition C (according to the invention) is obtained in the following manner: 4 g of the 10% by weight solution of polydiol copolymer Al-1 in the Group III base oil previously prepared are introduced into a flask. 76.8 mg of boronic ester polymer A2-2 and 4 g of the base oil group III are added to this solution. The solution thus obtained is stirred at 90 ° C. until the boronic ester polymer is completely dissolved. A solution containing 5% by weight of polydiol copolymer Al-1 and 1% by weight of boron ester polymer A2-2 is obtained relative to the total mass of the composition. Composition D (according to the invention) is obtained as follows: 6 g of the above composition C (ie a composition containing 5% by weight of polydiol copolymer Al-1 and 1% by mass of boronic ester polymer A2 -2 relative to the total mass of the composition) are introduced into a flask. 61.9 mg of boron ester polymer A2-2 are added to this solution. The solution thus obtained is stirred at 90 ° C. until the boronic ester polymer is completely dissolved. A 5% by weight solution of polydiol copolymer Al-1 and 2% by weight of boronic ester polymer A2-2 is obtained relative to the total mass of the composition.
[0044] Composition E (according to the invention) is obtained in the following manner: 3 g of the 10% by weight solution of polydiol copolymer Al-1 in the Group III base oil previously prepared are introduced into a flask. 176 mg of A2-2 boronic ester polymer and 3 g of the Group III base oil are added to this solution. The solution thus obtained is stirred at 90 ° C. until the boronic ester polymer is completely dissolved. A 5% by weight solution of polydiol copolymer A1-1 and 3% by weight of boron ester polymer A2-2 is obtained relative to the total mass of the composition. Results obtained in rheology The rheological behavior of the composition E was studied for a temperature range from 10 ° C. to 110 ° C. The results are shown in FIG. 7. The dynamic viscosity of composition E varies at low shear rates and at temperatures below 50 ° C. Composition E deforms under shear stress for temperatures below 50 ° C. For temperatures above 50 ° C., the dynamic viscosity of the composition E varies very slightly or does not vary at low shear rates. The composition E no longer deforms under the shear stress at these temperatures.
[0045] The relative viscosity of compositions A, B, C, D and E was investigated. The evolution of the relative viscosity of these compositions is illustrated in FIG. 8. This figure indicates that the polydiols / poly (boronic ester) systems make it possible to very significantly offset the natural viscosity drop of the base oil. temperature function. In addition, the effect obtained can be regulated by varying the mass concentrations of the various polymers in solution in the base oil III.

权利要求:
Claims (22)
[0001]
REVENDICATIONS1. Al random copolymer resulting from the copolymerization of at least one first monomer M1 of general formula (I): ## STR2 ## in which: R 1 is chosen from the group formed by -H, -CH 3, and-CH2-CH3; x is an integer from 2 to 18; y is an integer equal to 0 or 1; X1 and X2, which are identical or different, are chosen from the group formed by hydrogen, tetrahydropyranyl, methyloxymethyl, tert-butyl, benzyl, trimethylsilyl and t-butyl dimethylsilyl; or else X1 and X2 form with the oxygen atoms a bridge of the following formula R "2 in which: the stars (*) symbolize the bonds to the oxygen atoms, R'2 and R" 2, identical or different, are selected from the group consisting of hydrogen and a C1-C11 alkyl, preferably methyl; or else - X1 and X2 form with the oxygen atoms a boronic ester of the following formula RI "2 in which: - the stars (*) symbolize the bonds to the oxygen atoms, - R" '2 is chosen from the group formed by C 6 -C 18 aryl, C 7 -C 18 aralkyl and C 2 -C 18 alkyl, preferably C 6 -C 18 aryl; with at least one second monomer M2 of general formula (II): wherein R2 is selected from the group consisting of -H, -CH3 and -CH2-CH3 R3 is selected from the group consisting of aryl; C6-C18, 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.
[0002]
2. Copolymer according to claim 1 resulting from the copolymerization of at least one monomer M1 with at least two monomers M2 having different R3 groups.
[0003]
3. The copolymer of claim 2 wherein one of the monomers M2 has the general formula (II-A): H 2 C (II-A) wherein: R 2 is selected from the group consisting of -H, -CH 3 and CH 2 -CH 3 - R "3 is a C 1 -C 14 alkyl group, and the other monomer M2 has the general formula (II-B): ## STR2 ## wherein: R 2 is selected from the group consisting of -H, -CH3 and -CH2-CH3R "; 3 is a C15-C30 alkyl group.
[0004]
4. Copolymer according to one of claims 1 to 3, wherein the side chains of the copolymer have an average length ranging from 8 to 20 carbon atoms, preferably from 9 to 15 carbon atoms.
[0005]
5. Copolymer according to one of claims 1 to 4 having a molar percentage of monomer M1 of formula (I) ranging from 1 to 30%, preferably from 5 to 25%, more preferably from 9 to 21%. 10
[0006]
6. Copolymer according to one of claims 1 to 5 having a number average degree of polymerization ranging from 100 to 2000, preferably from 150 to 1000.
[0007]
7. The copolymer according to one of claims 1 to 6 having a polydispersity index (Ip) ranging from 1.05 to 3.75; preferably from 1.10 to 3.45.
[0008]
8. Process for the preparation of a random copolymer according to one of claims 1 to 7 comprising at least one polymerization step (a) wherein is brought into contact at least: i) a first monomer M1 of general formula (I) Wherein: R 1 is selected from the group consisting of -H, -CH 3, -CH 2 -CH 3 where x is an integer from 2 to 18; y is an integer equal to 0 or 1; X1 and X2, which are identical or different, are 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, identical or different, are chosen from among the group consisting of hydrogen and a C 1 -C 11 alkyl, preferably methyl, or - X 1 and X 2 form with the oxygen atoms a boronic ester of the following formula R 1 - 2 in which: - the stars (* ) symbolize the bonds to the oxygen atoms; R "'2 is selected from the group consisting of C 6 -C 18 aryl, C 7 -C 18 aralkyl and C 2 -C 18 alkyl, preferably C 6 -C 18 aryl; ii) at least one second monomer M2 of the 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-R'3 and -C (O) -N (H) -R'3 with R'3 a C1-C30 alkyl group iii) at least a source of free radicals.
[0009]
The method of claim 8 further comprising iv) at least one chain transfer agent.
[0010]
10. Process for preparing a random copolymer according to one of claims 1 to 7, the process comprising - at least one polymerization step (a) as defined in one of claims 8 and 9, wherein monomers M1 and M2 are chosen with Xi and X2 different from hydrogen, and in addition at least one step of deprotection (b) of the diol functions of the copolymer obtained at the end of step (a), so as to obtain a copolymer in which X 1 and X 2 are identical and are a hydrogen atom.
[0011]
11. Composition resulting from the mixture of at least: a random copolymer Al according to one of claims 1 to 7; and a compound A2 comprising at least two boronic ester functions.
[0012]
12. A composition according to claim 11 wherein compound A2 is a compound of formula (III) III wherein: w1 and w2, the same or different, are integers selected from 0 to 1; R4, R5, R6 and R7, which are identical or different, are chosen from the group formed by hydrogen and a hydrocarbon group containing from 1 to 24 carbon atoms, preferably from 4 to 18 carbon atoms, preferably from 6 to 14 carbon atoms; carbon atoms; L is a divalent linking group and selected from a C6-C18 aryl, a C6-C18 aralkyl and a C2-C24 hydrocarbon chain.
[0013]
13. A composition according to claim 11 wherein compound A2 is a random copolymer resulting from the copolymerization of at least one M3 monomer of formula (IV): ## STR2 ## Wherein: t is an integer equal to 0 or 1; u is an integer equal to 0 or 1; M and R8 are divalent linking groups, which may be identical or different, 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): R12H2CR13 (V) in which: R12 is chosen from the group formed by -H, -CH3 and -CH2-CH3 R13 is chosen from the group formed by a C 6 -C 18 aryl, a C 6 -C 18 aryl substituted with a group R '13, -C (O) -O-R' 13, -O-R '13, -S-R' 13 and -C ( 0) -N (H) -R '13 with R' 13 a C1-C25 alkyl group.
[0014]
14. A composition according to claim 13 wherein the chain formed by the sequence of groups R10, M, X and (R8) 'with u equal to 0 or 1 of the monomer of general formula (IV) has a total number of atoms. carbon number ranging from 8 to 38, preferably from 10 to 26.
[0015]
15. Composition according to one of claims 13 to 14, wherein the side chains of the copolymer A2 have an average length greater than or equal to 8 carbon atoms, preferably ranging from 11 to 16 carbon atoms.
[0016]
16. Composition according to one of claims 13 to 15 wherein the copolymer A2 has a molar percentage of monomer of formula (IV) ranging from 0.25 to 20%, preferably from 1 to 10%.
[0017]
17. Composition according to one of claims 13 to 16, wherein the copolymer A2 has a number average degree of polymerization ranging from 50 to 1500, preferably from 80 to 800.
[0018]
18. Composition according to one of claims 13 to 17, wherein the copolymer A2 has a polydispersity index (Ip) ranging from 1.04 to 3.54; preferably ranging from 1.10 to 3.10.
[0019]
19. Composition according to one of claims 11 to 18 wherein the copolymer Al content is from 0.1% to 50% by weight relative to the total weight of the composition.
[0020]
20. Composition according to one of claims 11 to 19 wherein the content of compound A2 ranges from 0.1% to 50% by weight relative to the total weight of the composition.
[0021]
21. Composition according to one of Claims 11 to 20, in which the mass ratio between the copolymer Al and the compound A2 (Al / A2 ratio) ranges from 0.005 to 200, preferably from 0.05 to 20, moreover more preferred from 0.1 to 10.
[0022]
22. A composition according to any one of claims 11 to 21 further comprising at least one additive selected from the group consisting of polymers, pigments, dyes, fillers, plasticizers, fibers, antioxidants, additives lubricants, compatibilizers, anti-foaming agents, dispersant additives, adhesion promoters and stabilizers.

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CN106459307B|2019-11-05|

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BR112016017352A2|2018-02-06|

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EP3099722A1|2016-12-07|

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US20170008989A1|2017-01-12|

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WO2015110642A1|2015-07-30|

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KR20160130759A|2016-11-14|

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JP2017507228A|2017-03-16|

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CN106459307A|2017-02-22|

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FR3016885B1|2017-08-18|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

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

---

EP0570073A1|1992-05-15|1993-11-18|Ministero Dell' Universita' E Della Ricerca Scientifica E Tecnologica|Boron-containing additive for lubricating oils, and process for preparing said additive|US10329414B2|2015-08-20|2019-06-25|Ecole Superieure De Physique Et De Chimie Industrielles De La Ville De Paris|Boronic polymer crosslinking|US4002699A|1971-08-16|1977-01-11|Ford Motor Company|Powder coating composition with hydroxy functional copolymer and amino functional crosslinking agent|

---

US4889664A|1988-11-25|1989-12-26|Vistakon, Inc.|Method of forming shaped hydrogel articles including contact lenses|

---

DE4325776A1|1993-07-31|1995-02-02|Roehm Gmbh|Process for crosslinking organic polymers|

---

FR2844193A1|2002-09-06|2004-03-12|Oreal|MAKE-UP COMPOSITION OF KERATINIC FIBERS WITH A HIGH CURED EXTRACT COMBINED WITH A PARTICULAR RHEOLOGICAL PROFILE|

---

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

---

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

---

EP2012803A4|2006-04-20|2012-08-01|Univ Utah Res Found|Polymeric compositions and methods of making and using thereof|

---

US8747870B2|2006-04-20|2014-06-10|University Of Utah Research Foundation|Polymeric compositions and methods of making and using thereof|

---

EP2154172A4|2007-05-11|2010-05-05|Sumitomo Chemical Co|Polymer compound and method for producing the same, and light-emitting material, liquid composition, thin film, polymer light-emitting device, surface light source, display device, organic transistor and solar cell, each using the polymer compound|

---

JP2009132883A|2007-10-31|2009-06-18|Sumitomo Chemical Co Ltd|Polymer compound and polymer light emitting element using it|

---

TWI429694B|2009-09-22|2014-03-11|Coopervision Int Holding Co Lp|Materials for use in ophthalmic applications and methods|

---

CN104204009B|2012-03-29|2016-08-17|英派尔科技开发有限公司|Dioxaborinate copolymer and application thereof|FR3016887B1|2014-01-27|2016-02-05|Total Marketing Services|LUBRICATING COMPOSITIONS COMPRISING THERMOASSOCIATIVE AND EXCHANGEABLE COPOLYMERS|

---

FR3031744B1|2015-01-15|2017-02-10|Total Marketing Services|COMPOSITIONS OF THERMOASSOCIATIVE ADDITIVES WHERE THE ASSOCIATION IS CONTROLLED AND LUBRICATING COMPOSITIONS CONTAINING SAME|

---

FR3051792B1|2016-05-30|2020-01-24|Ecole Superieure De Physique Et De Chimie Industrielles De La Ville De Paris|NOVEL COMPOUNDS, FUNCTIONALIZED DIOXOBOROLANE OR DIOXABORINANE DERIVATIVES, PROCESS FOR THEIR PREPARATION AND USES THEREOF|

---

US10396647B2|2016-10-10|2019-08-27|Mando Corporation|Converter controlling device for hybrid vehicle and converter controlling method for hybrid vehicle|

---

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

---

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

---

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

---

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

---

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

---

FR3081464B1|2018-05-24|2020-09-18|Total Marketing Services|ASSOCIATIVE AND EXCHANGEABLE OLIGOMERS, COMPOSITION INCLUDING THEM|

---

FR3081466B1|2018-05-24|2020-06-12|Total Marketing Services|ASSOCIATIVE AND EXCHANGEABLE OLIGOMERS, COMPOSITION COMPRISING THE SAME|

---

FR3081465B1|2018-05-24|2020-06-12|Total Marketing Services|ASSOCIATIVE AND EXCHANGEABLE OLIGOMERS, COMPOSITION COMPRISING THE SAME|

---

FR3081467B1|2018-05-24|2020-07-10|Total Marketing Services|ASSOCIATIVE AND EXCHANGEABLE OLIGOMERS, COMPOSITION COMPRISING THE SAME|

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

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

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

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

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2021-01-21| PLFP| Fee payment|Year of fee payment: 8 |

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2022-01-19| PLFP| Fee payment|Year of fee payment: 9 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1450654A|FR3016885B1|2014-01-27|2014-01-27|THERMOASSOCIATIVE AND EXCHANGEABLE COPOLYMERS, COMPOSITIONS COMPRISING THE SAME|FR1450654A| FR3016885B1|2014-01-27|2014-01-27|THERMOASSOCIATIVE AND EXCHANGEABLE COPOLYMERS, COMPOSITIONS COMPRISING THE SAME|

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MA39195A| MA39195B1|2014-01-27|2015-01-26|Thermoassociative and exchangeable copolymers, compositions comprising them|

---

KR1020167023442A| KR102225788B1|2014-01-27|2015-01-26|Thermoassociative and exchangeable copolymers, and compositions comprising same|

---

CA2937927A| CA2937927A1|2014-01-27|2015-01-26|Thermoassociative and exchangeable copolymers, and compositions comprising same|

---

US15/114,111| US10377844B2|2014-01-27|2015-01-26|Thermoassociative and exchangeable copolymers, and compositions comprising same|

---

CN201580006037.8A| CN106459307B|2014-01-27|2015-01-26|Heat association and commutative copolymer and the composition comprising it|

---

BR112016017352-0A| BR112016017352A2|2014-01-27|2015-01-26|thermo-associative and exchangeable copolymers, compositions comprising them|

---

JP2016565567A| JP2017507228A|2014-01-27|2015-01-26|Thermally associative and exchangeable copolymer and composition containing the same|

---

EP15703495.0A| EP3099722A1|2014-01-27|2015-01-26|Thermoassociative and exchangeable copolymers, and compositions comprising same|

---

UAA201609100A| UA119161C2|2014-01-27|2015-01-26|Thermoassociative and exchangeable copolymers, and compositions comprising same|

---

PCT/EP2015/051517| WO2015110642A1|2014-01-27|2015-01-26|Thermoassociative and exchangeable copolymers, and compositions comprising same|

---

ZA2016/05210A| ZA201605210B|2014-01-27|2016-07-26|Thermoassociative and exchangeable copolymers, and compositions comprising same|

---

JP2019142517A| JP6757835B2|2014-01-27|2019-08-01|Thermally associative and exchangeable copolymers and compositions containing them|