Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
  • C07D303/02—Compounds containing oxirane rings
  • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
  • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
  • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
  • C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
• • 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
  • C08C19/04—Oxidation
  • C08C19/06—Epoxidation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/32—Compounds containing nitrogen bound to oxygen

Definitions

• the present invention relates to a rubber composition, in particular intended for the manufacture of tires, based on at least one diene elastomer, at least one reinforcing filler, at least one crosslinking agent and at least one compound. particular carrying at least one epoxy ring.
• the application also relates to a process for preparing such a composition and as well as a semi-finished article for a tire and a tire comprising such a rubber composition. In the industrial field, mixtures of polymers with fillers are often used.
• document WO2019102132A1 discloses a rubber composition comprising a copolymer of styrene and butadiene onto which has been grafted a functionalizing agent, 2- (glycidyloxy) -1-naphtonitrile oxide.
• This modified copolymer makes it possible to obtain a rubber composition whose reinforcement index is improved and whose non-linearity is significantly reduced compared to a rubber composition comprising a copolymer of unmodified styrene and butadiene.
• An object of the present invention is therefore to provide novel rubber compositions exhibiting an improvement in the reinforcement index and an improvement in the hysteresis properties without reducing the properties of stiffness when cooked.
• the Applicant has surprisingly discovered that a composition based on at least one diene elastomer, a reinforcing filler, a crosslinking system and a specific compound, an aromatic nitrile oxide having an epoxy ring linked to the aromatic group carrying the nitrile oxide by a specific divalent group, simultaneously exhibited an improvement in the reinforcement index and an improvement in the hysteresis properties.
• the composition thus obtained also exhibits an improvement in the stiffness properties when fired.
• a first object of the present invention therefore relates to a rubber composition based on at least one diene elastomer, a reinforcing filler, a crosslinking agent and at least one compound of formula (I), optionally already grafted onto said diene elastomer in which: - A represents an arenediyl ring in C 6 -VS 14 , optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C 5 -VS 12 optionally comprising one or more heteroatoms; - X 1 , X 2 , X 3 identical or different, represent a hydrogen atom, a C alkyl 1 -VS 6 or a C aryl 6 -VS 14 .
• Another object of the present invention relates to a semi-finished article for a tire comprising at least one rubber composition defined above.
• Another subject of the present invention relates to a tire comprising at least one rubber composition defined above or a semi-finished article for a tire defined above.
• a first object of the present invention therefore relates to a rubber composition based on at least one diene elastomer, a reinforcing filler, a crosslinking agent and at least one compound of formula (I), optionally already grafted onto said elastomer.
• diene in which: - A represents an arenediyl ring in C 6 -VS 14 , optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C 5 -VS 12 optionally comprising one or more heteroatoms; - X 1 , X 2 , X 3 identical or different, represent a hydrogen atom, a C alkyl 1 -VS 6 or a C aryl 6 -VS 14 . In the present document, unless expressly indicated otherwise, all the percentages (%) indicated are percentages (%) by mass.
• 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.
• composition based on should be understood to mean a composition comprising the mixture and / or the in situ reaction product of the various constituents used, some of these constituents which can react and / or are intended to react with each other, at least partially, during the various phases of manufacture of the composition; the composition may thus be in the fully or partially crosslinked state or in the non-crosslinked state.
• 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.
• a “predominant” compound it is understood, within the meaning of the present invention, that this compound is predominant among the compounds of the same type in the composition, that is to say that it is the one which represents the greatest amount by mass among compounds of the same type.
• a major elastomer is the elastomer representing the greatest mass relative to the total mass of elastomers in the composition.
• a so-called majority filler is that representing the greatest mass among the fillers of the composition.
• 1,3-dipolar compound is understood as defined by IUPAC.
• a 1,3-dipolar compound comprises a dipole.
• hydrocarbon chain is understood to mean a chain comprising one or more carbon atoms and one or more hydrogen atoms.
• C1-Cj alkyl denotes a linear, branched or cyclic hydrocarbon group comprising from i to j carbon atoms; i and j being whole numbers.
• C1-Cj aryl denotes an aromatic group comprising from i to j carbon atoms; i and j being whole numbers.
• 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.
• modified elastomer obtained by grafting or “modified elastomer by grafting” is meant an elastomer comprising functions, in particular epoxy rings, which have been introduced into the elastomer chain.
• the modified elastomer is obtained by grafting reaction of a compound carrying functions which are epoxy rings and carrying a function being capable of forming a covalent bond with an unsaturation of the elastomer, this function capable of forming a covalent bond being a nitrile oxide.
• the grafting reaction is therefore the attachment by a covalent bond of the compound of formula (I) carrying epoxy rings on at least one unsaturation of the elastomer chain.
• an elastomer generally comprises at least one main elastomer chain.
• This elastomeric chain can be qualified as the main one from the moment when all the other chains of the elastomer are considered as pendant chains like the mentions the document “Glossary of basic terms in polymer science” (IUPAC recommendations 1996), PAC, 1996, 68, 2287, p2294.
• unsaturation is meant a multiple covalent bond between two carbon atoms; this multiple covalent bond possibly being a carbon-carbon double bond or a carbon-carbon triple bond, preferably a carbon-carbon double bond.
• initial elastomer chain is meant within the meaning of the present invention the chain of the elastomer before the grafting reaction; this chain comprising at least one unsaturation capable of reacting with the compound of formula (I) described above.
• the initial elastomer is therefore the elastomer serving as the starting reagent during the grafting reaction.
• the grafting reaction allows from an initial elastomer to obtain a modified elastomer.
• the rubber composition of the invention comprises at least one compound of formula (I), optionally already grafted onto the diene elastomer in which: - A represents an arenediyl ring in C 6 -VS 14 , optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C 5 -VS 12 optionally comprising one or more heteroatoms; - X 1 , X 2 , X 3 identical or different, represent a hydrogen atom, a C alkyl 1 -VS 6 or a C aryl 6 -VS 14 .
• formula (I) optionally already grafted onto the diene elastomer in which: - A represents an arenediyl ring in C 6 -VS 14 , optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon
• this compound comprises a group A which represents an arenediyl ring at C 6 -VS 14 , optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched.
• 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.
• monocyclic or polycyclic aromatic hydrocarbon group is meant one or more aromatic rings whose backbone consists of carbon atoms. In other words, there are no heteroatoms in the backbone of the cycle.
• the arenediyl ring can be monocyclic, that is, made up of a single ring, or polycyclic, that is to say made up of several condensed aromatic hydrocarbon rings; such condensed rings then have at least two successive carbon atoms in common. These rings can be ortho-condensed or ortho- and per-condensed.
• the arenediyl ring has 6 to 14 carbon atoms.
• the arenediyl ring can be unsubstituted, partially substituted or fully substituted.
• An arenediyl ring is partially substituted when one or two or more hydrogen atoms (but not all atoms) are replaced by one or two or more hydrocarbon, aliphatic, preferably saturated, linear or branched chains.
• Said chains are also called substituents. If all the hydrogen atoms are replaced by said chains, then the arenediyl ring is completely substituted.
• the substituents of the arenediyl ring can be the same or different from each other.
• this or these chain (s) are inert with respect to the epoxy ring and nitrile oxide.
• the term “inert hydrocarbon chain (s) with respect to the epoxy cycle and to the nitrile oxide” is understood to mean a hydrocarbon chain which neither reacts with said cycle. epoxy ni with said nitrile oxide.
• said hydrocarbon chain inert with respect to said ring and to said nitrile oxide is, for example, a hydrocarbon chain which does not have alkenyl or alkynyl functions, capable of reacting with said ring or said nitrile oxide.
• these hydrocarbon chains are aliphatic, saturated, linear or branched, and can comprise from 1 to 24 carbon atoms.
• A represents an arenediyl ring at C 6 -VS 14 , optionally substituted by one or more hydrocarbon chain (s), identical or different, saturated at C 1 -VS 24 .
• the group A is an arenediyl ring in C 6 -VS 14 , optionally substituted by one or more substituents, identical or different, the substituents being C alkyls 1 -VS 12 , preferably in C 1 -VS 6 , more preferably still in C 1 -VS 4 .
• the compound of formula (I) according to the invention is chosen from compounds of formula (Ia) and compounds of formula (Ib) in which: - a group chosen from R1 to R5 of formula (Ia) and a group chosen from R1 to R7 of formula (Ib) denote the following group of formula (II): in which E, X1, X2 and X3 are as defined above and below and the symbol (*) represents the attachment of group (II) to the rest of molecule (Ia) or (Ib); - the four groups of formula (Ia) chosen from R1 to R5 other than that designating the group of formula (II) and the six groups of formula (Ib) chosen from R1 to R7 other than that designating the group of formula ( II), which are identical or different, represent, independently of one another, a hydrogen atom or an aliphatic hydrocarbon chain, preferably saturated, linear or branched.
• the four groups of formula (Ia) chosen from R1 to R5 other than that designating the group of formula (II) and the six groups of formula (Ib) chosen from R1 to R7 other than that designating the group of formula (II), which are identical or different, represent, independently of each other, a hydrogen atom or an aliphatic, saturated, linear or branched, C-shaped hydrocarbon chain 1 -VS 24 .
• the four groups of formula (Ia) chosen from R1 to R5 other than that designating the group of formula (II) and the six groups of formula ( Ib) chosen from R1 to R7 other than that designating the group of formula (II), identical or different, are chosen from the group consisting of the hydrogen atom, C alkyls 1 -VS 12 , preferably in C 1 -VS 6 , more preferably still in C 1 -VS 4 .
• the four groups of formula (Ia) chosen from R1 to R5 other than that designating the group of formula (II) and the six groups of formula ( Ib) chosen from R1 to R7 other than that designating the group of formula (II), which are identical or different, represent, independently of one another, a hydrogen atom or a methyl.
• R2 represents a group of formula (II) and R1, R3, R4 and R5, identical or different, represent a hydrogen atom or a hydrocarbon chain aliphatic, preferably saturated, linear or branched, in C 1 -VS 24 .
• R2 represents a group of formula (II) and R1, R3, R4 and R5, identical or different, are chosen from the group consisting of an atom hydrogen, C1-C12 alkyl, more preferably C 1 -VS 6 , more preferably still in C 1 -VS 4 . More preferably still in this embodiment, R2 represents a group of formula (II), R4 represents a hydrogen atom and R1, R3 and R5 represent an aliphatic hydrocarbon chain, preferably saturated, linear or branched, in C 1 -VS 24 .
• R2 represents a group of formula (II)
• R4 represents a hydrogen atom and R1, R3 and R5, identical or different, represent a C1-C12 alkyl, more preferably a C 1 -VS 6 , more preferably still in C 1 -VS 4 .
• R1 represents a group of formula (II) and R2 to R7 which are identical or different, represent a hydrogen atom or an aliphatic hydrocarbon chain, preferably saturated, linear or branched, in C 1 -VS 24 .
• R1 represents a group of formula (II) and R2 to R7, identical or different, are chosen from the group consisting of a hydrogen atom, a C1-C12 alkyl, more preferably a C 1 -VS 6 , more preferably still in C 1 -VS 4 . More preferably still in this embodiment, R1 represents a group of formula (II) and R2 to R7, which are identical, represent a hydrogen atom.
• E represents a divalent hydrocarbon group at C 5 -VS 12 possibly containing one or more heteroatom (s).
• the term “divalent hydrocarbon group” means a spacer group (or a linking group) forming a bridge between the oxygen atom attached to A and the epoxy ring bearing the groups X1, X2, X3. , this spacer group E comprising from 5 to 12 carbon atoms.
• This spacer group can be a hydrocarbon chain at C 5 -VS 1 , 2 preferably saturated, linear or branched, possibly containing one or more heteroatom (s) such as for example N, O and S. Said hydrocarbon chain can optionally be substituted, provided that the substituents do not react with the nitrile oxide and the epoxy ring as defined above.
• the compound of formula (I) when E comprises a divalent hydrocarbon group of 5 to 12 carbon atoms, the compound of formula (I), optionally already grafted onto a diene elastomer, gives the compositions improved hysteresis and strengthening properties compared to the compositions. of the prior art. Surprisingly, the improvement in these properties does not come at the expense of baked-on stiffness properties.
• E represents a divalent hydrocarbon group at C 5 -VS 10 , preferably in C 5 -VS 9 , more preferably in C 6 -VS 9 , more preferably still in C 7 -VS 9 , possibly containing one or more heteroatom (s) such as for example N, O and S.
• group E is this divalent compound as described above
• the compound of formula (I) optionally already grafted onto a diene elastomer, gives the compositions improved hysteresis and reinforcement properties compared to the compositions of the prior art.
• E represents an alkanediyl in C 5 -C10, preferably a C-alkanediyl 5 -VS 9 , more preferably a C6-C alkanediyl 9 , more preferably still a C7-C alkanediyl 9 .
• the compound of formula (I) when E is this alkanediyl as described above, the compound of formula (I), optionally already grafted onto a diene elastomer, gives the compositions improved hysteresis and strengthening properties compared to the compositions of the diene elastomer. prior art. Surprisingly, the improvement in these properties does not come at the expense of baked-on stiffness properties.
• X1, X2, X3, identical or different are chosen from the group consisting of the hydrogen atom, C alkyls 1 -VS 6 and aryls in C 6 -VS 14 .
• X1, X2, X3, which are identical or different, are chosen from the group consisting of the hydrogen atom, methyl, ethyl and phenyl.
• X1, X2 and X3 are identical and represent a hydrogen atom.
• X1 and X2 represent a hydrogen atom and X3 represents a phenyl.
• X3 is a hydrogen atom
• X1 and X2, which are identical or different represent a d atom. hydrogen or methyl.
• the compound of formula (I) can be the compound of formula (I) as described above.
• the compound of formula (I) can be the compound of formula (Ib) in which the group R1 is the group of formula (II) with the group E representing a C-alkanediyl 5 -C10, preferably a C-alkanediyl 5 -VS 9 , more preferably a C6-C alkanediyl 9 , more preferably still a C7-C alkanediyl 9 , the groups X1, X2, X3, identical or different, are chosen from the group consisting of the hydrogen atom, C alkyls 1 -VS 6 and aryls in C 6 -VS 14 (preferably are selected from the group consisting of the hydrogen atom and C-alkyls 1 -VS 6 ), and the same or different R2 to R7 groups are selected from the group consisting of the hydrogen atom and C1-C12 alkyls.
• the group R1 is the group of formula (II) with the group E representing a C-alkanedi
• a particularly preferred compound of formula (I) is the compound of formula (III):
• the compounds of the invention (I), (Ia), (Ib) and (III) can be obtained in particular by a preparation process comprising at least one reaction (d) of an oxime compound of formula (IV) with a oxidizing agent in the presence of at least one organic solvent SL1 according to the following reaction scheme to give the compound of formula (I) and in particular its preferred compounds: in which: - A represents an arenediyl ring in C 6 -VS 14 , optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C 5 -VS 12 optionally comprising one or more heteroatoms; - X1, X2, X3, identical or different, represent a hydrogen atom, a C alkyl 1 -VS 6 or a C aryl 6 -VS 14 .
• Preferred modes of A, E, X1, X2 and X3 as described above also apply to the process for preparing the compound of formula (I) from a compound of formula (IV).
• said oxidizing agent is chosen from sodium hypochlorite, N-bromosuccinimide in the presence of a base, N-chlorosucinimide in the presence of a base, and hydrogen peroxide in the presence of a catalyst.
• the catalyst is chosen from the group consisting of sodium hypochlorite and N-bromosuccinimide in the presence of a base.
• the base can be triethylamine.
• the amount of oxidizing agent is 1 to 5 molar equivalents, preferably 1 to 2 molar equivalents relative to the molar amount of the oxime compound of formula (IV).
• 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.
• the oxime compound of formula (IV) represents from 1 to 30% by weight, preferably from 1 to 20% by weight, relative to the total weight of the assembly comprising said oxime compound of formula (IV), said organic solvent SL1 and said oxidizing agent.
• the oxime of formula (IV) can in particular be obtained from a preparation process comprising at least one reaction (c) of a compound of formula (V) with an aqueous solution of hydroxylamine NH2OH (compound of formula ( VI)) according to the following reaction scheme: with - A represents an arenediyl ring in C 6 -VS 14 , optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C 5 -VS 12 optionally comprising one or more heteroatoms; - X1, X2, X3, identical or different, represent a hydrogen atom, a C alkyl 1 -VS 6 or a C aryl 6 -VS 14 .
• Preferred modes of A, E, X1, X2 and X3 as described above are also applicable to the methods of preparing a compound of formula (IV) from a compound of formula (V).
• the addition of hydroxylamine is carried out at a temperature ranging from 1 ° C to 100 ° C, more preferably between 20 ° C and 70 ° C.
• the compound of formula (V) can be obtained by a preparation process comprising at least one reaction (b) of the compound of formula (VII) with a compound of formula (VIII) in the presence of at least one base and at a temperature ranging from 20 ° C to 150 ° C according to the following reaction scheme: with - A represents an arenediyl ring in C 6 -VS 14 , optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C 5 -VS 12 optionally comprising one or more heteroatoms; - X1, X2, X3, identical or different, represent a hydrogen atom, a C alkyl 1 -VS 6 or a C aryl 6 -VS 14 ; - Z represents a nucleofuge group.
• Preferred modes of A, E, X1, X2 and X3 are also applicable to the process of preparing a compound of formula (V) from compounds of formula (VIII) and (VII).
• the term “nucleofuge group” is understood to mean a leaving group.
• the Z group can be selected from chlorine, bromine, iodine, fluorine, mesylate group, tosylate group, acetate group, and trifluoromethylsulfonate group.
• 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.
• the base is chosen from sodium methanolate, potassium carbonate and sodium hydroxide, more preferably potassium carbonate.
• 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).
• the compounds of formula (VII) as defined above are commercially available from suppliers such as Sigma –Aldrich, Merk, Chimieliva, and the like.
• the compound of formula (VIII) can be obtained by epoxidation of the corresponding alkene of formula (IX) according to the reaction scheme below.
• the synthesis of a compound comprising an epoxy ring from its corresponding alkene is well known. For example, this oxidation can take place in the presence of peracid such as metachloroperbenzoic acid, peracetic acid, performic acid.
• Another well-known technique is the use of dimethyldioxirane.
• - E represents a divalent hydrocarbon group at C 5 -VS 12 optionally comprising one or more heteroatoms
• - X1, X2, X3, identical or different represent a hydrogen atom, a C alkyl 1 -VS 6 or a C aryl 6 -VS 14
• - Z represents a nucleofuge group as described above.
• Preferred modes of E, X1, X2 and X3 are also applicable to the process of preparing a compound of formula (VIII) from the compound of formula (IX).
• Compounds of formula (IX) are commercially available from suppliers such as Sigma Aldrich, ABCR.
• the rubber composition according to the invention also comprises, as constituent, at least one diene elastomer, in particular at least one diene elastomer onto which the compound of formula I is optionally already grafted, in particular the compound of formula (Ib), more particularly the compound of formula (III).
• diene elastomer or indiscriminately rubber
• diene elastomers can be classified into two categories: “essentially unsaturated” or “essentially saturated”.
• essentially unsaturated is understood to mean in general a diene elastomer derived at least in part from conjugated diene monomers, having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (% by moles); it is thus that diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not fall within the preceding definition and can in particular be qualified as “essentially saturated” diene elastomers (level of diene. units of weak or very weak diene origin, always less than 15% (% in moles)).
• diene elastomer capable of being used in the context of the present invention is particularly understood: any homopolymer of a diene monomer, conjugated or not, having from 4 to 18 carbon atoms; - any copolymer of a diene, conjugated or not, having 4 to 18 carbon atoms and at least one other monomer.
• the other monomer can be ethylene, an olefin or a diene, conjugated or not.
• Suitable conjugated dienes are conjugated dienes having from 4 to 12 carbon atoms, in particular 1,3-dienes, such as in particular 1,3-butadiene and isoprene.
• Suitable unconjugated dienes are unconjugated dienes having 6 to 12 carbon atoms, such as 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene.
• Suitable olefins are vinyl aromatics having 8 to 20 carbon atoms and aliphatic ⁇ -monoolefins having 3 to 12 carbon atoms.
• Suitable vinyl aromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the commercial mixture “vinyl-toluene”, para-tert-butylstyrene.
• Suitable aliphatic ⁇ -monoolefins in particular are acyclic aliphatic ⁇ -monoolefins having from 3 to 18 carbon atoms.
• the diene elastomer is: - any homopolymer of a conjugated diene monomer, in particular any homopolymer obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms; - any copolymer obtained by copolymerization of one or more dienes conjugated with one another or with one or more vinyl aromatic compounds having from 8 to 20 carbon atoms; - a copolymer of isobutene and isoprene (butyl rubber), as well as the halogenated versions, in particular chlorinated or brominated, of this type of copolymer.
• the diene elastomer is chosen from the group consisting of ethylene-propylene-diene monomer copolymers (EPDM), natural rubber (NR), synthetic polyisoprenes (IR), polybutadienes (BR), copolymers of butadiene, isoprene copolymers and mixtures of these elastomers.
• EPDM ethylene-propylene-diene monomer copolymers
• NR natural rubber
• IR synthetic polyisoprenes
• BR polybutadienes
• the diene elastomer is chosen from the group consisting of ethylene-propylene-diene monomer copolymers (EPDM), natural rubber (NR), synthetic polyisoprenes (IR), polybutadienes (BR), copolymers of butadiene and styrene (SBR), copolymers of ethylene and butadiene (EBR), copolymers of isoprene and butadiene (BIR) or copolymers of isoprene, butadiene and styrene (SBIR), copolymers isobutene and isoprene (butyl rubber IIR), isoprene-styrene (SIR) copolymers and mixtures of these elastomers.
• EPDM ethylene-propylene-diene monomer copolymers
• NR natural rubber
• IR synthetic polyisoprenes
• BR polybutadienes
• SBR copolymers of butadiene and s
• the diene elastomer is chosen from the group consisting of ethylene-propylene-diene monomer copolymers, butyl rubber and a mixture of these rubbers.
• the diene elastomer is chosen from the group consisting of natural rubber, synthetic polyisoprenes, polybutadienes, butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
• the diene elastomer is chosen from the group consisting of natural rubber, synthetic polyisoprenes, polybutadienes, butadiene and styrene copolymers, ethylene and butadiene copolymers, isoprene and butadiene copolymers, copolymers of isoprene, butadiene and styrene, copolymers of isobutene and isoprene, copolymers of isoprene and styrene and mixtures of these elastomers.
• the diene elastomer is chosen from the group consisting of polybutadienes, butadiene copolymers, isoprene copolymers and mixtures of these elastomers. More preferably, the diene elastomer is chosen from the group consisting of polybutadienes, copolymers of butadiene and of styrene, copolymers of ethylene and of butadiene, copolymers of isoprene and of butadiene, copolymers of isoprene, of butadiene and styrene, copolymers of isobutene and isoprene, copolymers of isoprene and styrene and mixtures of these elastomers.
• the diene elastomers can have any microstructure which depends on the polymerization conditions used. These diene elastomers can be, for example, block, random, sequenced, microsequenced, and be prepared in dispersion in emulsion or in solution. They can be coupled and / or starred, for example by means of a silicon or tin atom which binds the polymer chains together.
• the rubber composition according to the invention is based on at least one diene elastomer and on at least one compound of formula (I), in particular a compound of formula (Ib), more particularly a compound of formula (III), optionally already grafted onto the diene elastomer.
• the diene elastomer can be grafted with the compound of formula (I), in particular with the compound of formula (Ib), more particularly with the compound of formula (III) prior to its introduction into the rubber composition, or else can be grafted by reaction with the compound of formula (I), in particular with that of formula (Ib), more particularly with that of formula (III) during the manufacture of the rubber composition.
• the rubber composition comprises at least one diene elastomer grafted beforehand with the compound of formula (I), in particular with the compound of formula (Ib), more particularly with the compound of formula (III),
• the molar grafting rate of the compound of formula (I) on said diene elastomer, in particular of the compound of formula (Ib), in particular of the compound of formula (III) is within a range ranging from 0.01% to 15%, preferably from 0, 05% to 10%, more preferably from 0.07 to 5%.
• the level of the compound of formula (I), in particular the level of the compound of formula (Ib), more particularly the level of the compound of formula (III) in the rubber composition according to the invention of rubber is included in an area ranging from 0.01 to 15pce.
• the rubber composition according to the invention may contain a single diene elastomer grafted with the compound of formula (I), in particular with the compound of formula (Ib), plus particularly with the compound of formula (III) (either grafted prior to its introduction into the rubber composition, or grafted by reaction with said compound of formula (I), in particular with said compound of formula (Ib), more particularly with said compound of formula (III) during the manufacture of the rubber composition), or a mixture of several diene elastomers grafted, or some of which are grafted and others not.
• the other diene elastomer (s) used as a mixture with the grafted diene elastomer are diene elastomers as described above, whether they are stellate, coupled, functionalized or not.
• the grafted diene elastomer is the predominant elastomer in the rubber composition. It will be noted that the improvement in the properties of the rubber composition according to the invention will be all the greater, the smaller the proportion of said additional elastomer (s) in the rubber composition according to the invention.
• the grafted diene elastomer (s) can be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers, for example with thermoplastic polymers.
• another component of the rubber composition according to the invention is a reinforcing filler.
• Any type of so-called reinforcing filler can be used, known for its capacity to reinforce a rubber composition which can be used in particular for the manufacture of tires, for example an organic filler such as carbon black, an inorganic filler such as silica or else. a mixture of these two types of fillers.
• the reinforcing filler is chosen from carbon black, an inorganic filler and their mixtures.
• Suitable carbon blacks are all carbon blacks, in particular the blacks conventionally used in tires or their treads. Among the latter, there will be mentioned more particularly the reinforcing carbon blacks of the 100, 200, 300 series, or the blacks of the 500, 600 or 700 series (grades ASTM D-1765-2017), such as for example the blacks N115, N134, N234, N326, N330, N339, N347, N375, N550, N683, N772). These carbon blacks can be used in the isolated state, as available commercially, or in any other form, for example as a support for some of the rubber additives used.
• the carbon blacks could for example already be incorporated into the diene elastomer, in particular isoprene in the form of a masterbatch (see for example applications WO97 / 36724-A2 or WO99 / 16600-A1).
• the STSA specific surface area is determined according to the ASTM D6556-2016 standard.
• reinforcing inorganic filler should be understood here any inorganic or mineral filler, whatever its color and its origin (natural or synthetic), also called “white” filler, "light” filler or even “non-black” filler.
• reinforcing inorganic fillers can be characterized in particular by the presence of hydroxyl groups (—OH) at their surface.
• suitable in particular mineral fillers of the siliceous type preferably silica (SiO2) or of the aluminous type, in particular alumina (Al2O3).
• the silica used can be any reinforcing silica known to those skilled in the art, in particular any precipitated or pyrogenic silica having a BET specific surface area as well as a CTAB specific surface area both less than 450 m2 / g, preferably within a range of from 30 to 400 m2 / g.
• Any type of precipitated silica can be used, in particular highly dispersible precipitated silicas (called “HDS” for “highly dispersible” or “highly dispersible silica”). These precipitated silicas, which may or may not be highly dispersible, are well known to those skilled in the art.
• the commercial HDS silicas it is possible in particular to use the silicas “Ultrasil® 5000GR”, “Ultrasil® 7000GR” from the company Evonik, the silicas “Zeosil® 1085GR”, “Zeosil® 1115 MP”, “Zeosil® 1165MP”, “ Zeosil® Premium 200MP ”,“ Zeosil® HRS 1200 MP ”from the Solvay Company.
• the BET specific surface for the inorganic filler in particular for the silica, is determined by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society”. (Vol. 60, page 309, February 1938), and more precisely according to a method adapted from standard NF ISO 5794-1, appendix E of June 2010 [multipoint volumetric method (5 points) - gas: nitrogen - vacuum degassing: one hour at 160 ° C - relative pressure range p / in: 0.05 to 0.17].
• the CTAB specific surface values were determined according to standard NF ISO 5794-1, appendix G of June 2010.
• this reinforcing inorganic filler preferably has a BET surface area within a range ranging from 45 to 400 m2 / g , more preferably within a range ranging from 60 to 300 m2 / g.
• the physical state in which the reinforcing inorganic filler is present is immaterial, whether in the form of powder, microbeads, granules, or even beads or any other suitable densified form.
• the term “reinforcing inorganic filler” is understood to mean mixtures of different reinforcing inorganic fillers, in particular of silicas as described above.
• an at least bifunctional coupling agent or binding agent intended to ensure a sufficient connection, of a chemical and / or physical nature, between the filler.
• bifunctional organosilanes or polyorganosiloxanes are used.
• bifunctional is meant a compound having a first functional group capable of interacting with the inorganic filler and a second functional group capable of interacting with the diene elastomer.
• a bifunctional compound can comprise a first functional group comprising a silicon atom, the said first functional group being able to interact with the hydroxyl groups of an inorganic charge and a second functional group comprising a sulfur atom, the said second functional group being able to interact with the diene elastomer.
• the organosilanes are chosen from the group consisting of polysulfurized organosilanes (symmetrical or asymmetrical) such as bis (3-triethoxysilylpropyl) tetrasulfide, in short TESPT marketed under the name “Si69” by the company Evonik or bis disulfide.
• polysulfurized organosilanes symmetrical or asymmetrical
• bis (3-triethoxysilylpropyl) tetrasulfide in short TESPT marketed under the name “Si69” by the company Evonik or bis disulfide.
• the organosilane is a polysulfurized organosilane.
• the coupling agents described above could also be used.
• the content of coupling agent in the composition of the invention is advantageously less than or equal to 35 phr, it being understood that it is generally desirable to use as little as possible.
• the level of coupling agent represents from 0.5% to 15% by weight relative to the amount of reinforcing inorganic filler.
• a reinforcing filler of another nature could be used, since this reinforcing filler of another nature would be covered with an inorganic layer. such as silica, or else would include on its surface functional sites, in particular hydroxyls, requiring the use of a coupling agent to establish the bond between this reinforcing filler and the diene elastomer.
• carbon blacks partially or entirely covered with silica or carbon blacks modified with silica, such as, without limitation, the fillers of the “Ecoblack®” type of the series. CRX2000 ”or the“ CRX4000 ”series from Cabot Corporation.
• Those skilled in the art will know how to adapt the rate of reinforcing filler in the rubber composition of the invention according to the use concerned, in particular according to the type of tire concerned, for example tire for a motorcycle, for a passenger vehicle or even for a commercial vehicle. such as a pickup truck or heavy truck.
• this level of reinforcing filler is within a range ranging from 10 to 200 phr, more preferably from 30 to 180 phr, the optimum being in a known manner different according to the particular applications targeted.
• the reinforcing filler mainly comprises silica; preferably consists essentially of silica, more preferably still consists of silica.
• the level of carbon black present in the rubber composition is preferably within a range ranging from 2 to 20 phr.
• the reinforcing filler mainly comprises carbon black, or even consists essentially of carbon black, more preferably still consists of carbon black.
• the crosslinking agent can be any type of system known to those skilled in the art in the field of rubber compositions for tires. It can in particular be based on sulfur. Preferably, the crosslinking agent is sulfur-based, this is called a vulcanization system.
• the sulfur can be provided in any form, in particular in the form of molecular sulfur, or of a sulfur donor agent. At least one vulcanization accelerator is also preferably present, and, optionally, also preferentially, one can use various known vulcanization activators such as zinc oxide, stearic acid or equivalent compound such as salts of stearic acid and salts.
• transition metals transition metals, guanide derivatives (in particular diphenylguanidine), or also known vulcanization retarders.
• Sulfur is used at a preferential rate of between 0.5 and 12 phr, in particular between 1 and 10 phr.
• the vulcanization accelerator is used at a preferential rate of between 0.5 and 10 phr, more preferably between 0.5 and 5.0 phr.
• MBTS 2-mercaptobenzothiazyl disulfide
• CBS N-cyclohexyl-2-benzothiazyl sulfenamide
• DCBS N-dicyclohexyl- 2-benzothiazyl sulfenamide
• TBBS N-ter-butyl-2-benzothiazyl sulfenamide
• TZTD tetrabenzylthiuram disulfide
• ZBEC zinc dibenzyldithiocarbamate
• the rubber compositions in accordance with the invention may also comprise all or part of the usual additives and processing agents, known to those skilled in the art and usually used in rubber compositions for tires, in particular rubber bands.
• bearing such as for example plasticizers (such as plasticizing oils and / or plasticizing resins), non-reinforcing fillers, pigments, protection agents such as anti-ozone waxes, chemical anti-ozonants, anti-oxidants, anti-fatigue agents, reinforcing resins (as described for example in application WO 02/10269).
• a process for preparing the rubber composition defined above is also described.
• the rubber composition in accordance with the invention is manufactured in suitable mixers, using two successive preparation phases well known to those skilled in the art: a first thermomechanical working or mixing phase (so-called “non-productive” phase) carried out at a maximum temperature within a range ranging from 110 ° C to 200 ° C, preferably from 130 ° C to 185 ° C, for a period generally of between 2 and 10 minutes, - a second phase of mechanical work (phase called "productive"), which is carried out in an external mixer such as a roller mixer, after cooling the mixture obtained during the first non-productive phase to a lower temperature, typically less than 120 ° C, for example between 40 ° C and 100 ° C.
• the crosslinking agent is then incorporated, and the whole is mixed for a few minutes, for example between 5 and 15 min.
• all the basic constituents of the composition according to the invention with the exception of the chemical crosslinking agent, namely the reinforcing filler (s), the coupling agent where appropriate, are incorporated.
• the diene elastomer has been grafted with the compound of formula (I), in particular with the compound of formula (Ib), more particularly still with the compound of formula (III) prior to the manufacture of the rubber composition.
• the grafted diene elastomer which is introduced during the first so-called non-productive phase.
• this first embodiment of the method comprises the following steps: ⁇ modify the diene elastomer by grafting in solution or in bulk with at least one compound of formula (I), in particular with at least one compound of formula (Ib), more particularly with at least one compound of formula (III) such as as defined above, incorporate into the diene elastomer thus grafted with the compound of formula (I), in particular with the compound of formula (Ib), more particularly with the compound of formula (III), the reinforcing filler and all the basic constituents of the composition, with the exception of the crosslinking agent, by thermomechanically kneading the mixture, in one or more times, until a maximum temperature of between 110 ° C and 200 ° C is reached, of preferably between 130 ° C and 185 ° C ⁇ cool the previous mixture to a temperature below 100 ° C, ⁇ then incorporate the crosslinking agent, ⁇ knead the mixture obtained in the previous step to a temperature below 120 ° C.
• the grafting of the diene elastomer is carried out by reaction of said diene elastomer with the nitrile oxide function of the compound of formula (I), in particular with the nitrile oxide of the compound of formula (Ib), more particularly with the oxide of nitrile of the compound of formula (III). During this reaction, this nitrile oxide forms a covalent bond with the chain of said diene elastomer. More precisely, the grafting of the compound of formula (I), in particular of the compound of formula (Ib), more particularly of the compound of formula (III) is carried out by [3 + 2] cycloaddition of the nitrile oxide function with a unsaturation of the chain of the initial diene elastomer.
• a [3 + 2] cycloaddition mechanism is described in document WO2012 / 007441.
• the diene elastomer carries along the main elastomer chain one or more pendant groups resulting from the grafting reaction of the compound of formula (I), in particular of the compound of formula (Ib), more particularly of the compound of formula (III) as defined above.
• these pendant groups are distributed along the main elastomeric chain in a random fashion.
• the grafting of the compound of formula (I), in particular of the compound of formula (Ib), more particularly of the compound of formula (III) can be carried out in bulk, for example in an internal mixer or an external mixer such as a mixer with cylinders.
• the grafting is then carried out either at a temperature of the external mixer or of the internal mixer below 60 ° C, followed by a grafting reaction step in a press or in an oven at temperatures ranging from 80 ° C to 200 ° C. , or at a temperature of the external mixer or of the internal mixer above 60 ° C without subsequent heat treatment.
• the grafting process can also be carried out in solution continuously or batchwise.
• the diene elastomer thus grafted can be separated from its solution by any type of known means, in particular by a steam stripping operation.
• the grafting of the diene elastomer with the compound of formula (I), in particular with the compound of formula (Ib), plus particularly by the compound of formula (III) is carried out concomitantly with the manufacture of the rubber composition.
• both the diene elastomer not yet grafted and the compound of formula (I), in particular the compound of formula (Ib), more particularly the compound of formula (III) are introduced during the first phase called ungrafted. -productive.
• the reinforcing filler is then added subsequently during this same non-productive phase in order to prevent any side reaction with the compound of formula (I), in particular with the compound of formula (Ib), more particularly with the compound of formula (Ib).
• the latter comprises the following steps: incorporating into the diene elastomer at least one compound of formula (I), in particular at least one compound of formula (Ib), more particularly at least one compound of formula (III) as defined above, and, preferably subsequently, the reinforcing filler, as well as all the basic constituents of the composition, with the exception of the chemical crosslinking agent , by thermomechanically kneading the mixture, in one or more times, until a maximum temperature of between 110 ° C and 200 ° C, preferably between 130 ° C and 185 ° C, is reached; ⁇ cool the mixture obtained in the previous step to a temperature below 100 ° C, ⁇ then incorporate the crosslinking agent, ⁇ knead the mixture obtained in the previous step to a maximum temperature below 120 ° C.
• the molar degree of grafting of the compound of formula (I), in particular of the compound of formula (Ib), more particularly of the compound of formula (III) is within a range ranging from 0.01 % to 15%, preferably from 0.05% to 10%, more preferably from 0.07 to 5%.
• the term “molar grafting rate” means the number of mol of the compound of formula (I), in particular of the compound of formula (Ib), in particular of the compound of formula (III), grafted onto the diene elastomer per 100 moles. of monomer unit constituting the diene elastomer.
• the molar grafting rate can be determined by conventional methods of polymer analysis, such as for example NMR analysis 1 H.
• the final rubber composition thus obtained can then be calendered, for example in the form of a sheet or of a plate, in particular for characterization, or else extruded in the form of a rubber profile which can be used as a semi-finished article for pneumatic.
• Another object of the present invention is a semi-finished article for a tire comprising at least one rubber composition as defined above, preferably the semi-finished article is a tread.
• a subject of the invention is also a tire comprising at least one rubber composition according to the invention as defined above; preferably in all or part of its tread.
• the tire according to the invention will be chosen from the tires intended to be fitted to a two-wheeled vehicle, a passenger vehicle, or even a so-called “heavy goods vehicle” (that is to say metro, bus, vehicles outside the vehicle. - the road, road transport vehicles such as trucks, tractors, trailers), or even planes, civil engineering, agrarian or handling equipment.
• a so-called “heavy goods vehicle” that is to say metro, bus, vehicles outside the vehicle.
• road, road transport vehicles such as trucks, tractors, trailers
• the invention relates to at least one of the objects described in the following embodiments: 1.
• Rubber composition based on at least one diene elastomer, a reinforcing filler, a crosslinking agent and at least a compound of formula (I), optionally already grafted onto said diene elastomer in which: - A represents an arenediyl ring in C 6 -VS 14 , optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C 5 -VS 12 optionally comprising one or more heteroatoms; - X1, X2, X3, identical or different, represent a hydrogen atom, a C alkyl 1 -VS 6 or a C aryl 6 -VS 14 . 2.
• Rubber composition according to any one of the preceding embodiments in which X1, X2, X3, identical or different, are selected from the group consisting of the hydrogen atom, C-alkyls 1 -VS 6 and aryls in C 6 -VS 14 . 5. Rubber composition according to one of embodiments 1 to 3, in which X1, X2, X3, identical or different, represent a hydrogen atom, a methyl, an ethyl or a phenyl. 6. Rubber composition according to one of embodiments 1 to 3, in which X1, X2, X3 represent a hydrogen atom. 7. A rubber composition according to any one of embodiments 1 to 3, wherein X1 and X2 represent a hydrogen atom and X3 represents a phenyl. 8.
• the compound of formula (I) is chosen from the compounds of formula (Ia) and (Ib) in which: a group chosen from R1 to R5 of formula (Ia) and a group chosen from R1 to R7 of formula (Ib) denote the following group of formula (II): in which E, X1, X2 and X3 are as defined in any one of embodiments 1 to 8 and the symbol (*) represents the attachment to (Ia) or to (Ib), - the four groups of the formula ( Ia) chosen from R1 to R5 other than that designating the group of formula (II) and the six groups of formula (Ib) chosen from R1 to R7 other than that designating the group of formula (II), which are identical or different, represent independently of each
• Process for preparing a rubber composition as defined in any one of embodiments 1 to 21, comprising the following steps: modifying a diene elastomer by grafting in solution or in mass with at least one compound of formula ( I), in which: - A represents an arenediyl ring in C 6 -VS 14 , optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C 5 -VS 12 optionally comprising one or more heteroatoms; - X1, X2, X3, identical or different, represent a hydrogen atom, a C alkyl 1 -VS 6 or a C aryl 6 -VS 14 ; ⁇ incorporate into the diene elast
• Process for preparing a rubber composition as defined in any one of points 1 to 21, comprising the following stages: incorporating, during the mass mixing with the diene elastomer, at least one compound of formula (I) in which: - A represents an arenediyl ring in C 6 -VS 14 , optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched; - E represents a divalent hydrocarbon group at C 5 -VS 12 optionally comprising one or more heteroatoms; - X1, X2, X3, identical or different, represent a hydrogen atom, a C alkyl 1 -VS 6 or a C aryl 6 -VS 14 , and preferably subsequently, the reinforcing filler, by thermomechanically kneading the mixture, in one or more times, until a maximum temperature of between 110 ° C and 200 ° C is reached, preferably between 130 ° C and 185 ° C; ⁇ cool the
• the diene elastomer is chosen from the group consisting of polybutadienes, butadiene copolymers, isoprene copolymers and mixtures of these elastomers. . 28.
• diene elastomer is chosen from the group consisting of polybutadienes, styrene-butadiene copolymers, ethylene-butadiene copolymers, isobutene-isoprene copolymers, isoprene-styrene copolymers, isoprene-butadiene copolymers, isoprene-butadiene-styrene copolymers and mixtures of these elastomers. 29.
• E represents a C-alkanediyl 5 -VS 10 , preferably a C 5 -VS 9 , more preferably a C 6 -VS 9, more preferably still an alkanediyl in C 7 -VS 9 .
• 32 A process for preparing a rubber composition according to any one of embodiments 22 to 31, wherein X 1 , X 2 , X 3 , identical or different, are chosen from the group consisting of the hydrogen atom, C-alkyls 1 -VS 6 and aryls in C 6 -VS 14 .
• Methods 1.1 Measurement of the number-average molar masses (Mn), by weight (Mw) and of the polydispersity index of the elastomers Size exclusion chromatography (SEC) is used.
• SEC Size exclusion chromatography
• 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 ⁇ L.
• the detector is a "WATERS 2410" differential refractometer with a wavelength of 810 nm.
• the software of chromatographic data is the “WATERS EM POWER” system.
• the average molar masses calculated relate to a calibration curve produced from commercial standard polystyrenes “PSS READY CAL-KIT”.
• PSD READY CAL-KIT commercial standard polystyrenes “PSS READY CAL-KIT”.
• 1.2. Characterizations of the molecules The structural analysis as well as the determination of the molar purities of the synthetic molecules are carried out by an NMR analysis. The spectra are acquired on an "Avance 3400 MHz BRUKER" spectrometer equipped with a "broadband BBFO-zgrad 5 mm” probe.
• the NMR experiment 1 Quantitative H uses a 30 ° single pulse sequence and a 3 second repeat delay between each of the 64 acquisitions. The samples are solubilized in a deuterated solvent, deuterated dimethyl sulfoxide (DMSO) unless otherwise indicated.
• 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 NMR spectrum 1 H coupled with 2D HSQC experiments 1 H / 13C and HMBC 1 H / 13C allow the structural determination of molecules (see allocation tables).
• the molar quantifications are carried out from the 1D NMR spectrum 1 H quantitative.
• Mass spectrometry analysis is performed by direct injection by an electrospray ionization mode (ID / ESI).
• the analyzes were carried out on a Bruker HCT spectrometer (flow rate 600 ⁇ L / min, pressure of the nebulizer gas 10 psi, flow rate of the nebulizer gas 4 L / min).
• 1.3. Characterizations of the Compounds Grafted on the Diene Elastomers The determination of the molar content of the compounds grafted on the diene elastomers is carried out by an NMR analysis. The spectra are acquired on a "500 MHz BRUKER" spectrometer equipped with a "BBFO-zgrad-5 mm CryoSonde".
• the NMR experiment 1 H quantitative, uses a 30 ° single pulse sequence and a 5 second repetition delay between each acquisition.
• 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 ( ⁇ ) at 60 ° C and the difference in modulus ( ⁇ G *) between the values at 0.1% and 100% deformation (Payne effect).
• G * 25% return the complex dynamic shear modulus of dynamic shears G * at 25% deformation
• ⁇ G * the difference in modulus between the values at 0.1% and 100% deformation
• the results are indicated in base 100; the arbitrary value 100 being assigned to the control to calculate and then compare tan ( ⁇ ) max at 60 ° C, G * 25% return at 60 ° C and ⁇ G * of the different samples tested.
• tan ( ⁇ ) max at 60 ° C the value in base 100 for the sample to be tested is calculated according to the operation: (value of tan ( ⁇ ) max at 60 ° C of the sample to be tested / value of tan ( ⁇ ) max at 60 ° C of the control) ⁇ 100.
• a result less than 100 indicates a decrease in hysteresis which corresponds to an improvement in rolling resistance performance.
• the value in base 100 for the sample to be tested is calculated according to the operation: (value of G * 25% return at 60 ° C of the sample to be tested / value of G * 25% return to 60 ° C of the control) ⁇ 100.
• a result greater than 100 indicates an improvement in the complex dynamic shear modulus G * 25% return at 60 ° C, which corroborates an improvement in the stiffness of the material.
• the value in base 100 for the sample to be tested is calculated according to the operation: (value of ⁇ G * of the sample to be tested / value of ⁇ G * of the control) ⁇ 100.
• 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% (NMR 1 H).
• Step a3 Synthesis of 2 - ((9- (oxiran-2-yl) nonyl) oxy) -1-naphthaldehyde oxime 1.521 g of hydroxylamine (23.02 mmol or 1.5 equivalents) are added, to room temperature 20 ° C, to a suspension of 2 - ((9- (oxiran-2-yl) nonyl) oxy) -1-naphthaldehyde (5.225 g, 15.35 mmol) in ethanol (50 ml). The reaction mixture is stirred for 3 hours; at the end of the reaction, a yellow solid precipitates. 30 ml of distilled water are then added and the medium is left to stir for an additional 10 minutes.
• Test 1 The purpose of this test is to show the improvement in the reinforcement of a rubber composition comprising natural rubber modified by the compound of the invention (composition C2) compared with a comparative composition (composition C1). The rate of the various constituents of these compositions expressed in phr, part by weight per hundred parts by weight of elastomer, are presented in Table 5.
• compositions C1 and C2 comprise the same number of moles of grafted compound A or B, namely 0.3 mole%.
• Compositions C1 and C2 are prepared as follows: the natural rubber modified by compound A or by compound B. Then, for each of the compositions, the reinforcing fillers are introduced, the agent for coupling the filler with the diene elastomer, then after one to two minutes of mixing, the various other ingredients with the exception of the vulcanization system. Thermomechanical work (non-productive phase) is then carried out in one step, which lasts in total about 5 to 6 minutes, until a maximum drop temperature of 160 ° C. is reached.
• the mixture thus obtained is recovered, it is cooled and then the vulcanization system (sulfur and sulfenamide type accelerator) is added on an external mixer (homo-finisher) at 23 ° C, while mixing the whole (productive phase) for about 5 to 12 minutes.
• the compositions thus obtained are then calendered in the form of plates (thickness of 2 to 3 mm) or of thin rubber sheets for the measurement of their physical or mechanical properties. The rubber properties of these compositions are measured after curing at 150 ° C. for 60 minutes. The results obtained are shown in Table 6.
• the rubber composition of the invention C2 exhibits, compared with the comparative composition C1, a significant improvement in the hysteresis properties while having also an increase in linearization ( ⁇ G *) and an improvement in the reinforcement index (MA300 / M100). Surprisingly, this significant improvement in hysteresis does not take place to the detriment of the stiffness properties when cooked. On the contrary, the baked-on stiffness properties are even improved compared to the comparative composition. 5.
• the object of this test is to show the improvement in the reinforcement of a rubber composition comprising a synthetic polyisoprene modified by the compound of the invention (composition C4) compared with a comparative composition (composition C3).
• compositions C3 and C4 comprise the same number of moles of grafted compound A or B, namely 0.3 mole%.
• Compositions C3 and C4 are prepared according to the process described above for compositions C1 and C2. The rubber properties of these compositions are measured after curing at 150 ° C. for 60 minutes. The results obtained are shown in Table 8. [Table 8]
• the rubber composition of the invention C4 exhibits, compared with the comparative composition C3, a significant improvement in the hysteresis properties while also having an increase in linearization ( ⁇ G *) and an improvement in the reinforcement index (MA300 / M100). Surprisingly, this significant improvement in hysteresis does not take place to the detriment of the stiffness properties when cooked. On the contrary, the baked-on stiffness properties are even improved compared to the comparative composition.

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