Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F236/06—Butadiene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/22—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having three or more carbon-to-carbon double bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
  • C08F4/545—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof rare earths being present, e.g. triethylaluminium + neodymium octanoate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2420/00—Metallocene catalysts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
  • C08F2500/36—Terpolymer with exactly three olefinic monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages

Definitions

• the field of the invention is that of copolymers of conjugated dienes and of ethylene, rich in ethylene unit and which can be used as elastomers in a rubber composition for tires.
• the diene elastomers most widely used in the manufacture of tires are polybutadienes, polyisoprenes, in particular natural rubber, and copolymers of 1,3-butadiene and of styrene. What these elastomers have in common is the high molar proportion of diene units in the elastomer, generally much greater than 50%, which can make them sensitive to oxidation, in particular under the action of ozone.
• elastomers which, on the contrary, are relatively poor in diene units, in particular with a view to reducing their sensitivity to oxidation phenomena.
• These elastomers are for example described in document WO 2007054223. They are copolymers of 1,3-butadiene and of ethylene containing more than 50% by mole of ethylene unit. These elastomers are referred to as diene elastomers rich in ethylene.
• the copolymers of 1,3-butadiene and ethylene rich in ethylene are crystalline and their crystallinity increases with the ethylene level.
• the presence of crystalline moieties in the copolymer can be problematic when using the copolymer in a rubber composition.
• a rubber composition containing such a copolymer also sees its rigidity decrease when it is brought to temperatures equal to or exceeding the melting point of the crystalline parts. Rigidity as a function of temperature can therefore lead to fluctuations in the properties of the rubber composition and make it less suitable for certain uses which require better stability of the properties in temperature. It is of interest to have diene polymers rich in ethylene units, the crystallinity of which is reduced, or even eliminated.
• a first object of the invention is a terpolymer, preferably an elastomer, of ethylene, of a first 1,3-diene having 4 to 6 carbon atoms and of a second 1,3-diene of formula (I ), which terpolymer contains more than 50 mol% ethylene units and at least 1 mol% units of the second 1,3-diene,
• a second subject of the invention is a process for preparing the terpolymer in accordance with the invention.
• the invention also relates to a rubber composition
• a rubber composition comprising a terpolymer according to the invention, a reinforcing filler and a crosslinking system, which terpolymer is an elastomer.
• the invention also relates to a tire which comprises a rubber composition in accordance with the invention.
• any interval of values designated by the expression “between a and b” represents the range of values greater than “a” and less than “b” (that is to say bounds a and b excluded) while any interval of values designated by the expression “from a to b” signify the range of values going from “a” to "b” (that is to say including the strict limits a and b).
• the abbreviation “phr” means parts by weight per hundred parts by weight of elastomer (of the total elastomers if more than one elastomer is present).
• the rates of the units resulting from the insertion of a monomer into a copolymer are expressed as a molar percentage relative to the totality of the monomer units of the copolymer.
• the compounds 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 elastomers, plasticizers, fillers, etc.
• the essential characteristic of the first 1,3-diene is that it contains 4 to 6 carbon atoms.
• the first 1,3-diene is a single compound that is to say a single (in English "one") 1,3-diene having 4 to 6 carbon atoms or is a mixture of different 1,3-dienes having 4 to 6 carbon atoms.
• 1,3-diene having 4 to 6 carbon atoms mention may in particular be made of 1,3-butadiene and isoprene.
• the first 1,3-diene is preferably 1,3-butadiene.
• the second 1,3-diene has the essential characteristic of responding to formula (I) in which the symbol R represents a hydrocarbon chain having 3 to 20 carbon atoms.
• the second 1,3-diene is a single compound, that is to say a single (in English "one") 1,3-diene of formula (I) or is a mixture of 1,3-dienes of formula (I), the 1,3-dienes of the mixture differing from each other by the group represented by the symbol R.
• the symbol R represents a hydrocarbon chain having 6 to 16 carbon atoms.
• the hydrocarbon chain represented by the symbol R can be a saturated or unsaturated chain.
• the symbol R represents an aliphatic chain in which case, in formula (I) for 1,3-diene, the hydrocarbon chain represented by the symbol R is an aliphatic hydrocarbon chain. It can be a straight or branched chain, in which case the symbol R represents a straight or branched chain.
• the hydrocarbon chain is acyclic, in which case the symbol R represents an acyclic chain. More preferably, the symbol R represents an acyclic unsaturated and branched hydrocarbon chain.
• the hydrocarbon chain represented by the symbol R is advantageously an unsaturated and branched acyclic chain containing from 3 to 20 carbon atoms, in particular from 6 to 16 carbon atoms.
• the 1,3-diene is myrcene or b-farnesene. According to a preferred embodiment of the invention, the 1,3-diene is myrcene.
• the 1,3-diene is b-farnesene.
• the terpolymer according to the invention is a terpolymer of ethylene, of a first 1,3-diene and of a second 1,3-diene, which implies that the monomer units of the terpolymer are units resulting from the polymerization.
• the copolymer therefore comprises ethylene units, units of the first 1,3-diene and units of the second 1,3-diene.
• the second 1,3-diene being a substituted 1,3 diene, its polymerization can give rise to units of 1,2 configuration represented by formula (1), of 3,4 configuration represented by formula (2) and of 1.4 configuration whose trans form is shown below after by formula (3).
• the first 1, B-diene can give rise to 1,3-diene units which are units of 1,2 or 3,4 configuration as is the case for example of isoprene and 1.4 configuration units.
• the ethylene unit is a unit of unit - (CH2-CH2) -.
• the terpolymer in accordance with the invention is advantageously a random terpolymer according to any one of the embodiments of the invention.
• the terpolymer is an atactic polymer according to any one of the embodiments of the invention.
• the terpolymer contains more than 50 mol% of ethylene units.
• the terpolymer contains more than 60 mole% ethylene units. More preferably, it contains at least 70 mol% of ethylene units.
• the terpolymer preferably contains at most 90% by mole of ethylene units, more preferably at most 85% by mole of ethylene units.
• the terpolymer contains at least 1 mol% of units of the second 1,3-diene.
• the terpolymer contains at most 20 mole% units of the second 1,3-diene. More preferably, the terpolymer contains at most 10 mol% of units of the second 1,3-diene.
• the terpolymer contains more than 60% to 90% by mole of ethylene units and from 1% to 20%, preferably from 1% to 10% by mole of units of the second 1, 3-diene. According to this embodiment of the invention, the terpolymer preferably contains less than 30% by mole of units of the first 1,3-diene or preferably contains less than 20% by mole of units of the first 1,3-diene.
• the terpolymer contains from 70% to 90% by mole of ethylene units and from 1% to 20%, preferably from 1% to 10% by mole of units of the second 1, 3-diene. According to this embodiment of the invention, the terpolymer preferably contains less than 20% by mole of units of the first 1,3-diene.
• the terpolymer contains more than 60% to 85% by mole of ethylene units and from 1% to 20%, preferably from 1% to 10% by mole. mole of units of the second 1,3-diene. According to this embodiment of the invention, the terpolymer preferably contains less than 30% by mole of units of the first 1,3-diene or preferably contains less than 20% by mole of units of the first 1,3-diene.
• the terpolymer contains from 70% to 85% by mole of ethylene units and from 1% to 20%, preferably from 1% to 10% by mole of units of the second 1. , 3-diene. According to this embodiment of the invention, the terpolymer preferably contains less than 20% by mole of units of the first 1,3-diene.
• the terpolymer preferably contains less than 80% by mole of ethylene unit, more preferably at most 75% by mole of ethylene unit.
• the terpolymer in particular when the first 1,3-diene is 1,3-butadiene or a mixture of 1,3-dienes, one of which is 1,3-butadiene, the terpolymer contains further 1,2-cyclohexanediyl unit units.
• the presence of these cyclic structures in the terpolymer results from a very particular insertion of ethylene and 1,3-butadiene during the polymerization.
• the content of 1,2-cyclohexanediyl unit units in the terpolymer varies according to the respective contents of ethylene and 1,3-butadiene in the terpolymer.
• the terpolymer preferably contains less than 15 mole% of 1,2-cyclohexanediyl unit units.
• the terpolymer in accordance with the invention has a glass transition temperature of less than -35 ° C, preferably between -70 ° C and -35 ° C.
• the terpolymer can be prepared by a process, another object of the invention, which comprises the polymerization of a mixture of ethylene, the first 1,3-diene and the second 1,3-diene in the presence of a catalytic system. based at least on a metallocene of formula (II) and an organomagnesium agent of formula (III)
• Cp 1 and Cp 2 identical or different, being chosen from the group consisting of the cyclopentadienyl group of formula C5H4, the unsubstituted fluorenyl group of formula C13H8 and substituted fluorenyl groups,
• P being a group bridging the two groups Cp 1 and Cp 2 and representing a group ZR 3 R 4 , Z representing a silicon or carbon atom, R 3 and R 4 , identical or different, each representing an alkyl group comprising 1 with 20 carbon atoms, preferably a methyl, y, an integer, being equal to or greater than 0, x, an integer or not, being equal to or greater than 0,
• L representing an alkali metal chosen from the group consisting of lithium, sodium and potassium
• N representing a molecule of an ether, preferably diethyl ether or tetrahydrofuran
• R 1 and R 2 identical or different, representing a carbon group.
• substituted fluorenyl groups of those substituted by alkyl radicals having 1 to 6 carbon atoms or by aryl radicals having 6 to 12 carbon atoms.
• the choice of radicals is also oriented by accessibility to the corresponding molecules, which are the substituted fluorenes, because the latter are commercially available or easily synthesized.
• positions 2, 7,-ditertiobutyl-fluorenyl and 3,6-ditertiobutyl-fluorenyl groups there may be mentioned more particularly the 2,7-ditertiobutyl-fluorenyl and 3,6-ditertiobutyl-fluorenyl groups.
• Positions 2, 3, 6 and 7 respectively denote the position of the carbon atoms of the rings as shown in the diagram below, position 9 corresponding to the carbon atom to which the P bridge is attached.
• the catalytic system can be prepared in a traditional manner by a process analogous to that described in patent application WO 2007054224 or WO 2007054223.
• the organomagnesium and the metallocene are reacted in a hydrocarbon solvent, typically at a temperature ranging from 20 to 80 ° C for a period of between 5 and 60 minutes.
• the catalytic system is generally prepared in a hydrocarbon solvent, aliphatic such as methylcyclohexane or aromatic such as toluene.
• the catalytic system is used as it is in the process for synthesizing the polymer in accordance with the invention.
• the catalytic system can be prepared by a process analogous to that described in patent application WO 2017093654 A1 or in patent application WO 2018020122 A1.
• the catalytic system also contains a preformation monomer chosen from a conjugated diene, ethylene or a mixture of ethylene and a conjugated diene, in which case the catalytic system is based at least on the metallocene, the organomagnesium and the preformation monomer.
• the organomagnesium and the metallocene are reacted in a hydrocarbon solvent, typically at a temperature of 20 to 80 ° C for 10 to 20 minutes to obtain a first reaction product, then with this first reaction product is reacted at a temperature ranging from 40 to 90 ° C for 1 h to 12 h the preformation monomer chosen from a conjugated diene, ethylene or a mixture of ethylene and a conjugated diene.
• the catalytic system as well obtained can be used immediately in the process according to the invention or be stored under an inert atmosphere before its use in the process according to the invention.
• the metallocene used to prepare the catalytic system can be in the form of crystallized powder or not, or in the form of single crystals.
• the metallocene can be in a monomeric or dimeric form, these forms depending on the method of preparation of the metallocene, as for example that is described in patent application WO 2007054224 or WO 2007054223.
• the metallocene can be prepared in a traditional manner by a process analogous to that described in patent application WO 2007054224 or WO 2007054223, in particular by reaction under inert and anhydrous conditions of the salt of an alkali metal of the ligand with a rare earth borohydride in a suitable solvent, such as an ether, such as diethyl ether or tetrahydrofuran or any other solvent known to those skilled in the art. After reaction, the metallocene is separated from the reaction by-products by techniques known to those skilled in the art, such as filtration or precipitation in a second solvent. The metallocene is finally dried and isolated in solid form.
• a suitable solvent such as an ether, such as diethyl ether or tetrahydrofuran or any other solvent known to those skilled in the art.
• the synthesis of the metallocene and that of the catalytic system take place under anhydrous conditions under an inert atmosphere.
• the reactions are carried out from solvents and anhydrous compounds under nitrogen or anhydrous argon.
• the organomagnesium agent useful for the purposes of the invention is of formula MgR 1 R 2 in which R 1 and R 2 , which are identical or different, represent a carbon group.
• the term “carbon group” is understood to mean a group which contains one or more carbon atoms.
• R 1 and R 2 contain 2 to 10 carbon atoms. More preferably, R 1 and R 2 each represent an alkyl.
• the organomagnesium is advantageously a dialkylmagnesium, better still butylethylmagnesium or butyloctylmagnesium, even better still butyloctylmagnesium.
• the molar ratio of the organomagnesium agent to the Nd metal constituting the metallocene is preferably within a range ranging from 1 to 100, more preferably is greater than or equal to 1 and less than 10.
• the range of values going from 1 to less than 10 is in particular more favorable for obtaining polymers of high molar masses.
• the terpolymer is a polymer which comprises units of 1,2-cyclohexanediyl unit, it is prepared according to the process mentioned in the present application using a metallocene of formula (II) in which Cp 1 and Cp 2 , identical or different, are selected from the group consisting of substituted fluorenyl groups and the unsubstituted fluorenyl group of formula C13H8.
• a metallocene of formula (II) in which Cp 1 and Cp 2 , identical or different, are selected from the group consisting of substituted fluorenyl groups and the unsubstituted fluorenyl group of formula C13H8.
• the metallocenes of the following formulas are particularly suitable in which the symbol Flu has the fluorenyl group of formula C13H8: [ ⁇ Me2SiFlu2Nd (p-BH4) 2Li (THF) ⁇ 2]; [Me2SiFlu2Nd (p-BH4) 2Li (THF)]; [Me 2 SiFlu2Nd (p-BH 4 ) (THF)]; [ ⁇ Me 2 SiFlu2Nd (p-BH 4 ) (THF) ⁇ 2]; [Me 2 SiFlu 2 Nd (p-BH 4 )].
• a person skilled in the art also adapts the polymerization conditions and the concentrations of each of the reactants (constituents of the catalytic system, monomers) according to the equipment (tools, reactors) used to carry out the polymerization and the various chemical reactions.
• the polymerization as well as the handling of the monomers, of the catalytic system and of the polymerization solvent (s) are carried out under anhydrous conditions and under an inert atmosphere.
• Polymerization solvents are typically hydrocarbon, aliphatic or aromatic solvents.
• the polymerization is preferably carried out in solution, continuously or batchwise.
• the polymerization solvent can be a hydrocarbon, aromatic or aliphatic solvent.
• a polymerization solvent mention may be made of toluene and methylcyclohexane.
• the monomers can be introduced into the reactor containing the polymerization solvent and the catalytic system or conversely the catalytic system can be introduced into the reactor containing the polymerization solvent and the monomers.
• the copolymerization is typically carried out under anhydrous conditions and in the absence of oxygen, in the optional presence of an inert gas.
• the polymerization temperature generally varies within a range ranging from 30 to 150 ° C, preferably from 30 to 120 ° C.
• the copolymerization is carried out at constant ethylene pressure.
• the polymerization can be stopped by cooling the polymerization medium or by adding an alcohol.
• the polymer can be recovered according to conventional techniques known to those skilled in the art such as, for example, by precipitation, by evaporation of the solvent under reduced pressure or by steam stripping.
• the terpolymer carries an amine, alkoxysilane or silanol function.
• the functionalizing agent is preferably a compound of formula (IV), Si (Fc 1 ) 3-g (Rc 2 ) g (Rca) ( IV) the symbols Fc 1 , identical or different, representing an alkoxy group, the symbols Rc 2 , identical or different, representing a hydrogen atom or a hydrocarbon chain, the symbol Rca representing a hydrocarbon chain substituted by an amine function, g being an integer ranging from 0 to 1.
• the alkoxy group represented by the symbol Fc 1 in formula (IV) is preferably methoxy or ethoxy.
• the amine function designated in the symbol Rca in formula (IV), namely the amine function of the functionalizing agent is a protected primary amine function, a protected secondary amine function or a tertiary amine function.
• groups protecting the primary amine and secondary amine functions mention may be made of silyl groups, for example trimethylsilyl and terbutyldimethylsilyl groups.
• the amine function of the functionalizing agent is a tertiary amine function.
• the amine function of the functionalizing agent is a tertiary amine of formula -N (RB) 2 in which each RB represents an alkyl, preferably a methyl or an ethyl.
• the functionalizing agent is preferably a compound of formula (V),
• the alkoxy group is preferably methoxy or ethoxy.
• the symbol Fc 1 represents a halogen atom in formula (V)
• the halogen atom is preferably chlorine.
• alkyls preferably alkyls having at most 6 carbon atoms, more preferably methyl or ethyl, better still methyl.
• alkanediyl chains preferably those comprising at most 6 carbon atoms, more preferably the group 1,3-propanediyl, the alkanediyl group carrying a substituent, the chemical function Fc 2 , in other words, one valence of the alkanediyl chain for the function Fc 2 , the other valence for the silicon atom of the methoxysilane function.
• chemical function is meant a group which is different from a saturated hydrocarbon group and which can participate in chemical reactions.
• chemical function Fc 2 in formula (V) is a group chemically inert with respect to the chemical species present in the polymerization medium.
• the chemical function Fc 2 in formula (V) can be in a protected form, such as for example in the case of the primary amine, secondary amine or thiol function. Mention may be made, as chemical function Fc 2 , of the functions of ether, thioether, protected primary amine, protected secondary amine, tertiary amine, protected thiol, silyl.
• the chemical function Fc 2 in formula (V) is a protected primary amine function, a protected secondary amine function, a tertiary amine function or a protected thiol function.
• groups protecting the primary amine, secondary amine and thiol functions mention may be made of silyl groups, for example trimethylsilyl and terbutyldimethylsilyl groups.
• a functionalizing agent for preparing a polymer carrying a silanol or alkoxysilane function mention may be made of the compounds dimethoxydimethylsilane, diethoxydimethylsilane, dimethoxydiethylsilane, diethoxydiethylsilane, (N, N-dimethyl-3-aminopldimethyl) methoxide , N-dimethyl-3-aminopropyl) methyldiethoxysilane, (N, N-dimethyl-3-aminopropyl) ethyldimethoxysilane, (N, N-dimethyl-3-aminopropyl) ethyl-diethoxysilane, 3-methoxy-3,8,8,9 , 9-pentamethyl-2-oxa-7-thia-3,8-disiladecane, trimethoxy-methylsilane, triethoxymethylsilane, trimethoxyeth
• the functionalizing agent is typically added to the polymerization medium. It is typically added to the polymerization medium at a rate of conversion of the monomers chosen by those skilled in the art according to the desired macrostructure of the copolymer. Since the polymerization step is generally carried out under ethylene pressure, degassing of the polymerization reactor can be carried out before adding the functionalizing agent.
• the functionalizing agent is added under inert and anhydrous conditions to the polymerization medium, maintained at the polymerization temperature. It is typically used from 0.25 to 10 moles of functionalizing agent per 1 mole of cocatalyst, preferably from 2 to 4 moles of functionalizing agent per 1 mole of cocatalyst.
• the functionalization agent is brought into contact with the polymerization medium for a time sufficient to allow the functionalization reaction.
• This contact time is judiciously chosen by those skilled in the art as a function of the concentration of the reaction medium and the temperature of the reaction medium.
• the functionalization reaction is carried out with stirring, at a temperature ranging from 17 to 80 ° C., for 0.01 to 24 hours.
• the polymer functionalization step can be followed by a hydrolysis reaction to form a copolymer carrying a deprotected function, such as a primary amine, a secondary amine or a thiol function.
• a deprotected function such as a primary amine, a secondary amine or a thiol function.
• a hydrolysis reaction can also follow the functionalization reaction of the polymer when the functionalization reaction leads to the formation of a polymer bearing an alkoxysilane function.
• the hydrolysis of the polymer carrying an alkoxysilane function leads to the preparation of a polymer carrying a silanol function.
• the terpolymer in accordance with the invention exhibits both a lower rigidity and a degree of crystallinity which is comparable, or even lower than. a copolymer of ethylene and of 1,3-butadiene which nevertheless has the same level of ethylene.
• the substitution in a rubber composition of the terpolymer in accordance with the invention for a copolymer of ethylene and of 1,3-butadiene which nevertheless has the same level of ethylene makes it possible to give a rubber composition a lower rigidity.
• the terpolymer in accordance with the invention is advantageously an elastomer. It is in particular intended for use in a rubber composition, in particular for a tire.
• the rubber composition another subject of the invention, has the characteristic of comprising the elastomer in accordance with the invention, a reinforcing filler and a crosslinking system.
• the rubber composition can comprise any type of so-called reinforcing filler, known for its ability to reinforce a rubber composition which can be used for the manufacture of tires, for example an organic filler such as carbon black, an inorganic reinforcing filler such as silica with which is associated in a known manner a coupling agent, or a mixture of these two types of filler.
• Such a reinforcing filler typically consists of nanoparticles whose average size (by mass) is less than one micrometer, generally less than 500 nm, most often between 20 and 200 nm, in particular and more preferably between 20 and 150 nm.
• the level of reinforcing filler is adjusted by those skilled in the art depending on the use of the rubber composition.
• the crosslinking system can be based on sulfur, sulfur donors, peroxides, bismaleimides or their mixtures.
• the crosslinking system is preferably a vulcanization system, that is to say a system based on sulfur (or on a sulfur donor agent) and on a primary vulcanization accelerator.
• a vulcanization system can be added various secondary accelerators or known vulcanization activators such as zinc oxide, stearic acid or equivalent compounds, guanide derivatives (in particular diphenylguanidine), or else known vulcanization retarders.
• the rubber composition may further contain other additives known to be used in rubber compositions for tires, such as plasticizers, anti-ozonants, antioxidants.
• the rubber composition in accordance with the invention is typically 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) at high temperature, up to a maximum temperature between 130 ° C and 200 ° C, followed by a second mechanical work phase (so-called “productive” phase) down to a lower temperature, typically less than 110 ° C , for example between 40 ° C and 100 ° C, finishing phase during which the crosslinking system is incorporated.
• the rubber composition in accordance with the invention which can be either in the uncured state (before crosslinking or vulcanization) or in the cured state (after crosslinking or vulcanization), can be used in a semi-finished article for a tire.
• the tire another subject of the invention, comprises the rubber composition in accordance with the invention defined in any one of the embodiments of the invention.
• Mode 1 Terpolymer of ethylene, of a first 1,3-diene having 4 to 6 carbon atoms and of a second 1,3-diene of formula (I), which terpolymer contains more than 50 mol% ethylene units and at least 1 mol% of units of the second 1,3-diene,
• Mode 2 Terpolymer according to Mode 1, which terpolymer contains more than 60 mol% of ethylene units.
• Mode 3 Terpolymer according to mode 1 or 2, which terpolymer contains at least 70% by moles of ethylene units.
• Mode 4 Terpolymer according to any one of modes 1 to 3, which terpolymer contains at most 90 mol% of ethylene units.
• Mode 5 Terpolymer according to any one of modes 1 to 4, which terpolymer contains at most 85% by mole of ethylene units.
• Mode 6 Terpolymer according to any one of modes 1 to 5, which terpolymer contains at most 20% by mole unit of the second 1,3-diene.
• Mode 7 Terpolymer according to any one of modes 1 to 6, which terpolymer contains at most 10% by mole of unit of the second 1,3-diene.
• Mode 8 Terpolymer according to Mode 1, which terpolymer contains more than 60% to 90% by mole of ethylene units and from 1% to 20%, preferably from 1% to 10% by mole of units of the second 1.3 -diene.
• Mode 9 Terpolymer according to Mode 1, which terpolymer contains from 70% to 90% by mole of ethylene units and from 1% to 20%, preferably from 1% to 10% by mole of units of the second 1,3- diene.
• Mode 10 Terpolymer according to Mode 1, which terpolymer contains more than 60% to 85% by mole of ethylene units and from 1% to 20%, preferably from 1% to 10% by mole of units of the second 1.3 -diene.
• Mode 11 Terpolymer according to Mode 1, which terpolymer contains from 70% to 85% by mole of ethylene units and from 1% to 20%, preferably from 1% to 10% by mole of units of the second 1,3- diene.
• Mode 12 Terpolymer according to any one of modes 8 to 10, which terpolymer contains less than 30% by mole of units of the first 1,3-diene.
• Mode 13 Terpolymer according to any one of modes 8 to 11, which terpolymer contains less than 20% by mole of units of the first 1,3-diene.
• Mode 14 Terpolymer according to any one of modes 1 to 13 in which the first 1,3-diene is 1,3-butadiene, isoprene or a mixture of 1,3-dienes, one of which is 1,3- butadiene.
• Mode 15 Terpolymer according to any one of modes 1 to 14 in which the first 1,3-diene is 1,3-butadiene.
• Mode 16 Terpolymer according to Mode 14 or 15, which terpolymer additionally contains 1,2-cyclohexanediyl unit units.
• Mode 17 Terpolymer according to Mode 16, which terpolymer contains less than 15 mol% of 1,2-cyclohexanediyl unit units.
• Mode 18 Terpolymer according to any one of modes 1 to 17 in which the symbol R represents a hydrocarbon chain having 6 to 16 carbon atoms.
• Mode 19 Terpolymer according to any one of modes 1 to 18 in which the symbol R represents a saturated or unsaturated chain.
• Mode 20 Terpolymer according to any one of modes 1 to 19 in which the symbol R represents an aliphatic chain.
• Mode 21 Terpolymer according to any one of modes 1 to 20 in which the symbol R represents an acyclic chain.
• Mode 22 Terpolymer according to any one of modes 1 to 21 in which the symbol R represents a linear or branched chain.
• Mode 23 A terpolymer according to any one of modes 1 to 22, which terpolymer has a glass transition temperature below -35 ° C.
• Mode 24 Terpolymer according to any one of modes 1 to 23, which terpolymer has a glass transition temperature between -70 ° C and -35 ° C.
• Mode 25 Terpolymer according to any one of modes 1 to 24 in which the second 1,3-diene is myrcene.
• Mode 26 Terpolymer according to any one of modes 1 to 24 in which the second 1,3-diene is b-farnesene.
• Mode 27 A terpolymer according to any one of modes 1 to 26, which terpolymer is a random terpolymer.
• Mode 28 Terpolymer according to any one of modes 1 to 27, which terpolymer bears an amine, alkoxysilane or silanol function.
• Mode 29 Terpolymer according to any one of modes 1 to 28, which terpolymer contains less than 80% by mole of ethylene unit.
• Mode 30 Terpolymer according to any one of modes 1 to 29, which terpolymer contains at most 75% by mole of ethylene unit.
• Mode 31 A rubber composition which comprises at least one terpolymer defined according to any one of modes 1 to 30, a reinforcing filler and a crosslinking system, which terpolymer is an elastomer.
• Mode 32 Rubber composition according to mode 31 in which the reinforcing filler comprises a carbon black or a silica.
• Mode 33 Rubber composition according to mode 31 or 32 in which the crosslinking system is a vulcanization system.
• Mode 34 A tire which comprises a rubber composition defined according to any one of modes 31 to 33.
• Mode 35 A process for preparing the terpolymer according to any one of modes 1 to 30 which comprises polymerizing a mixture of ethylene, the first 1,3-diene and the second 1,3-diene in the presence of a catalytic system based on at least one metallocene of formula (II) and one organomagnesium
• Cp 1 and Cp 2 identical or different, being chosen from the group consisting of the cyclopentadienyl group of formula C5H4, the unsubstituted fluorenyl group of formula C13H8 and substituted fluorenyl groups,
• P being a group bridging the two groups Cp 1 and Cp 2 and representing a group ZR 3 R 4 , Z representing a silicon or carbon atom, R 3 and R 4 , identical or different, each representing an alkyl group comprising 1 with 20 carbon atoms, preferably a methyl, y, an integer, being equal to or greater than 0, x, an integer or not, being equal to or greater than 0,
• L representing an alkali metal chosen from the group consisting of lithium, sodium and potassium
• N representing a molecule of an ether, preferably diethyl ether or tetrahydrofuran, R 1 and R 2 , identical or different, representing a carbon group.
• the size exclusion chromatography or SEC Size Exclusion Chromatography makes it possible to separate the macromolecules in solution according to their size through columns filled with a porous gel. Macromolecules are separated according to their hydrodynamic volume, the larger ones being eluted first.
• the SEC makes it possible to apprehend the distribution of absolute molar masses of a polymer.
• the various number (Mn), weight (Mw) and dispersity (D Mw / Mn) absolute molar masses can also be calculated.
• the number-average molar mass (Mn), the weight-average molar mass (Mw) and the polydispersity index of the polymer (hereinafter sample) are determined absolutely, by size exclusion chromatography (SEC: Size Exclusion Chromatography) triple detection.
• SEC Size Exclusion Chromatography
• Triple detection size exclusion chromatography has the advantage of measuring average molar masses directly without calibration.
• the value of the refractive index increment dn / dc of the sample solution is measured online using the area of the peak detected by the refractometer (RI) of the liquid chromatography equipment. To apply this method, it must be verified that 100% of the sample mass is injected and eluted through the column.
• the area of the RI peak depends on the concentration of the sample, the constant of the RI detector and the value of dn / dc.
• the 1g / l solution previously prepared and filtered is used, which is injected into the chromatographic system.
• the apparatus used is a “WATERS alliance” chromatographic line.
• the elution solvent is tetrahydrofuran containing 250 ppm of BHT (2,6-diter-butyl 4-hydroxy toluene), the flow rate is 1 mL.min 1 , the system temperature 35 ° C and the duration of 60 min analysis.
• the columns used are a set of three AGILENT columns with the trade name “PL GEL MIXED B LS”.
• the injected volume of the sample solution is 100 pL.
• the detection system is composed of a Wyatt differential viscometer with the trade name "VISCOSTAR II”, a Wyatt differential refractometer with the trade name “OPTILAB T-REX” with a wavelength of 658 nm, a diffusion detector of static light Wyatt multi-angle wavelength 658 nm and trade name “DAWN HELEOS 8+”.
• the value of the refractive index increment dn / dc of the solution of the sample obtained above is integrated.
• the chromatographic data processing software is the "Wyatt ASTRA" system.
• the spectral characterization and measurements of the Ethylene-Butadiene-Myrcene copolymer microstructure are carried out by Nuclear Magnetic Resonance (NMR) spectroscopy.
• a Bruker Avance III HD 400 MHz spectrometer is used, equipped with a Bruker cryo-BBFO z-grad 5 mm probe.
• the 1H experiments are recorded using a radiofrequency pulse with a tilting angle of 30 °, the number of repetitions is 128 with a recycling delay of 5 seconds.
• NMR correlation experiments are performed using a radiofrequency pulse with a tilting angle of 30 °, the number of repetitions is 128 with a recycling delay of 5 seconds.
• the 1,2-cyclohexanediyl unit has the following structure:
• the signals integrated for the quantification of the different units are: Ethylene: Total signals between 0.5 ppm and 3.0 ppm by subtracting the aliphatic contributions of the other units of the terpolymer. The calculation corresponds to 4 protons of the Ethylene unit.
• Form A signal n ° 7 (4.86 ppm) corresponding to 2 protons.
• the proportion of form C is not directly accessible but can be calculated from signal n ° 3 + 8 '' by subtracting the contribution of form A.
• PB1-4 Signal between 5.71 ppm and 5.32 ppm corresponds to 2 protons (by removing the contribution PB1-2).
• PB1-2 signal between 5.11 ppm and 4.92 ppm corresponds to 2 protons.
• Cyclohexane cycles signal between 1.80 ppm and 1.70 ppm corresponds to 2 protons.
• the quantification of the microstructure is carried out in molar percentage (mol%) as follows:
• Molar% of a unit 1 H integral of a unit * 100 / ⁇ ( 1 H integral of each unit).
• NMR Nuclear Magnetic Resonance
• the 1H-13C HSQC (Heteronuclear Single Quantum Coherence) and HMBC (Heteronuclear Multiple-Bond Correlation) NMR correlation experiments are recorded with a repetition number of 128 and an increment number of 128.
• the experiments are carried out at 25 ° C. . 25 mg of sample are dissolved in 1 mL of deuterated orthodichlorobenzene (ODCB).
• ODCB deuterated orthodichlorobenzene
• the signals of the insertion form of farnesene A were observed on the various spectra recorded.
• the integrated signals for the quantization of the different patterns are:
• Farnesene pattern form B from the signal h ° 1, specific to this form, for 1 proton.
• PB1-4 Signal between 5.71 ppm and 5.32 ppm corresponds to 2 protons (by removing the contribution PB1-2).
• PB1-2 signal between 5.11 ppm and 4.92 ppm corresponds to 2 protons.
• Cyclohexane cycles signal between 1.80 ppm and 1.70 ppm corresponds to 2 protons Ethylene unit by integrating all the aliphatic signals (from ⁇ 0.5 to 3 ppm) and by subtracting the contribution of all the other aliphatic units (PB1-4, PB1-2 , EBR cycle, farnesene form A and C).
• the glass transition temperature is measured by means of a differential calorimeter ("Diffe rential Scanning Calorimeter") according to standard ASTM D3418 (1999).
• the measurements are carried out on an Anton Paar model MCR301 rheometer in Shear mode with cylindrical specimens of controlled geometry (thickness between 1.5mm and 3mm and diameter between 22mm and 28mm).
• the sample is subjected to a sinusoidal stress in shear, at a fixed temperature (corresponding to the end of the passage of the glass transition of the elastomer on a temperature sweep at 10Hz), and over a frequency range going from 0.01Hz to 100Hz.
• the rigidity value retained as being the rigidity of the rubber plate of the sample is the value of the shear modulus G 'for the frequency at which the loss modulus G' 'reaches its minimum, in accordance with the method described by C. Liu , J. He, E. van Ruymbeke, R. Keunings, C. Bailly, Evaluation of different methods for the determination of the plateau modulus and the entanglement molecular weight, Polymer 47 (2006) 4461-4479.
• the ISO 11357-3: 2011 standard is used to determine the temperature and enthalpy of melting and crystallization of polymers used by differential scanning calorimetry (DSC).
• the reference enthalpy of polyethylene is 277.1 J / g (according to Handbook of Polymer 4th Edition, J. BRANDRUP, EH IMMERGUT, and EA GRULKE, 1999)
• the first 1,3-diene used is
• the second 1,3-diene is myrcene or b-farnesene.
• Myrcene is a
• Example 1 not in accordance with the invention: synthesis of a copolymer of ethylene and of 1,3-butadiene
• the polymer is synthesized according to the following procedure:
• the polymerization reaction is stopped by cooling, degassing the reactor and adding 10 mL of ethanol. An antioxidant is added to the polymer solution.
• the copolymer is recovered by drying in an oven under vacuum to constant mass.
• Example 2 not in accordance with the invention: synthesis of a copolymer of ethylene and of 1,3-butadiene
• the polymer is synthesized according to the following procedure:
• the polymerization reaction is stopped by cooling, degassing the reactor and adding 10 mL of ethanol. An antioxidant is added to the polymer solution.
• the copolymer is recovered by drying in an oven under vacuum to constant mass.
• Example 3 not in accordance with the invention: synthesis of a copolymer of ethylene and of 1,3-butadiene
• the polymer is synthesized according to the following procedure:
• the polymerization is carried out at 80 ° C. and at a constant pressure of 4 bars.
• the polymerization reaction is stopped by cooling, degassing the reactor and adding ethanol.
• An antioxidant is added to the polymer solution.
• the copolymer is recovered by drying in an oven under vacuum to constant mass.
• Examples 4 to 10 in accordance with the invention terpolymers of ethylene, of 1,3-butadiene and of myrcene or of b-farnesene
• the polymers are synthesized according to the following procedure:
• a reactor containing the hydrocarbon solvent: methylcyclohexane (MCH), the cocatalyst, butyloctylmagnesium (BOMAG) then the metallocene [Me2Si (Flu) 2Nd (p- BFU LHTHF)] are added.
• the alkylation time is 10 minutes , the reaction temperature is 20 ° C.
• the polymerization is carried out at 80 ° C and at a constant pressure of 4 bars in a 500 ml glass reactor containing 300 ml of polymerization solvent, methylcyclohexane, the catalytic system and the monomers, myrcene (Myr) or b - farnesene (Far) being introduced in liquid form into the reactor and ethylene / 1, 3-butadiene being introduced in gaseous form.
• the polymerization reaction is stopped by cooling and degassing the reactor.
• the copolymer is recovered by precipitation in methanol, then dried or by direct drying.
• the elastomers of Examples 4 to 9 have a much lower crystallinity level than the elastomer of Example 1, even if they have a comparable or much higher level of ethylene unit. Even the elastomers of Examples 7 and 10 which have an ethylene unit level greater than 80% exhibit a much lower crystallinity level than the elastomer of Example 1, however, much less rich in ethylene unit.
• Example 4 shows that the insertion of units of the second 1,3-diene into the polymer at levels in accordance with the invention makes it possible to reduce the rigidity of the polymer, while the ethylene unit levels are comparable.
• the comparison of Examples 5 and 9 with Example 2 shows moreover that the insertion of units of the second 1,3-diene at rates as low as 1% makes it possible to reduce the rigidity of the elastomer, even though the elastomers of Examples 5 and 9 have a level of ethylene units as high as that of Example 2.
• the elastomers of Examples 5 and 9 also have a lower level of crystallinity than that of the elastomer of Example 3 which has a similar ethylene unit level.

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