Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
  • C07D233/61—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms not forming part of a nitro radical, attached to ring nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/22—Incorporating nitrogen atoms into the molecule

Definitions

• the present invention relates to novel 1,3-dipolar compounds comprising a heteroaromatic ring, said 1,3-dipolar compounds being capable of being grafted onto a polymer.
• a subject of the present invention is also a process for preparing these novel compounds.
• the modification of the structure of a polymer is particularly sought after when it is desired to bring together a polymer and a filler in 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, in fine, to improve the properties of the composition.
• the Applicant has continued his research and has sought to improve 1,3-dipolar compounds having an imidazole ring. After numerous tests, the Applicant has discovered that a family of particular 1,3-dipolar compounds exhibits an improved grafting yield compared to the 1,3-dipolar compounds of the prior art comprising an aromatic or non-aromatic ring and a imidazole cycle.
• - Q represents a dipole comprising at least one nitrogen atom
• - A represents a divalent heteroaromatic ring optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms;
• - E represents a divalent hydrocarbon bonding group which may optionally contain one or more heteroatoms
• - Ri represents a hydrogen atom or a C1-C20 alkyl group
• Y and Z identical or different, each represent a hydrogen atom or a hydrocarbon chain
• Y and Z can also together form a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached.
• the compound of formula (I) is chosen from the compounds of formula (Ha)
• - A represents a divalent heteroaromatic ring optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms;
• - E represents a divalent hydrocarbon bonding group which may optionally contain one or more heteroatoms
• - Ri represents a hydrogen atom or a C 1 -C 20 alkyl group
• Y and Z identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z can also together form a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached;
• R 2 is chosen from a hydrogen atom, a linear or branched C 1 -C 20 alkyl, a C 3 -C 20 cycloalkyl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and a C 6 -C 20 aryl optionally substituted by one or more aliphatic, preferably saturated, linear or branched hydrocarbon-based chains; and
• R 3 is selected from the group consisting of alkyl C 1 -C 20 linear or branched, cycloalkyl C 3 -C 20 optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and the aryl C 6 -C 20 optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon chains.
• Another object of the present invention is a process for the synthesis of a compound of formula (Ha) as defined above, comprising at least one reaction of a compound of formula (III) with a compound of formula (IV) according to the following reaction scheme
• A represents a divalent heteroaromatic ring optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms;
• - E represents a divalent hydrocarbon bonding group which may optionally contain one or more heteroatoms;
• - Ri represents a hydrogen atom or a C 1 -C 20 alkyl group
• Y and Z identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z can also together form a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached;
• R 2 is chosen from a hydrogen atom, a linear or branched C 1 -C 20 alkyl, a C 3 -C 20 cycloalkyl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched, and a C 6 -C 20 aryl optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon-based chains; and R 3 is selected from the group consisting of alkyl C 1 -C 20 linear or branched, cycloalkyl C 3 -C 20 optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and the aryl C 6 -C 20 optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon chains.
• 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 bounds 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 interval represented by the expression "between a and b" is also and preferably designated.
• heteroatom an atom selected from the group consisting of a sulfur atom, an oxygen atom and a nitrogen atom.
• the compounds comprising carbon mentioned in the description can be of fossil or biobased origin. In the latter case, they can be partially or totally derived from biomass or obtained from renewable raw materials derived from biomass. This concerns in particular polymers, plasticizers, fillers, etc.
• - Q represents a dipole comprising at least one nitrogen atom
• - A represents a divalent heteroaromatic ring optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms;
• - E represents a divalent hydrocarbon bonding group which may optionally contain one or more heteroatoms
• - Ri represents a hydrogen atom or a C1-C20 alkyl group
• Y and Z identical or different, each represent a hydrogen atom or a hydrocarbon chain
• Y and Z can also together form a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached.
• the compound according to the invention contains a Q group designating a dipole which comprises at least one nitrogen atom.
• dipole is understood to mean a function capable of forming a 1,3-dipolar addition on an unsaturated carbon-carbon bond.
• the dipole comprising at least one nitrogen atom is selected from the group consisting of nitrile oxide, nitrone and nitrile imine.
• nitrile oxide means a dipole corresponding to the formula -CoN®0, including its mesomeric forms.
• nitrile imine is understood to mean a dipole corresponding to the formula —CoN®N, including its mesomeric forms.
• Q is a group of formula (II), (III) or (IV) in which :
• R 2 and R 4 are chosen, independently of one another, from a hydrogen atom, a linear or branched C 1 -C 20 alkyl, a C 3 -C 20 cycloalkyl optionally substituted by one or several aliphatic hydrocarbon chains, preferably saturated, linear or branched, and a C 6 -C 20 aryl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched;
• R 3 is selected from the group consisting of alkyl C 1 -C 20 linear or branched, cycloalkyl C 3 -C 20 optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and the aryl C 6 -C 20 optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon chains.
• R 2 and R 4 are chosen independently of one another from a hydrogen atom, a linear or branched C 1 -C 20 alkyl, a C 3 -C 30 cycloalkyl optionally by one or more C I -C O, linear or branched, aryl C (- C 20 optionally substituted by one or more C I -C O linear or branched, and R is selected from the group consisting of alkyls C 1 -C 20 linear or branched, cycloalkyl C 3 -C 20 optionally substituted by one or more C I -C O linear or branched and the aryl in C 6 -C 20 optionally substituted by one or more alkyl in C I -C ⁇ , linear or branched.
• the compound of formula (I) is chosen from the compounds of formula (Ha)
• - A represents a divalent heteroaromatic ring optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms;
• - E represents a divalent hydrocarbon bonding group which may optionally contain one or more heteroatoms
• - Ri represents a hydrogen atom or a C 1 -C 20 alkyl group
• Y and Z identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z can also together form a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached;
• R 2 is chosen from a hydrogen atom, a linear or branched C 1 -C 20 alkyl, a C 3 -C 20 cycloalkyl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and a C 6 -C 20 aryl optionally substituted by one or more aliphatic, preferably saturated, linear or branched hydrocarbon-based chains; and
• R 3 is selected from the group consisting of alkyl C 1 -C 20 linear or branched, cycloalkyl C 3 -C 20 optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and the aryl C 6 -C 20 optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon chains.
• the compounds of the invention of formula (I) and (Ha) contain a group A which represents a divalent heteroaromatic ring optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms.
• divalent heteroaromatic ring is meant a cyclic aromatic system comprising one or more heteroatoms selected from the group consisting of nitrogen, sulfur and oxygen.
• This system can be monocyclic or bicyclique and can be formed from 5 to 10 atoms. Preferably, this system is monocyclic and is formed from 5 to 6 atoms.
• This system can optionally be substituted with one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms such as, for example, O, N and S.
• the divalent heteroaromatic ring is substituted by one or more hydrocarbon chains, identical or different, aliphatic, linear or branched, optionally substituted or interrupted by one or more heteroatoms
• this chain or chains are preferably inert with respect to the imidazole ring carrying the substituents R 1, X and Y and with respect to the Q group.
• hydrocarbon chain (s) inert with respect to the imidazole ring bearing the substituents R 1, X and Y and vis-à-vis the group Q is understood to mean. a hydrocarbon chain which reacts neither with said imidazole heterocycle nor with said group Q.
• said hydrocarbon chain inert with respect to said heterocycle and to said group is, for example, a hydrocarbon chain which does not have alkenyl or alkynyl functions, capable of react with this cycle or group.
• these linear or branched aliphatic hydrocarbon chains contain from 1 to 24 carbon atoms and are saturated.
• A is a divalent heteroaromatic ring formed from 5 to 10 atoms, preferably from 5 to 6 atoms, optionally substituted by one or more C1-C24 hydrocarbon chains, identical or different, aliphatic, linear or branched, optionally substituted or interrupted by one or more heteroatoms.
• A is a divalent heteroaromatic ring formed from 5 to 10 atoms, preferably from 5 to 6 atoms, optionally substituted by one or more substituents chosen from the group consisting of by linear or branched alkyls, in C1-C12, (more preferably in C I -C ⁇ , more preferably still in C1-C4), groups -OR ', groups -NHR', groups -SR 'where R is an alkyl C1-C12, preferably C I -C O, more preferably C1-C4.
• A is chosen from furan-diyl, thiophene-diyl, pyrrole-diyl, thiazol-diyl, imidazole-diyl, pyridine-diyl , pyrazine-diyl, pyrimidin-diyl, indole-diyl, benzofuran-diyl, risoindole-diyl, isobenzofuran-diyl and benzothiophene-diyl; these rings being optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, optionally substituted or interrupted by one or more heteroatoms such as, for example, O, N and S; more preferably these rings may be substituted by one or more C I -C ⁇ . More preferably still, these rings are not substituted.
• A is chosen from furan-diyl, thiophene-diyl, pyrrole-diyl, more preferably still is furan-diyl.
• - X represents a heteroatom chosen from among the sulfur atom, the oxygen atom or the nitrogen atom, preferably X is an oxygen atom;
• - E represents a divalent hydrocarbon bonding group which may optionally contain one or more heteroatoms
• - Ri represents a hydrogen atom or a C 1 -C 20 alkyl group
• Y and Z identical or different, each represent a hydrogen atom or a hydrocarbon group, Y and Z can also together form a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached;
• R 2 is chosen from a hydrogen atom, a linear or branched C 1 -C 20 alkyl, a C 3 -C 20 cycloalkyl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and a C 6 -C 20 aryl optionally substituted by one or more aliphatic, preferably saturated, linear or branched hydrocarbon-based chains; and
• R 3 is selected from the group consisting of alkyl C 1 -C 20 linear or branched, cycloalkyl C 3 -C 20 optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and the aryl C 6 -C 20 optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon chains.
• the compounds of the invention of formula (I), (Ha) and (IIb) contain a group E which represents a divalent hydrocarbon bonding group which may optionally contain one or more heteroatoms.
• the term “divalent hydrocarbon bonding group” means a spacer group forming a bridge between the group A and the imidazole ring carrying the substituents R 1, X and Y, this spacer group being a hydrocarbon chain, aliphatic, preferably saturated, linear or branched, preferably C 1 -C 24 , 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 group Q and the imidazole ring carrying the substituents R 1, X and Y.
• E is chosen from hydrocarbon-based, aliphatic, saturated, linear or branched chains, in C 1 -C 24 , more preferably in C 1 -C 10 , even more preferably in C I -C ⁇ , optionally interrupted by one or more heteroatom (s), such as N, S and O.
• s heteroatom
• E is chosen from the group consisting of -R-, -NH-R-, -OR- and -SR- with R a linear or branched alkylene C 1 -C 24, preferably C 1 -C 10, more preferably C I -C ⁇ .
• E is chosen from the group consisting of -R- and -OR- with R being a linear or branched C 1 alkylene -C 24 , preferably C 1 -C 10 , more preferably C I -C ⁇ .
• E is chosen from -CH 2- , -CH 2- CH 2- , -CH 2- CH 2- CH 2- , -CH 2- CH 2- CH 2- , -CH 2- CH 2- CH 2- CH 2- , -0-CH 2- , -0-CH 2- CH 2- , -0-CH 2- CH 2- CH 2- and -0- CH 2- CH 2- CH 2- CH 2-
• E is chosen from a linear or branched C 1 -C 24 alkylene, preferably C 1 -C 10 , more preferably in C I -C ⁇ , more preferably still is chosen from -CH 2- ,
• E is chosen from -CH 2- , -CH 2- CH 2- , -CH 2- CH 2- CH 2- and -CH 2- CH 2- CH 2- CH 2-
• the compounds of the invention of formula (I), (Ha) and (Ilb) contain a group R 1 which represents a hydrogen atom or a C 1 -C 2 alkyl group.
• R 1 represents a hydrogen atom or a C 1 -C 6 alkyl group , preferably methyl.
• These alkyl groups can be linear or branched.
• the compounds of the invention of formula (I), (Ha) and (Ilb) contain groups Y and Z, identical or different, which each represent a hydrogen atom or a hydrocarbon chain, Y and Z possibly also forming together a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached.
• Y and Z which are identical or different, each represent a hydrogen atom or an alkyl, linear or branched, in Ci-C 24, preferably C 1 -C 10, more preferably C I -C O, Y and Z may also together form a ring, including aromatic, with the carbon atoms of imidazole ring to which they are attached.
• Y and Z are a hydrogen atom.
• Y and Z together form an aromatic ring with the carbon atoms of the imidazole ring to which they are attached, from preferably Y and Z form a benzene ring with the carbon atoms of the imidazole ring to which they are attached.
• R 2 represents a hydrogen atom or a group chosen from linear or branched C 1 -C 20 alkyls, optionally substituted C 3 -C 20 cycloalkyls. alkyl-SO-O or C aryl, C 6 -C 20 optionally substituted alkyl C I -C ⁇ .
• R 3 is selected from alkyl C 1 -C 20 linear or branched, cycloalkyl C 3 -C 20 optionally substituted with alkyl CI-C O or aryl, C 6 -C 20 optionally substituted by a C I -C ⁇ .
• R 2 is a hydrogen atom and R 3 is selected from alkyl C 1 -C 20 aryl and C 6 -C 20.
• R 2 is a hydrogen atom and R 3 is phenyl.
• a subject of the invention is also a process for preparing a compound (Ha) as defined above, said process comprising at least one reaction (c) of a compound of formula (III) with a compound of formula ( IV) according to the following reaction scheme
• - A represents a divalent heteroaromatic ring optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms;
• - E represents a divalent hydrocarbon bonding group which may optionally contain one or more heteroatoms
• - Ri represents a hydrogen atom or a C 1 -C 20 alkyl group
• Y and Z identical or different, each represent a hydrogen atom or a hydrocarbon group, Y and Z can also together form a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached;
• R 2 is chosen from a hydrogen atom, a linear or branched C 1 -C 20 alkyl, a C 3 -C 20 cycloalkyl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and a C 6 -C 20 aryl optionally substituted by one or more aliphatic, preferably saturated, linear or branched hydrocarbon-based chains; and
• R 3 is selected from the group consisting of alkyl C 1 -C 20 linear or branched, cycloalkyl C 3 -C 20 optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and the aryl C 6 -C 20 optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon chains.
• Preferred modes of A, E, Ri, R 2 , R 3 Y and Z also apply to the process for preparing a compound of formula (Ha) from a compound of formula (III) and formula ( IV).
• the compound of formula (IV) is commercially available from suppliers such as Sigma Aldrich, Fischer ...
• the process for preparing the compound for preparing a compound (Ha) as defined above further comprises at least one reaction (b) of a compound of formula (V) with at least one compound of formula (IV ) to form the compound of formula (III)
• the T group is chosen from chlorine, bromine, iodine, fluorine, the mesylate group, the tosylate group, the acetate group, and the trifluoromethylsulfonate group.
• the compound of formula (IV) is commercially available from suppliers of chemicals such as Aldrich, ABCR, ...
• the process for preparing the compound for preparing a compound (Ha) as defined above further comprises at least one electrophilic activation reaction (a) of the compound of formula (VII) to form the compound of formula ( V) in the presence of an electrophilic activating agent according to the following reaction scheme
• T a leaving group provided by the electrophilic activating agent
• the group T represents is chosen from chlorine, bromine, iodine, fluorine,
• electrophilic activating agent an agent which reacts with a hydroxyl group —OH gives it an electrophilic character.
• electrophilic activating agents and this electrophilic activation reaction on a hydroxyl group are well known to those skilled in the art. Mention may be made, as an electrophilic activating agent, for example, thionyl chloride, mesyl chloride, 4-toluenesulfonyl chloride, paratoluenesulfonic acid chloride, etc.
• the group T leaving provided by the electrophilic agent is chosen from the group consisting of chlorine, bromine, iodine, the mesylate group, the tosylate group.
• the process for preparing a compound of formula (Ha) comprises at least the following successive reactions: reaction (b) followed by reaction (c) as they have been defined above.
• the process for preparing a compound of formula (Ha) comprises at least the following successive reactions: reaction (a), followed by reaction (b), followed by reaction (c) as defined above.
• the compound of formula (VII) is obtained by dehydration of fructose or glucose; more preferably still, the compound of formula (VII) is obtained by dehydration of bio-based fructose or bio-based glucose.
• biobased fructose and biobased glucose is meant within the meaning of the present invention fructose and glucose obtained from biomass which can be differentiated respectively from fructose and glucose synthesized from fossil raw materials by the methods described in ASTM D6866-12 standard.
• the compounds of formula (I), in particular those of formula (Ha) or (Ilb), are used as grafting agent. They can be grafted onto one or more polymers, said polymers comprising at least one unsaturated carbon-carbon bond.
• this polymer can be an elastomer and more particularly a diene elastomer.
• the compounds of formula (I), in particular those of formula (Ha) and (Ilb) advantageously exhibit an improved grafting yield on polymers having at least one unsaturation compared to the compounds of the prior art.
• diene elastomer or rubber without distinction
• an elastomer consisting at least in part ie a homopolymer or a copolymer of diene monomer units (monomers bearing two double bonds carbon-carbon, conjugated or not).
• the grafting of the polymer comprising at least one unsaturated carbon-carbon bond is carried out by reaction of the polymer with the compound of formula (I), in particular the compound of formula (Ha) or of formula (IIb).
• the grafting of these compounds is carried out by cycloaddition [3 + 2] of the group Q of the compound of formula (I) (respectively of the nitrone of the compound of formula (Ha) or of formula (IIb) on an unsaturated carbon-carbon bond of the polymer chain.
• the mechanism of this cycloaddition is illustrated in particular in document WO2012 / 007441.
• said compound of formula (I), in in particular that of formula (Ha) or of formula (Ilb) forms covalent bonds with the polymer chain.
• the grafting of the compound of formula (I), in particular of the compound of formula (Ha) or of formula (Ilb) can be carried out in bulk, for example in an extruder, 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 polymer thus obtained by grafting 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.
• the invention relates to at least one of the objects described in the following embodiments:
• Q represents a dipole comprising at least one nitrogen atom
• A represents a divalent heteroaromatic ring optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, linear or branched, optionally substituted or interrupted by one or more heteroatoms;
• - E represents a divalent hydrocarbon bonding group which may optionally contain one or more heteroatoms
• - Ri represents a hydrogen atom or a C1-C20 alkyl group
• Y and Z identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z can also together form a ring, in particular an aromatic ring, with the carbon atoms of the imidazole ring to which they are attached.
• R- 2 and R 4 are chosen, independently of one another, from a hydrogen atom, a linear or branched C 1 -C 20 alkyl, a C 3 -C 20 cycloalkyl optionally substituted by a or several aliphatic hydrocarbon chains, preferably saturated, linear or branched, and a C 6 -C 20 aryl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched; and
• R 3 is selected from the group consisting of alkyl C 1 -C 20 linear or branched, cycloalkyl C 3 -C 20 optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and the aryl C 6 -C 20 optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon chains.
• - A represents a divalent heteroaromatic ring optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, linear or branched, optionally substituted or interrupted by one or more heteroatoms;
• - E represents a divalent hydrocarbon bonding group which may optionally contain one or more heteroatoms
• - Ri represents a hydrogen atom or a C 1 -C 20 alkyl group
• - Y and Z identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z also being able to form together a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached;
• R- 2 is chosen from a hydrogen atom, a linear or branched C 1 -C 20 alkyl, a C 3 -C 20 cycloalkyl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and a C 6 -C 20 aryl optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon-based chains; and
• R 3 is selected from the group consisting of alkyl C 1 -C 20 linear or branched, cycloalkyl C 3 -C 20 optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and the aryl C 6 -C 20 optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon chains.
• A is a divalent heteroaromatic ring formed from 5 to 10 atoms, preferably from 5 to 6 atoms, optionally substituted by one or more C 1 -C 24 hydrocarbon chains, identical or different, aliphatic, linear or branched, optionally substituted or interrupted by one or more heteroatoms.
• A is a divalent heteroaromatic ring formed from 5 to 10 atoms, preferably from 5 to 6 atoms, optionally substituted by one or more substituents chosen from the group consisting of alkyls linear or branched, in C 1 -C 12 , (more preferably in C I -C ⁇ , more preferably still in C 1 -C 4 ), the groups -OR ', the groups -NHR', the groups -SR 'where R 'is an alkyl group C 1 -C 12, preferably C I -C O, more preferably C 1 -C 4.
• A is chosen from furan-diyl, thiophene-diyl, pyrrole-diyl, thiazol-diyl, imidazol-diyl, pyridin-diyl, pyrazine-diyl, pyrimidin-diyl, indole-diyl, benzofuran-diyl, isoindole-diyl, isobenzofuran-diyl and benzothiophene-diyl; these rings being optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, optionally substituted or interrupted by one or more heteroatoms such as, for example, O, N and S; more preferably these rings may be substituted by one or more C I -C ⁇ .
• - X represents a heteroatom group selected from the sulfur atom, the oxygen atom or the nitrogen atom, preferably X is an oxygen atom;
• - E represents a divalent hydrocarbon bonding group which may optionally contain one or more heteroatoms
• - Ri represents a hydrogen atom or a C 1 -C 20 alkyl group
• Y and Z identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z can also together form a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached;
• R 2 is chosen from a hydrogen atom, a linear or branched C 1 -C 20 alkyl, a C 3 -C 20 cycloalkyl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and a C 6 -C 20 aryl optionally substituted by one or more aliphatic, preferably saturated, linear or branched hydrocarbon-based chains; and
• R 3 is selected from the group consisting of alkyl C 1 -C 20 linear or branched, cycloalkyl C 3 -C 20 optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and the aryl C 6 -C 20 optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon chains.
• R 2 is a hydrogen atom and R 3 is selected from alkyl C 1 -C 20 aryl and C 6 -C 20.
• E is chosen from aliphatic, linear or branched hydrocarbon chains, saturated with C 1 -C 24 , preferably with C 1 -C 10 , more preferably with C I -C ⁇ optionally interrupted by one or more nitrogen, sulfur or oxygen atoms.
• E is chosen from the groups -R-, -NHR-, -OR- and -SR- where R is an alkylene, linear or branched, C 1 -C. 24 , preferably C 1 -C 10 , more preferably C 1 -C 6.
• Y and Z which are identical or different, each represent a hydrogen atom or an alkyl, linear or branched, in Ci-C 24 , preferably in C1-C10, more preferably C I -C O, Y and Z may also together form a ring, including aromatic, with the carbon atoms of imidazole ring to which they are attached.
• Ri is a hydrogen atom or a C I -C O, preferably methyl.
• - A represents a divalent heteroaromatic ring optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, linear or branched, optionally substituted or interrupted by one or more heteroatoms;
• - E represents a divalent hydrocarbon bonding group which may optionally contain one or more heteroatoms
• - Ri represents a hydrogen atom or a C 1 -C 20 alkyl group
• Y and Z identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z can also together form a ring, in particular aromatic, with the carbon atoms of the imidazole ring to which they are attached;
• R 2 is chosen from a hydrogen atom, a linear or branched C 1 -C 20 alkyl, a C 3 -C 20 cycloalkyl optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and a C 6 -C 20 aryl optionally substituted by one or more aliphatic, preferably saturated, linear or branched hydrocarbon-based chains; and
• R 3 is selected from the group consisting of alkyl C 1 -C 20 linear or branched, cycloalkyl C 3 -C 20 optionally substituted by one or more aliphatic hydrocarbon chains, preferably saturated, linear or branched and the aryl C 6 -C 20 optionally substituted with one or more aliphatic, preferably saturated, linear or branched hydrocarbon chains.
• 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 quantitative 1 H NMR experiment uses a 30 ° single pulse sequence and a 3 second repetition delay between each of the 64 acquisitions.
• the samples are solubilized in a deuterated solvent, deuterated dimethyl sulfoxide (DMSO) unless otherwise indicated.
• DMSO deuterated dimethyl sulfoxide
• the deuterated solvent is also used for the "lock" signal.
• the calibration is performed on the proton signal of deuterated DMSO at 2.44 ppm relative to a TMS reference at 0 ppm.
• the determination of the molar content of the grafted compound tested on a diene elastomer is carried out by an NMR analysis.
• the spectra are acquired on a 500 MHz BRUKER spectrometer equipped with a "CryoSonde BBFO-zgrad-5 mm" probe.
• 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 a deuterated solvent, deuterated chloroform (CDCf) unless otherwise indicated 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.
• the average molar masses in number and in weight of the diene elastomers used are measured by the technique of size exclusion chromatography or SEC (Size Exclusion Chromatography). SEC makes it possible to separate 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.
• 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 for dissolving the relastomer.
• the flow rate is 0.7 ml / min, the system temperature is 35 ° C and the analysis 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 Telastomer sample solution is 100 pL.
• the detector is a "WATERS 2410" differential refractometer with a wavelength of 810 nm.
• the chromatographic data processing software is the system
• the average molar masses calculated relate to a calibration curve produced from commercial standard polystyrenes “PSS READY CAL-KIT”.
• the 1 - (5 - ((2-methyl- 1H-imidazol-1 -yl) methylfuran-2-yl) -N-phenylmethanimine oxide is synthesized in 2 steps which are described below. All the chemical compounds used in of this synthesis come from "Sigma Aldrich” or “Fischer Scientific”
• 5- (hydroxymethyl) furan-2-carbaldehyde (compound A, CAS 67-47-0) is commercial or can be synthesized biochemically or chemically from fructose.
• N-phenylhydroxylamine (compound D, CAS 100-65-2) is commercial or perhaps synthesized from nitrobenzene according to the procedure described in Organic Syntheses, Coll. Flight. 1. p. 445 (1941); Flight. 4.p. 57 (1925).
• 5- (Chloromethyl) furan-2-carbaldehyde (compound B) can be synthesized from fructose or 5- (hydroxymethyl) furan-2-carbaldehyde according to the procedure described in Sanda, Komla et al, Synthesis of 5- (bromomethyl) - and of 5- (chloromethyl) -2-furancarboxaldehyde, Carbohydrate Research, 187 (1), 15-23; 1989
• This compound can be prepared in 5 steps according to the following reaction scheme:
• Step 3 Synthesis of 4 - ((2-methyl-1H-imidazol-1-yl)) methyl) phenylmethanol: A solution of L1AIH 4 (1.50 g, 0.039 mol) in anhydrous THF (230 ml) is cooled to -60 ° C. A solution of ethyl 4 - ((2-methyl-1H-imidazol-1-yl) methyl) benzoate (7.80 g, 0.028 mol, 81% mol) in anhydrous THF (100 ml) is added under argon for 15 minutes. The reaction medium is stirred for 1 hour at -60 ° C., then 10-12 hours at room temperature.
• Phenylhydroxylamine was synthesized according to the procedure described in Org. Syntheses, Coll. Flight. 1, p. 445, 1941; Org. Syntheses, Coll. Flight. 3, p. 668, 1955
• the yellow precipitate thus formed is filtered off after 20 minutes of stirring and washed with a mixture of EtOH (10 ml) and water (20 ml), then with water (50 ml). The two portions of solid are combined and dried for 10-12 hours under atmospheric pressure at room temperature. A yellow solid (3.71 g, 89% molar yield) with a molar purity greater than 82% ( 1 H NMR) is obtained. Additional purification is applied by stirring for 1.5 hours at room temperature, filtration, washing on the filter with 50 ml of ethyl ether, drying for 2 days at room temperature.
• a styrene-butadiene copolymer used is an SBR containing 26.5% by weight of styrene relative to the total weight of the copolymer and in its butadienic part, relative to the weight of the butadiene part, 24% by weight of butadiene-1 units. , 2.28% by weight of 1,4-cis-butadienic units and 48% by weight of trans-1,4-butadiene units relative to the weight of the butadienic part. Its Mn is equal to 120,000 g / mol and its Ip is equal to 1.84, they are measured according to the method described in paragraph 3.

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