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
  • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/04—Polymerisation in solution
  • C08F2/06—Organic solvent
• • 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
• • 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
  • C08F210/14—Monomers containing five or more carbon atoms
• • 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
  • 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
  • C08F4/60—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 refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
  • C08F4/652—Pretreating with metals or metal-containing compounds
  • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
  • C08F4/6546—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof organo-magnesium compounds
• • 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
  • C08F2438/00—Living radical polymerisation
• • 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
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains

Definitions

• the field of the invention is that of processes for the functionalization at the end of the chain of copolymers of a 1,3-diene and of ethylene and optionally of an ⁇ -monolefin.
• the modification of a polymer at one of its chain ends can proceed from a simple functionalization of the polymer by a functional group or proceed from an insertion of a block of a second polymer at the chain end. of the polymer to be modified.
• the modification of a hydrocarbon-based polymer by inserting a block of a second polar polymer generally results in drastically modifying the skeleton of the hydrocarbon-based polymer and consequently its properties, in particular rheological and thermal. This is why modification by functionalization of a hydrocarbon-based polymer with a polar functional group at the end of the chain may be preferred to preserve some of the intrinsic properties of the hydrocarbon-based polymer, the polar functional group not being a polymer block.
• a functional group in particular a polar one
• the functionalization of the ends of the polymer chains produced by anionic polymerization is based on the living character of the polymer chains, the living character resulting in the absence of a transfer reaction and of a termination reaction during the polymerization reaction. Living polymerization is also characterized by the fact that only one polymer chain is produced per mole of initiator or metal.
• the patent application describes, for example, the modification of a polyethylene at the chain end by subsequent polymerization of methyl methacrylate to the polymerization of ethylene by means of a catalytic system composed of di-n- hexyl-magnesium and the reaction product of neodymium borohydride and pentamethylcyclopentadiene.
• the modification reaction takes place in a solvent mixture of toluene and tetrahydrofuran.
• the introduction of a block of a second polymer at the chain end of a polymer can modify the intrinsic properties of the copolymer containing diene units and ethylenic units, such as for example its glass transition temperature.
• a first object of the invention is a process for the preparation of a copolymer of a 1,3-diene and an olefin, the copolymer bearing at one of its chain ends a functional group of formula -CH2 -CH(CH B )-COOZ, Z being a hydrogen atom or a carbon group, which process comprises the successive steps a), b) and c) and, where appropriate, a step d),
• step a) being the polymerization of a monomer mixture containing a 1,3-diene and an olefin in the presence of a catalytic system based on at least one metallocene of formula (Ia) and an organomagnesium
• Cp 1 and Cp 2 identical or different, being chosen from the group consisting of fluorenyl groups, cyclopentadienyl groups and indenyl groups, the groups being substituted or unsubstituted,
• P being a group bridging the two Cp 1 and Cp 2 groups, and comprising a silicon or carbon atom
• L representing an alkali metal chosen from the group consisting of lithium, sodium and potassium
• N representing a molecule of an ether, x, whole number or not, being equal to or greater than 0, y, whole number, being equal to or greater than 0, the olefin being ethylene or a mixture of ethylene and d an a-monoolefin,
• step b) being the reaction of a methacrylate with the reaction product of the polymerization of step a), - step c) being a chain termination reaction,
• a second object of the invention is a copolymer which is capable of being obtained by the process in accordance with the invention.
• the copolymer is a copolymer of a 1,3-diene and an olefin and bears at one of its chain ends a functional group of formula -CH2-CH(CH B )-COOZ, Z being an atom of hydrogen or a carbon group, the olefin being ethylene or a mixture of ethylene and an ⁇ -monoolefin.
• the copolymer according to the invention is a copolymer of which one chain end bears an ester function which derives from a methacrylate, hydrolyzed where appropriate, without its intrinsic properties such as its glass transition temperature being modified.
• the copolymer in accordance with the invention also has the advantage of bearing two functions at one and the same chain end: the ester function of the methacrylate and the function of the methacrylate functional, if necessary hydrolyzed.
• any interval of values denoted by the expression “between a and b” represents the range of values greater than “a” and less than “b” (i.e. limits a and b excluded) while any interval of values denoted by the expression “from a to b” means the range of values going from “a” to “b” (that is to say including the strict limits a and b).
• alkyl denotes an alkyl radical having 1 to 2 carbon atoms
• alkoxy denotes an alkoxy radical having 1 to 2 carbon atoms.
• the compounds mentioned in the description can be of fossil origin or biobased. In the latter case, they can be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. In the same way, the compounds mentioned can also come from the recycling of materials already used, that is to say they can be, partially or totally, from a recycling process, or obtained from materials raw materials themselves from a recycling process.
• the expression “based on” used to define the constituents of the catalytic system means the mixture of these constituents, or the product of the reaction of some or all of these constituents with each other.
• the purpose of the process in accordance with the invention is to prepare a copolymer which bears a functional group covalently attached to one of the chain ends of the copolymer, the copolymer being a copolymer of a 1,3-diene and of ethylene or a copolymer of a 1,3-diene, ethylene and an ⁇ -monoolefin.
• ⁇ -monoolefin is meant an ⁇ -olefin which has a single carbon-carbon double bond, the double bonds in the aromatic compounds not being taken into account.
• styrene is considered an ⁇ -monoolefin.
• Step a) of the process in accordance with the invention is a polymerization reaction of a monomer mixture of a 1,3-diene and an olefin which makes it possible to prepare the copolymer chains of a 1,3-diene and an olefin, growing chains intended to react in the next step, step b), with a functionalizing agent, a methacrylate.
• the 1,3-diene of the monomer mixture of step a) is a single compound, that is to say a single (in English “one”) 1,3-diene, or a mixture of 1,3- dienes that differ from each other in chemical structure.
• Suitable 1,3-dienes are 1,3-dienes having 4 to 20 carbon atoms, such as 1,3-butadiene, isoprene, myrcene, b-farnesene and mixtures thereof.
• the 1,3-diene is preferably 1,3-butadiene, isoprene, myrcene, b-farnesene or their mixtures, in particular a mixture of at least two of them.
• the olefin of the monomer mixture of step a) is ethylene.
• the monomer mixture is a mixture of a 1,3-diene and ethylene and the reaction product of the polymerization of step a) is a polymer chain whose constituent units result from the insertion of ethylene and 1,3-diene in the growing chain.
• the copolymer prepared by this first variant is a copolymer of ethylene and of a 1,3-diene.
• the monomer mixture of step a) is a mixture of a 1,3-diene and an olefin which is itself a mixture of ethylene and an ⁇ - monoolefin.
• the reaction product of the polymerization of step a) is a polymer chain whose constituent units result from the insertion of ethylene, ⁇ -monoolefin and 1,3-diene in the growing chain.
• the ⁇ -monoolefin is preferably styrene or a styrene whose benzene ring is substituted by alkyl groups, more preferably styrene.
• the copolymer prepared by a preferred embodiment of the second variant is a copolymer of ethylene, of a 1,3-diene and of styrene.
• the monomer mixture from step a) contains more than 50% by mole of ethylene, the percentage being expressed relative to the total number of moles of monomers of the monomer mixture from step a).
• the monomer mixture contains an ⁇ -monoolefin, such as styrene, it preferably contains less than 40% by mole of the ⁇ -monoolefin, the percentage being expressed relative to the total number of moles of monomers of the monomer mixture of the step a).
• the copolymerization of the monomer mixture can be carried out in accordance with patent applications WO 2007054223 A2 and WO 2007054224 A2 using a catalytic system composed of a metallocene and an organomagnesium.
• metallocene an organometallic complex whose metal, in this case the neodymium atom, is linked to a molecule called ligand and consisting of two groups Cp 1 and Cp 2 linked together by a bridge P
• Cp 1 and Cp 2 groups which are identical or different, are chosen from the group consisting of fluorenyl groups, cyclopentadienyl groups and indenyl groups, these groups possibly being substituted or unsubstituted.
• the metallocene used as base constituent in the catalytic system corresponds to the formula (la)
• P being a group bridging the two Cp 1 and Cp 2 groups, and comprising a silicon or carbon atom
• Cp 1 and Cp 2 identical or different, being chosen from the group consisting of fluorenyl groups, cyclopentadienyl groups and indenyl groups, the groups being substituted or unsubstituted, Nd denoting the neodymium atom,
• L representing an alkali metal chosen from the group consisting of lithium, sodium and potassium
• N representing a molecule of an ether, x, whole number or not, being equal to or greater than 0, y, whole number, being equal to or greater than 0.
• Suitable ether is any ether which has the power to complex the alkali metal, in particular diethyl ether, methyltetrahydrofuran and tetrahydrofuran.
• substituted cyclopentadienyl, fluorenyl and indenyl groups mention may be made of those substituted by alkyl radicals having 1 to 6 carbon atoms or by aryl radicals having 6 to 12 carbon atoms or alternatively by trialkylsilyl radicals such as SiMe3.
• the choice of the radicals is also oriented by the accessibility to the corresponding molecules which are the substituted cyclopentadienes, fluorenes and indenes, because the latter are commercially available or easily synthesized.
• substituted fluorenyl groups mention may be made of those substituted in position 2, 7, 3 or 6, particularly 2,7-ditertiobutyl-fluorenyl, 3,6-ditertiobutyl-fluorenyl.
• Positions 2, 3, 6 and 7 respectively designate the position of the carbon atoms of the cycles as shown in the diagram below, position 9 corresponding to the carbon atom to which the bridge P is attached.
• cyclopentadienyl groups As substituted cyclopentadienyl groups, mention may be made of those substituted both in position 2 (or 5) and in position 3 (or 4), particularly those substituted in position 2, more particularly the tetramethylcyclopentadienyl group.
• Position 2 (or 5) designates the position of the carbon atom which is adjacent to the carbon atom to which the P bridge is attached, as shown in the diagram below. It is recalled that a substitution in position 2 or 5 is also called substitution in alpha of the bridge.
• Position 2 denotes the position of the carbon atom that is adjacent to the carbon atom to which the P bridge is attached, like this is shown in the diagram below.
• Cp and Cp 2 which are identical or different, are cyclopentadienyls substituted in alpha of the bridge, substituted fluorenyls, substituted indenyls or fluorenyl of formula CH or alternatively indenyl of formula C9H7. More preferably, Cp and Cp 2 , which are identical or different, are chosen from the group consisting of substituted fluorenyl groups and the unsubstituted fluorenyl group of formula CH .
• Cp and Cp are identical and each represents an unsubstituted fluorenyl group of formula CH, represented by the symbol Flu.
• the bridge P connecting the Cp and Cp groups has the formula ZR R 2 , in which Z represents a silicon or carbon atom, R and R 2 , which are identical or different, each represent an alkyl group comprising from 1 to 20 carbon atoms, preferably methyl.
• ZR R 2 Z advantageously represents a silicon atom, Si.
• metallocene is of formula (1-1), (1-2), (1-3), (1-4) or (1-5):
• the metallocene useful for the synthesis of the catalytic system can be in the form of crystallized powder or not, or even in the form of monocrystals.
• the metallocene can be present in a monomer or dimer form, these forms depending on the mode of preparation of the metallocene, as for example that is described in the patent application WO 2007054224 A2 or WO 2007054223 A2.
• the metallocene can be prepared conventionally by a process analogous to that described in patent application WO 2007054224 A2 or WO 2007054223 A2, in particular by reaction under inert and anhydrous conditions of the salt of an alkali metal of the ligand with a borohydride of rare earth, neodymium, 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.
• Organomagnesium another basic constituent of the catalytic system is the co-catalyst of the catalytic system.
• the organomagnesium can be a diorganomagnesium or a halide of an organomagnesium.
• the organomagnesium is of formula (IIa), (Mb), (Ile) or (lld) in which R 3 , R 4 , R 5 , R B , identical or different, represent a carbon group, R A represents a divalent carbon group, X is a halogen atom, m is a greater number or equal to 1, preferably equal to 1.
• R A can be a divalent aliphatic hydrocarbon chain, interrupted or not by one or more oxygen or sulfur atoms or else by one or more arylene groups.
• carbon group is meant a group which contains one or more carbon atoms.
• the carbon group can be a hydrocarbon group (hydrocarbyl group) or else a heterohydrocarbon group, that is to say a group comprising, in addition to carbon and hydrogen atoms, one or more heteroatoms.
• organomagnesians having a heterohydrocarbon group the compounds described as transfer agents in patent application WO2016092227 Al may be suitable.
• the carbon group represented by the symbols R 3 , R 4 , R 5 , R B and R A are preferably hydrocarbon groups.
• R A contains 3 to 10 carbon atoms, in particular 3 to 8 carbon atoms.
• R A is a divalent hydrocarbon chain.
• R A is an alkanediyl, branched or linear, a cycloalkanediyl or a xylenediyl radical. More preferably, R A is an alkanediyl. Even more preferably, R A is an alkanediyl having 3 to 10 carbon atoms.
• R A is an alkanediyl having 3 to 8 carbon atoms. Very advantageously, R A is a linear alkanediyl.
• 1,3-propanediyl, 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,8-octanediyl are very particularly suitable as group R A.
• the carbon groups represented by R 3 , R 4 , R 5 , R B can be aliphatic or aromatic. They can contain one or more heteroatoms such as an oxygen, nitrogen, silicon or sulfur atom. Preferably they are alkyl, phenyl or aryl. They can contain 1 to 20 carbon atoms.
• the alkyls represented R 3 , R 4 , R 5 , R B can contain 2 to 10 carbon atoms and are in particular ethyl, butyl, octyl.
• the aryls represented R 3 , R 4 , R 5 , R B can contain 7 to 20 carbon atoms and are in particular a phenyl substituted by one or more alkyls such as methyl, ethyl, isopropyl.
• R 3 , R 4 , R 5 are preferably alkyls containing 2 to 10 carbon atoms, phenyls or aryls containing 7 to 20 carbon atoms.
• R 3 comprises a benzene ring substituted by the magnesium atom, one of the carbon atoms of the benzene ring ortho to the magnesium being substituted by a methyl, an ethyl, an isopropyl or forming a ring with the carbon atom which is its nearest neighbor and which is meta to the magnesium, the other carbon atom of the benzene ring ortho to the magnesium being substituted by a methyl, an ethyl or an isopropyl and R 4 is alkyl.
• R 3 is advantageously the 1,3-dimethylphenyl, 1,3-diethylphenyl, mesityl, or 1,3,5 triethylphenyl and R 4 is advantageously ethyl, butyl, octyl.
• R 3 and R 4 are alkyls containing 2 to 10 carbon atoms, in particular ethyl, butyl, octyl.
• R 5 is an alkyl containing 2 to 10 carbon atoms, in particular ethyl, butyl, octyl.
• R B comprises a benzene ring substituted by the magnesium atom, one of the carbon atoms of the benzene ring ortho to the magnesium being substituted by a methyl, an ethyl, an isopropyl or forming a ring with the atom of carbon which is its nearest neighbor and which is meta to the magnesium, the other carbon atom of the benzene ring ortho to the magnesium being substituted by a methyl, an ethyl or an isopropyl. More preferably, R B is 1,3-dimethylphenyl, 1,3-diethylphenyl, mesityl, or 1,3,5 triethylphenyl.
• Suitable organomagnesium are butylethylmagnesium, butyloctylmagnesium, ethylmagnesium chloride, butylmagnesium chloride, ethylmagnesium bromide, butylmagnesium bromide, octylmagnesium chloride, octylmagnesium bromide, 1,3- dimethylphenylbutylmagnesium, 1,3-diethylphenylethylmagnesium, butylmesitylmagnesium, ethylmesitylmagnesium, 1,3-diethylphenylbutylmagnesium, 1,3-diethylphenylethylmagnesium, 1,3-diisopropylphenylbutylmagnesium, 1,3-disopropylphenylethylmagnesium, 1,3,5 -triethylphenylbutylmagnesium, 1,3,5-triethylmagnesium
• the organomagnesium compound of formula (Ile) can be prepared by a process, which comprises reacting a first organomagnesium of formula X'Mg-R A -MgX' with a second organomagnesium of formula R B -Mg-X', X 'representing a halogen atom, preferably bromine or chlorine, R B and R A being as defined above.
• X' is more preferably a bromine atom.
• the stoichiometry used in the reaction determines the value of m in formula (Ile).
• a molar ratio of 0.5 between the quantity of the first organomagnesium and the quantity of the second organomagnesium is favorable to the formation of an organomagnesium compound of formula (Ile) in which m is equal to 1, whereas a molar ratio greater than 0.5 will be more favorable to the formation of an organomagnesium compound of formula (Ile) in which m is greater than 1.
• a solution of the second organomagnesium is typically added to a solution of the first organomagnesium.
• the solutions of the first organomagnesium and of the second organomagnesium are generally solutions in an ether, such as diethyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran or the mixture of two or more of these ethers.
• the respective concentrations of the solutions of the first organomagnesium and of the second organomagnesium are respectively from 0.01 to 3 mol/L and from 0.02 to 5 mol/L. So more preferentially, the respective concentrations of the first organomagnesium and of the second organomagnesium are respectively from 0.1 to 2 mol/L and from 0.2 to 4 mol/L.
• the first organomagnesium and the second organomagnesium can be prepared beforehand by a Grignard reaction from magnesium metal and a suitable precursor in a reactor.
• the respective precursors have the formula X'-R A -X' and R B -X', R A , R B and X' being as defined previously.
• the Grignard reaction is typically implemented by adding the precursor to magnesium metal which is generally in the form of chips.
• iodine (b) typically in the form of a bead is introduced into the reactor before the addition of the precursor in order to activate the Grignard reaction in a known manner.
• the organomagnesium compound of formula (Ile) can be prepared by reaction of an organometallic compound of formula MR A -M and the organomagnesium of formula R B -Mg-X', M representing a lithium atom, sodium or potassium, X', R B and R A being as defined above.
• M represents a lithium atom, in which case the organometallic of formula MR A -M is an organolithium.
• the reaction of the organolithium and the organomagnesium is typically carried out in an ether such as diethyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, methylcyclohexane, toluene or their mixture.
• the reaction is also typically carried out at a temperature ranging from 0°C to 60°C.
• the contacting is preferably carried out at a temperature between 0°C and 23°C.
• the bringing into contact of the organometallic compound of formula MR A -M with the organomagnesium of formula R B -Mg-X' is preferably done by adding a solution of the organometallic compound MR A -M to a solution of the organomagnesium R B -Mg-X'.
• the solution of the organometallic compound MR A -M is generally a solution in a hydrocarbon solvent, preferably n-hexane, cyclohexane or methylcyclohexane
• the solution of the organomagnesium R B - Mg-X' is generally a solution in an ether, of preferably diethyl ether or dibutyl ether.
• the respective concentrations of the solutions of the organometallic compound and of the organomagnesium MR A -M and R B -Mg-X' are respectively from 0.01 to 1 mol/L and from 0.02 to 5 mol/L. More preferably, the respective concentrations of the solutions of the organometallic compound and of the organomagnesium MR A -M and R B -Mg-X' are respectively from 0.05 to 0.5 mol/L and from 0.2 to 3 mol/L.
• organomagnesiums take place under anhydrous conditions under an inert atmosphere, in stirred reactors. Typically, solvents and solutions are used under anhydrous nitrogen or argon.
• organomagnesium of formula (Ile) is formed, it is generally recovered in solution after filtration carried out under an inert and anhydrous atmosphere. It can be stored before use in its solution in airtight containers, for example capsulated bottles, at a temperature between -25°C and 23°C.
• the compounds of formula (IId) which are Grignard reagents are described for example in the book “Advanced Organic Chemistry” by J. March, 4th Edition , 1992, page 622-623 or in the book “Handbook of Grignard Reagents”, Edition Gary S. Silverman, Philip E. Rakita, 1996, page 502-503. They can be synthesized by bringing magnesium metal into contact with a dihalogen compound of formula XR A -X, R A being as defined according to the invention. For their synthesis, one can for example refer to the collection of volumes of “Organic Synthesis”.
• the organomagnesium compound constituting the catalytic system in particular of formula (IIa), (Mb), (Ile) or (IId) can be in the form of a monomer entity or in the form of an entity polymer.
• the organomagnesium (Ile) can be in the form of a monomer entity (R B -(Mg-R A ) m -Mg-R B )i or in the form of a polymer entity (R B -(Mg-R A ) m -Mg-R B ) p , p being an integer greater than 1, in particular dimer (R B -(Mg-R A ) m -Mg-R B )2, m being as previously defined.
• the organomagnesium of formula (IId) can be in the form of a monomer entity (X-Mg-R A -Mg-X)i or in the form of a polymer entity (X-Mg-R A -Mg-X) p , p being an integer greater than 1, in particular dimer (X-Mg-R A -Mg-X)2.
• the organomagnesium can also be in the form of an entity coordinated with one or more molecules of a solvent, preferably an ether such as diethyl ether, tetrahydrofuran or methyltetrahydrofuran.
• a solvent preferably an ether such as diethyl ether, tetrahydrofuran or methyltetrahydrofuran.
• X is preferably a bromine or chlorine atom, more preferably a bromine atom.
• the organomagnesium is preferably of formula (IIa).
• the quantities of co-catalyst and of metallocene reacted are such that the ratio between the number of moles of Mg of the co-catalyst and the number of moles of the rare earth of the metallocene, neodymium, preferably ranges from 0.5 to 200, more preferably from 1 to less than 20.
• the range of values ranging from 1 to less than 20 is in particular more favorable for obtaining copolymers of high molar masses.
• the catalytic system can be prepared conventionally by a method similar to that described in patent application WO 2007054224 A2 or WO 2007054223 A2.
• the co-catalyst in this case the organomagnesium and the metallocene, is 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, preferably in an aliphatic hydrocarbon solvent such as methylcyclohexane.
• the catalytic system is used as it is for step a).
• the catalytic system can be prepared by a method similar to that described in patent application WO 2017093654 Al or in patent application WO 2018020122 Al: it is said to be of the preformed type. For example, reacting in a solvent hydrocarbon the organomagnesium and the metallocene 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 lh to 12h a preformation monomer.
• the preformation monomer is preferably used according to a molar ratio (preformation monomer / metallocene metal) ranging from 5 to 1000, preferably from 10 to 500.
• the catalytic system of the preformed type Before its use in polymerization, the catalytic system of the preformed type can be stored under atmosphere inert, in particular at a temperature ranging from -20°C to room temperature (23°C).
• the catalytic system of the preformed type has as base constituent a preformation monomer chosen from 1,3-dienes, ethylene and their mixtures.
• the so-called preformed catalytic system contains, in addition to the metallocene and the co-catalyst, a preformation monomer.
• the preformation monomer is preferably 1,3-butadiene.
• the catalytic system is typically present in a solvent which is preferably the solvent in which it was prepared, and the concentration of rare earth metal, that is to say neodymium, of metallocene is then included in a range ranging from preferentially from 0.0001 to 0.2 mol/L more preferentially from 0.001 to 0.03 mol/L.
• the synthesis of the metallocene, the synthesis of the organomagnesium and the synthesis of the catalytic system take place under anhydrous conditions under an inert atmosphere.
• the reactions are carried out from solvents and anhydrous compounds under anhydrous nitrogen or argon.
• the polymerization of the monomer mixture is preferably carried out in solution, continuously or discontinuously.
• the polymerization solvent is typically a hydrocarbon solvent, preferably aliphatic.
• methylcyclohexane is most particularly suitable.
• the monomer mixture 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 monomer mixture.
• the monomer mixture and the catalytic system can be introduced simultaneously into the reactor containing the polymerization solvent, in particular in the case of continuous polymerization.
• the polymerization 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 40 to 150°C, preferably 40 to 120°C.
• a person skilled in the art adapts the polymerization conditions such as the polymerization temperature, the concentration of each of the reactants, the pressure of the reactor according to the composition of the monomer mixture, of the polymerization reactor, of the microstructure and of the desired macrostructure. of the copolymer chain.
• the polymerization is preferably carried out at constant monomer pressure.
• a continuous addition of each of the monomers or of one of them can be carried out in the polymerization reactor, in which case the polymerization reactor is a fed reactor.
• This embodiment is particularly suitable for random incorporation of the monomers.
• the polymerization of step a) is a random polymerization, which results in a random incorporation of the monomers of the monomer mixture used in step a).
• step b) is carried out.
• Step b) of the process in accordance with the invention brings together a functionalizing agent, a methacrylate, with the reaction product of step a) to introduce a single methacrylate monomer unit at one of the ends of the chain copolymer produced at the end of step a).
• Step b) is a functionalization reaction of the end of the chain of the copolymer without there being any subsequent polymerization of the methacrylate.
• step c After deactivation of the reactive sites by a polymer chain termination reaction (step c), a copolymer of a 1,3-diene and an olefin bearing at one of its chain ends a functional group is obtained. of formula -CH2-CH(CH B )-COOZ, Z being a carbon group.
• the function, substituent of the hydrocarbon group of the symbol R′ is a tertiary amine function, an alkoxysilane function, an ether function, a thioether function, a protected amine function or a protected thiol function.
• R' is a hydrocarbon group substituted by a tertiary amine function, an alkoxysilane function or an ether function.
• the hydrocarbon group of the symbols R and R′ is preferably saturated.
• the number of carbon atoms of the hydrocarbon group of the symbols R and R' is not limited per se.
• the hydrocarbon group can contain up to 20 carbon atoms.
• the hydrocarbon group of the symbol R contains from 1 to 8 carbon atoms, more preferably from 1 to 6 carbon atoms.
• the hydrocarbon group of the symbol R is advantageously an alkyl.
• the hydrocarbon group of the symbol R′ contains from 1 to 6 carbon atoms, more preferably from 1 to 3 carbon atoms.
• the hydrocarbon group of the symbol R′ is an alkyl group substituted by said function.
• An aralkyl is a monovalent radical which is derived from an alkyl radical by the replacement of one or more hydrogen atoms by aryl groups.
• R is more preferably alkyl.
• R' is an alkyl substituted by an al
• the methacrylate is preferably an alkoxy (Ci-C 2 )dialkyl (Ci-C 2 )silylalkyl (Ci-C 3 ) methacrylate such as methoxydimethylsilylmethyl methacrylate, ethoxydimethylsilylmethyl methacrylate, methoxydimethylsilylpropyl methacrylate, ethoxydimethylsilylpropyl methacrylate, a dialkoxy(Ci-C 2 )alkyl(Ci-C 2 )silylalkyl(Ci-C 3 ) methacrylate such as dimethoxymethylsilylmethyl methacrylate, diethoxymethylsilylmethyl methacrylate, dimethoxymethylsilylpropyl methacrylate , diethoxymethylsilylpropyl methacrylate, a trialkoxy (Ci-C 2 )silyl(Ci-C 3 )alkyl methacrylate such as me
• the second embodiment of the second alternative is most particularly preferred.
• the methacrylate is more preferably an alkoxydialkylsilylalkyl methacrylate, in particular an alkoxy(Ci-C 2 )dialkyl(Ci-C 2 )silylalkyl(Ci-C 3 ) methacrylate such as methoxydimethylsilylmethyl methacrylate, ethoxydimethylsilylmethyl methacrylate , methoxydimethylsilylpropyl methacrylate, ethoxydimethylsilylpropyl methacrylate, or a dialkoxyalkylsilylalkyl methacrylate, in particular a dialkoxy (Ci-C 2 )alkyl (Ci-C 2 )silylalkyl (Ci-C 3 ) methacrylate such as dimethoxy methacrylate (methyl)silyl)methyl, diethoxymethylsilylmethyl methacrylate, dimethoxymethylsilylpropyl methacrylate, diethoxy
• the methacrylates useful for the purposes of the invention can be commercial products. These are generally commercially available products. When the methacrylates are conditioned in the presence of a stabilizer, as is the case for most commercial methacrylates, they are typically used after removal of the stabilizer which can be carried out in a well-known manner by distillation or by treatment on columns of alumina.
• step b) is carried out in an aliphatic hydrocarbon solvent, such as methylcyclohexane.
• an aliphatic hydrocarbon solvent such as methylcyclohexane.
• it is carried out in the reaction medium resulting from step a). It is generally implemented by adding the methacrylate to the reaction product of step a) in its reaction medium with stirring.
• the reactor Before adding the methacrylate, the reactor is preferably degassed and inerted.
• the degassing of the reactor makes it possible to eliminate the gaseous residual monomers and also facilitates the addition of the methacrylate to the reactor. Inerting the reactor, for example with nitrogen, makes it possible not to deactivate the metal carbon bonds present in the reaction medium and necessary for the functionalization reaction of the copolymer.
• the methacrylate can be added pure or diluted in a hydrocarbon solvent, preferably aliphatic, such as methylcyclohexane. The methacrylate is left in contact with the reaction product of step a) for the time necessary for the functionalization reaction of the end of the chain of the copolymer.
• the functionalization reaction can typically be followed by chromatographic analysis to follow the consumption of the methacrylate.
• the functionalization reaction is preferably carried out at a temperature ranging from 23 to 120° C., for 1 to 60 minutes with stirring.
• the functionalization reaction is preferably carried out with a molar excess of methacrylate relative to the number of moles of neodymium and magnesium.
• the molar ratio between the number of moles of the methacrylate and the number of moles of neodymium and of magnesium is greater than 2, in particular greater than 5, more particularly comprised between 10 and 50.
• step b) is followed by step c).
• Stage c) chain termination reaction, is typically a reaction which makes it possible to deactivate the reactive sites still present in the reaction medium resulting from stage b).
• a chain terminator is brought into contact with the reaction product of step b), generally in its reaction medium, for example by adding the terminating agent to the reaction medium after of step b) or by pouring the reaction medium obtained at the end of step b) onto a solution containing the terminating agent.
• the terminating agent is generally in stoichiometric excess.
• the terminating agent is typically a protic compound, a compound which has a relatively acidic proton.
• terminating agent By way of terminating agent, mention may be made of water, carboxylic acids, in particular C -C fatty acids such as acetic acid, stearic acid, alcohols, aliphatic or aromatic, such as methanol, ethanol, isopropanol, phenolic antioxidants.
• carboxylic acids in particular C -C fatty acids such as acetic acid, stearic acid, alcohols, aliphatic or aromatic, such as methanol, ethanol, isopropanol, phenolic antioxidants.
• the relatively acidic proton can be a deuterium atom, which makes it possible to mark with an isotope the unit resulting from the 1,2 addition of the methacrylate on the chain end of the copolymer of 1,3-diene and 1 olefin.
• the process leads to a copolymer of a 1,3-diene and an olefin, monomers used in step a).
• the copolymer is a copolymer whose constituent units are those of 1,3-diene and olefin and whose chain end is bonded so covalent to a functional group of formula -CH2-CH(CH B )-COOZ.
• Z is a hydrocarbon group, preferably alkyl, aryl or arakyl, preferably containing 1 to 8 carbon atoms, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.
• Z is a hydrocarbon group substituted by a tertiary amine function, an alkoxysilane function, an ether function, a thioether function, a protected amine function or a protected thiol function.
• Step d) is an optional step depending on whether or not it is desired to hydrolyze the ester function of the non-functional methacrylate or to hydrolyze the alkoxysilane function, the ether function, the protected amine function or the protected thiol function by which the group is substituted.
• functional methacrylate hydrocarbon is typically a hydrolysis reaction of the ester function of the functional group or of the function by which the hydrocarbon group of R′ is substituted.
• step d) is a hydrolysis reaction of the ester function
• the ester function is hydrolyzed into the carboxylic acid function and the process thus leads to a copolymer of 1,3-diene and of the olefin bearing at the end of chain a functional group of formula -CH2-CH(CH B )-COOH.
• the methacrylate is preferably tert-butyl methacrylate.
• the hydrolysis reaction of the ester function to carboxylic acid can be carried out by treatment of the copolymer in solution with a solution of paratoluene sulphonic acid in tetrahydrofuran, followed by steam distillation, an operation commonly known as the term stripping, carried out under such acidic conditions, as described for example in patent application WO 03046066 Al.
• step d) is a reaction of hydrolysis of the alkoxysilane function into a silanol function
• the process leads to a copolymer of 1,3-diene and of the olefin bearing at the end of the chain a functional group of formula -CH2- CH(CH B )-COOZ, Z being a hydrocarbon group substituted by a silanol function.
• the hydrolysis reaction of the alkoxysilane function to the silanol function can be carried out by treating the copolymer in solution with aqueous hydrochloric acid, followed by stripping, for example according to the conditions described in patent application EP 2266819 Al .
• step d) is a hydrolysis reaction of the ether function to the alcohol function
• a trimethylsilyl halide such as trimethylsilyl iodide known to catalyze the hydrolysis of ethers to alcohols under mild conditions and the process then leads to a copolymer of 1,3-diene and of the olefin bearing at the end of the chain a functional group of formula —CH2-CH(CH B )—COOZ, Z being a hydrocarbon group substituted by an alcohol function.
• step d) is a hydrolysis reaction to deprotect an amine or thiol function protected, for example, by a trimethylsilyl group
• the hydrolysis reaction can be carried out in an acidic or preferably basic medium, for example under the conditions described in patent application WO 2017097831 Al.
• the copolymer prepared according to the process in accordance with the invention can be separated from the reaction medium of stage c) or d) according to processes well known to those skilled in the art, for example by an operation of evaporation of the solvent under pressure reduced or by a steam stripping operation.
• the copolymer, another object of the invention is a copolymer which can be prepared by the process in accordance with the invention.
• the olefin is ethylene or a mixture of ethylene and an ⁇ -monoolefin.
• the constituent units of the copolymer are those which result from the polymerization of the 1,3-diene and the olefin.
• the olefin is ethylene
• the constituent units are those resulting from the polymerization of 1,3-diene and ethylene
• the copolymer is a copolymer of ethylene and of a
• the olefin is a mixture of ethylene and an ⁇ -monoolefin
• the constituent units are those resulting from the polymerization of 1,3-diene, ethylene and ⁇ -monoolefin and the copolymer is a copolymer of ethylene, a 1,3-diene and an ⁇ -monoolefin.
• the ⁇ -monoolefin is styrene.
• 1,3-diene is a single compound, that is to say a single (in English "one") 1,3-diene, or a mixture of 1,3-dienes which differ from each other by the chemical structure. Suitable as
• the copolymer is a random copolymer of 1,3-diene and of the olefin.
• Such a copolymer can be prepared by the process in accordance with the invention according to the mode in which the polymerization reaction is carried out at constant monomer pressure and a continuous addition of each of the monomers or of one of them is carried out in the polymerization reactor.
• the 1,3-diene is 1,3-butadiene, isoprene, myrcene, b-farnesene or their mixtures such as a mixture of at least two of them.
• the mixture of at least two of them is advantageously a mixture which contains 1,3-butadiene.
• the 1,3-diene is a mixture of 1,3-dienes which contains 1,3-butadiene.
• the copolymer in accordance with the invention contains 1,3-butadiene units and cyclic units, 1,2-cyclohexane units.
• the 1,2-cyclohexane units are of formula (I).
• the mechanism for obtaining such a microstructure is for example described in the document Macromolecules 2009, 42, 3774-3779.
• the polymer in accordance with the invention contains 1,2-cyclohexane units, it preferably contains at most 15% by mole, the percentage being expressed relative to all the units resulting from the polymerization of 1,3-diene and olefin.
• a copolymer can be prepared by the process in accordance with the invention according to the mode in which the metallocene of the catalytic system has as ligand two fluorenyl groups, substituted or not.
• the copolymer contains more than 50% by mole of ethylene unit, the percentage being expressed relative to all the units resulting from the polymerization of the 1,3-diene and the olefin.
• the copolymer in accordance with the invention also has the other characteristic of carrying at one of its chain ends a functional group of formula —CH2-CH(CH B )-COOZ.
• the functional group is covalently attached to the chain end of the copolymer.
• the methylene (CH2) of the functional group is covalently bonded to a carbon atom of a constituent unit of the copolymer of a 1,3-diene and an olefin.
• the functional group carried at the end of the chain by the copolymer of a 1,3-diene and an olefin is of formula -CH2-CH(CH B )-COOZ, Z being a hydrogen atom or a hydrocarbon group, preferably saturated.
• the number of carbon atoms of the hydrocarbon group represented by Z is not limited per se.
• the hydrocarbon group represented by Z can contain up to 20 carbon atoms. Preferably, it contains from 1 to 8 carbon atoms, more preferably from 1 to 6 carbon atoms. It is alkyl, aryl or arakyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, benzyl.
• the functional group carried at the end of the chain by the copolymer of a 1,3-diene and an olefin is of formula -CH2-CH(CH B )-COOZ, Z being a hydrocarbon group substituted by an amine, alkoxysilane, silanol, ether, alcohol, thioether or thiol function, preferably by an amine, alkoxysilane, silanol or ether function.
• the hydrocarbon group substituted by said function is an alkyl substituted by said function, more preferably an alkyl substituted by said function and having 1 to 3 atoms.
• Z represents an alkyl substituted by a dialkylamino group, in particular Z represents an N,N-dialkyl(Ci-C3)aminoalkyl (C1-C3), such as 2-(dimethylamino) ethyl, 2-(diethylamino)ethyl, 2-(diisopropylamino)ethyl.
• Z represents an alkyl substituted by an alkoxydialkylsilyl group, in particular alkoxy(Ci-C2)dialkyl(Ci-C2)silyl such as methoxydimethylsilyl, methoxydiethylsilyl, ethoxydimethylsilyl, ethoxydiethylsilyl, by a dialkoxyalkylsilyl group, in particular dialkoxy(Ci-C2)alkyl(Ci-C2)silyl such as dimethoxymethylsilyl, diethoxymethylsilyl, dimethoxyethysilyl, diethoxyethylsilyl, or by a trialkoxysilyl group, in particular trialkoxy(Ci-C2)silyl such as trimethoxysilyl, triethoxysilyl.
• alkoxydialkylsilyl group in particular alkoxy(Ci-C2)dialkyl(Ci-C2)silyl such as methoxydi
• Z preferably represents an alkoxy (Ci-C2)dialkyl (Ci-C2)silylalkyl (Ci-C3) such as methoxydimethylsilylpropyl, ethoxydimethylsilylpropyl, a dialkoxy (Ci-C2)alkyl (Ci-C2 )silylalkyl(Ci-C3) such as dimethoxymethylsilylmethyl, diethoxymethylsilylpropyl, or a trialkoxy(Ci-C2)silylalkyl(Ci-C3) such as trimethoxysilylmethyl, 3-trimethoxysilylpropyl.
• alkoxy (Ci-C2)dialkyl (Ci-C2)silylalkyl (Ci-C3) such as methoxydimethylsilylpropyl, ethoxydimethylsilylpropyl
• Z represents an alkyl substituted by a hydroxydialkylsilyl group, in particular hydroxydialkyl (Ci-C2)silyl such as hydroxydimethylsilyl, hydroxydiethylsilyl, by a dihydroxyalkylsilyl group, in particular dihydroxyalkyl (Ci -C2)silyl such as dihydroxymethylsilyl, dihydroxyethylsilyl.
• Z preferably represents a hydroxydialkyl (Ci-C2)silylalkyl (Ci-C3) such as hydroxydimethylsilylpropyl.
• Z represents an alkyl substituted by an ether function, in particular is 2-ethoxyethyl, ethyleneglycolmethylether, diethyleneglycolbutylether, diethyleneglycolmethylether, furfuryl, tetrahydrofurfuryl.
• Z represents an alkyl substituted by a thioether function and is preferably alkylthioalkyl such as 2-(methylthio)ethyl.
• Z is an alkyl substituted by a protected amine function, namely primary or secondary amine protected, for example by trialkylsilyl groups, in particular trimethylsilyl groups.
• Z is an alkyl substituted by a primary or secondary amine function.
• Z is an alkyl substituted by a thiol function protected, for example by trialkylsilyl groups, in particular trimethylsilyl groups.
• Z is an alkyl substituted by a thiol function.
• the copolymer in accordance with the invention bears at the end of the chain a functional group of formula —CH2-CH(CH B )—COOZ, Z being a hydrocarbon group substituted by an alkoxysilane or silanol function.
• Z being a hydrocarbon group substituted by an alkoxysilane or silanol function.
• the copolymer according to the first variant can be prepared by the first alternative of the process involving a non-functional methacrylate and, where appropriate, comprising a hydrolysis reaction of the ester function into the carboxylic acid function, as described in the particular embodiments of the process. .
• the copolymer according to the second variant can be prepared according to the second alternative of the process involving a functional methacrylate, more particularly by the implementation of one of the six embodiments described of this second alternative according to the nature of the function of the methacrylate.
• the process comprises, where appropriate, a hydrolysis reaction of the function of the methacrylate chosen from the hydrolysis modes described according to the nature of the function to be hydrolyzed.
• Mode 1 Process for the preparation of a copolymer of a 1,3-diene and an olefin bearing at one of its chain ends a functional group of formula -CH2-CH(CH B )-COOZ, Z being a hydrogen atom or a carbon group, which process comprises the successive stages a), b) and c) and, where appropriate, a stage d),
• step a) being the polymerization of a monomer mixture containing a 1,3-diene and an olefin in the presence of a catalytic system based on at least one metallocene of formula (la) and a organomagnesium
• Cp 1 and Cp 2 identical or different, being chosen from the group consisting of fluorenyl groups, cyclopentadienyl groups and indenyl groups, the groups being substituted or unsubstituted,
• P being a group bridging the two Cp 1 and Cp 2 groups, and comprising a silicon or carbon atom
• L representing an alkali metal chosen from the group consisting of lithium, sodium and potassium
• N representing a molecule of an ether, x, whole number or not, being equal to or greater than 0, y, whole number, being equal to or greater than 0, the olefin being ethylene or a mixture of ethylene and d an a-monoolefin,
• step b) being the reaction of a methacrylate with the reaction product of the polymerization of step a),
• Mode 3 Process according to mode 2 in which the hydrocarbon group of the symbol R contains 1 to 8 carbon atoms.
• Mode 4 Process according to mode 2 or 3 in which the hydrocarbon group of the symbol R is an alkyl.
• Mode 5 Process according to any one of modes 2 to 4, in which step d) is a hydrolysis reaction of the ester function of the functional group to form a carboxylic acid.
• Mode 7 Process according to mode 6 in which R′ is a hydrocarbon group substituted by a tertiary amine function, an alkoxysilane function or an ether function.
• Mode 8 Process according to mode 6 or 7 in which the hydrocarbon group of the symbol R' contains 1 to 3 carbon atoms.
• Mode 9 Process according to any one of modes 6 to 8 in which the hydrocarbon group of the symbol R' is an alkyl.
• Method 15 Process according to any one of modes 6 to 14, in which step d) is a hydrolysis reaction of the function by which the hydrocarbon group of R′ is substituted.
• Mode 16 Process according to mode 15 in which step d) is a hydrolysis reaction of the alkoxysilane function by which the hydrocarbon group of R′ is substituted with the silanol function.
• Mode 17 Process according to any one of modes 1 to 16 in which step b) is carried out with a molar ratio between the number of moles of the methacrylate and the number of moles of neodymium and magnesium greater than 2.
• Mode 18 Process according to any one of modes 1 to 17, in which step b) is carried out in an aliphatic hydrocarbon solvent.
• Method 19 Process according to any one of modes 1 to 18, in which Cp 1 and Cp 2 , identical or different, are chosen from the group consisting of substituted fluorenyl groups and the unsubstituted fluorenyl group of formula C13H8.
• Mode 20 A process according to any of Modes 1 to 19, wherein Cp 1 and Cp 2 are the same and each represents an unsubstituted fluorenyl group of formula C13H8.
• Mode 21 Process according to any one of modes 1 to 20, in which the bridge P connecting the groups Cp 1 and Cp 2 is of formula ZR 1 R 2 , in which Z represents a silicon or carbon atom, R 1 and R 2 , which are identical or different, each represent an alkyl group comprising from 1 to 20 carbon atoms.
• Mode 22 Process according to any one of modes 1 to 21, in which the metallocene is of formula (1-1), (1-2), (1-3), (1-4) or (1-5 ):
• Mode 23 Process according to any one of modes 1 to 22, in which the organomagnesium is of formula (IIa), (Mb), (Ile) or (lld) in which R 3 , R 4 , R 5 , R B identical or different, represent a carbon group, R A represents a divalent carbon group, X is a halogen atom, m is a number greater than or equal to 1
• Mode 24 Process according to mode 23 in which R A is an alkanediyl having 3 to 10 carbon atoms.
• Mode 25 Process according to mode 23 in which R 3 comprises a benzene ring substituted by the magnesium atom, one of the carbon atoms of the benzene ring ortho to the magnesium being substituted by a methyl, an ethyl, an isopropyl or forming a ring with the carbon atom which is its nearest neighbor and which is meta to the magnesium, the other carbon atom of the benzene ring ortho to the magnesium being substituted by a methyl, an ethyl or an isopropyl and R 4 is an alkyl.
• Mode 26 Process according to mode 23 in which R 3 and R 4 are alkyls containing 2 to 10 carbon atoms.
• Mode 27 Process according to mode 23 in which R 5 is an alkyl containing 2 to 10 carbon atoms.
• Mode 28 Process according to mode 23 or 24 in which R B comprises a benzene ring substituted by the magnesium atom, one of the carbon atoms of the benzene ring ortho to the magnesium being substituted by a methyl, an ethyl, a isopropyl or forming a ring with the carbon atom which is its closest neighbor and which is meta to the magnesium, the other carbon atom of the benzene ring ortho to the magnesium being substituted by a methyl, an ethyl or an isopropyl.
• Mode 29 Process according to mode 23 or 24 or 27 in which X is a bromine or chlorine atom.
• Mode 30 Process according to any one of Modes 1 to 29, in which the ratio between the number of moles of Mg of the co-catalyst and the number of moles of the rare earth of the metallocene, neodymium, ranges from 0.5 at 200.
• Mode 31 Process according to any one of modes 1 to 30, in which the ratio between the number of moles of Mg of the co-catalyst and the number of moles of the rare earth of the metallocene, neodymium, ranges from 1 to less of 20.
• Mode 32 Process according to any one of modes 1 to 31, in which the monomer mixture of step a) contains more than 50% by mole of ethylene, the percentage being expressed relative to the total number of moles of monomers of the monomer mixture from step a).
• Mode 33 A process according to any of Modes 1 to 32, wherein the 1,3-diene contains 4 to 20 carbon atoms.
• Mode 34 Process according to any one of Modes 1 to 33, in which the 1,3-diene is 1,3-butadiene, isoprene, myrcene, b-farnesene or mixtures thereof.
• Mode 35 Process according to any one of modes 1 to 34 in which the copolymer of a 1,3-diene and an olefin is a copolymer of ethylene and a 1,3-diene or a copolymer of ethylene, a 1,3-diene and styrene.
• Mode 36 Process according to any one of modes 1 to 35 in which the molar ratio between the number of moles of the methacrylate and the number of moles of neodymium and of magnesium is greater than 2.
• Mode 37 Process according to any one of modes 1 to 36 in which the molar ratio between the number of moles of the methacrylate and the number of moles of neodymium and of magnesium is greater than 5.
• Mode 38 Process according to any one of modes 1 to 37 in which the molar ratio between the number of moles of the methacrylate and the number of moles of neodymium and of magnesium is between 10 and 50.
• Mode 39 Process according to any one of modes 1 to 38 in which in step c) a protic compound is brought into contact with the reaction product of step b).
• Mode 40 Process according to mode 39 in which the protic compound is an alcohol, aliphatic or aromatic.
• Mode 41 Copolymer of a 1,3-diene and an olefin bearing at one of its chain ends a functional group of formula -CH2-CH(CHB)-COOZ, Z being a hydrogen atom or a carbon group, the olefin being ethylene or a mixture of ethylene and an ⁇ -monoolefin.
• Mode 42 Copolymer according to mode 41 in which the functional group is of formula -CH2-CH(CHB)-COOZ, Z being a hydrogen atom or a hydrocarbon group.
• Mode 43 Copolymer according to mode 41 in which the functional group is of formula -CH2-CH(CHB)-COOZ, Z being a hydrocarbon group substituted by an amine, alkoxysilane, silanol, ether, alcohol, thioether or thiol function.
• Mode 44 Copolymer according to mode 43 in which Z is a hydrocarbon group substituted by an amine, alkoxysilane, silanol or ether function.
• Mode 45 Copolymer according to mode 43 or 44 in which the hydrocarbon group substituted by said function is an alkyl substituted by said function.
• Mode 46 A copolymer of any one of Modes 43 to 45 wherein the hydrocarbon group substituted by said function is an alkyl substituted by said function and having 1 to 3 carbon atoms.
• Mode 47 Copolymer according to any one of modes 43 to 46 in which Z represents an N,N-dialkyl (Ci-C3)aminoalkyl (C1-C3).
• Mode 48 Copolymer according to any one of modes 43 to 46 in which Z is a hydrocarbon group substituted by an alkoxysilane or silanol function.
• Mode 49 Copolymer according to mode 48 in which Z represents an alkoxy (Ci-C2)dialkyl(Ci-C2)silylalkyl(Ci-C3), a dialkoxy(Ci-C2)alkyl(Ci-C2)silylalkyl(Ci-C3 ) or a trialkoxy (Ci-C2)silylalkyl (Ci-C 3 ).
• Mode 50 Copolymer according to mode 48 in which Z represents a hydroxydialkyl (Ci-C 2 )silylalkyl (Ci-C3).
• Mode 51 A copolymer according to any of modes 41 to 50, which copolymer is a random copolymer of 1,3-diene and olefin.
• Mode 52 Copolymer according to any one of modes 41 to 51 in which ⁇ -monoolefin is styrene.
• Mode 53 Copolymer according to any one of modes 41 to 52, which copolymer contains more than 50% by mole of ethylene unit.
• Mode 54 Copolymer according to any one of modes 41 to 53 in which the 1,3-diene is 1,3-butadiene, isoprene, myrcene, b-farnesene or mixtures thereof.
• Mode 55 A copolymer according to any of Modes 41 to 54, which copolymer contains 1,3-butadiene units and 1,2-cycloclohexane units.
• Mode 56 Copolymer according to mode 55, which copolymer contains at most 15% by mole of 1,2-cycloclohexane units, the percentage being expressed relative to all the units resulting from the polymerization of 1,3-diene and olefin.
• Steric exclusion chromatography or SEC Size Exclusion Chromatography
• the macromolecules are separated according to their hydrodynamic volume, the largest being eluted first.
• 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 steric exclusion chromatography (SEC: Size Exclusion Chromatography) triple detection.
• SEC Size Exclusion Chromatography
• Triple detection steric 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 the dn/dc.
• the 1 g/l solution in tetrahydrofuran previously prepared and filtered is used, which is injected into the chromatographic chain.
• the equipment used is a “Wyatt” chromatographic chain.
• 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 made up 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 Wyatt multi-angle static light with a wavelength of 658 nm and trade name “DAWN HELEOS 8+”.
• the value of the refractive index increment dn/dc of the sample solution obtained above is integrated.
• the chromatographic data processing software is the “ASTRA from Wyatt” system.
• the functionalization products of the copolymers are characterized by 1 H, 13 C, 29 Si NMR spectrometry.
• the NMR spectra are recorded on a Brüker Avance III 500 MHz spectrometer equipped with a “wide band” BBFOz-grad 5 mm cryoprobe.
• the quantitative X H NMR experiment uses a simple 30° pulse sequence and a repetition delay of 5 seconds between each acquisition. 64 to 256 accumulations are made.
• the quantitative 13 C NMR experiment uses a simple 30° pulse sequence with proton decoupling and a repetition delay of 10 seconds between each acquisition. 1024 to 10240 accumulations are made.
• Two-dimensional 1 H/ 13 C and 1 H/ 29 Si experiments are used to determine the structure of functional polymers.
• the axis of chemical shifts 29 Si is calibrated with respect to the signal of the tetramethylsilane (TMS) at 0 ppm (addition of a few micro liters of TMS in the NMR tube).
• the metallocene [ ⁇ Me2SiFlu2Nd(p-BH 4 )2Li(THF) ⁇ is prepared according to the procedure described in patent application WO 2007054224.
• the BOMAG butyloctylmagnesium (20% in heptane, at 0.88 mol L 1 ) comes from Chemtura and is stored in a Schlenk tube under an inert atmosphere.
• Ethylene of N35 quality, comes from Air Liquide and is used without prior purification.
• 1,3-butadiene and myrcene are purified on alumina guards.
• the functionalizing agents used are methyl methacrylate (MMA), 2- (dimethylamino) ethyl methacrylate (DMAEMA), furfuryl methacrylate (FurMA), 3- (trimethoxysilyl) propyl methacrylate (TMSiPMA) from Sigma-Aldrich and 3- (dimethoxymethylsilyl)propylmethacrylate (DMMSiPMA) from ABCR.
• MMA methyl methacrylate
• DMAEMA 2- (dimethylamino) ethyl methacrylate
• FurMA furfuryl methacrylate
• TMSiPMA 3- (trimethoxysilyl) propyl methacrylate
• DMMSiPMA 3- (dimethoxymethylsilyl)propylmethacrylate
• the methacrylates and acrylates are used after purification on alumina guards and after bubbling with nitrogen.
• MCH methylcyclohexane
• Examples 1 to 6 Synthesis of copolymers of ethylene and 1,3-butadiene with 80% by mole of ethylene and 20% by mole of 1,3-butadiene:
• catalytic systems are prepared according to the method disclosed in patent application WO 2007054224 and described below.
• the co-catalyst is added, then the metallocene.
• the quantity of metallocene introduced is 40 mg, the ratio between the number of moles of Mg of the co-catalyst and the number of moles of Nd of the metallocene is 4.5.
• the activation time is 10 minutes, the reaction temperature is 20°C.
• the polymerization is carried out at 80° C. and at an initial pressure of 4 bars absolute in the 500 ml glass reactor containing 300 ml of polymerization solvent, methylcyclohexane, the catalytic system.
• the 1,3-butadiene and the ethylene are introduced in the form of a gaseous mixture containing 20% molar of 1,3-butadiene.
• the polymerization reaction is stopped by cooling and degassing the reactor.
• the copolymer is recovered by precipitation in methanol, then dried.
• the reactor is degassed, then a functionalization agent is added to carry out the functionalization reaction according to the procedure described.
• the contents of the reactor are degassed, then the functionalizing agent, a methacrylate or an acrylate, is introduced under an inert atmosphere by overpressure according to a number of equivalents which is equal to the ratio between the number of moles of functionalizing agent and the total number of moles of magnesium and neodymium.
• the reaction medium is stirred for 15 to 60 minutes at 80° C., then degassed. Unless otherwise indicated, the reaction medium is then precipitated in methanol.
• the polymer is redissolved in toluene, then precipitated in methanol.
• the polymer is dried at 60° C. under vacuum to constant mass. It is then analyzed by SEC (THF), CH, 13 C , 29 Si NMR.
• the functionalization reaction is followed by the addition of deuterated methanol (1ml, MeOD) before precipitation of the polymer in the methanol.
• the catalyst system is a preformed catalyst system. It is prepared in methylcyclohexane from the metallocene, [Me2Si(Flu)2Nd(p-BH 4 )2Li(THF)j, from the co-catalyst, butyloctylmagnesium (BOMAG), and from a preformation monomer, 1,3-butadiene. It is prepared according to a preparation method in accordance with paragraph 11.1 of patent application WO 2017093654 Al.
• the polymerization reaction is carried out in a steinie bottle according to the following procedure:
• the steinie bottle is then immersed in a bath thermostated at 80° C. for 60 min before the functionalization step carried out according to the procedure described for Examples 2 to 6, with the difference that the steinie bottle is used instead of the reactor. .
• the conditions of the functionalization reaction specific to each example, as well as the characteristics of the copolymers appear in Table 2.
• the NMR analyzes show a level of functionalization greater than 80%.
• Examples 11 to 13 Synthesis of copolymers of ethylene, 1,3-butadiene and myrcene with 70% by mole of ethylene, 15% by mole of 1,3-butadiene and 15% by mole of myrcene:
• the ethylene flow rate is set at 40 g/min, the myrcene and the butadiene are injected independently and are slaved to the ethylene flow rate according to the myrcene/ethylene mass ratio equal to 1.54 and according to the butadiene/ethylene mass ratio equal to 0.24.
• 950 mL of the preformed catalytic system at a concentration of 0.007 mol/L prepared according to the preceding protocol is introduced into the polymerization medium.
• the polymerization reaction carried out at 80° C. is stopped when nearly 6500 g of polymer are formed: the polymer is recovered after a stripping step.
• the polymer is then dried on a worm machine equipped with a single screw at 150°C.
• the polymerization is stopped by adding the functionalizing agent at 80° C. after formation of 6300 to 6500 g of polymer.
• Example 4 is an example not in accordance with the invention, since the functionalizing agent is not a methacrylate, but an acrylate, methyl acrylate.
• Example 4 shows that the functionalization of the polymer does not take place when an acrylate is used instead of a methacrylate.
• the other examples 6 to 13 illustrate the functionalization of the polymers by using methacrylates with a structure different from that of an alkyl methacrylate, in particular by using functional methacrylates.

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