WO2022003280A1

WO2022003280A1 - Rubber composition based on at least one nitrile oxide compound bearing an epoxide ring

Info

Publication number: WO2022003280A1
Application number: PCT/FR2021/051162
Authority: WO
Inventors: François JEAN-BAPTISTE-DIT-DOMINIQUE; Kahina MAMMERI
Original assignee: Compagnie Generale Des Etablissements Michelin
Priority date: 2020-06-29
Filing date: 2021-06-24
Publication date: 2022-01-06
Also published as: EP4172151A1; FR3111905B1; FR3111905A1

Abstract

The invention relates to a rubber composition based on at least one diene elastomer, at least one reinforcing filler, at least one crosslinking agent and at least one compound having formula (I), optionally already grafted onto said elastomer; wherein: - A is a C₆-C₁₄ arenediyl ring, optionally substituted with one or more hydrocarbon chains, which may be identical or different, aliphatic, preferably saturated, linear or branched; - E is a C₅-C₁₂ divalent hydrocarbon group optionally comprising one or more heteroatoms; - X₁, X₂, X₃, which may be identical or different, represent a hydrogen atom, a C₁-C₆ alkyl or a C₆-C₁₄ aryl. The invention also relates to a semi-finished article for a tyre and to a tyre comprising such a composition or such a semi-finished article.

Description

RUBBER COMPOSITION BASED ON AT LEAST ONE NITRILE OXIDE COMPOUND CARRYING AN EPOXIDE CYCLE. The present invention relates to a rubber composition, in particular intended for the manufacture of tires, based on at least one diene elastomer, at least one reinforcing filler, at least one crosslinking agent and at least one compound. particular carrying at least one epoxy ring. The application also relates to a process for preparing such a composition and as well as a semi-finished article for a tire and a tire comprising such a rubber composition. In the industrial field, mixtures of polymers with fillers are often used. In order for such mixtures to exhibit good properties, means are always sought to improve the dispersion of fillers within the polymers. In particular for rubber compositions intended for the manufacture of tires, the manufacturers constantly seek that the filled rubber compositions have good mechanical properties, such as reinforcement, and as low a hysteresis as possible. Indeed, the decrease in hysteresis of a rubber composition is favorable to the decrease in the rolling resistance of a tire and therefore to a decrease in the fuel consumption of a vehicle traveling with such tires. It is known that, in general, in order to obtain the optimum reinforcing properties conferred by a reinforcing filler, the latter should be present in the elastomeric matrix in the final form which is both as finely divided as possible and distributed as a whole. as homogeneous as possible. Numerous solutions have already been tested for achieving good dispersion of the reinforcing filler in a rubber composition and for obtaining rubber compositions exhibiting good reinforcing properties. In particular, mention may be made of the use, in a rubber composition, of polymers whose structure has been modified by means of functionalizing, coupling or starring agents in order to obtain a good interaction between the polymer. thus modified and the reinforcing filler, whether it is carbon black or an inorganic reinforcing filler. Mention may be made, for example, of diene elastomers comprising functional groups comprising epoxy rings. For example, document WO2019102132A1 discloses a rubber composition comprising a copolymer of styrene and butadiene onto which has been grafted a functionalizing agent, 2- (glycidyloxy) -1-naphtonitrile oxide. This modified copolymer makes it possible to obtain a rubber composition whose reinforcement index is improved and whose non-linearity is significantly reduced compared to a rubber composition comprising a copolymer of unmodified styrene and butadiene. The improvement in the reinforcement and the nonlinear behavior of this composition are obtained by maintaining the hysteresis properties at a level almost identical to that of a composition comprising the unmodified styrene-butadiene copolymer. However, there is a continuing need for rubber compositions having improved hysteresis properties. Indeed, since fuel economy and the need to protect the environment have become a priority, it is necessary to ensure the lowest possible rolling resistance. The rubber compositions used for the manufacture of pneumatic tires must therefore exhibit as low a hysteresis as possible in order to limit fuel consumption. Obtaining a rubber composition exhibiting as low a hysteresis as possible, while maintaining a good level for other properties, such as reinforcement and stiffness, is an ongoing challenge for tire manufacturers. Indeed, it is known that a decrease in the hysteresis of rubber compositions can be accompanied by a decrease in the stiffness when cooked. However, a tread must be sufficiently rigid to ensure a good level of road behavior of the tire. An object of the present invention is therefore to provide novel rubber compositions exhibiting an improvement in the reinforcement index and an improvement in the hysteresis properties without reducing the properties of stiffness when cooked. Continuing his research, the Applicant has surprisingly discovered that a composition based on at least one diene elastomer, a reinforcing filler, a crosslinking system and a specific compound, an aromatic nitrile oxide having an epoxy ring linked to the aromatic group carrying the nitrile oxide by a specific divalent group, simultaneously exhibited an improvement in the reinforcement index and an improvement in the hysteresis properties. In addition, advantageously, the composition thus obtained also exhibits an improvement in the stiffness properties when fired. Thus, a first object of the present invention therefore relates to a rubber composition based on at least one diene elastomer, a reinforcing filler, a crosslinking agent and at least one compound of formula (I), optionally already grafted onto said diene elastomer

in which: - A represents an arenediyl ring in C₆-VS₁₄, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C₅-VS₁₂ optionally comprising one or more heteroatoms; - X₁, X₂, X₃ identical or different, represent a hydrogen atom, a C alkyl₁-VS₆ or a C aryl₆-VS₁₄. Another object of the present invention relates to a semi-finished article for a tire comprising at least one rubber composition defined above. Another subject of the present invention relates to a tire comprising at least one rubber composition defined above or a semi-finished article for a tire defined above. A first object of the present invention therefore relates to a rubber composition based on at least one diene elastomer, a reinforcing filler, a crosslinking agent and at least one compound of formula (I), optionally already grafted onto said elastomer. diene in which: - A represents an arenediyl ring in C₆-VS₁₄, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C₅-VS₁₂ optionally comprising one or more heteroatoms; - X₁, X₂, X₃ identical or different, represent a hydrogen atom, a C alkyl₁-VS₆ or a C aryl₆-VS₁₄. In the present document, unless expressly indicated otherwise, all the percentages (%) indicated are percentages (%) by mass. On the other hand, any interval of values designated by the expression “between a and b” represents the domain of values going from more than a to less than b (that is to say limits a and b excluded) while any range of values designated by the expression “from a to b” signifies the range of values going from a to b (that is to say including the strict limits a and b). The compounds comprising carbon mentioned in the description can be of fossil origin or biobased. In the latter case, they may be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. This concerns in particular polymers, plasticizers, fillers, etc. The expression “composition based on” should be understood to mean a composition comprising the mixture and / or the in situ reaction product of the various constituents used, some of these constituents which can react and / or are intended to react with each other, at least partially, during the various phases of manufacture of the composition; the composition may thus be in the fully or partially crosslinked state or in the non-crosslinked state. By the expression "part by weight per hundred parts by weight of elastomer" (or phr), is meant within the meaning of the present invention, the part, by mass per hundred parts by mass of elastomer. When reference is made to a “predominant” compound, it is understood, within the meaning of the present invention, that this compound is predominant among the compounds of the same type in the composition, that is to say that it is the one which represents the greatest amount by mass among compounds of the same type. Thus, for example, a major elastomer is the elastomer representing the greatest mass relative to the total mass of elastomers in the composition. Likewise, a so-called majority filler is that representing the greatest mass among the fillers of the composition. By way of example, in a system comprising a single elastomer, the latter is in the majority within the meaning of the present invention; and in a system comprising two elastomers, the majority elastomer represents more than half of the mass of the elastomers, preferably more than 51% by mass of the total mass of the elastomers. The term 1,3-dipolar compound is understood as defined by IUPAC. By definition, a 1,3-dipolar compound comprises a dipole. For the purposes of the present invention, the term “hydrocarbon chain” is understood to mean a chain comprising one or more carbon atoms and one or more hydrogen atoms. The expression "C1-Cj alkyl" denotes a linear, branched or cyclic hydrocarbon group comprising from i to j carbon atoms; i and j being whole numbers. The expression "C1-Cj aryl" denotes an aromatic group comprising from i to j carbon atoms; i and j being whole numbers. By "alkanediyl" is meant a hydrocarbon group, derived from an alkane in which two hydrogen atoms have been deleted. An alkanediyl is therefore a divalent group. By "modified elastomer obtained by grafting" or "modified elastomer by grafting" is meant an elastomer comprising functions, in particular epoxy rings, which have been introduced into the elastomer chain. In practice, the modified elastomer is obtained by grafting reaction of a compound carrying functions which are epoxy rings and carrying a function being capable of forming a covalent bond with an unsaturation of the elastomer, this function capable of forming a covalent bond being a nitrile oxide. The grafting reaction is therefore the attachment by a covalent bond of the compound of formula (I) carrying epoxy rings on at least one unsaturation of the elastomer chain. In known manner, an elastomer generally comprises at least one main elastomer chain. This elastomeric chain can be qualified as the main one from the moment when all the other chains of the elastomer are considered as pendant chains like the mentions the document “Glossary of basic terms in polymer science” (IUPAC recommendations 1996), PAC, 1996, 68, 2287, p2294. By “unsaturation” is meant a multiple covalent bond between two carbon atoms; this multiple covalent bond possibly being a carbon-carbon double bond or a carbon-carbon triple bond, preferably a carbon-carbon double bond. By "initial elastomer chain" is meant within the meaning of the present invention the chain of the elastomer before the grafting reaction; this chain comprising at least one unsaturation capable of reacting with the compound of formula (I) described above. The initial elastomer is therefore the elastomer serving as the starting reagent during the grafting reaction. The grafting reaction allows from an initial elastomer to obtain a modified elastomer. The invention and its advantages will be easily understood in the light of the description and the exemplary embodiments which follow. The rubber composition of the invention comprises at least one compound of formula (I), optionally already grafted onto the diene elastomer

in which: - A represents an arenediyl ring in C₆-VS₁₄, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C₅-VS₁₂ optionally comprising one or more heteroatoms; - X₁, X₂, X₃ identical or different, represent a hydrogen atom, a C alkyl₁-VS₆ or a C aryl₆-VS₁₄. In accordance with formula (I), this compound comprises a group A which represents an arenediyl ring at C₆-VS₁₄, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched. For the purposes of the present invention, the term “arenediyl ring” is understood to mean a monocyclic or polycyclic aromatic hydrocarbon group derived from an arene in which two hydrogen atoms have been deleted. An arenediyl ring is therefore a divalent group. By "monocyclic or polycyclic aromatic hydrocarbon group" is meant one or more aromatic rings whose backbone consists of carbon atoms. In other words, there are no heteroatoms in the backbone of the cycle. The arenediyl ring can be monocyclic, that is, made up of a single ring, or polycyclic, that is to say made up of several condensed aromatic hydrocarbon rings; such condensed rings then have at least two successive carbon atoms in common. These rings can be ortho-condensed or ortho- and per-condensed. The arenediyl ring has 6 to 14 carbon atoms. The arenediyl ring can be unsubstituted, partially substituted or fully substituted. An arenediyl ring is partially substituted when one or two or more hydrogen atoms (but not all atoms) are replaced by one or two or more hydrocarbon, aliphatic, preferably saturated, linear or branched chains. Said chains are also called substituents. If all the hydrogen atoms are replaced by said chains, then the arenediyl ring is completely substituted. The substituents of the arenediyl ring can be the same or different from each other. Preferably, when the arenediyl ring is substituted by one or more hydrocarbon chain (s), identical or different, independent of each other, this or these chain (s) are inert with respect to the epoxy ring and nitrile oxide. For the purposes of the present invention, the term “inert hydrocarbon chain (s) with respect to the epoxy cycle and to the nitrile oxide” is understood to mean a hydrocarbon chain which neither reacts with said cycle. epoxy ni with said nitrile oxide. Thus, said hydrocarbon chain inert with respect to said ring and to said nitrile oxide is, for example, a hydrocarbon chain which does not have alkenyl or alkynyl functions, capable of reacting with said ring or said nitrile oxide. Preferably, these hydrocarbon chains are aliphatic, saturated, linear or branched, and can comprise from 1 to 24 carbon atoms. Preferably, A represents an arenediyl ring at C₆-VS₁₄, optionally substituted by one or more hydrocarbon chain (s), identical or different, saturated at C₁-VS₂₄. More preferably still, the group A is an arenediyl ring in C₆-VS₁₄, optionally substituted by one or more substituents, identical or different, the substituents being C alkyls₁-VS₁₂, preferably in C₁-VS₆, more preferably still in C₁-VS₄. Preferably, the compound of formula (I) according to the invention is chosen from compounds of formula (Ia) and compounds of formula (Ib)

in which: - a group chosen from R1 to R5 of formula (Ia) and a group chosen from R1 to R7 of formula (Ib) denote the following group of formula (II):

in which E, X1, X2 and X3 are as defined above and below and the symbol (*) represents the attachment of group (II) to the rest of molecule (Ia) or (Ib); - the four groups of formula (Ia) chosen from R1 to R5 other than that designating the group of formula (II) and the six groups of formula (Ib) chosen from R1 to R7 other than that designating the group of formula ( II), which are identical or different, represent, independently of one another, a hydrogen atom or an aliphatic hydrocarbon chain, preferably saturated, linear or branched. Preferably, in the compounds of formulas (Ia) and (Ib), the four groups of formula (Ia) chosen from R1 to R5 other than that designating the group of formula (II) and the six groups of formula (Ib) chosen from R1 to R7 other than that designating the group of formula (II), which are identical or different, represent, independently of each other, a hydrogen atom or an aliphatic, saturated, linear or branched, C-shaped hydrocarbon chain₁-VS₂₄. More preferably still, in the compounds of formulas (Ia) and (Ib), the four groups of formula (Ia) chosen from R1 to R5 other than that designating the group of formula (II) and the six groups of formula ( Ib) chosen from R1 to R7 other than that designating the group of formula (II), identical or different, are chosen from the group consisting of the hydrogen atom, C alkyls₁-VS₁₂, preferably in C₁-VS₆, more preferably still in C₁-VS₄. More preferably still, in the compounds of formulas (Ia) and (Ib), the four groups of formula (Ia) chosen from R1 to R5 other than that designating the group of formula (II) and the six groups of formula ( Ib) chosen from R1 to R7 other than that designating the group of formula (II), which are identical or different, represent, independently of one another, a hydrogen atom or a methyl. According to a preferred embodiment of the invention, in formula (Ia), R2 represents a group of formula (II) and R1, R3, R4 and R5, identical or different, represent a hydrogen atom or a hydrocarbon chain aliphatic, preferably saturated, linear or branched, in C₁-VS₂₄. More preferably, R2 represents a group of formula (II) and R1, R3, R4 and R5, identical or different, are chosen from the group consisting of an atom hydrogen, C1-C12 alkyl, more preferably C₁-VS₆, more preferably still in C₁-VS₄. More preferably still in this embodiment, R2 represents a group of formula (II), R4 represents a hydrogen atom and R1, R3 and R5 represent an aliphatic hydrocarbon chain, preferably saturated, linear or branched, in C₁-VS₂₄. More preferably still, R2 represents a group of formula (II), R4 represents a hydrogen atom and R1, R3 and R5, identical or different, represent a C1-C12 alkyl, more preferably a C₁-VS₆, more preferably still in C₁-VS₄. According to another preferred embodiment of the invention, in formula (Ib), R1 represents a group of formula (II) and R2 to R7 which are identical or different, represent a hydrogen atom or an aliphatic hydrocarbon chain, preferably saturated, linear or branched, in C₁-VS₂₄. More preferably, R1 represents a group of formula (II) and R2 to R7, identical or different, are chosen from the group consisting of a hydrogen atom, a C1-C12 alkyl, more preferably a C₁-VS₆, more preferably still in C₁-VS₄. More preferably still in this embodiment, R1 represents a group of formula (II) and R2 to R7, which are identical, represent a hydrogen atom. In the compounds of formula (I), (Ia) and (Ib), E represents a divalent hydrocarbon group at C₅-VS₁₂ possibly containing one or more heteroatom (s). For the purposes of the present invention, the term “divalent hydrocarbon group” means a spacer group (or a linking group) forming a bridge between the oxygen atom attached to A and the epoxy ring bearing the groups X1, X2, X3. , this spacer group E comprising from 5 to 12 carbon atoms. This spacer group can be a hydrocarbon chain at C₅-VS₁,₂ preferably saturated, linear or branched, possibly containing one or more heteroatom (s) such as for example N, O and S. Said hydrocarbon chain can optionally be substituted, provided that the substituents do not react with the nitrile oxide and the epoxy ring as defined above. Surprisingly, when E comprises a divalent hydrocarbon group of 5 to 12 carbon atoms, the compound of formula (I), optionally already grafted onto a diene elastomer, gives the compositions improved hysteresis and strengthening properties compared to the compositions. of the prior art. Surprisingly, the improvement in these properties does not come at the expense of baked-on stiffness properties. Preferably, in the compounds of formula (I), (Ia) and (Ib), E represents a divalent hydrocarbon group at C₅-VS₁₀, preferably in C₅-VS₉, more preferably in C₆-VS₉, more preferably still in C₇-VS₉, possibly containing one or more heteroatom (s) such as for example N, O and S. Surprisingly, when the group E is this divalent compound as described above, the compound of formula (I) , optionally already grafted onto a diene elastomer, gives the compositions improved hysteresis and reinforcement properties compared to the compositions of the prior art. Surprisingly, the improvement in these properties does not come at the expense of baked-on stiffness properties. More preferably, in the compounds of formula (I), (Ia) and (Ib), E represents an alkanediyl in C₅-C10, preferably a C-alkanediyl₅-VS₉, more preferably a C6-C alkanediyl₉, more preferably still a C7-C alkanediyl₉. Surprisingly, when E is this alkanediyl as described above, the compound of formula (I), optionally already grafted onto a diene elastomer, gives the compositions improved hysteresis and strengthening properties compared to the compositions of the diene elastomer. prior art. Surprisingly, the improvement in these properties does not come at the expense of baked-on stiffness properties. In the compounds of formula (I), (Ia) and (Ib), X1, X2, X3, identical or different, are chosen from the group consisting of the hydrogen atom, C alkyls₁-VS₆ and aryls in C₆-VS₁₄. Preferably, in the compounds of formula (I), (Ia) and (Ib), X1, X2, X3, which are identical or different, are chosen from the group consisting of the hydrogen atom, methyl, ethyl and phenyl. According to a preferred embodiment of the invention, in the compounds of formula (I), (Ia) and (Ib), X1, X2 and X3 are identical and represent a hydrogen atom. According to another preferred embodiment of the invention, in the compounds of formula (I), (Ia) and (Ib), X1 and X2 represent a hydrogen atom and X3 represents a phenyl. According to another preferred embodiment of the invention, in the compounds of formula (I), (Ia) and (Ib), X3 is a hydrogen atom, and X1 and X2, which are identical or different, represent a d atom. hydrogen or methyl. Preferably, the compound of formula (I) can be the compound of formula (I) as described above. More preferably still, the compound of formula (I) can be the compound of formula (Ib) in which the group R1 is the group of formula (II) with the group E representing a C-alkanediyl₅-C10, preferably a C-alkanediyl₅-VS₉, more preferably a C6-C alkanediyl₉, more preferably still a C7-C alkanediyl₉, the groups X1, X2, X3, identical or different, are chosen from the group consisting of the hydrogen atom, C alkyls₁-VS₆ and aryls in C₆-VS₁₄ (preferably are selected from the group consisting of the hydrogen atom and C-alkyls₁-VS₆), and the same or different R2 to R7 groups are selected from the group consisting of the hydrogen atom and C1-C12 alkyls. A particularly preferred compound of formula (I) is the compound of formula (III):

The compounds of the invention (I), (Ia), (Ib) and (III) can be obtained in particular by a preparation process comprising at least one reaction (d) of an oxime compound of formula (IV) with a oxidizing agent in the presence of at least one organic solvent SL1 according to the following reaction scheme to give the compound of formula (I) and in particular its preferred compounds:

in which: - A represents an arenediyl ring in C₆-VS₁₄, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C₅-VS₁₂ optionally comprising one or more heteroatoms; - X1, X2, X3, identical or different, represent a hydrogen atom, a C alkyl₁-VS₆ or a C aryl₆-VS₁₄. Preferred modes of A, E, X1, X2 and X3 as described above also apply to the process for preparing the compound of formula (I) from a compound of formula (IV). Preferably, said oxidizing agent is chosen from sodium hypochlorite, N-bromosuccinimide in the presence of a base, N-chlorosucinimide in the presence of a base, and hydrogen peroxide in the presence of a catalyst. More preferably, the catalyst is chosen from the group consisting of sodium hypochlorite and N-bromosuccinimide in the presence of a base. Preferably, the base can be triethylamine. Advantageously, the amount of oxidizing agent is 1 to 5 molar equivalents, preferably 1 to 2 molar equivalents relative to the molar amount of the oxime compound of formula (IV). Preferably, the organic solvent SL1 is chosen from chlorinated solvents and solvents of ester, ether and alcohol type, more preferably chosen from dichloromethane, trichloromethane, ethyl acetate, butyl acetate, diethyl ether , isopropanol and ethanol, even more preferably is chosen from ethyl acetate, trichloromethane, dichloromethane and butyl acetate. Preferably, the oxime compound of formula (IV) represents from 1 to 30% by weight, preferably from 1 to 20% by weight, relative to the total weight of the assembly comprising said oxime compound of formula (IV), said organic solvent SL1 and said oxidizing agent. The oxime of formula (IV) can in particular be obtained from a preparation process comprising at least one reaction (c) of a compound of formula (V) with an aqueous solution of hydroxylamine NH2OH (compound of formula ( VI)) according to the following reaction scheme:

with - A represents an arenediyl ring in C₆-VS₁₄, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C₅-VS₁₂ optionally comprising one or more heteroatoms; - X1, X2, X3, identical or different, represent a hydrogen atom, a C alkyl₁-VS₆ or a C aryl₆-VS₁₄. Preferred modes of A, E, X1, X2 and X3 as described above are also applicable to the methods of preparing a compound of formula (IV) from a compound of formula (V). Preferably, the addition of hydroxylamine (compound of formula (VI)) is carried out at a temperature ranging from 1 ° C to 100 ° C, more preferably between 20 ° C and 70 ° C. The compound of formula (V) can be obtained by a preparation process comprising at least one reaction (b) of the compound of formula (VII) with a compound of formula (VIII) in the presence of at least one base and at a temperature ranging from 20 ° C to 150 ° C according to the following reaction scheme:

with - A represents an arenediyl ring in C₆-VS₁₄, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C₅-VS₁₂ optionally comprising one or more heteroatoms; - X1, X2, X3, identical or different, represent a hydrogen atom, a C alkyl₁-VS₆ or a C aryl₆-VS₁₄ ; - Z represents a nucleofuge group. Preferred modes of A, E, X1, X2 and X3 are also applicable to the process of preparing a compound of formula (V) from compounds of formula (VIII) and (VII). The term “nucleofuge group” is understood to mean a leaving group. The Z group can be selected from chlorine, bromine, iodine, fluorine, mesylate group, tosylate group, acetate group, and trifluoromethylsulfonate group. Preferably, Z is bromine. The reaction between the compound of formula (VIII) and that of formula (VII) is carried out in the presence of at least one base and at a temperature ranging from 20 ° C to 150 ° C. The base can be chosen from alkaline alcoholates, alkaline carbonates, alkaline earth carbonates, alkali hydroxides, alkaline earth hydroxides and mixtures thereof. Preferably, the base is chosen from sodium methanolate, potassium carbonate and sodium hydroxide, more preferably potassium carbonate. Preferably, the molar amount of base is from 1.5 to 8 molar equivalents, preferably from 2 to 6 molar equivalents relative to the molar amount of compound of formula (VII). According to one embodiment, it is possible to add one or more catalysts chosen from a catalyst of silver salt type such as silver oxide Ag2O, a phase transfer catalyst of quaternary ammonium type, and mixtures thereof. . The compounds of formula (VII) as defined above are commercially available from suppliers such as Sigma –Aldrich, Merk, Chimieliva, and the like. The compound of formula (VIII) can be obtained by epoxidation of the corresponding alkene of formula (IX) according to the reaction scheme below. The synthesis of a compound comprising an epoxy ring from its corresponding alkene is well known. For example, this oxidation can take place in the presence of peracid such as metachloroperbenzoic acid, peracetic acid, performic acid. Another well-known technique is the use of dimethyldioxirane.

with: - E represents a divalent hydrocarbon group at C₅-VS₁₂ optionally comprising one or more heteroatoms; - X1, X2, X3, identical or different, represent a hydrogen atom, a C alkyl₁-VS₆ or a C aryl₆-VS₁₄ ; - Z represents a nucleofuge group as described above. Preferred modes of E, X1, X2 and X3 are also applicable to the process of preparing a compound of formula (VIII) from the compound of formula (IX). Compounds of formula (IX) are commercially available from suppliers such as Sigma Aldrich, ABCR. The rubber composition according to the invention also comprises, as constituent, at least one diene elastomer, in particular at least one diene elastomer onto which the compound of formula I is optionally already grafted, in particular the compound of formula (Ib), more particularly the compound of formula (III). By elastomer (or indiscriminately rubber) "diene", whether natural or synthetic, should be understood in a known manner an elastomer consisting at least in part (ie, a homopolymer or a copolymer) of diene monomer units (monomers carrying two carbon-carbon double bonds, conjugated or not). These diene elastomers can be classified into two categories: “essentially unsaturated” or “essentially saturated”. The term “essentially unsaturated” is understood to mean in general a diene elastomer derived at least in part from conjugated diene monomers, having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (% by moles); it is thus that diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the preceding definition and can in particular be qualified as “essentially saturated” diene elastomers (level of diene. units of weak or very weak diene origin, always less than 15% (% in moles)). By diene elastomer capable of being used in the context of the present invention is particularly understood: any homopolymer of a diene monomer, conjugated or not, having from 4 to 18 carbon atoms; - any copolymer of a diene, conjugated or not, having 4 to 18 carbon atoms and at least one other monomer. The other monomer can be ethylene, an olefin or a diene, conjugated or not. Suitable conjugated dienes are conjugated dienes having from 4 to 12 carbon atoms, in particular 1,3-dienes, such as in particular 1,3-butadiene and isoprene. Suitable unconjugated dienes are unconjugated dienes having 6 to 12 carbon atoms, such as 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene. Suitable olefins are vinyl aromatics having 8 to 20 carbon atoms and aliphatic α-monoolefins having 3 to 12 carbon atoms. Suitable vinyl aromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the commercial mixture “vinyl-toluene”, para-tert-butylstyrene. Suitable aliphatic α-monoolefins in particular are acyclic aliphatic α-monoolefins having from 3 to 18 carbon atoms. More particularly, the diene elastomer is: - any homopolymer of a conjugated diene monomer, in particular any homopolymer obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms; - any copolymer obtained by copolymerization of one or more dienes conjugated with one another or with one or more vinyl aromatic compounds having from 8 to 20 carbon atoms; - a copolymer of isobutene and isoprene (butyl rubber), as well as the halogenated versions, in particular chlorinated or brominated, of this type of copolymer. - any copolymer obtained by copolymerization of one or more dienes, conjugated or not, with ethylene, an α-monoolefin or their mixture such as for example elastomers obtained from ethylene or propylene with an unconjugated diene monomer of type cited above. Preferably, the diene elastomer is chosen from the group consisting of ethylene-propylene-diene monomer copolymers (EPDM), natural rubber (NR), synthetic polyisoprenes (IR), polybutadienes (BR), copolymers of butadiene, isoprene copolymers and mixtures of these elastomers. Preferably, the diene elastomer is chosen from the group consisting of ethylene-propylene-diene monomer copolymers (EPDM), natural rubber (NR), synthetic polyisoprenes (IR), polybutadienes (BR), copolymers of butadiene and styrene (SBR), copolymers of ethylene and butadiene (EBR), copolymers of isoprene and butadiene (BIR) or copolymers of isoprene, butadiene and styrene (SBIR), copolymers isobutene and isoprene (butyl rubber IIR), isoprene-styrene (SIR) copolymers and mixtures of these elastomers. Preferably, the diene elastomer is chosen from the group consisting of ethylene-propylene-diene monomer copolymers, butyl rubber and a mixture of these rubbers. Preferably, the diene elastomer is chosen from the group consisting of natural rubber, synthetic polyisoprenes, polybutadienes, butadiene copolymers, isoprene copolymers and mixtures of these elastomers. More preferably, the diene elastomer is chosen from the group consisting of natural rubber, synthetic polyisoprenes, polybutadienes, butadiene and styrene copolymers, ethylene and butadiene copolymers, isoprene and butadiene copolymers, copolymers of isoprene, butadiene and styrene, copolymers of isobutene and isoprene, copolymers of isoprene and styrene and mixtures of these elastomers. Preferably, the diene elastomer is chosen from the group consisting of polybutadienes, butadiene copolymers, isoprene copolymers and mixtures of these elastomers. More preferably, the diene elastomer is chosen from the group consisting of polybutadienes, copolymers of butadiene and of styrene, copolymers of ethylene and of butadiene, copolymers of isoprene and of butadiene, copolymers of isoprene, of butadiene and styrene, copolymers of isobutene and isoprene, copolymers of isoprene and styrene and mixtures of these elastomers. The diene elastomers can have any microstructure which depends on the polymerization conditions used. These diene elastomers can be, for example, block, random, sequenced, microsequenced, and be prepared in dispersion in emulsion or in solution. They can be coupled and / or starred, for example by means of a silicon or tin atom which binds the polymer chains together. As seen above, the rubber composition according to the invention is based on at least one diene elastomer and on at least one compound of formula (I), in particular a compound of formula (Ib), more particularly a compound of formula (III), optionally already grafted onto the diene elastomer. The diene elastomer can be grafted with the compound of formula (I), in particular with the compound of formula (Ib), more particularly with the compound of formula (III) prior to its introduction into the rubber composition, or else can be grafted by reaction with the compound of formula (I), in particular with that of formula (Ib), more particularly with that of formula (III) during the manufacture of the rubber composition. When the rubber composition comprises at least one diene elastomer grafted beforehand with the compound of formula (I), in particular with the compound of formula (Ib), more particularly with the compound of formula (III), the molar grafting rate of the compound of formula (I) on said diene elastomer, in particular of the compound of formula (Ib), in particular of the compound of formula (III) is within a range ranging from 0.01% to 15%, preferably from 0, 05% to 10%, more preferably from 0.07 to 5%. In the embodiment where the diene elastomer is grafted by reaction with the compound of formula (I), in particular with that of formula (Ib), more particularly with that of formula (III) during the manufacture of the composition of rubber, then the level of the compound of formula (I), in particular the level of the compound of formula (Ib), more particularly the level of the compound of formula (III) in the rubber composition according to the invention of rubber is included in an area ranging from 0.01 to 15pce. The rubber composition according to the invention may contain a single diene elastomer grafted with the compound of formula (I), in particular with the compound of formula (Ib), plus particularly with the compound of formula (III) (either grafted prior to its introduction into the rubber composition, or grafted by reaction with said compound of formula (I), in particular with said compound of formula (Ib), more particularly with said compound of formula (III) during the manufacture of the rubber composition), or a mixture of several diene elastomers grafted, or some of which are grafted and others not. The other diene elastomer (s) used as a mixture with the grafted diene elastomer are diene elastomers as described above, whether they are stellate, coupled, functionalized or not. When blended with at least one other diene elastomer, the grafted diene elastomer is the predominant elastomer in the rubber composition. It will be noted that the improvement in the properties of the rubber composition according to the invention will be all the greater, the smaller the proportion of said additional elastomer (s) in the rubber composition according to the invention. The grafted diene elastomer (s) can be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers, for example with thermoplastic polymers. As seen above, another component of the rubber composition according to the invention is a reinforcing filler. Any type of so-called reinforcing filler can be used, known for its capacity to reinforce a rubber composition which can be used in particular for the manufacture of tires, for example an organic filler such as carbon black, an inorganic filler such as silica or else. a mixture of these two types of fillers. Advantageously, the reinforcing filler is chosen from carbon black, an inorganic filler and their mixtures. Suitable carbon blacks are all carbon blacks, in particular the blacks conventionally used in tires or their treads. Among the latter, there will be mentioned more particularly the reinforcing carbon blacks of the 100, 200, 300 series, or the blacks of the 500, 600 or 700 series (grades ASTM D-1765-2017), such as for example the blacks N115, N134, N234, N326, N330, N339, N347, N375, N550, N683, N772). These carbon blacks can be used in the isolated state, as available commercially, or in any other form, for example as a support for some of the rubber additives used. The carbon blacks could for example already be incorporated into the diene elastomer, in particular isoprene in the form of a masterbatch (see for example applications WO97 / 36724-A2 or WO99 / 16600-A1). For carbon blacks, the STSA specific surface area is determined according to the ASTM D6556-2016 standard. By "reinforcing inorganic filler", should be understood here any inorganic or mineral filler, whatever its color and its origin (natural or synthetic), also called "white" filler, "light" filler or even "non-black" filler. »As opposed to the black of carbon, capable of reinforcing on its own, without any other means than an intermediate coupling agent, a rubber composition intended for the manufacture of tires. In known manner, certain reinforcing inorganic fillers can be characterized in particular by the presence of hydroxyl groups (—OH) at their surface. As reinforcing inorganic fillers, suitable in particular mineral fillers of the siliceous type, preferably silica (SiO2) or of the aluminous type, in particular alumina (Al2O3). The silica used can be any reinforcing silica known to those skilled in the art, in particular any precipitated or pyrogenic silica having a BET specific surface area as well as a CTAB specific surface area both less than 450 m2 / g, preferably within a range of from 30 to 400 m2 / g. Any type of precipitated silica can be used, in particular highly dispersible precipitated silicas (called “HDS” for “highly dispersible” or “highly dispersible silica”). These precipitated silicas, which may or may not be highly dispersible, are well known to those skilled in the art. Mention may be made, for example, of the silicas described in applications WO03 / 016215-A1 and WO03 / 016387-A1. Among the commercial HDS silicas, it is possible in particular to use the silicas “Ultrasil® 5000GR”, “Ultrasil® 7000GR” from the company Evonik, the silicas “Zeosil® 1085GR”, “Zeosil® 1115 MP”, “Zeosil® 1165MP”, “ Zeosil® Premium 200MP ”,“ Zeosil® HRS 1200 MP ”from the Solvay Company. As non-HDS silica, the following commercial silicas can be used: silicas “Ultrasil® VN2GR”, “Ultrasil® VN3GR” from the company Evonik, silica “Zeosil® 175GR” ”from the company Solvay, silicas“ Hi -Sil EZ120G (-D) ”,“ Hi-Sil EZ160G (-D) ”,“ Hi-Sil EZ200G (-D) ”,“ Hi-Sil 243LD ”,“ Hi-Sil 210 ”,“ Hi-Sil HDP 320G ”from PPG. In the present disclosure, the BET specific surface for the inorganic filler, in particular for the silica, is determined by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society". (Vol. 60, page 309, February 1938), and more precisely according to a method adapted from standard NF ISO 5794-1, appendix E of June 2010 [multipoint volumetric method (5 points) - gas: nitrogen - vacuum degassing: one hour at 160 ° C - relative pressure range p / in: 0.05 to 0.17]. The CTAB specific surface values were determined according to standard NF ISO 5794-1, appendix G of June 2010. The process is based on the adsorption of CTAB (N-hexadecyl-N, N, N-trimethylammonium bromide) on the “external” surface of the reinforcing filler. When a reinforcing inorganic filler is used in the rubber composition according to the invention, in particular if it is silica, this reinforcing inorganic filler preferably has a BET surface area within a range ranging from 45 to 400 m2 / g , more preferably within a range ranging from 60 to 300 m2 / g. The physical state in which the reinforcing inorganic filler is present is immaterial, whether in the form of powder, microbeads, granules, or even beads or any other suitable densified form. Of course, the term “reinforcing inorganic filler” is understood to mean mixtures of different reinforcing inorganic fillers, in particular of silicas as described above. In order to couple the reinforcing inorganic filler to the diene elastomer, it is possible to use, in a well-known manner, an at least bifunctional coupling agent (or binding agent) intended to ensure a sufficient connection, of a chemical and / or physical nature, between the filler. inorganic (surface of its particles) and the diene elastomer. In particular, at least bifunctional organosilanes or polyorganosiloxanes are used. By "bifunctional" is meant a compound having a first functional group capable of interacting with the inorganic filler and a second functional group capable of interacting with the diene elastomer. For example, such a bifunctional compound can comprise a first functional group comprising a silicon atom, the said first functional group being able to interact with the hydroxyl groups of an inorganic charge and a second functional group comprising a sulfur atom, the said second functional group being able to interact with the diene elastomer. Preferably, the organosilanes are chosen from the group consisting of polysulfurized organosilanes (symmetrical or asymmetrical) such as bis (3-triethoxysilylpropyl) tetrasulfide, in short TESPT marketed under the name “Si69” by the company Evonik or bis disulfide. - (triethoxysilylpropyle), abbreviated TESPD marketed under the name “Si75” by the company Evonik, the polyorganosiloxanes, the mercaptosilanes, the blocked mercaptosilanes, such as the octanethioate of S- (3- (triethoxysilyl) propyl) marketed by the company Momentive under the name "NXT Silane". More preferably, the organosilane is a polysulfurized organosilane. Of course, mixtures of the coupling agents described above could also be used. The content of coupling agent in the composition of the invention is advantageously less than or equal to 35 phr, it being understood that it is generally desirable to use as little as possible. Typically the level of coupling agent represents from 0.5% to 15% by weight relative to the amount of reinforcing inorganic filler. Those skilled in the art will understand that, replacing the reinforcing inorganic filler described above, a reinforcing filler of another nature could be used, since this reinforcing filler of another nature would be covered with an inorganic layer. such as silica, or else would include on its surface functional sites, in particular hydroxyls, requiring the use of a coupling agent to establish the bond between this reinforcing filler and the diene elastomer. By way of example, mention may be made of carbon blacks partially or entirely covered with silica, or carbon blacks modified with silica, such as, without limitation, the fillers of the “Ecoblack®” type of the series. CRX2000 ”or the“ CRX4000 ”series from Cabot Corporation. Those skilled in the art will know how to adapt the rate of reinforcing filler in the rubber composition of the invention according to the use concerned, in particular according to the type of tire concerned, for example tire for a motorcycle, for a passenger vehicle or even for a commercial vehicle. such as a pickup truck or heavy truck. Preferably, this level of reinforcing filler is within a range ranging from 10 to 200 phr, more preferably from 30 to 180 phr, the optimum being in a known manner different according to the particular applications targeted. According to one embodiment, the reinforcing filler mainly comprises silica; preferably consists essentially of silica, more preferably still consists of silica. In this embodiment where the reinforcing filler mainly comprises silica, the level of carbon black present in the rubber composition is preferably within a range ranging from 2 to 20 phr. According to another embodiment of the invention, the reinforcing filler mainly comprises carbon black, or even consists essentially of carbon black, more preferably still consists of carbon black. Another component of the rubber composition according to the invention is a crosslinking agent. The crosslinking agent can be any type of system known to those skilled in the art in the field of rubber compositions for tires. It can in particular be based on sulfur. Preferably, the crosslinking agent is sulfur-based, this is called a vulcanization system. The sulfur can be provided in any form, in particular in the form of molecular sulfur, or of a sulfur donor agent. At least one vulcanization accelerator is also preferably present, and, optionally, also preferentially, one can use various known vulcanization activators such as zinc oxide, stearic acid or equivalent compound such as salts of stearic acid and salts. transition metals, guanide derivatives (in particular diphenylguanidine), or also known vulcanization retarders. Sulfur is used at a preferential rate of between 0.5 and 12 phr, in particular between 1 and 10 phr. The vulcanization accelerator is used at a preferential rate of between 0.5 and 10 phr, more preferably between 0.5 and 5.0 phr. Can be used as accelerator any compound capable of acting as vulcanization accelerator of diene elastomers in the presence of sulfur, in particular accelerators of the thiazole type as well as their derivatives, accelerators of the sulfenamides, thiurams, dithiocarbamates, dithiophosphates, thioureas and xanthates types. By way of examples of such accelerators, there may be mentioned in particular the following compounds: 2-mercaptobenzothiazyl disulfide (abbreviated as “MBTS”), N-cyclohexyl-2-benzothiazyl sulfenamide (“CBS”), N, N-dicyclohexyl- 2-benzothiazyl sulfenamide ("DCBS"), N-ter-butyl-2-benzothiazyl sulfenamide ("TBBS"), N-ter-butyl-2-benzothiazyl sulfenimide ("TBSI"), tetrabenzylthiuram disulfide ("TBZTD"), zinc dibenzyldithiocarbamate ("ZBEC") and mixtures of these compounds. The rubber compositions in accordance with the invention may also comprise all or part of the usual additives and processing agents, known to those skilled in the art and usually used in rubber compositions for tires, in particular rubber bands. bearing, such as for example plasticizers (such as plasticizing oils and / or plasticizing resins), non-reinforcing fillers, pigments, protection agents such as anti-ozone waxes, chemical anti-ozonants, anti-oxidants, anti-fatigue agents, reinforcing resins (as described for example in application WO 02/10269). A process for preparing the rubber composition defined above is also described. The rubber composition in accordance with the invention is manufactured in suitable mixers, using two successive preparation phases well known to those skilled in the art: a first thermomechanical working or mixing phase (so-called “non-productive” phase) carried out at a maximum temperature within a range ranging from 110 ° C to 200 ° C, preferably from 130 ° C to 185 ° C, for a period generally of between 2 and 10 minutes, - a second phase of mechanical work (phase called "productive"), which is carried out in an external mixer such as a roller mixer, after cooling the mixture obtained during the first non-productive phase to a lower temperature, typically less than 120 ° C, for example between 40 ° C and 100 ° C. The crosslinking agent is then incorporated, and the whole is mixed for a few minutes, for example between 5 and 15 min. In general, all the basic constituents of the composition according to the invention, with the exception of the chemical crosslinking agent, namely the reinforcing filler (s), the coupling agent where appropriate, are incorporated. intimately, by mixing, with the diene elastomer or with the diene elastomers during the first so-called non-productive phase, that is to say which is introduced into the mixer and which is thermomechanically mixed, in one or more stages, at least these different basic constituents until reaching the maximum temperature between 110 ° C and 200 ° C, preferably between 130 ° C and 185 ° C. According to a first preferred embodiment of the invention, the diene elastomer has been grafted with the compound of formula (I), in particular with the compound of formula (Ib), more particularly still with the compound of formula (III) prior to the manufacture of the rubber composition. Thus, in this case, it is the grafted diene elastomer which is introduced during the first so-called non-productive phase. Thus according to this first embodiment of the method, it comprises the following steps: ^ modify the diene elastomer by grafting in solution or in bulk with at least one compound of formula (I), in particular with at least one compound of formula (Ib), more particularly with at least one compound of formula (III) such as as defined above, incorporate into the diene elastomer thus grafted with the compound of formula (I), in particular with the compound of formula (Ib), more particularly with the compound of formula (III), the reinforcing filler and all the basic constituents of the composition, with the exception of the crosslinking agent, by thermomechanically kneading the mixture, in one or more times, until a maximum temperature of between 110 ° C and 200 ° C is reached, of preferably between 130 ° C and 185 ° C ^ cool the previous mixture to a temperature below 100 ° C, ^ then incorporate the crosslinking agent, ^ knead the mixture obtained in the previous step to a temperature below 120 ° C. The grafting of the diene elastomer is carried out by reaction of said diene elastomer with the nitrile oxide function of the compound of formula (I), in particular with the nitrile oxide of the compound of formula (Ib), more particularly with the oxide of nitrile of the compound of formula (III). During this reaction, this nitrile oxide forms a covalent bond with the chain of said diene elastomer. More precisely, the grafting of the compound of formula (I), in particular of the compound of formula (Ib), more particularly of the compound of formula (III) is carried out by [3 + 2] cycloaddition of the nitrile oxide function with a unsaturation of the chain of the initial diene elastomer. A [3 + 2] cycloaddition mechanism is described in document WO2012 / 007441. The diene elastomer carries along the main elastomer chain one or more pendant groups resulting from the grafting reaction of the compound of formula (I), in particular of the compound of formula (Ib), more particularly of the compound of formula (III) as defined above. Advantageously, these pendant groups are distributed along the main elastomeric chain in a random fashion. The grafting of the compound of formula (I), in particular of the compound of formula (Ib), more particularly of the compound of formula (III) can be carried out in bulk, for example in an internal mixer or an external mixer such as a mixer with cylinders. The grafting is then carried out either at a temperature of the external mixer or of the internal mixer below 60 ° C, followed by a grafting reaction step in a press or in an oven at temperatures ranging from 80 ° C to 200 ° C. , or at a temperature of the external mixer or of the internal mixer above 60 ° C without subsequent heat treatment. The grafting process can also be carried out in solution continuously or batchwise. The diene elastomer thus grafted can be separated from its solution by any type of known means, in particular by a steam stripping operation. According to a second preferred embodiment of the invention, the grafting of the diene elastomer with the compound of formula (I), in particular with the compound of formula (Ib), plus particularly by the compound of formula (III) is carried out concomitantly with the manufacture of the rubber composition. In this case, both the diene elastomer not yet grafted and the compound of formula (I), in particular the compound of formula (Ib), more particularly the compound of formula (III) are introduced during the first phase called ungrafted. -productive. Preferably, the reinforcing filler is then added subsequently during this same non-productive phase in order to prevent any side reaction with the compound of formula (I), in particular with the compound of formula (Ib), more particularly with the compound of formula (Ib). compound of formula (III). Thus, according to this second embodiment of the preferred method, the latter comprises the following steps: incorporating into the diene elastomer at least one compound of formula (I), in particular at least one compound of formula (Ib), more particularly at least one compound of formula (III) as defined above, and, preferably subsequently, the reinforcing filler, as well as all the basic constituents of the composition, with the exception of the chemical crosslinking agent , by thermomechanically kneading the mixture, in one or more times, until a maximum temperature of between 110 ° C and 200 ° C, preferably between 130 ° C and 185 ° C, is reached; ^ cool the mixture obtained in the previous step to a temperature below 100 ° C, ^ then incorporate the crosslinking agent, ^ knead the mixture obtained in the previous step to a maximum temperature below 120 ° C. In these two preferred embodiments, the molar degree of grafting of the compound of formula (I), in particular of the compound of formula (Ib), more particularly of the compound of formula (III) is within a range ranging from 0.01 % to 15%, preferably from 0.05% to 10%, more preferably from 0.07 to 5%. The term “molar grafting rate” means the number of mol of the compound of formula (I), in particular of the compound of formula (Ib), in particular of the compound of formula (III), grafted onto the diene elastomer per 100 moles. of monomer unit constituting the diene elastomer. The molar grafting rate can be determined by conventional methods of polymer analysis, such as for example NMR analysis¹H. The final rubber composition thus obtained can then be calendered, for example in the form of a sheet or of a plate, in particular for characterization, or else extruded in the form of a rubber profile which can be used as a semi-finished article for pneumatic. Another object of the present invention is a semi-finished article for a tire comprising at least one rubber composition as defined above, preferably the semi-finished article is a tread. A subject of the invention is also a tire comprising at least one rubber composition according to the invention as defined above; preferably in all or part of its tread. Preferably, the tire according to the invention will be chosen from the tires intended to be fitted to a two-wheeled vehicle, a passenger vehicle, or even a so-called “heavy goods vehicle” (that is to say metro, bus, vehicles outside the vehicle. - the road, road transport vehicles such as trucks, tractors, trailers), or even planes, civil engineering, agrarian or handling equipment. In addition, to the objects described above, the invention relates to at least one of the objects described in the following embodiments: 1. Rubber composition based on at least one diene elastomer, a reinforcing filler, a crosslinking agent and at least a compound of formula (I), optionally already grafted onto said diene elastomer

in which: - A represents an arenediyl ring in C₆-VS₁₄, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C₅-VS₁₂ optionally comprising one or more heteroatoms; - X1, X2, X3, identical or different, represent a hydrogen atom, a C alkyl₁-VS₆ or a C aryl₆-VS₁₄. 2. Rubber composition according to embodiment 1, wherein E represents is a divalent hydrocarbon group in C₅-C10, preferably C₅-VS₉, more preferably in C6-C₉, more preferably still in C7-C₉. 3. Rubber composition according to embodiment 1 or 2, in which E represents a C-alkanediyl₅-C10, preferably a C-alkanediyl₅-VS₉, more preferably a C6-C alkanediyl₉, more preferably still a C7-C alkanediyl₉. 4. Rubber composition according to any one of the preceding embodiments, in which X1, X2, X3, identical or different, are selected from the group consisting of the hydrogen atom, C-alkyls₁-VS₆ and aryls in C₆-VS₁₄. 5. Rubber composition according to one of embodiments 1 to 3, in which X1, X2, X3, identical or different, represent a hydrogen atom, a methyl, an ethyl or a phenyl. 6. Rubber composition according to one of embodiments 1 to 3, in which X1, X2, X3 represent a hydrogen atom. 7. A rubber composition according to any one of embodiments 1 to 3, wherein X1 and X2 represent a hydrogen atom and X3 represents a phenyl. 8. A rubber composition according to any one of embodiments 1 to 3, in which X3 is a hydrogen atom and the groups X1 and X2, identical or different, represent a hydrogen atom or a methyl. 9. Rubber composition according to any one of the preceding embodiments, in which the compound of formula (I) is chosen from the compounds of formula (Ia) and (Ib)

in which: a group chosen from R1 to R5 of formula (Ia) and a group chosen from R1 to R7 of formula (Ib) denote the following group of formula (II):

in which E, X1, X2 and X3 are as defined in any one of embodiments 1 to 8 and the symbol (*) represents the attachment to (Ia) or to (Ib), - the four groups of the formula ( Ia) chosen from R1 to R5 other than that designating the group of formula (II) and the six groups of formula (Ib) chosen from R1 to R7 other than that designating the group of formula (II), which are identical or different, represent independently of each other, a hydrogen atom or an aliphatic hydrocarbon chain, preferably saturated, linear or branched. 10. Rubber composition according to embodiment 9, in which the compound of formula (I) is chosen from the compounds of formula (Ia) and (Ib) in which: - a group chosen from R1 to R5 of formula (Ia) and a group chosen from R1 to R7 of formula (Ib) denote the following group of formula (II):

in which E, X1, X2 and X3 are as defined in any one of embodiments 1 to 8 and the symbol (*) represents the attachment to (Ia) or to (Ib), - the four groups of the formula ( Ia) chosen from R1 to R5 other than that designating the group of formula (II) and the six groups of formula (Ib) chosen from R1 to R7 other than that designating the group of formula (II), which are identical or different, represent independently of each other, a hydrogen atom or a methyl. 11. A rubber composition according to any one of embodiments 9 to 10, wherein the compound of formula (I) is the compound of formula (Ib). 12. Rubber composition according to any one of embodiments 1 to 4, in which the compound of formula (I) is the compound of formula (III)

13. Rubber composition according to any one of the preceding embodiments, in which the diene elastomer is chosen from the group consisting of ethylene-propylene-diene monomer copolymers, natural rubber, synthetic polyisoprenes, polybutadienes, butadiene copolymers, isoprene copolymers and mixtures of these elastomers. 14. Rubber composition according to any one of embodiments 1 to 12, in which the diene elastomer is chosen from the group consisting of natural rubber, synthetic polyisoprenes, polybutadienes, butadiene copolymers, and copolymers of. isoprene and mixtures of these elastomers. 15. A rubber composition according to any one of embodiments 1 to 12, in which the diene elastomer is selected from the group consisting of natural rubber, synthetic polyisoprenes, isoprene copolymers and mixtures of these elastomers. 16. A rubber composition according to any one of the preceding embodiments, in which the reinforcing filler is chosen from carbon black, an inorganic reinforcing filler and mixtures thereof. 17. A rubber composition according to embodiment 16, in which the reinforcing filler comprises carbon black. 18. A rubber composition according to embodiment 16, wherein the reinforcing filler comprises an inorganic reinforcing filler. 19. A rubber composition according to embodiment 18, in which the inorganic reinforcing filler is silica. Rubber composition according to any one of the preceding embodiments, in which the molar grafting rate of the compound of formula (I) is within a range ranging from 0.01% to 15%, preferably from 0.05% to 10%, more preferably from 0.07 to 5%. 21. Rubber composition according to any one of the preceding embodiments, in which the level of reinforcing filler is within a range ranging from 10 to 200 phr, preferably ranging from 30 to 180 phr. 22. Process for preparing a rubber composition as defined in any one of embodiments 1 to 21, comprising the following steps: modifying a diene elastomer by grafting in solution or in mass with at least one compound of formula ( I),

in which: - A represents an arenediyl ring in C₆-VS₁₄, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C₅-VS₁₂ optionally comprising one or more heteroatoms; - X1, X2, X3, identical or different, represent a hydrogen atom, a C alkyl₁-VS₆ or a C aryl₆-VS₁₄ ; ^ incorporate into the diene elastomer thus grafted with the compound of formula (I), the reinforcing filler, by kneading the mixture in one or more times, until a maximum temperature of between 110 ° C and 200 ° C is reached, from preferably between 130 ° C and 185 ° C; ^ cool the previous mixture to a temperature less than or equal to 100 ° C, ^ then incorporate the chemical crosslinking agent, and ^ knead the mixture obtained in the previous step to a temperature below 120 ° C. 23. Process for preparing a rubber composition as defined in any one of points 1 to 21, comprising the following stages: incorporating, during the mass mixing with the diene elastomer, at least one compound of formula (I)

in which: - A represents an arenediyl ring in C₆-VS₁₄, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C₅-VS₁₂ optionally comprising one or more heteroatoms; - X1, X2, X3, identical or different, represent a hydrogen atom, a C alkyl₁-VS₆ or a C aryl₆-VS₁₄, and preferably subsequently, the reinforcing filler, by thermomechanically kneading the mixture, in one or more times, until a maximum temperature of between 110 ° C and 200 ° C is reached, preferably between 130 ° C and 185 ° C; ^ cool the mixture obtained in the previous step to a temperature less than or equal to 100 ° C; ^ then incorporate the chemical crosslinking agent, º knead the mixture obtained in the previous step to a temperature below 120 ° C. 24. Process for preparing a rubber composition according to embodiment 22 or 23, in which the diene elastomer is chosen from the group consisting of ethylene-propylene-diene monomer copolymers, natural rubber, synthetic polyisoprenes. , polybutadienes, butadiene copolymers, isoprene copolymers and mixtures of these elastomers. 25. Process for preparing a rubber composition according to embodiment 22 or 23, in which the diene elastomer is chosen from the group by natural rubber, synthetic polyisoprenes, polybutadienes, butadiene copolymers, copolymers of isoprene and mixtures of these elastomers. 26. Process for preparing a rubber composition according to embodiment 22 or 23, in which the diene elastomer is chosen from the group consisting of natural rubber, synthetic polyisoprenes, polybutadienes, butadiene copolymers, copolymers of isoprene and mixtures of these elastomers. 27. Process for preparing a rubber composition according to embodiment 22 or 23, in which the diene elastomer is chosen from the group consisting of polybutadienes, butadiene copolymers, isoprene copolymers and mixtures of these elastomers. . 28. Process for preparing a rubber composition according to embodiment 22 or 23, in which the diene elastomer is chosen from the group consisting of polybutadienes, styrene-butadiene copolymers, ethylene-butadiene copolymers, isobutene-isoprene copolymers, isoprene-styrene copolymers, isoprene-butadiene copolymers, isoprene-butadiene-styrene copolymers and mixtures of these elastomers. 29. Process for preparing a rubber composition according to any one of embodiments 22 to 28, in which the molar grafting rate of the compound of formula (I) is within a range ranging from 0.01% to 15% , preferably from 0.05% to 10%, more preferably from 0.07 to 5%. 30. A process for preparing a rubber composition according to any one of embodiments 22 to 29, in which E represents is a divalent hydrocarbon group at C₅-VS₁₀, preferably in C₅-VS₉, more preferably in C₆-VS₉, more preferably still in C₇-VS₉. 31. A process for preparing a rubber composition according to any one of the embodiments 22 to 29, in which E represents a C-alkanediyl₅-VS₁₀, preferably a C₅-VS₉, more preferably a C₆-VS_9, more preferably still an alkanediyl in C₇-VS₉. 32. A process for preparing a rubber composition according to any one of embodiments 22 to 31, wherein X₁, X₂, X₃, identical or different, are chosen from the group consisting of the hydrogen atom, C-alkyls₁-VS₆ and aryls in C₆-VS₁₄. 33. A process for preparing a rubber composition according to any one of embodiments 22 to 31, in which X1, X2, X3, identical or different, represent a hydrogen atom, a methyl, an ethyl or a phenyl. 34. A process for preparing a rubber composition according to any one of embodiments 22 to 31, wherein X1, X2, X3 represent a hydrogen atom. 35. A process for preparing a rubber composition according to any one of embodiments 22 to 31, wherein X1 and X2 represent a hydrogen atom and X3 represents a phenyl. 36. Process for preparing a rubber composition according to any one of the embodiments 22 to 31, in which X3 is a hydrogen atom and the groups X1 and X2, which are identical or different, represent a hydrogen atom or a hydrogen atom. methyl. 37. Process for preparing a rubber composition according to any one of the embodiments 22 to 36, which the compound of formula (I) is chosen from the compounds of formula (Ia) and (Ib)

in which E, X1, X2 and X3 are as defined in any of the embodiments 22 to 36 and the symbol (*) represents the attachment to (Ia) or to (Ib), - the four groups of formula (Ia) chosen from R1 to R5 other than that designating the group of formula (II) and the six groups of formula (Ib) chosen from R1 to R7 other than that designating the group of formula ( II), which are identical or different, represent, independently of one another, a hydrogen atom or an aliphatic hydrocarbon chain, preferably saturated, linear or branched. 38. Process for preparing a rubber composition according to embodiment 37, which the compound of formula (I) is chosen from the compounds of formula (Ia) and (Ib) in which: - a group chosen from R1 to R5 of formula (Ia) and a group chosen from R1 to R7 of formula (Ib) denote the following group of formula (II):

in which E, X1, X2 and X3 are as defined in any one of embodiments 22 to 36 and the symbol (*) represents the attachment to (Ia) or to (Ib), - the four groups of the formula ( Ia) chosen from R1 to R5 other than that designating the group of formula (II) and the six groups of formula (Ib) chosen from R1 to R7 other than that designating the group of formula (II), which are identical or different, represent independently of each other, a hydrogen atom or a methyl. 39. Process for preparing a rubber composition according to one of embodiments 22 to 32, which compound of formula (I) is the compound of formula (Ib). 40. Process for preparing a rubber composition according to one of embodiments 22 to 32, which compound of formula (I) is the compound of formula (III)

41. Semi-finished article for a tire comprising at least one rubber composition as defined in any one of embodiments 1 to 19 or else obtained according to the process as defined in any one of embodiments 20 to 37. 42. A tire comprising at least one rubber composition as defined in any one of embodiments 1 to 19 or else obtained according to the process as defined in any one of points 20 to 37. The examples which follow illustrate the invention without however limit it. Examples: The following examples illustrate the invention; however, the latter cannot be limited to these examples alone. 1. Methods 1.1 Measurement of the number-average molar masses (Mn), by weight (Mw) and of the polydispersity index of the elastomers Size exclusion chromatography (SEC) is used. The SEC makes it possible to separate the macromolecules in solution according to their size through columns filled with a porous gel. Macromolecules are separated according to their hydrodynamic volume, the larger ones being eluted first. Without being an absolute method, SEC makes it possible to understand the distribution of the molar masses of an elastomer. From commercial standard products, the different average molar masses in number (Mn) and in weight (Mw) can be determined and the polymolecularity index (Ip = Mw / Mn) calculated via a so-called MOORE calibration. Preparation of the elastomer sample to be tested There is no particular treatment of the elastomer sample before analysis. This is simply dissolved at a concentration of approximately 1 g / L, in chloroform or in the following mixture: tetrahydrofuran + 1% vol. of diisopropylamine + 1% vol. of triethylamine + 1% vol. of distilled water (% vol. =% volume). The solution is then filtered through a filter with a porosity of 0.45 μm before injection. SEC analysis The apparatus used is a “WATERS alliance” chromatograph. The elution solvent is the following mixture: tetrahydrofuran + 1% vol. of diisopropylamine + 1% vol. triethylamine or chloroform depending on the solvent used to dissolve the elastomer. The flow rate is 0.7 mL / min, the system temperature is 35 ° C and the run time is 90 min. A set of four WATERS columns in series, with the trade names “STYRAGEL HMW7”, “STYRAGEL HMW6E” and two “STYRAGEL HT6E” is used. The injected volume of the elastomer sample solution is 100 μL. The detector is a "WATERS 2410" differential refractometer with a wavelength of 810 nm. The software of chromatographic data is the “WATERS EM POWER” system. The average molar masses calculated relate to a calibration curve produced from commercial standard polystyrenes “PSS READY CAL-KIT”. 1.2. Characterizations of the molecules The structural analysis as well as the determination of the molar purities of the synthetic molecules are carried out by an NMR analysis. The spectra are acquired on an "Avance 3400 MHz BRUKER" spectrometer equipped with a "broadband BBFO-zgrad 5 mm" probe. The NMR experiment¹Quantitative H uses a 30 ° single pulse sequence and a 3 second repeat delay between each of the 64 acquisitions. The samples are solubilized in a deuterated solvent, deuterated dimethyl sulfoxide (DMSO) unless otherwise indicated. The deuterated solvent is also used for the "lock" signal. For example, the calibration is performed on the proton signal of deuterated DMSO at 2.44 ppm relative to a TMS reference at 0 ppm. The NMR spectrum¹H coupled with 2D HSQC experiments¹H / 13C and HMBC¹H / 13C allow the structural determination of molecules (see allocation tables). The molar quantifications are carried out from the 1D NMR spectrum¹H quantitative. Mass spectrometry analysis is performed by direct injection by an electrospray ionization mode (ID / ESI). The analyzes were carried out on a Bruker HCT spectrometer (flow rate 600 μL / min, pressure of the nebulizer gas 10 psi, flow rate of the nebulizer gas 4 L / min). 1.3. Characterizations of the Compounds Grafted on the Diene Elastomers The determination of the molar content of the compounds grafted on the diene elastomers is carried out by an NMR analysis. The spectra are acquired on a "500 MHz BRUKER" spectrometer equipped with a "BBFO-zgrad-5 mm CryoSonde". The NMR experiment¹H quantitative, uses a 30 ° single pulse sequence and a 5 second repetition delay between each acquisition. The samples are solubilized in deuterated chloroform (CDCl3) in order to obtain a "lock" signal. 2D NMR experiments made it possible to verify the nature of the grafted motif thanks to the chemical shifts of the carbon and proton atoms. 1.4. Dynamic Properties of the Rubber Compositions The dynamic properties G * and tan (δ) max are measured on a viscoanalyst (Metravib VA4000), according to standard ASTM D5992-96. We record the response of a sample of vulcanized composition (cylindrical test piece 4 mm thick and 400 mm2 in section), subjected to a sinusoidal stress in alternating simple shear, at a frequency of 10 Hz, at a temperature of 60 ° C. A strain amplitude sweep is carried out from 0.1% to 100% peak-peak (forward cycle) then from 100% to 0.1% peak-peak (return cycle). The results used are the complex dynamic shear modulus G * at 25% deformation (G *_25% return), the dynamic loss factor tan (δ) at 60 ° C and the difference in modulus (ΔG *) between the values at 0.1% and 100% deformation (Payne effect). For the return, one records the value of the complex modulus of dynamic shears G * at 25% deformation, note G * 25% return at 60 ° C and the maximum value of the dynamic loss factor tan (δ) observed, noted tan (δ) max at 60 ° C. The results are indicated in base 100; the arbitrary value 100 being assigned to the control to calculate and then compare tan (δ) max at 60 ° C, G *_{25% return} at 60 ° C and ΔG * of the different samples tested. For tan (δ) max at 60 ° C, the value in base 100 for the sample to be tested is calculated according to the operation: (value of tan (δ) max at 60 ° C of the sample to be tested / value of tan (δ) max at 60 ° C of the control) × 100. In this way, a result less than 100 indicates a decrease in hysteresis which corresponds to an improvement in rolling resistance performance. For G *_{25% return} at 60 ° C, the value in base 100 for the sample to be tested is calculated according to the operation: (value of G * 25% return at 60 ° C of the sample to be tested / value of G * 25% return to 60 ° C of the control) × 100. In this way, a result greater than 100 indicates an improvement in the complex dynamic shear modulus G * 25% return at 60 ° C, which corroborates an improvement in the stiffness of the material. For (ΔG *), the value in base 100 for the sample to be tested is calculated according to the operation: (value of ΔG * of the sample to be tested / value of ΔG * of the control) × 100. In this way, a result of less than 100 reflects a reduction in the difference in modulus, or an increase in the linearization of the rubber composition. 1.6. Tensile test. These tensile tests are used to determine the elasticity stresses. Unless otherwise indicated, they are carried out in accordance with the French standard NF T46-002 of September 1988. Processing of the tensile records also makes it possible to plot the modulus curve as a function of the elongation. The nominal secant modulus calculated by reducing to the initial section of the test piece (or apparent stress, in MPa) at 100% elongation denoted MSA100 and 300% elongation denoted MSA300 is measured at first elongation. All these tensile measurements are carried out under normal temperature conditions (23 ± 2 ° C) according to standard NF T46-002. The MSA300 / MSA100 ratio is the index of strengthening. The value in base 100 for the sample to be tested is calculated according to the operation: (value of MSA300 / MSA100 of the sample to be tested / value of MSA300 / MSA100 of the control) × 100. In this way, a result greater than 100 indicates an improvement in the reinforcement index. 2. Synthesis of the compounds 2.1. Synthesis of compound A: 2 - ((9-oxiran-2yl) nonyl) oxy) -1-naphtonitrile oxide

The synthesis of compound A is carried out according to the following reaction scheme:

11-Bromo-1-undecene, 3-chloroperbenzoic acid, 2-hydroxy-1-naphthaldehyde, and hydroxylamine and trimethylamine are commercial products. They can be obtained from Sigma-Aldrich 2.1.1. Step a1: preparation of 2- (9-bromononyl) oxirane 10 g of 11-Bromo-1-undecene (42.9 mmol) are dissolved in 200 ml of CH2Cl2. Then, 11.84 g of 3-chloroperbenzoic acid (68.6 mmol or 1.4 eq, MCPBA) are added in several portions over approximately 15 minutes and the reaction medium is stirred for 15 hours. The white precipitate is filtered off and washed with CH2Cl2 (2 x 20 ml). Then, the filtrate is stirred in the presence of an aqueous solution of NaHSO3 (40 g of NaHSO3 in 400 ml of distilled water) for 5 hours at room temperature (20 ° C). The organic phase is recovered by decantation and is left to react with a solution of NaHCO3 (40 g) in water (400 mL) for 5 hours. After having separated by decantation, the residual aqueous phase is extracted with CH2Cl2. The organic phases are combined, then dried with Na2SO4 and concentrated. under reduced pressure (12 mbar; bath temperature = 30 ° C). A yellow oil is obtained (10.613 g, 42.90 mmol, yield 99%). The molar purity is> 90% (NMR¹H).

Solvent CDCl₃ 2.1.2 Step a2: Synthesis of 2 - ((9- (oxiran-2-yl) nonyl) oxy) -1-naphthaldehyde A suspension of 2-hydroxy-1-naphthaldehyde (11.05 g; 64.2 mmol), 2- (9- bromononyl) oxirane (15.99g; 64.2 mmol) and K₂CO₃ (8.87 g; 64.2 mmol) in 20 ml of N, N-dimethylformamide (DMF) is heated at 70 ° C. for 3 hours with stirring at 500 rpm (rpm = rotation per minute). The reaction medium is then poured into 250 ml of distilled water; then extracted with ethyl acetate (4 x 60 mL). The combined organic phases are then evaporated off under reduced pressure (bath temperature = 40 ° C., 10 mbar) to obtain a brown oil (24.95 g). The product is then purified by chromatography on a silica gel column with a mixture of petroleum ether / ethyl acetate as eluent: 3/1 (v / v) The residual yellow oil is triturated with petroleum ether allowing crystallization. The precipitate is filtered off and air dried. A yellowish solid (14.545 g, 42.7 mmol, yield 67%) is obtained. The molar purity is greater than 97% (NMR¹H).

Solvent: CDCl3 2.1.3 Step a3: Synthesis of 2 - ((9- (oxiran-2-yl) nonyl) oxy) -1-naphthaldehyde oxime 1.521 g of hydroxylamine (23.02 mmol or 1.5 equivalents) are added, to room temperature 20 ° C, to a suspension of 2 - ((9- (oxiran-2-yl) nonyl) oxy) -1-naphthaldehyde (5.225 g, 15.35 mmol) in ethanol (50 ml). The reaction mixture is stirred for 3 hours; at the end of the reaction, a yellow solid precipitates. 30 ml of distilled water are then added and the medium is left to stir for an additional 10 minutes. The precipitate obtained is filtered off, washed with 2x5 ml of a distilled water: ethanol (1: 1, v / v) mixture; then is air dried. A yellow solid (4.979 g, 14.01 mmol, yield 91%) is obtained. The molar purity is 93% (NMR).

Solvent: CDCl ₃ 2.1.4 Step a4: Synthesis of 2 - ((9- (oxiran-2-yl) nonyl) oxy) -1-naphthonitrile N-oxide (Compound A) 1.824 g of trimethylamine (18.03 mmol) and 2.037 g of N-chlorosuccinimide (15.25 mmol) in several portions for 10 to 12 min in a solution of 2 - ((9- (oxiran-2-yl) nonyl) oxy) -1-naphthaldehyde oxime ( 4.929 g; 13.87 mmol) in 100 ml of CHCl ₃ cooled to a temperature of 0-2 ° C. The reaction mixture is stirred in the cold for 90 min. Then, the organic phase is washed with distilled water (3 x 50 ml), dried with Na ₂ SO ₄ and concentrated under reduced pressure (bath temperature = 25 ° C; up to 2 mbar) to obtain 5.005 g a yellow solid. The product is re-solubilized in the minimum volume of ethyl acetate to obtain a homogeneous solution; then petroleum ether is poured until the first cloudiness (not very clear either, it would be preferable to indicate the volume to be poured). This solution is filtered through a column of silica gel (l = 5 cm), eluting with a mixture of ethyl acetate: petroleum ether (1: 3, v / v). The permeate is evaporated off under reduced pressure (bath temperature = 25 ° C., up to 1 mbar). A yellow solid (4.593g, 12.99 mmol, yield 94%) of melting point 52-53 ° C is obtained. The molar purity is 92% ( ¹ H NMR).

Solvent: CDCl ₃ 2.2. Synthesis of 2- (glycidyloxy) -1-naphtonitrile oxide 2- (glycidyloxy) -1-naphtonitrile oxide, compound B, is synthesized according to the procedure described in patent application US20120046418A1. 3. Obtaining of the modified diene elastomers 3.1 Rubber modified with compound A The oxide of 2 - ((9- (oxiran-2-yl) nonyl) oxy) -1-naphthonitrile (811 mg; 2.3 mmol or a molar fraction of 0.3% mol), compound A obtained according to the process described above, with an NMR purity of 96% mol, at 50 g of natural rubber on a roller tool (external mixer at 30 ° C.). The mixture is homogenized in 15 wallet passes. This phase The mixing process is followed by a heat treatment at 120 ° C. for 10 min in a press at 10 bar pressure. Analysis by ¹ H NMR made it possible to determine a molar grafting rate of 0.16 mol% with a molar grafting yield of 54%. 3.2 Rubber modified with compound B The oxide of 2- (glycidyloxy) -1-naphtonitrile (564 mg, 2.34 mmol or a molar fraction of 0.3% mol), NMR purity of 94% mol, is incorporated, compound B, 50 g of natural rubber on a roller tool (external mixer at 30 ° C). The mixture is homogenized in 15 wallet passes. This mixing phase is followed by a heat treatment (10 min at 120 ° C.) in a press at 10 bar pressure. Analysis by ¹ H NMR made it possible to determine the molar grafting rate of 0.16 mol% and the molar grafting yield of 54%. 3.3 Synthetic polyisoprene modified with compound A The oxide of 2 - ((9- (oxiran-2-yl) nonyl) oxy) -1-naphthonitrile (811 mg; 2.3 mmol or a molar fraction of 0 , 3% mol), compound A obtained according to the process described above, with an NMR purity of 96% mol, at 50 g of synthetic polyisoprene (containing 99.35% by weight of cis-1,4-isoprene unit and 0.65% by weight of unit isoprene 3.4; Mn = 375000 g / mol and Ip = 3.6 measured according to the method described above) on a roller tool (external mixer at 30 ° C). The mixture is homogenized in 15 wallet passes. This mixing phase is followed by a heat treatment at 120 ° C. for 10 min in a press at 10 bar pressure. Analysis by ¹ H NMR made it possible to determine a molar grafting rate of 0.22 mol% with a molar grafting yield of 74%. 3.4 Synthetic polyisoprene modified with compound B 2- (glycidyloxy) -1-naphtonitrile oxide (564 mg, 2.34 mmol or a molar fraction of 0.3% mol), NMR purity of 94%, is incorporated. mol, compound B, to 50 g of synthetic polyisoprene (containing 99.35% by weight of cis-1,4-isoprene unit and 0.65% by weight of 3,4-isoprene unit; Mn = 375,000 g / mol and Ip = 3.6 measured according to the method described above) on a roller tool (external mixer at 30 ° C). The mixture is homogenized in 15 wallet passes. This mixing phase is followed by a heat treatment (10 min at 120 ° C.) in a press at 10 bar pressure. Analysis by ¹ H NMR made it possible to determine a molar grafting rate of 0.16 mol% with a molar grafting yield of 54%. 4. Ingredients used in the rubber compositions (1) Silica “Zeosil 1165MP” marketed by Solvay; (2) Bis [3- (triethoxysilyl) propyl] tetrasulfide silane (TESPT) sold by Evonik under the reference “Si69”; (3) N234 grade carbon black marketed by Cabot Corporation; (4) N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine sold by Flexys under the reference “Santoflex 6-PPD”; (5) 2,2,4-trimethyl-1,2-dihydroquinoline sold by the company Flexys; (6) Zinc oxide (industrial grade) marketed by the company Umicore; (7) “Pristerene 4031” stearin marketed by the company Uniquema; (8) N-cyclohexyl-2-benzothiazyl-sulfenamide sold by Flexys under the reference “Santocure CBS”. (9) natural rubber modified by compound B, obtained according to the process described in paragraph 3.1; (10) natural rubber modified by compound A, obtained according to the process described in paragraph 3.2; (11) synthetic polyisoprene modified with compound B, obtained according to the process described in paragraph 3.3; (12) synthetic polyisoprene modified with compound A, obtained according to the process described in paragraph 3.4. 5. Test 1 The purpose of this test is to show the improvement in the reinforcement of a rubber composition comprising natural rubber modified by the compound of the invention (composition C2) compared with a comparative composition (composition C1). The rate of the various constituents of these compositions expressed in phr, part by weight per hundred parts by weight of elastomer, are presented in Table 5.

Compositions C1 and C2 comprise the same number of moles of grafted compound A or B, namely 0.3 mole%. Compositions C1 and C2 are prepared as follows: the natural rubber modified by compound A or by compound B. Then, for each of the compositions, the reinforcing fillers are introduced, the agent for coupling the filler with the diene elastomer, then after one to two minutes of mixing, the various other ingredients with the exception of the vulcanization system. Thermomechanical work (non-productive phase) is then carried out in one step, which lasts in total about 5 to 6 minutes, until a maximum drop temperature of 160 ° C. is reached. The mixture thus obtained is recovered, it is cooled and then the vulcanization system (sulfur and sulfenamide type accelerator) is added on an external mixer (homo-finisher) at 23 ° C, while mixing the whole (productive phase) for about 5 to 12 minutes. The compositions thus obtained are then calendered in the form of plates (thickness of 2 to 3 mm) or of thin rubber sheets for the measurement of their physical or mechanical properties. The rubber properties of these compositions are measured after curing at 150 ° C. for 60 minutes. The results obtained are shown in Table 6. [Table 6]

The rubber composition of the invention C2 exhibits, compared with the comparative composition C1, a significant improvement in the hysteresis properties while having also an increase in linearization (ΔG *) and an improvement in the reinforcement index (MA300 / M100). Surprisingly, this significant improvement in hysteresis does not take place to the detriment of the stiffness properties when cooked. On the contrary, the baked-on stiffness properties are even improved compared to the comparative composition. 5. Test 2 The object of this test is to show the improvement in the reinforcement of a rubber composition comprising a synthetic polyisoprene modified by the compound of the invention (composition C4) compared with a comparative composition (composition C3). The level of the various constituents of these compositions expressed in phr, part by weight per hundred parts by weight of elastomer, are presented in Table 7.

Compositions C3 and C4 comprise the same number of moles of grafted compound A or B, namely 0.3 mole%. Compositions C3 and C4 are prepared according to the process described above for compositions C1 and C2. The rubber properties of these compositions are measured after curing at 150 ° C. for 60 minutes. The results obtained are shown in Table 8. [Table 8]

The rubber composition of the invention C4 exhibits, compared with the comparative composition C3, a significant improvement in the hysteresis properties while also having an increase in linearization (ΔG *) and an improvement in the reinforcement index (MA300 / M100). Surprisingly, this significant improvement in hysteresis does not take place to the detriment of the stiffness properties when cooked. On the contrary, the baked-on stiffness properties are even improved compared to the comparative composition.

Claims

Claims 1. Rubber composition based on at least one diene elastomer, a reinforcing filler, a crosslinking agent and at least one compound of formula (I), optionally already grafted onto said diene elastomer

in which: A represents a C ₆ -C ₁₄ arenediyl ring, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent C ₅ -C ₁₂ hydrocarbon group optionally comprising one or more heteroatoms; - X1, X2, X3, which are identical or different, represent a hydrogen atom, a C ₁ -C ₆ alkyl or a C ₆ -C ₁₄ aryl. 2. Rubber composition according to claim 1, in which E represents is a divalent C ₅ -C10, preferably C ₅ -C ₉ , more preferably C6-C ₉ , more preferably still C7-C _{9 hydrocarbon group.} . 3. Rubber composition according to claim 1 or 2, in which E represents a C ₅ -C10 alkanediyl, preferably a C ₅ -C ₉ alkanediyl, more preferably a C6-C ₉ alkanediyl, more preferably still an alkanediyl. in C7-C ₉ . 4. Rubber composition according to any one of the preceding claims, in which X1, X2, X3, identical or different, are chosen from the group consisting of the hydrogen atom, C ₁ -C ₆ alkyls and C ₆ -C ₁₄ aryls. 5. A rubber composition according to any one of claims 1 to 3, wherein X1, X2, X3 represent a hydrogen atom. 6. A rubber composition according to any one of claims 1 to 3, wherein X1 and X2 represent a hydrogen atom and X3 represents a phenyl. 7. A rubber composition according to any one of claims 1 to 3, in which X3 is a hydrogen atom and the groups X1 and X2, which are identical or different, represent a hydrogen atom or a methyl. 8. Rubber composition according to any one of the preceding claims, in which the compound of formula (I) is chosen from the compounds of formulas (Ia) and (Ib).

wherein E, X1, X2 and X3 are as defined in any one of claims 1 to 7 and the symbol (*) represents the attachment to (Ia) or to (Ib); - the four groups of formula (Ia) chosen from R1 to R5 other than that designating the group of formula (II) and the six groups of formula (Ib) chosen from R1 to R7 other than that designating the group of formula ( II), which are identical or different, represent, independently of one another, a hydrogen atom or an aliphatic hydrocarbon chain, preferably saturated, linear or branched. 9. The rubber composition according to claim 8, in which the compound of formula (I) is chosen from the compounds of formula (Ia) and (Ib) in which: - a group chosen from R1 to R5 of formula (Ia) and a group chosen from R1 to R7 of formula (Ib) denote the following group of formula (II):

wherein E, X1, X2 and X3 are as defined in any one of claims 1 to 7 and the symbol (*) represents the attachment to (Ia) or to (Ib); - the four groups of formula (Ia) chosen from R1 to R5 other than that designating the group of formula (II) and the six groups of formula (Ib) chosen from R1 to R7 other than that designating the group of formula ( II), which are identical or different, represent, independently of one another, a hydrogen atom or a methyl. 10. A rubber composition according to any one of claims 8 to 9, wherein the compound of formula (I) is the compound of formula (Ib). 11. A rubber composition according to any one of claims 1 to 4, wherein the compound of formula (I) is the compound of formula (III).

12. Rubber composition according to any one of the preceding claims, in which the diene elastomer is chosen from the group consisting of ethylene-propylene-diene monomer copolymers, natural rubber, synthetic polyisoprenes, polybutadienes, butadiene copolymers, isoprene copolymers and mixtures of these elastomers. 13. A rubber composition according to any one of the preceding claims, in which the reinforcing filler is chosen from carbon black, an inorganic reinforcing filler and mixtures thereof. 14. Semi-finished article for a tire comprising at least one rubber composition defined in any one of claims 1 to 13. 15. A tire comprising at least one rubber composition defined in any one of claims 1 to 13.