EP4172150A1

EP4172150A1 - Compound comprising an epoxide group

Info

Publication number: EP4172150A1
Application number: EP21746068.2A
Authority: EP
Inventors: François JEAN-BAPTISTE-DIT-DOMINIQUE; Sergey Ivanov; Ruslan NASYBULLIN
Original assignee: Compagnie Generale des Etablissements Michelin SCA
Current assignee: Compagnie Generale des Etablissements Michelin SCA
Priority date: 2020-06-29
Filing date: 2021-06-24
Publication date: 2023-05-03
Also published as: CN115734967A; FR3111894A1; US20230312765A1; FR3111894B1; WO2022003278A1; JP2023530622A

Abstract

The present invention relates to a compound having the following formula (I): wherein: - T is selected from the group consisting of CN⁺-O^-, CH = NOH and CHO; - 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 the process for synthesising compounds having formula (I); a modified polymer obtained by grafting the compound having formula (I) where T = CN⁺-O^-; a composition based on said modified polymer and an additive and a composition based on at least one additive and at least one compound having formula (I) where T = CN⁺-O^-.

Description

COMPOUND INCLUDING AN EPOXIDE GROUP

The field of the present invention is that of modifiers intended to functionalize unsaturated polymers, that is to say polymers carrying unsaturated carbon-carbon bonds in their chains. More specifically, these modifying agents are 1,3-dipolar compounds. The invention also relates to a process for the synthesis of these compounds and their synthesis intermediates.

Modification of the structure of a polymer is particularly desirable when it is desired to bring together a polymer and a filler to form a composition. This modification can make it possible to improve, for example, the dispersion of the filler in a polymer matrix and thus make it possible to obtain a more homogeneous material and ultimately to improve the properties of the composition.

The modification of the structure of the polymers can in particular be carried out by means of functionalizing agents (or modifying agents), coupling or starring or post-polymerization, in particular with the aim of obtaining a good interaction between the polymer thus modified. and the filler, whether carbon black or a reinforcing inorganic filler.

Many functionalizing agents have been proposed to improve the interaction between the filler and the polymer.

For example, document WO2019102132A1 is known, as a functionalizing agent, an aromatic nitrile oxide compound comprising an epoxy ring, the epoxy ring being connected to the aromatic ring carrying the nitrile oxide by a divalent group -OCH2-. This functionalizing agent, 2- (glycidyloxy) -1-naphtonitrile oxide, once grafted onto a copolymer of styrene and butadiene makes it possible to improve the reinforcement index of a composition containing such a modified copolymer and to reduce Significantly the non-linearity of this composition with respect to a 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 an unmodified styrene-butadiene copolymer.

However, there is a constant need for modified polymers, in particular elastomers, in particular modified diene elastomers, which make it possible to obtain compositions having improved hysteresis properties compared to the compositions of the prior art.

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 the other properties, such as reinforcement and rigidity, is a permanent challenge for tire manufacturers. In fact, it is known that a decrease in the hysteresis of rubber compositions can be accompanied by a decrease in the stiffness when cured. However, a tread must be sufficiently rigid to ensure a good level of road behavior of the tire.

An aim of the present invention is therefore to provide new polymer modifying agents which, once grafted to these polymers, make it possible to obtain compositions exhibiting an improvement in the reinforcement index and an improvement in the hysteresis properties without decrease in stiffness properties when cooked.

Continuing his research, the Applicant has surprisingly discovered that an aromatic nitrile oxide, having an epoxy ring linked to the aromatic group carrying the nitrile oxide by a specific -O-alkanediyl group of a specific length, once grafted onto an elastomer comprising unsaturated carbon-carbon bonds made it possible to obtain compositions simultaneously exhibiting 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.

The present invention therefore relates to these nitrile oxide compounds as well as to their synthesis intermediates. Thus, a first object of the present invention therefore relates to a compound of formula (I) in which :

T is selected from the group consisting of CN ⁺ -0 ^~ , CH = NOH and CHO;

- A represents an arenediyl ring in CY, -Ci ₄ , 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; and

- Xi, X _2, X _3, identical or different, represent a hydrogen atom, an alkyl or CI-C _O C _O aryl -CM.

Advantageously, a compound of preferred formula (I) is a compound of formula (Ia) in which :

- A represents an arenediyl ring in CV, -C ₁₄ , optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched;

- Xi, X _2, X _3, identical or different, represent a hydrogen atom, alkyl-C CI _O or a C6-C14.

Advantageously, a preferred compound of formula (I) is a compound of formula (Ib) in which :

- A represents an arenediyl ring in CV, -C ₁ 4, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched;

Advantageously, a preferred compound of formula (I) is a compound of formula (Ie) - A represents an arenediyl ring in CY-C ₁₄ , optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched;

Another subject of the present invention relates to a polymer, preferably an elastomer, in particular diene, modified obtained by grafting at least one compound of formula (Ia) defined above onto at least one unsaturated carbon-carbon bond of the chain. an initial polymer.

Another subject of the present invention relates to a composition based on at least one additive and on at least one polymer, preferably an elastomer, in particular diene, obtained by grafting at least one compound of formula (Ia). .

Another object of the present invention is a composition based on at least one additive and a compound of formula (Ia).

Another object of the present invention is a process for preparing a compound of formula (Ia), said process comprising at least one reaction of a compound of formula (Ib) with an oxidizing agent in the presence of at least one solvent. organic SL1 according to the reaction scheme:

(Ib) (la) with:

- A represents an arenediyl ring in CY, -C14, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched;

- Xi, X _2, X _3, identical or different, represent a hydrogen atom, a C -C alkyl or aryl _O C _O -CM.

As mentioned above, a first object of the present invention therefore relates to a compound of formula (I) in which :

T is selected from the group consisting of CN ⁺ -0 ^~ , CH = NOH and CHO;

E represents a divalent C5-C12 hydrocarbon group optionally comprising one or more heteroatoms; and

- Xi, X2, X3 are identical or different, represent a hydrogen atom, an alkyl or CI-C _O C _O aryl -CM.

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.

By the expression “composition based on” is meant a composition comprising the mixture and / or the in situ reaction product of the various constituents used, some of these constituents being able to react and / or being intended to react with each other, less 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.

The term 1,3-dipolar compound is understood as defined by IUP AC. By definition, a 1,3-dipolar compound comprises a dipole. When T is CN -O, the dipole is a nitrile oxide 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.

The invention and its advantages will be easily understood in the light of the description and the exemplary embodiments which follow.

In the compound of formula (I), the group T is chosen from the group consisting of CN ⁺ -0; CH = NOH and CHO, also represented as follows with the symbol (*) representing the attachment to A.

In accordance with formula (I), the compound according to the invention comprises the group A which represents an arenediyl ring in CY, -Ci ₄ , 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, i.e. consisting of a single ring, or polycyclic, i.e. consisting 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 the atoms) are replaced by one or two or more hydrocarbon chains, aliphatic, preferably saturated, linear or branched. Said chains are also called substituents. If all the hydrogen atoms are replaced by said chains, then the cycle arenediyl is fully 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 cycle and the chemical group represented by the symbol T (called for more conciseness the group T in the remainder of the document).

For the purposes of the present invention, the term “hydrocarbon chain (s) inert with respect to the epoxy ring and to the group T” is understood to mean a hydrocarbon chain which reacts neither with said epoxy cycle nor with said group T. Thus, said hydrocarbon chain inert with respect to said ring and said group T is, for example, a hydrocarbon chain which does not have alkenyl or alkynyl functions capable of reacting with said ring or said group T. 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 in CY-C ₁₄ , optionally substituted by one or more hydrocarbon chain (s), identical or different, saturated in C ₁ -C ₂₄ . More preferably still, the group A is an arenediyl ring in CY-C 1 ₄ , optionally substituted by one or more substituents, identical or different, the substituents being alkyls in C ₁ -C ₁₂ , preferably in Ci -CY ,, more preferably still in C1-C4.

Preferably, the compound of formula (I) according to the invention is chosen from the compounds of formula (II) and the compounds of formula (III) in which: a group chosen from R 1 to R 5 of formula (II) and a group chosen from R 1 to R ₇ of formula (III) denote the following group of formula (IV): in which T, E, Xi, X ₂ and X ₃ are as defined above and below and the symbol (*) represents the attachment of group (IV) to the rest of molecule (II) or

(or); the four groups of formula (II) chosen from R 1 to R ₅ other than that designating the group of formula (IV) and the six groups of formula (III) chosen from R 1 to R ₇ other than that designating the group of formula (IV), 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 (II) and (III), the four groups of formula (II) chosen from R 1 to R ₅ other than that designating the group of formula (IV) and the six groups of formula (III ) chosen from R 1 to R ₇ other than that designating the group of formula (IV), which are identical or different, represent, independently of each other, a hydrogen atom or an aliphatic, saturated, linear or branched, C1- hydrocarbon chain C24.

More preferably still, in the compounds of formulas (II) and (III), the four groups of formula (II) chosen from R 1 to R ₅ other than that designating the group of formula (IV) and the six groups of formula (III) chosen from R 1 to R ₇ other than that designating the group of formula (IV), which are identical or different, are chosen from the group consisting of the hydrogen atom, C ₁ -C ₁₂ alkyls, preferably in C 1 -CY ,, more preferably still in C ₁ -C ₄ .

More preferably still, in the compounds of formulas (II) and (III), the four groups of formula (II) chosen from R 1 to R ₅ other than that designating the group of formula (IV) and the six groups of formula (III) chosen from R 1 to R ₇ other than that designating the group of formula (IV), 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 (II), R ₂ represents a group of formula (IV) and Ri, R ₃ , R ₄ and R ₅ , which are identical or different, represent a hydrogen atom. or an aliphatic hydrocarbon chain, preferably saturated, linear or branched, C ₁ -C ₂₄ . More preferably, R ₂ represents a group of formula (IV) and Ri, R ₃ , R ₄ and R ₅ , identical or different, are chosen from the group consisting of a hydrogen atom and a C ₁ -C _{12 alkyl} , more preferably in CY-CY, more preferably still in C1-C4.

More preferably still in this embodiment, R ₂ represents a group of formula (IV), R ₄ represents a hydrogen atom and R 1, R ₃ and R ₅ represent an aliphatic hydrocarbon chain, preferably saturated, linear or branched, in C ₁ -C ₂₄ . More preferably still, R ₂ represents a group of formula (IV), R ₄ represents a hydrogen atom and R 1, R ₃ and R ₅ , identical or different, represent a C ₁ -C ₁₂ alkyl, more preferably C _I -C _Ô , more preferably still in C ₁ -C ₄ . According to another preferred embodiment of the invention, in formula (III), R 1 represents a group of formula (IV) and R ₂ to R _{7 which are} identical or different, represent a hydrogen atom or an aliphatic hydrocarbon chain, preferably saturated, linear or branched, C ₁ -C ₂₄ . More preferably, R 1 represents a group of formula (IV) and R ₂ to R ₇ , identical or different, are chosen from the group consisting of a hydrogen atom and a C ₁ -C ₁₂ alkyl, more preferably C 1 - CY ,, more preferably still in C ₁ -C ₄ . More preferably still in this embodiment, R 1 represents a group of formula (IV) and R ₂ to R ₇ , which are identical, represent a hydrogen atom.

In the compounds of formula (I), (II) and (III), E represents a divalent C ₅ -C ₁₂ hydrocarbon group which may optionally contain 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 carrying the groups Xi, X ₂ , X ₃ , this spacer group E comprising from 5 to 12 carbon atoms. This spacer group can be a C ₅ -C ₁₂ hydrocarbon chain, 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 T group and the epoxy ring as defined above.

Preferably, in the compounds of formula (I), (II) and (III), E represents a divalent C ₅ -C ₁₀ , preferably C ₅ -C ₉ , more preferably C ₆ -C ₉ , hydrocarbon-based group, more preferably still in C ₇ -C _9, possibly containing one or more heteroatom (s) such as for example N, O and S.

More preferably, in the compounds of formula (I), (II) and (III), E represents a C ₅ -C ₁₀ alkanediyl, preferably a C ₅ -C ₉ alkanediyl, more preferably a CY-CY alkanediyl . more preferably still a C ₇ -C ₉ alkanediyl.

Among the compounds of formula (I), the compounds of formula (Ia) are particularly preferred with

A represents a CY-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; and

Surprisingly, in compound (Ia), when E represents a divalent group of 5 to 12 carbon atoms, the compound of formula (Ia), once grafted onto a polymer, preferably an elastomer in particular diene, confers on the compositions with base of said grafted polymer with 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 formula (Ia), A represents a C ₆ _{-Ci 4} arenediyl ring, optionally substituted by one or more hydrocarbon chain (s), identical or different, saturated in C ₁ -C ₂₄ . More preferably still, the group A is an arenediyl ring in CY-C ₁₄ , optionally substituted by one or more substituents, identical or different, the substituents being alkyls in C ₁ -C ₁₂ , preferably in Ci -CY ,, more more preferably in C ₁ -C ₄ .

Preferably, the compound of formula (Ia) is chosen from the compounds of formula (Ha) and (Dla) in which: a group chosen from R 1 to R ₅ of formula (Ha) and a group chosen from R 1 to R ₇ of formula (Ilia) denote the following group of formula (IV): in which E, Xi, X ₂ and X ₃ are as defined above and the symbol (*) represents the attachment to (Ha) or to (Ilia); the four groups of formula (Ha) chosen from Ri to R ₅ other than that designating the group of formula (IV) and the six groups of formula (Ilia) chosen from R 1 to R ₇ other than that designating the group of formula (IV), 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 (Ha) and (Ilia), the four groups of formula (Ha) chosen from Ri to R ₅ other than that designating the group of formula (IV) and the six groups of formula (Ilia ) chosen from R 1 to R ₇ other than that designating the group of formula (IV), which are identical or different, represent, independently of each other, a hydrogen atom or an aliphatic, saturated, linear or branched, C1- hydrocarbon chain C24.

More preferably still, in the compounds of formulas (Ha) and (Ilia), the four groups of formula (Ha) chosen from R 1 to R ₅ other than that designating the group of formula (IV) and the six groups of formula (Ilia) chosen from R 1 to R ₇ other than that designating the group of formula (IV), which are identical or different, are chosen from the group consisting of the hydrogen atom, C ₁ -C ₁₂ alkyls, preferably in C 1 -CY ,, more preferably still in C ₁ -C ₄ .

More preferably still, in the compounds of formulas (Ha) and (Ilia), the four groups of formula (Ha) chosen from R 1 to R ₅ other than that designating the group of formula (IV) and the six groups of formula (Ilia) chosen from R 1 to R ₇ other than that designating the group of formula (IV), 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 (Ha), R ₂ represents a group of formula (IV) and Ri, R ₃ , R ₄ and R ₅ , which are identical or different, represent a hydrogen atom. or an aliphatic hydrocarbon chain, preferably saturated, linear or branched, C ₁ -C ₂₄ . More preferably, R ₂ represents a group of formula (IV) and Ri, R ₃ , R ₄ and R ₅ , identical or different, are chosen from the group consisting of a hydrogen atom and a C ₁ -C _{12 alkyl} , more preferably in CY-CY, more preferably still in C1-C4. More preferably still in this embodiment, R ₂ represents a group of formula (IV), R ₄ represents a hydrogen atom and R 1, R ₃ and R ₅ represent an aliphatic hydrocarbon chain, preferably saturated, linear or branched, in C ₁ -C ₂₄ . More preferably still, R ₂ represents a group of formula (IV), R ₄ represents a hydrogen atom and R 1, R ₃ and R ₅ , identical or different, represent a C ₁ -C ₁₂ alkyl, more preferably C _I -C _Ô , more preferably still in C ₁ -C ₄ .

According to another preferred embodiment of the invention, in formula (Ilia), R 1 represents a group of formula (IV) and R ₂ to R _{7 which are} identical or different, represent a hydrogen atom or an aliphatic hydrocarbon chain, preferably saturated, linear or branched, C ₁ -C ₂₄ . More preferably, R 1 represents a group of formula (IV) and R ₂ to R ₇ , identical or different, are chosen from the group consisting of a hydrogen atom and a C ₁ -C ₁₂ alkyl, more preferably C ₁ -CV _> , more preferably still in C ₁ -C ₄ . More preferably still in this embodiment, R 1 represents a group of formula (IV) and R ₂ to R ₇ , which are identical, represent a hydrogen atom.

In the compounds of formula (Ia), (Ha) and (Ilia), E represents a divalent C ₅ -C ₁₂ hydrocarbon group which may optionally contain one or more heteroatom (s). Preferably, this spacer group can be a C ₅ -C ₁₂ hydrocarbon chain, preferably saturated, linear or branched, possibly containing one or more heteroatom (s) such as for example N, O and S. Said chain hydrocarbon may optionally be substituted, provided that the substituents do not react with the nitrile oxide group and the epoxy ring as defined above.

Preferably, in the compounds of formula (Ia), (Ha) and (Ilia), E represents a divalent C ₅ -C ₁₀ , preferably C ₅ -C ₉ , more preferably C ₆ -C ₉ , hydrocarbon-based group, more preferably still in C ₇ -C ₉ , possibly containing one or more heteroatom (s) such as for example N, O and S. Surprisingly, when E is this divalent group as described above, then the compounds of formula (Ia), (Ha) and (Ilia), once grafted onto a polymer, preferably an elastomer in particular diene, give the compositions based on said grafted polymer improved hysteresis and reinforcement properties compared with compositions of the prior art. Surprisingly, the improvement of these properties does not take place to the detriment of the baked-on stiffness properties.

More preferably, in the compounds of formula (I), (Ha) and (Ilia), E represents a C ₅ -C ₁₀ alkanediyl, preferably a C ₅ -C ₉ alkanediyl, more preferably a C ₆ - alkanediyl C _9, more preferably still a C ₇ -C ₉ alkanediyl. Surprisingly, when E is this alkanediyl as described above, then the compounds of formula (la), (Ha) and (Ilia), once grafted onto a polymer, preferably an elastomer in particular diene, give the compositions based on said grafted elastomer, improved hysteresis and reinforcement properties compared to the compositions of the prior art. Surprisingly, the improvement of these properties does not take place to the detriment of the baked-on stiffness properties. Preferably, in the compounds of formula (I), (II) and (III) and in the preferred compounds (Ia), (Ha), (Ilia), Xi, X ₂ , X ₃ , which are identical or different, are chosen from the group consisting of hydrogen, alkyl C _I -C _O and aryls CY-C _14.

Preferably, in the compounds of formula (I), (II) and (III) and in the preferred compounds (Ia), (Ha), (Ilia), Xi, X ₂ , X ₃ , which are identical or different, are chosen from the group consisting of hydrogen, methyl, ethyl and phenyl.

According to a preferred embodiment of the invention, in the compounds of formula (I), (II) and (III) and in the preferred compounds (Ia), (Ha), (Ilia), Xi, X ₂ and X ₃ are identical and represent a hydrogen atom.

According to another preferred embodiment of the invention, in the compounds of formula (I), (II) and (III) and in the preferred compounds (Ia), (Ha), (Ilia), Xi and X ₂ represent a hydrogen atom and X ₃ represents a phenyl.

According to another embodiment of the invention, in the compounds of formula (I), (II) and (III) and in the preferred compounds (la), (Ha), (Ilia), X ₃ is an atom d 'hydrogen, and Xi and X ₂ , identical or different, represents a hydrogen atom or a methyl.

Even more preferably, the compound of formula (I) can be the compound of formula (Ilia) in which the group R 1 is the group of formula (IV) with the group E representing a C ₅ -C ₁₀ alkanediyl, preferably a C ₅ -C ₉ alkanediyl, more preferably a C ₆ -C ₉ alkanediyl, more preferably a C ₇ -C ₉ alkanediyl, the groups Xi, X ₂ , X ₃ , which are identical or different, are chosen from the group consisting of the hydrogen atom, C ₁ -CY alkyls, and CY-C ₁₄ aryls (preferably are selected from the group consisting of the hydrogen atom and C 1 - alkyls CY 3), and the groups R ₂ to R _{7, which are} identical or different, represent a hydrogen atom.

A particularly preferred compound of formula (Ia) is the compound of formula (Y):

Among the compounds of formula (I), the compounds of formula (Ib) below are of particular interest because they are preferred intermediates for the synthesis of compounds of formula (Ia): with

- A represents an arenediyl ring in CVC ₁₄ , optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched;

The preferred modes of A, E, Xi, X ₂ , X ₃ described for formulas (I), (II) and (III) also apply to compounds of formula (Ib).

The compounds of formulas (Ia) above are also of particular interest because they are intermediates for the synthesis of the compounds of formula (Ia) preferred: with

The preferred modes of A, E, Xi, X ₂ , X ₃ described for formulas (I), (II) and (III) also apply to compounds of formula (Ie).

Another object of the present invention relates to a process for preparing a compound of formula (Ia) comprising at least one reaction (d) of a compound of formula (Ib) with an oxidizing agent in the presence of at least one solvent. organic SL1 according to the following reaction scheme

(Ib) (ïa ⁾ with:

- Xi, X _2, X 3, identical or different, represent a hydrogen atom, an alkyl or CI-C _O C _O aryl -CM.

Preferred modes of A, E, Xi, X2 and X3 as described above also apply to the process for preparing the compound of formula (Ia) from a compound of formula (Ib).

Preferably, said oxidizing agent is selected from sodium hypochlorite, N-bromosuccinimide in the presence of a base, N-chlorosuccinimide 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 compound of formula (Ib).

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 compound of formula (Ib) represents from 1 to 30% by weight, preferably from 1 to 20% by weight, relative to the total weight of the assembly comprising said compound of formula (Ib), said organic solvent SL1 and said oxidizing agent.

The compound of formula (Ib) can be obtained in particular from a preparation process comprising at least one reaction (c) of a compound of formula (Ie) with an aqueous solution of hydroxylamine NH2OH (compound of formula ( VI)) according to the following reaction scheme:

with

The preferred modes of A, E, Xi, X ₂ and X ₃ as described above also apply to the processes for preparing a compound of formula (Ib) from a compound of formula (Ie) .

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 (Ie) 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 :

E represents a divalent C ₅ -C ₁₂ hydrocarbon group optionally comprising one or more heteroatoms; - Xi, X _2, X _3, identical or different, represent a hydrogen atom, an alkyl or CI-C _O C _O aryl -CM;

Z represents a nucleofuge group.

Preferred modes of A, E, Xi, X ₂ and X ₃ also apply to the process for preparing a compound of formula (Ie) from compounds of formula (VIII) and compounds of formula (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 Ag20), a phase transfer catalyst of quaternary ammonium type and theirs. mixtures.

The compounds of formula (VII) as defined above are commercially available from suppliers such as Sigma -Aldrich, Merk, Chimieliva, etc.

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 epoxidation can be carried out in the presence of a peracid such as metachloroperbenzoic acid, peracetic acid, performic acid. Another well known technique is the use of dimethyl dioxirane.

(IX) (VIII) with E represents a divalent C5-C12 hydrocarbon group optionally comprising one or more heteroatoms;

- Xi, X _2, X _3, identical or different, represent a hydrogen atom, an alkyl or CI-C _O C _O aryl -CM;

Z represents a nucleofuge group as described above.

Preferred modes of E, Xi, X2 and X3 are also applicable to the process of preparing a compound of formula (VIII) from compounds of formula (IX).

Compounds of formula (IX) are commercially available from suppliers such as Sigma Aldrich, ABCR.

As explained previously, the compounds of formula (Ia) and its preferred embodiments, in particular the compound of formula (V), are used as a functionalizing agent. They can be grafted onto one or more polymers comprising at least one unsaturated carbon-carbon bond, in particular this polymer can be an elastomer and more particularly a diene elastomer. The compounds of the invention advantageously make it possible to obtain graft polymers (also called modified polymers), in particular elastomers, in particular grafted diene elastomers, whatever the initial microstructure of the polymer, the only condition being that the polymer comprises at least one bond. unsaturated carbon-carbon, preferably a carbon-carbon double bond.

The grafting of the polymer comprising at least one unsaturated carbon-carbon bond is carried out by reaction of the initial polymer with the compound of formula (Ia) and its preferred embodiments, in particular the compound of formula (V). The grafting of these compounds is carried out by cycloaddition [3 + 2] of the nitrile oxide of said compounds on an unsaturated carbon-carbon bond of the polymer chain. The mechanism of this cycloaddition is in particular illustrated in document WO2012 / 007441. During this reaction, said compound of formula (Ia) and its preferred embodiments, in particular the compound of formula (V), forms covalent bonds with the polymer chain.

The grafting of the compound of formula (Ia) and its preferred embodiments, in particular the compound of formula (V), can be carried out in bulk, for example in an internal mixer or in an external mixer such as a roller mixer. , or in solution. The grafting process can be carried out in solution continuously or batchwise. The modified polymer can be separated from its solution by any type of means known to those skilled in the art and in particular by a steam stripping operation.

Thus, another subject of the present invention is a modified polymer obtained by grafting at least one compound of formula (Ia) defined above and its preferred embodiments, in particular the compound of formula (V), onto at least one unsaturated carbon-carbon bond of the chain of an initial polymer.

For the purposes of the present invention, the term “initial polymer chain” is understood to mean the polymer chain before the grafting reaction; this chain comprising at least one bond unsaturated carbon-carbon capable of reacting with the compound of formula (Ia) described above. The initial polymer is therefore the polymer serving as the starting reagent during the grafting reaction. The grafting reaction makes it possible, starting from an initial polymer, to obtain a modified polymer.

Another object of the present invention is a composition based on an additive (preferably the additive is a polymer, more preferably an elastomer, in particular a diene) and on at least one compound of formula (Ia) defined above (and its preferred embodiments, in particular the compound of formula (V)). Another subject of the present invention is a composition based on at least one additive and on at least one polymer modified with a compound of formula (Ia) defined above (and its preferred embodiments, in particular the compound of formula (V). Preferably, the additive can be any additive usually used in rubber compositions, in particular those intended to equip the tires. The additives which can be used in the composition according to the invention can be plasticizers (such as plasticizing oils). and / or plasticizing resins), fillers (reinforcing or not reinforcing) pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, anti-oxidants, anti-fatigue agents, reinforcing resins (such as described for example in application WO 02/10269), a crosslinking system, for example based on sulfur and other vulcanizing agents, and / or peroxide and / or bismaleimide.

In addition to the objects described above, the invention relates to at least one of the objects described in the following embodiments:

1. Compound of formula (I) below in which :

T is selected from the group consisting of CN ⁺ -0; CH = NOH and CHO;

- A represents an arenediyl ring in CV, -C 1 ₄ , optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched;

2. Compound of formula (I) according to embodiment 1, in which T is CH = NOH. 3. Compound of formula (I) according to embodiment 1, in which T is CHO.

4. Compound of formula (I) according to embodiment 1, in which T is CN ⁺ -0 ·

5. Compound of formula (I) according to any one of embodiments 1 to 4, in which E represents is a divalent C ₅ -C ₁₀ , preferably C ₅ -C ₉ , more preferably C ₆ - hydrocarbon-based group. C ₉ , more preferably still in C ₇ -C ₉ .

6. Compound of formula (I) according to any one of embodiments 1 to 4, in which E represents a C ₅ -C ₁₀ alkanediyl, preferably a C ₅ -C ₉ alkanediyl, more preferably a C _{6 alkanediyl.} -C _9, more preferably still a C7-C ₉ alkanediyl. 7. Compound of formula (I) according to any one of the preceding embodiments, in which Xi,

X _2, X _3, identical or different, are selected from the group consisting of hydrogen, alkyls CI _C-O and the aryl C6-C14.

8. A compound of formula (I) according to any one of embodiments 1 to 6, in which Xi, X2, X3, identical or different, represent a hydrogen atom, a methyl, an ethyl or a phenyl.

9. Compound of formula (I) according to any one of embodiments 1 to 6, in which X ₁ , X _{2, X 3} represent a hydrogen atom.

10. Compound of formula (I) according to any one of embodiments 1 to 6, in which X ₁ and X 2 represent a hydrogen atom and X ₃ represents a phenyl. 11. Compound of formula (I) according to any one of embodiments 1 to 6, in which X ₃ is a hydrogen atom and the groups Xi and X2, which are identical or different, represent a hydrogen atom or a methyl.

12. Compound of formula (I) according to any one of the preceding embodiments, which compound of formula (I) is chosen from the compounds of formula (II) and (III) in which : a group chosen from R 1 to R 5 of formula (II) and a group chosen from R 1 to R 7 of formula (III) denote the following group of formula (IV): in which T, E, Xi, X2 and X3 are as defined in any one of embodiments 1 to 11 and the symbol (*) represents the attachment to (II) or to (III), the four groups of the formula (II) chosen from R 1 to R5 other than that designating the group of formula (IV) and the six groups of formula (III) chosen from R 1 to R7 other than that designating the group of formula (IV), which are identical or different, represent, independently of one another, a hydrogen atom or an aliphatic hydrocarbon chain, preferably saturated, linear or branched.

13. A compound of formula (I) according to any one of embodiment 12, which compound of formula

(I) is chosen from the compounds of formula (II) and (III) in which a group chosen from R 1 to R 5 of formula (II) and a group chosen from R 1 to R 7 of formula (III) denote the group of following formula (IV): in which E, Xi, X2 and X3 are as defined in any one of embodiments 1 to 11 and the symbol (*) represents the attachment to (II) or to (III), the four groups of formula (II ) chosen from R 1 to R5 other than that designating the group of formula (IV) and the six groups of formula (III) chosen from R 1 to R7 other than that designating the group of formula (IV), which are identical or different, independently represent from each other, a hydrogen atom or a methyl.

14. Compound of formula (I) according to any one of embodiments 4 to 7, which compound of formula (I) is the compound of formula (V)

Modified polymer obtained by grafting at least one compound of formula (I) defined according to any one of embodiments 4 to 14 onto at least one unsaturated carbon-carbon bond of the chain of an initial polymer.

16. Modified polymer according to embodiment 15, which initial polymer is an elastomer, preferably a diene elastomer.

17. Composition based on at least one additive and on a compound of formula (I) defined according to any one of embodiments 4 to 14

18. Composition according to embodiment 17, in which the additive is a polymer, preferably an elastomer, in particular a diene elastomer.

19. Composition based on at least one additive and / or on a polymer as defined according to any one of the embodiments 15 to 16.

20. Process for preparing a compound of formula (Ia), said process comprising at least one reaction of a compound of formula (Ib) with an oxidizing agent in the presence of at least one organic solvent SL1 according to the reaction scheme.

(Ib) (la) with:

- A represents an arenediyl ring in CV, -Ci ₄ , optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched;

- Xi, X 2, X _3, identical or different, represent a hydrogen atom, an alkyl or CI-C _O C _O aryl -CM. 21. Process according to embodiment 20, further comprising a step of reacting a compound of formula (Ie) with an aqueous solution of hydroxylamine NH2OH according to the following reaction scheme: with

- A represents an arenediyl ring in CV, -C 14, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched;

E represents a divalent C5-C12 hydrocarbon group optionally comprising one or more heteroatoms;

22. Method according to embodiment 21, further comprising a step of reacting 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 a C6-C14 arenediyl ring, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched;

E represents a divalent C5-C12 hydrocarbon group optionally comprising one or more heteroatoms; - Xi, X2, X3 are identical or different, represent a hydrogen atom, alkyl-C CI _O or a C6-C14;

Z represents a nucleofuge group.

23. Process according to any one of embodiments 20 to 22, in which E represents is a divalent C5-C10, preferably C5-C9, more preferably C6-C9, more preferably still C7-C9 hydrocarbon group.

24. Process according to any one of embodiments 20 to 22, in which E represents a C ₅ -C ₁₀ alkanediyl, preferably a C ₅ -C ₉ alkanediyl, more preferably a C ₆ -C ₉ alkanediyl. more preferably still a C ₇ -C ₉ alkanediyl.

25. A method according to any of the embodiments 20 to 22, wherein Xi, X2, X3 are identical or different, are selected from the group consisting of hydrogen, alkyls CI-C _O and aryls C6-C14.

26. A method according to any one of embodiments 20 to 24, in which X1, X2, X3, identical or different, represent a hydrogen atom, a methyl, an ethyl or a phenyl.

27. A method according to any one of embodiments 20 to 24, wherein Xi, X2, X3 represent a hydrogen atom.

28. A method according to any one of embodiments 20 to 24, wherein X1 and X2 represent a hydrogen atom and X3 represents a phenyl.

29. Process according to any one of embodiments 20 to 24, in which X3 is a hydrogen atom and the groups Xi and X2, identical or different, represent a hydrogen atom or a methyl.

Examples:

The examples which follow illustrate the invention; however, the latter cannot be limited to these examples alone.

1 Methods

1.1 Measurement of number-average molar masses (Mn). by weight and 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 polydispersity 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 chromatographic data processing software 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 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 BBLO-zgrad 5 mm” probe. The quantitative 1 H NMR experiment 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 1 H NMR spectrum coupled to the 2D HSQC ¹ H / ^{1 '} C and HMBC ¹ H / ^1' C experiments allow the structural determination of the molecules (cf. allocation tables). The molar quantifications are carried out from the quantitative 1D ′ H NMR spectrum.

Mass spectrometry analysis is performed by direct injection by an electrospray ionization mode (ID / ESI). Analyzes were performed on a Bruker HCT spectrometer (flow rate 600 pL / min, nebulizer gas pressure 10 psi, nebulizer gas flow rate 4 L / min).

1.3. Characterizations of compounds grafted on 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 “CryoSonde BBLO-zgrad-5 mm”. The quantitative 1 H NMR experiment uses a 30 ° single pulse sequence and a 5 second repetition delay between each acquisition. The samples are solubilized in deuterated chloroform (CDCb) 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 rubber compositions

The dynamic properties G * and tan (ô) max are measured on a viscoanalyst (Metravib VA4000), according to standard ASTM D5992-96. The response of a sample of vulcanized composition is recorded (cylindrical test piece 4 mm thick and 400 mm ² 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 (ô) at 60 ° C and the difference in modulus (AG *) between the values at 0.1% and 100% deformation (Payne effect). For the return, one records the value of the complex dynamic shear modulus G * at 25% deformation, note G * 25% return at 60 ° c and the maximum value of the dynamic loss factor tan (ô) observed, noted tan (§ ) max at 60 ° C.

The results are indicated in base 100; the arbitrary value 100 being attributed to the control in order to calculate and then compare tan (ô) _max at 6o ° C, G * 25% return at 6o ° C and AG * of the different samples tested.

For tan (ô) _max at 6o ° c, the value in base 100 for the sample to be tested is calculated according to the operation: (value of tan (ô) _max at 6o ° c of the sample to be tested / value of tan (ô) _max at 60 ° C of the control) x 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 to 6o ° c, the value in base 100 for the sample to be tested is calculated according to the operation: (value of G * 25% return to 6o ° c of the sample to be tested / value of G * 25% return to 6o ° c of the control) x 100. In this way, a result greater than 100 indicates an improvement in the complex dynamic shear modulus G * 25% return to 6o ° c, which corroborates an improvement in the rigidity of the material.

For (AG *), the value in base 100 for the sample to be tested is calculated according to the operation: (value of AG * of the sample to be tested / value of AG * of the control) x 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 make it possible 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 in first elongation. All of 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) x 100. In this way, a result greater than 100 indicates an improvement in the reinforcement index.

2. Synthesis of compounds

2.L Synthesis of compound A: 2- (Y9-oxiran-2yl) nonyl) oxy) -l -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 al: preparation of 2- (9-bromonony0oxirane

10 g of 11-Bromo-l-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 NaHSCL (40 g of NaHSCL 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 NaHCCL (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 Na ₂ SC> ₄ 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% ( ¹ H NMR).

[Table 1]

Solvent CDCI3

2 1 2 Step a2: Synthesis of 2- (Y9- ( ^' oxiran-2-yl) nonyl) oxy) - 1 -naphthaldehydc A suspension of 2-hydroxy-1-naphthaldehyde (11.05g; 64.2 mmol), of

2- (9-bromononyl) oxirane (15.99g; 64.2 mmol) and K2CO3 (8.87g; 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%.

[Table 2]

Solvent: CDCb

2 1.3 Step a3: Synthesis of 2-tt9-toxiran-2-yl) nonyl) oxy) - 1 -naphthaldehydc oxime

1.521 g of hydroxylamine (23.02 mmol or 1.5 equivalents) are added, at room temperature 20 ° C, to a suspension of 2 - ((9- (oxiran-2-yl) nonyl) oxy) -l -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 mixture of distilled water: ethanol (1: 1, v / v); then is air dried. A yellow solid (4.979 g, 14.01 mmol, yield 91%) is obtained. The molar purity is 93% (NMR)

Solvent: CDCb

2 1 4 Step a4: Synthesis of 2-tt9-toxiran-2-yl) nonyl) oxy) -l -naphthonitrilc N-oxide (Compound

AT)

1.824 g of trimethylamine (18.03 mmol) and 2.037 g of N-chlorosuccinimide (15.25 mmol) are added in several portions over 10 to 12 min to a solution of 2 - ((9- (oxiran-2-yl) nonyl) oxy) -1-naphthaldehyde oxime (4.929 g; 13.87 mmol) in 100 ml of CHCl3 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 (1 = 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, 94% yield) melting point 52-53 ° C is obtained. The molar purity is 92% ( ¹ H NMR).

[Table 4] Solvent: CDCb

2.2. Synthesis of 2- (glvcidyloxy) -l-naphtonitrile oxide

2- (Glycidyloxy) -1-naphtonitrile oxide, compound B, is synthesized according to the procedure described in patent application US20120046418 A1.

3. Obtaining modified diene elastomers

3.1 Rubber modified with compound A

The oxide of 2 - ((9- (oxiran-2-yl) nonyl) oxy) -l-naphthonitrile (811 mg; 2.3 mmol or a molar fraction of 0.3 mol%) is incorporated, 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 mixing phase is followed by a heat treatment at 120 ° C. for 10 min in a press at 10 bar pressure.

The 1 H NMR analysis 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

2- (glycidyloxy) -l-naphtonitrile oxide (564 mg, 2.34 mmol or a molar fraction of 0.3% mol), of NMR purity of 94% mol, compound B, is incorporated into 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) -l-naphthonitrile (811 mg; 2.3 mmol or a molar fraction of 0.3 mol%) is incorporated, 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) -l-naphtonitrile oxide (564 mg, 2.34 mmol or a molar fraction of 0.3% mol), of NMR purity of 94% mol, compound B, is incorporated into 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 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.

4. Ingredients used in rubber compositions

(1) “Zeosil 1165MP” silica sold 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 to a comparative composition (composition C1).

Fe levels 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. [Table 5]

Compositions C1 and C2 comprise the same number of moles of grafted compound A or B, namely 0.3 mole%.

Cl and C2 compositions are prepared as follows: there is introduced into an internal mixer "Polylab" of 85 cm ^3, filled to 70% and an initial chamber temperature was about 110 ° C, the natural rubber modified by compound A or by compound B.

Then, for each of the compositions, one or more 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 to the comparative composition C1 a significant improvement in the hysteresis properties while also having an increase in linearization (AG *) and an improvement in the reinforcement index (MA300 / M100). Surprisingly, this significant improvement in hysteresis does not come at the expense of fired stiffness properties. On the contrary, the baked-on stiffness properties are even improved compared to the comparative composition.

5. Test 2

The purpose 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 to 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.

[Table 7] Compositions C3 and C4 comprise the same mol number of grafted compound A or B, namely 0.3 mol%.

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 to the comparative composition C3 a significant improvement in the hysteresis properties while also having an increase in linearization (AG *) and an improvement in the reinforcement index (MA300 / M100). Surprisingly, this significant improvement in hysteresis does not come at the expense of fired stiffness properties. On the contrary, the baked-on stiffness properties are even improved compared to the comparative composition.

Claims

1. Compound of formula (I) below: in which :

T is selected from the group consisting of CN ⁺ -0; CH = NOH and CHO;

2. A compound of formula (I) according to claim 1, wherein T is CH = NOH.

3. A compound of formula (I) according to claim 1, wherein T is CHO.

4. A compound of formula (I) according to claim 1, wherein T is CN ⁺ -0 ·

5. Compound of formula (I) according to any one of claims 1 to 4, in which E represents a divalent C ₅ -C ₁₀ , preferably C ₅ -C ₉ , more preferably C ₆ -C. ₉ , more preferably still in C ₇ -C ₉ .

6. Compound of formula (I) according to any one of claims 1 to 4, in which E represents a C5-C10 alkanediyl, preferably a C5-C9 alkanediyl, more preferably a C6-C9 alkanediyl, more preferably. still a C7-C9 alkanediyl.

7. Compound of formula (I) according to any one of the preceding claims, in which X1, X2, X3, which are identical or different, are chosen from the group consisting of the hydrogen atom, a methyl, an ethyl or a phenyl. .

8. A compound of formula (I) according to any one of claims 1 to 6, wherein Xi, X2, X3 represent a hydrogen atom.

9. A compound of formula (I) according to any one of the preceding claims, which compound of formula (I) is chosen from the compounds of formula (II) and (III).

in which: a group chosen from R 1 to R ₅ of formula (II) and a group chosen from R 1 to R 7 of formula (III) denote the following group of formula (IV): in which T, E, Xi, X ₂ and X ₃ are as defined in any one of claims 1 to 8 and the symbol (*) represents the attachment to (II) or to (III), the four groups of formula (II) chosen from R 1 to R ₅ other than that designating the group of formula (IV) and the six groups of formula (III) chosen from R 1 to R 7 other than that designating the group of formula (IV), which are identical or different, independently of one another, a hydrogen atom or an aliphatic hydrocarbon chain, preferably saturated, linear or branched.

10. A compound of formula (I) according to claim 9, which compound of formula (I) is the compound of formula (V)

11. Modified polymer obtained by grafting at least one compound of formula (I) defined according to any one of claims 4 to 10 onto at least one unsaturated carbon-carbon bond of the chain of an initial polymer.

12. Composition based on at least one additive and on a compound of formula (I) defined according to any one of claims 4 to 10 or on a polymer defined according to claim 11.

13. Process for preparing a compound of formula (Ia), said process comprising at least one reaction of a compound of formula (Ib) with an oxidizing agent in the presence of at least one organic solvent SL1 according to the reaction scheme.

(Ib) (la) with:

14. The method of claim 13 further comprising a step of reacting a compound of formula (Ie) with an aqueous solution of hydroxylamine NH2OH according to the following reaction scheme: with - A represents an arenediyl ring in CV, -C ₁₄ , 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;

15. The method of claim 14 further comprising a step of reacting 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 :

- Xi, X _2, X _3, identical or different, represent a hydrogen atom, alkyl-C CI _O or a C6-C14;

Z represents a nucleofuge group.