Telechelic polymers based on ethylene and 1,3-dienes

Abstract

The present invention relates to telechelic polymers of formula Z1-POLY-Z2, wherein the term "POLY" denotes a polymer chain comprising 1,3-diene units, ethylene units and cyclic units 1,2-cyclohexane units, Z1 and Z2 denote groups comprising a functionality, Z1 and Z2 are identical, said polymers having a macrostructure defined by a polydispersity of less than 1.5 or a number average molecular weight of more than 10000 g / mol.

Description

Technical Field

[0001] The field of this invention is based on telechelic copolymers of ethylene and 1,3-diene. Background Technology

[0002] Copolymers of ethylene and 1,3-diene are broadly described. They are typically obtained by catalytic polymerization of ethylene and 1,3-diene in the presence of metallocene and co-catalysts. In EP 1092731, WO 2004 / 035639, WO 2007 / 054224, and WO2018 / 224776, copolymers of ethylene and 1,3-diene are characterized by their pristine microstructure, as they also contain six-membered cyclic units resulting from very specific insertions of ethylene and 1,3-butadiene. This pristine microstructure has also been observed in ternary polymers based on ethylene, 1,3-butadiene, and another monomer, as described, for example, in WO 2020 / 128196A1.

[0003] In the synthesis of these polymers, the cocatalysts are organolithium, organomagnesium, or organoaluminum reagents. When the cocatalyst is an organomagnesium reagent, it is usually an organomagnesium chloride or an organomagnesium reagent in which magnesium atoms are bonded to two aliphatic groups (e.g., dibutylmagnesium, butylethylmagnesium, and butyloctylmagnesium).

[0004] Functional copolymers of ethylene and 1,3-diene are also described. These are obtained through a functionalization reaction following polymerization, typically carried out at the end of polymerization by the addition of a modifier. This first method enables functionalization of only one end of the polymer chain. An alternative to this first method is the proposed use of a functionalization transfer agent instead of a co-catalyst. Such functionalization transfer agents, described in patent applications WO 2016 / 092237 and WO 2013 / 135314, are, for example, organomagnesium reagents with amine, ether, or vinyl functionalization. This alternative effectively eliminates the additional functionalization step following polymerization to form the functionalized polymer. However, similar to the first method, this alternative results in functionalization of only one end of the polymer chain unless an additional functionalization step is performed at the end of polymerization.

[0005] Therefore, the synthesis of telechelic copolymers of ethylene and 1,3-diene requires a combination of the two functionalization methods described above. Since the chemical substances involved in the two functionalization methods are different, the functional groups that attach these functional groups to the end units of the polymer chain are different functional groups, even if the functions at both ends are the same. In other words, the functional groups carried at one end of the chain are not strictly the same as those carried at the other end.

[0006] However, copolymers of ethylene and 1,3-diene with exactly the same functional groups at the ends of the polymer chains may be of interest, for example, to obtain polymers with identical reactivity at the chain ends, or even to obtain completely symmetrical polymers without any structural and reactivity inhomogeneities.

[0007] A 1,3-butadiene homopolymer or copolymer functionalized with the same, partially hydrogenated groups at both chain ends has been described in patent application EP 1314744 A2. Functional groups are inserted at both chain ends using a dilithiation initiator via an anionic polymerization mechanism. The resulting functional polymer possesses both macroscopic and microscopic structures derived from polymers synthesized via anionic polymerization. Therefore, a relatively narrow molecular distribution of the functional polymer can be obtained, but the microstructure of the functional polymer is solely that obtained through anionic polymerization.

[0008] For example, WO 2008 / 27269A2 describes copolymers of propylene and 1,3-butadiene functionalized at both chain ends using the same group (in this case, vinyl). The insertion of functional groups at the polymer ends occurs through a degradation reaction of the propylene and 1,3-butadiene copolymer in the presence of ethylene. Due to the reaction mechanism of degradation of the polymer chains by substitution, the functionalized polymers exhibit a broad molecular distribution and relatively low number-average molecular weight. Summary of the Invention

[0009] The applicant has developed a novel copolymer based on ethylene and 1,3-diene, wherein the copolymer has the same functional groups at each end. Its advantage lies in simultaneously possessing the macroscopic structural characteristics of polymers obtained by anionic polymerization and the microscopic structural characteristics of polymers obtained by catalytic polymerization.

[0010] Therefore, the present invention relates to telechelic polymers of formula (I).

[0011] Z1-POLY-Z2(I)

[0012] The term "POLY" refers to a polymer chain containing 1,3-diene units, ethylene units, and 1,2-cyclohexane units of formula (II).

[0013]

[0014] Z1 and Z2 represent functional groups.

[0015] Z1 and Z2 are the same.

[0016] The polymer has a macroscopic structure defined by a dispersion of less than 1.5 or a number-average molecular weight of greater than 10,000 g / mol. Detailed Implementation

[0017] Any numerical interval expressed as “between a and b” represents a range of values ​​greater than “a” and less than “b” (i.e., excluding the limits a and b), while any numerical interval expressed as “from a to b” means a range of values ​​extending from “a” to “b” (i.e., including the strict limits a and b).

[0018] The term "based on" used to define the components of a catalytic system or composition means a mixture of these components, or some or all of these components and the reaction products of each other.

[0019] Unless otherwise stated, the content of units resulting from the insertion of monomers into copolymers is expressed as a molar percentage relative to all monomer units constituting the polymer.

[0020] The compounds mentioned in the specification may be fossil-derived compounds or bio-based compounds. In the case of bio-based compounds, they may be partially or wholly derived from biomass or obtained from renewable starting materials derived from biomass. Similarly, the mentioned compounds may also be derived from the recycling of already used materials, i.e., they may be partially or wholly derived from recycling processes or obtained from raw materials that are themselves derived from recycling processes.

[0021] The essential characteristic of the polymer according to the invention is that it comprises a polymer chain called POLY, which contains ethylene units. In a known manner, the ethylene unit is a unit having -(CH2-CH2)- units. Preferably, the polymer chain contains more than 50 mol% ethylene units.

[0022] The polymer chain comprises 1,3-diene units. In a known manner, 1,3-diene units can be inserted into the growing polymer chain via 1,4-intercalation, 2,1-intercalation, or 3,4-intercalation (in the case of substituted dienes (e.g., isoprene)) to form 1,3-diene units with 1,4, 1,2, or 3,4 configurations, respectively. Preferably, the 1,2-configured and 3,4-configured 1,3-diene units account for more than 50 moles of the total 1,3-diene units.

[0023] According to the present invention, the 1,3-diene constituting the monomer unit of the POLY polymer chain is a single compound (i.e., a single 1,3-diene) or a mixture of 1,3-dienes with different chemical structures. Any catalytically polymerizable 1,3-diene is suitable for use. For example, 1,3-dienes containing 4 to 20 carbon atoms may be mentioned. The 1,3-diene is preferably a mixture of 1,3-dienes (one of which is 1,3-butadiene) or 1,3-butadiene.

[0024] According to the present invention, the polymer chain comprises a six-membered ring unit corresponding to formula (II).

[0025]

[0026] The presence of these cyclic structures in the polymer chain arises from a very specific insertion during the copolymerization of ethylene and 1,3-butadiene, as described, for example, in Macromolecules 2009, 42, 3774-3779. Preferably, the polymer chain contains no more than 15 mol% of 1,2-cyclohexane units. The content of 1,2-cyclohexane units in the polymer chain varies depending on the respective contents of ethylene and 1,3-butadiene in the polymer chain. For the highest ethylene content in the polymer, the polymer chain typically contains less than 10 mol% of 1,2-cyclohexane units, and for the lowest ethylene content in the polymer, the polymer chain may contain more than 10% of 1,2-cyclohexane units, for example, up to 15%.

[0027] According to a first variant of the invention, the polymer chain referred to as "POLY" is a copolymer chain of 1,3-diene and ethylene. In other words, the monomer unit of the polymer chain represented by the name "POLY" is a unit produced by copolymerization of ethylene and 1,3-diene.

[0028] According to a second variant of the invention, the polymer chain referred to as "POLY" is a ternary polymer chain of 1,3-diene, ethylene, and α-monoolefin. The term "α-monoolefin" means an α-olefin containing a single carbon-carbon double bond (excluding double bonds in aromatic compounds). For example, styrene is considered an α-monoolefin. In the second variant, the polymer chain represented by the name "POLY" comprises a ternary comonomer (monomers other than ethylene and 1,3-diene), and the monomeric unit of the polymer chain represented by the name "POLY" is a unit produced by the ternary polymerization of ethylene, 1,3-diene, and α-monoolefin. The ternary comonomer is an α-monoolefin, preferably an aromatic α-monoolefin. As an aromatic α-monoolefin, a monoolefin substituted with a substituted or unsubstituted phenyl group at the α-position of the double bond may be mentioned, such as styrene, styrene substituted with one or more para-alkyl, meta-alkyl, or ortho-alkyl groups, or mixtures thereof. Styrene is advantageously the ternary comonomer.

[0029] Preferably, the polymer chain is a statistical copolymer chain, in which case the name POLY indicates a polymer chain in which monomer units are statistically distributed, due to the statistical binding of monomers into the growing polymer chain.

[0030] The functional groups represented by the symbols Z1 and Z2 are functional groups. Their essential characteristic is that they are identical. A further essential characteristic of each functional group represented by Z1 and Z2 is that it shares a covalent bond with a carbon atom of the monomer unit at the chain end. Possible functional groups include alcohols, amines, halogens, carbonyl groups (e.g., esters), alkoxysilanes, and silanols. The functional groups preferably include alcohols, amines, halogens, carbonyl groups (e.g., esters), alkoxysilanes, or silanols.

[0031] A key characteristic of the telechelic polymer according to the invention is that it has a specific macroscopic structure because it possesses at least one of the following characteristics: a dispersity of less than 1.5 and a number-average molecular weight of greater than 10,000 g / mol. In a known manner, the dispersity is the ratio between the polymer's mass-average molecular weight (usually denoted as Mw) and the polymer's number-average molecular weight (usually denoted as Mn).

[0032] According to one variant, the macroscopic structure is defined by a number-average molecular weight greater than 10,000 g / mol, preferably greater than 20,000 g / mol. According to this variant, the macroscopic structure is preferably defined by a number-average molecular weight greater than 10,000 g / mol and a dispersity of less than 1.5, more preferably by a number-average molecular weight greater than 20,000 g / mol and a dispersity of less than 1.5.

[0033] According to another variant, the macroscopic structure is defined by a dispersion of less than 1.5. According to this variant, the number-average molecular weight can vary considerably; in particular, it can be less than 10,000 g / mol.

[0034] The telechelic polymers according to the invention can be synthesized by catalytic polymerization in the presence of a catalytic system based on at least one metallocene and a cocatalyst. The term "based on" used to define the components of the catalytic system means a mixture of these components, or some or all of these components and the reaction products of each other.

[0035] In this patent application, the term "metallocene" refers to an organometallic complex in which the metal (in this case, a rare earth metal atom) is bonded to two groups Cp. 3 and Cp 4 Or bonded to two Cp groups 1 and Cp 2 The ligand molecule consists of the two groups Cp 1 and Cp 2 These groups are connected together via bridge P. 1 Cp 2 Cp 3 and Cp 4They may be the same or different, and are selected from fluorenyl, cyclopentadienyl, and indene, which may be substituted or unsubstituted. To recall, rare earth elements are metals and represent the elements scandium, yttrium, and lanthanides (with atomic numbers ranging from 57 to 71).

[0036] According to a first variant of the invention, the metallocene used as a basic component in the catalytic system corresponds to formula (IIIa).

[0037] {P(Cp 1 (Cp) 2 )Y}(IIIa)

[0038] in

[0039] Y represents a group containing metal atoms (which are rare earth metals).

[0040] Cp 1 and Cp 2 The groups may be the same or different, and are selected from fluorenyl, cyclopentadienyl, and indene, and the groups may be substituted or unsubstituted.

[0041] P is a bridging group between two Cp groups. 1 and Cp 2 It contains groups that contain silicon or carbon atoms.

[0042] According to a second variant of the invention, the metallocene used as a basic component in the catalytic system according to the invention corresponds to formula (IIIb).

[0043] Cp 3 Cp 4 Y(IIIb)

[0044] in

[0045] Y represents a group containing metal atoms (which are rare earth metals).

[0046] Cp 3 and Cp 4 The same or different, and selected from fluorenyl, cyclopentadienyl and indene, wherein the group is substituted or unsubstituted.

[0047] As substituted cyclopentadienyl, fluorenyl, and indole groups, references may be made to cyclopentadienyl, fluorenyl, and indole groups substituted with alkyl groups containing 1 to 6 carbon atoms or aryl or trialkylsilyl groups containing 6 to 12 carbon atoms (e.g., SiMe3). The choice of groups also depends on the availability of the corresponding molecules (substituted cyclopentadienyl, fluorenyl, and indole groups), as these molecules are commercially available or readily synthesized.

[0048] As substituted fluorenyl groups, those substituted at positions 2, 7, 3, or 6 can be mentioned, particularly 2,7-di(tert-butyl)fluorenyl and 3,6-di(tert-butyl)fluorenyl. Positions 2, 3, 6, and 7 represent the positions of carbon atoms in the ring shown in the diagram below, and position 9 corresponds to the carbon atom attached to bridge P.

[0049]

[0050] As a substituted cyclopentadienyl group, the cyclopentadienyl group substituted at position 2 is particularly noteworthy, especially the tetramethylcyclopentadienyl group. As shown in the figure below, position 2 (or 5) indicates the position of the carbon atom adjacent to the carbon atom connected to bridge P.

[0051]

[0052] As for substituted indenyl groups, those substituted at position 2 are particularly noteworthy, especially 2-methylindenyl or 2-phenylindenyl. As shown in the diagram below, position 2 indicates the position of the carbon atom adjacent to the carbon atom connected to bridge P.

[0053]

[0054] Preferably, the metallocene has formula (IIIa).

[0055] Preferably, Cp 1 and Cp 2 The same, and selected from substituted fluorene groups and formula C 13 The unsubstituted fluorene group of H8. Advantageously, Cp 1 and Cp 2 The same, and each representing the expression C denoted by the symbol Flu. 13 Unsubstituted fluorene group of H8.

[0056] Preferably, the symbol Y represents the group Met-G, where Met represents a metal atom (which is a rare earth metal), and G represents a group containing a borohydride unit BH4, or a halogen atom selected from chlorine, fluorine, bromine, and iodine. Advantageously, G represents a chlorine atom or a group of formula (IIIc):

[0057] (BH4) (1+y)- L y -N x (IIIc)

[0058] in

[0059] L indicates an alkali metal selected from lithium, sodium, and potassium.

[0060] N represents an ether molecule.

[0061] x can be an integer or a non-integer, and is greater than or equal to 0.

[0062] y is an integer, and is greater than or equal to 0.

[0063] Very advantageously, G represents the group of formula (IIIc).

[0064] Any ether that has the ability to coordinate with alkali metals (especially diethyl ether and tetrahydrofuran) is suitable as an ether.

[0065] The metal in the metallocene is preferably a lanthanide element (with an atomic number ranging from 57 to 71), and more preferably neodymium (Nd).

[0066] Linking group Cp 1 and Cp 2 The preferred bridge P corresponds to formula ZR. 1 R 2 Where Z represents a silicon atom or a carbon atom, R 1 and R 2 The same or different, and each representing an alkyl group containing 1 to 20 carbon atoms, preferably methyl. In formula ZR 1 R 2 In this context, Z favorably represents the silicon atom Si.

[0067] Metallocenes used in synthetic catalytic systems can be in crystalline or amorphous powder form, or in single-crystal form. Metallocenes can be in monomeric or dimer form, depending on the method of preparation, as described, for example, in patent applications WO 2007 / 054224 or WO 2007 / 054223. Metallocenes can be conventionally prepared by methods similar to those described in patent applications WO 2007 / 054224 or WO 2007 / 054223, particularly under inert and anhydrous conditions by reacting an alkali metal salt of a ligand with a rare earth metal borohydride in a suitable solvent (e.g., an ether (e.g., diethyl ether or tetrahydrofuran) or any other solvent known to those skilled in the art). After the reaction, the metallocene is separated from the reaction by techniques known to those skilled in the art (e.g., filtration or precipitation in a second solvent). Finally, the metallocene is dried and separated in solid form.

[0068] According to particularly preferred embodiments, metallocenes have formulas (III-1), (III-2), (III-3), (III-4), or (III-5):

[0069] [Me2Si(Flu)2Nd(μ-BH4)2Li(THF)] (III-1)

[0070] [{Me2SiFlu2Nd(μ-BH4)2Li(THF)}2] (III-2)

[0071] [Me2SiFlu2Nd(μ-BH4)(THF)] (III-3)

[0072] [{Me2SiFlu2Nd(μ-BH4)(THF)}2] (III-4)

[0073] [Me2SiFlu2Nd(μ-BH4)] (III-5)

[0074] Where Flu represents C 13 H8 group.

[0075] Another essential component of the catalytic system is a co-catalyst (an organomagnesium reagent of formula (IV) or (V)).

[0076] R B -(Mg-R A ) n -Mg-R B (IV)

[0077] X-Mg-R C -Mg-X (V)

[0078] R A It is a divalent aliphatic hydrocarbon chain, which may or may not be interrupted by one or more oxygen atoms, sulfur atoms, or one or more arylene groups.

[0079] R B It contains a benzene nucleus substituted with a magnesium atom, wherein one carbon atom of the benzene nucleus located adjacent to the magnesium atom is substituted with a methyl, ethyl, or isopropyl group, or forms a ring with the nearest carbon atom located meta-position of the magnesium atom, and another carbon atom of the benzene nucleus located adjacent to the magnesium atom is substituted with a methyl, ethyl, or isopropyl group.

[0080] n is a number greater than or equal to 1, preferably equal to 1.

[0081] R C It is a divalent aliphatic hydrocarbon chain, which may or may not be interrupted by one or more oxygen atoms, sulfur atoms, or one or more arylene groups.

[0082] X is a halogen atom.

[0083] The special feature of the cocatalysts of formulas (IV) and (V) is that they contain two magnesium-carbon bonds involving different magnesium atoms. In formula (IV), each of the two magnesium atoms is bonded to R. B The first carbon atom shares the first bond with R A The second carbon atom shares the second bond. The first carbon atom is R. B The second carbon atom is a component of the benzene ring. A The components of the aliphatic hydrocarbon chain R AIt may contain one or more heteroatoms selected from oxygen or sulfur, or one or more aryl groups within its chain. In the preferred case where n equals 1, each magnesium atom is thus associated with R. B The first carbon atom shares the first bond and is associated with R. A The second carbon atom shares the second bond. In formula (V), each magnesium atom thus shares the first bond with the halogen atom and with R. C The carbon atoms share the second bond.

[0084] In equation (IV), R B Its characteristic lies in the presence of a benzene ring replaced by a magnesium atom. R B The benzene ring is located at the two carbon atoms adjacent to magnesium, which may have the same or different substituents. Alternatively, R... B The benzene nucleus, located at one of the two carbon atoms adjacent to magnesium, can carry a substituent, and R B The benzene ring, located at the adjacent carbon atom of magnesium, can form a ring. The substituents are methyl, ethyl, or isopropyl. In R... B When one of the two carbon atoms adjacent to magnesium in the benzene ring is replaced by an isopropyl group, R B The second carbon atom of the benzene ring, located adjacent to magnesium, is preferably not substituted with an isopropyl group. Preferably, R... B The carbon atom of the benzene ring located adjacent to magnesium is replaced by a methyl or ethyl group. More preferably, R B The benzene ring, located at the position adjacent to the magnesium atom, is replaced by a methyl group.

[0085] The organomagnesium compounds of formula (IV) preferably correspond to formulas (IVa-n), wherein n is greater than or equal to 1, R1 and R5 are the same or different and represent methyl or ethyl, preferably methyl, R2, R3 and R4 are the same or different and represent hydrogen atoms or alkyl groups, R A It is a divalent aliphatic hydrocarbon chain, which may or may not be interrupted by one or more oxygen atoms or sulfur atoms or one or more aryl groups.

[0086] Preferably, R1 and R5 represent methyl groups. Preferably, R2 and R4 represent hydrogen atoms.

[0087]

[0088] Organomagnesium compounds of formula (IVa-n) have formula (IVa-1), in which n equals 1.

[0089]

[0090] According to preferred variants, in formula (IVa-n), particularly in formula (IVa-1), R1, R3, and R5 are identical. According to more preferred variants, R2 and R4 represent hydrogen, and R1, R3, and R5 are identical. In even more preferred variants, R2 and R4 represent hydrogen, and R1, R3, and R5 represent methyl groups.

[0091] In equations (IV) and (IVa-n), especially in equation (IVa-1), R A It is a divalent aliphatic hydrocarbon chain, which may contain one or more heteroatoms selected from oxygen or sulfur, or one or more aryl groups. Preferably, R A It is a branched or linear alkyldiyl, cycloalkyldiyl, or xylenediyl group. More preferably, R A It is an alkyl diol.

[0092] Preferably, R A It contains 3 to 10 carbon atoms, especially 3 to 8 carbon atoms.

[0093] Even more preferably, R A It is an alkyldiyl group containing 3 to 10 carbon atoms. Advantageously, R A It is an alkyldiyl group containing 3 to 8 carbon atoms. Very advantageously, R... A It is a linear alkyl diyl group. 1,3-propanediyl, 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, and 1,8-nonanediyl are most particularly suitable as the R group. A .

[0094] According to any embodiment of the invention, in formula (IV), particularly in formula (IVa-n), n is preferably equal to 1.

[0095] Organomagnesium compounds of formula (IV) can be derived by including formula X'Mg-R A -MgX' first organomagnesium reagent with formula R B The second organomagnesium reagent, -Mg-X', is prepared by a reaction method, where X' represents a halogen atom, preferably bromine or chlorine, and R... B and R A As defined above. X' is more preferably a bromine atom. The stoichiometry used in the reaction determines the value of n in formulas (IV) and (IVa). For example, a molar ratio of 0.5 between the amount of the first organomagnesium reagent and the amount of the second organomagnesium reagent favors the formation of organomagnesium compounds of formula (IV) with n equal to 1, while a molar ratio greater than 0.5 will favor the formation of organomagnesium compounds of formula (IV) with n greater than 1.

[0096] To carry out the reaction between the first and second organomagnesium reagents, a solution of the second organomagnesium reagent is typically added to a solution of the first organomagnesium reagent. The solutions of the first and second organomagnesium reagents are typically solutions of ethers (e.g., diethyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran) or mixtures of two or more of these ethers. Preferably, the concentrations of the first and second organomagnesium reagent solutions are 0.01 mol / L to 3 mol / L and 0.02 mol / L to 5 mol / L, respectively. More preferably, the concentrations of the first and second organomagnesium reagents are 0.1 mol / L to 2 mol / L and 0.2 mol / L to 4 mol / L, respectively.

[0097] The first and second organomagnesium reagents can be prepared in advance from magnesium metal and suitable precursors via a Grignard reaction. For both the first and second organomagnesium reagents, the respective precursors are of formula X'-R. A -X' and R B -X',R A R B X' is as defined above. The Grignard reaction is typically carried out by adding a precursor additive, usually in the form of fragmented magnesium metal. Preferably, iodine (I2), usually in the form of beads, is introduced into the reactor prior to the addition of the precursor, thereby activating the Grignard reaction in a known manner.

[0098] Alternatively, the organomagnesium compounds according to the present invention can be expressed by formula MR A -M organometallic compounds and formula R B The reaction preparation of -Mg-X' organomagnesium reagents, where M represents a lithium atom, sodium atom, or potassium atom, and X', R B and R A As defined above. Preferably, M represents a lithium atom, in which case the formula MR A -M organometallic compounds are organolithium reagents.

[0099] The reaction of organolithium reagents with organomagnesium reagents is typically carried out in ethers (e.g., diethyl ether, dibutyl ether, tetrahydrofuran, or methyltetrahydrofuran). The reaction is also typically conducted at temperatures ranging from 0°C to 60°C. Contact is preferably carried out at temperatures between 0°C and 23°C. Formula MR A -M organometallic compounds and formula R B Contact with organomagnesium reagents of -Mg-X' is preferably achieved by using organometallic compounds MR A -M solution added to organomagnesium reagent R B The reaction is carried out in a solution of -Mg-X'. Organometallic compounds MR AThe solution of -M is usually a solution of a hydrocarbon solvent (preferably n-hexane, cyclohexane, or methylcyclohexane), and the organomagnesium reagent R B The solution of -Mg-X' is typically an ether solution (preferably diethyl ether or dibutyl ether). Preferably, the organometallic compound MR... A -M solution and organomagnesium reagent R B The concentrations of the -Mg-X' solutions were respectively from 0.01 mol / L to 1 mol / L and from 1 mol / L to 5 mol / L. More preferably, the organometallic compound MR A -M solution and organomagnesium reagent R B The concentrations of the -Mg-X' solutions were 0.05 mol / L to 0.2 mol / L and 2 mol / L to 3 mol / L, respectively.

[0100] As with any synthesis in the presence of organometallic compounds, the synthesis described for organomagnesium reagents is carried out under anhydrous conditions in a stirred reactor under an inert atmosphere. Typically, solvents and solutions are used under anhydrous nitrogen or argon atmospheres.

[0101] Following the formation of an organomagnesia (formula IV), the solution is typically recovered after filtration under an inert, anhydrous atmosphere. Before use, the solution can be stored in a sealed container (e.g., a capped bottle) at a temperature between -25°C and 23°C.

[0102] Like any organomagnesia compound, organomagnesia compounds of formula (IV) can be monomeric substances (R B -(Mg-R A ) n -Mg-R B )1 in form or polymer (R) B -(Mg-R A ) n -Mg-R B ) p The form (especially dimer (R) B -(Mg-R A ) n -Mg-R B )2), where p is an integer greater than 1, and n is as defined above. Furthermore, regardless of whether it is in monomeric or polymeric form, it can also be a substance coordinated to one or more solvent molecules (preferably ethers, such as diethyl ether, tetrahydrofuran, or methyltetrahydrofuran).

[0103] In equation (V), R C It is a divalent aliphatic hydrocarbon chain, which may contain one or more heteroatoms selected from oxygen or sulfur, or one or more aryl groups. Preferably, RC It is a branched or linear alkyldiyl, cycloalkyldiyl, or xylenediyl group. More preferably, R C It is an alkyl diol.

[0104] Preferably, R C It contains 3 to 10 carbon atoms, especially 3 to 8 carbon atoms.

[0105] Even more preferably, R C It is an alkyldiyl group containing 3 to 10 carbon atoms. Advantageously, R C It is an alkyldiyl group containing 3 to 8 carbon atoms. Very advantageously, R... C It is a linear alkyl diyl group. 1,3-propanediyl, 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, and 1,8-nonanediyl are most particularly suitable as the R group. C .

[0106] Compounds of formula (V) are well-known Grignard reagents. However, they have not yet been used as co-catalysts in catalytic systems for the preparation of polyolefins. Grignard reagents of formula (V) are described, for example, in J. March's book "Advanced Organic Chemistry" (4th edition, 1992, pp. 622-623) or Gary S. Silverman and Philip E. Rakita's book "Handbook of Grignard Reagents" (1996, pp. 502-503). They can be obtained by reacting magnesium metal with formula XR C -X dihalogen compounds are synthesized by contacting R C As defined according to the present invention. For its synthesis, reference may be made to, for example, the volume "Organic Synthesis".

[0107] Like any organomagnesia compound, the organomagnesia reagent of formula (V) can be a monomer (X-Mg-R) C In the form of (-Mg-X)1 or polymeric substances (X-Mg-R) C -Mg-X) p (especially the dimer (X-Mg-R) C In the form of (-Mg-X)2), p is an integer greater than 1. Furthermore, regardless of whether it is in monomeric or polymeric form, it can also be in the form of a substance coordinated to one or more solvent molecules (preferably ethers, such as diethyl ether, tetrahydrofuran, or methyltetrahydrofuran). In formula (V), X is preferably a bromine atom or a chlorine atom, more preferably a bromine atom.

[0108] The catalytic system can be conventionally prepared by methods similar to those described in patent applications WO 2007 / 054224 or WO 2007 / 054223. For example, the cocatalyst (in this case, an organomagnesium reagent of formula (IV) or (V)) and the metallocene are typically reacted in a hydrocarbon solvent at a temperature of 20°C to 80°C for a time between 5 and 60 minutes. The amounts of the cocatalyst and the metallocene reacted are such that the ratio between the molar number of Mg in the cocatalyst and the molar number of rare earth metals in the metallocene is preferably 1 to 200, more preferably 1 to less than 20. The numerical range of 1 to less than 20 is particularly advantageous for obtaining polymers with high molar masses. The catalytic system is typically prepared in an aliphatic hydrocarbon solvent (e.g., methylcyclohexane) or an aromatic hydrocarbon solvent (e.g., toluene). Typically, after synthesis, the catalytic system is used in methods for synthesizing polymers according to the invention.

[0109] Alternatively, the catalytic system can be prepared by a method similar to that described in patent application WO 2017 / 093654 A1 or patent application WO2018 / 020122 A1. According to this alternative, the catalytic system further comprises a pre-formed monomer selected from conjugated dienes, ethylene, or mixtures of ethylene and conjugated dienes, in which case the catalytic system is at least based on metallocene, a cocatalyst, and the pre-formed monomer. For example, organomagnesia reagents and metallocenes are typically reacted in a hydrocarbon-based solvent at a temperature of 20°C to 80°C for 10 to 20 minutes to obtain a first reaction product, followed by reaction of the pre-formed monomer selected from conjugated dienes, ethylene, or mixtures of ethylene and conjugated dienes with the first reaction product at a temperature of 40°C to 90°C for 1 to 12 hours. As a pre-formed monomer, the conjugated diene is preferably a 1,3-diene, such as 1,3-butadiene, isoprene, or a 1,3-diene of the formula CH2=CR-CH=CH2, where the symbol R represents a hydrocarbon chain containing 3 to 20 carbon atoms, particularly myrcene or β-farnesene. The resulting catalytic system can be used directly in the method for synthesizing the polymer according to the invention, or it can be stored in an inert atmosphere, particularly at temperatures from -20°C to room temperature (23°C), before being used for polymer synthesis.

[0110] As with any synthesis in the presence of organometallic compounds, the synthesis of metallocenes, organomagnesia reagents, and catalytic systems is carried out under anhydrous conditions in an inert atmosphere. Typically, the reaction begins with anhydrous solvents and compounds under anhydrous nitrogen or argon.

[0111] When a hydrocarbon solvent is present, the catalytic system can be in solution form. The hydrocarbon solvent can be an aliphatic solvent (e.g., methylcyclohexane) or an aromatic solvent (e.g., toluene). The hydrocarbon solvent is preferably an aliphatic solvent, more preferably methylcyclohexane. Typically, the catalytic system is stored in a hydrocarbon solvent as a solution prior to polymerization. This can then be referred to as a catalytic solution containing the catalytic system and the hydrocarbon solvent. The catalytic system preferably contains a hydrocarbon solvent. When the catalytic system is in solution, its concentration is defined by the amount of metallocene in the solution. The concentration of the metallocene is preferably from 0.0001 mol / L to 0.2 mol / L, more preferably from 0.001 mol / L to 0.03 mol / L.

[0112] Polymerization is preferably carried out continuously or batchwise in solution. The polymerization solvent can be an aromatic or aliphatic hydrocarbon solvent. Examples of polymerization solvents include toluene and methylcyclohexane. The monomer can be introduced into a reactor containing the polymerization solvent and a catalytic system, or conversely, the catalytic system can be introduced into a reactor containing the polymerization solvent and the monomer. The monomer and the catalytic system can be introduced simultaneously into a reactor containing the polymerization solvent, particularly in the case of continuous polymerization. Polymerization is typically carried out under anhydrous and oxygen-free conditions in the optional presence of an inert gas. The polymerization temperature typically varies from 25°C to 120°C, preferably from 30°C to 100°C. The polymerization temperature is adjusted according to the monomer to be polymerized. Preferably, copolymerization is carried out at a constant ethylene pressure.

[0113] During the polymerization of ethylene and 1,3-diene in a polymerization reactor, ethylene and 1,3-diene can be continuously added to the reactor, in which case the polymerization reactor is a feed reactor. This embodiment is most particularly suitable for the synthesis of statistical copolymers.

[0114] The polymerization step can prepare a polymer characterized by having carbon-magnesium bonds at each of its ends. A subsequent functionalization step using a modifier yields the telechelic polymer according to the invention. The modifier is typically a compound known to react with compounds containing carbon-magnesium bonds. Particularly suitable modifiers are tertiary amines, protected amines, dihalogens, ketones, esters, and alkoxysilanes. The modifier is typically added to the polymerization medium. The functionalized polymer can be recovered using conventional techniques known to those skilled in the art (e.g., precipitation, solvent evaporation under reduced pressure, or steam stripping).

[0115] When the telechelicer polymer according to the present invention is synthesized according to the method described above, the telechelicer polymer contains a divalent group R within its polymer chain. A or R C The divalent group R A or R CThe cocatalysts constitute formulas (IV) and (V), respectively. The presence of the divalent group of the self-catalyst in the polymer chain originates from the polymerization mechanism involving a chain transfer reaction between the metallocene and the carbon-magnesium bond of the cocatalyst. Therefore, according to one embodiment of the invention, the telechelic polymer includes a divalent group R represented by the name "POLY" in formula (I) within the polymer chain, the divalent group R having the same characteristics as the divalent group R defined above. A and R C (Including preferred embodiments) with the same chemical structure.

[0116] In summary, the present invention is advantageously carried out according to any one of the following embodiments 1 to 17:

[0117] Implementation Scheme 1: Teleclaw Polymer of Formula (I)

[0118] Z1-POLY-Z2(I)

[0119] The term "POLY" refers to a polymer chain containing 1,3-diene units, ethylene units, and 1,2-cyclohexane units of formula (II).

[0120]

[0121] Z1 and Z2 represent functional groups.

[0122] Z1 and Z2 are the same.

[0123] The polymer has a macroscopic structure defined by a dispersion of less than 1.5 or a number-average molecular weight of greater than 10,000 g / mol.

[0124] Implementation Scheme 2: The telechelic polymer according to Implementation Scheme 1, wherein the polymer chain is a copolymer chain of 1,3-diene and ethylene, or a ternary polymer chain of 1,3-diene, ethylene and α-monoolefin.

[0125] Implementation Scheme 3: The teleclaw polymer according to Implementation Scheme 2, wherein the α-monoolefin is styrene.

[0126] Implementation Scheme 4: The telechelic polymer according to any one of Implementation Schemes 1 to 3, wherein the 1,3-diene is a mixture of 1,3-dienes or 1,3-butadiene, and one of the mixtures of 1,3-dienes is 1,3-butadiene.

[0127] Implementation Scheme 5: The telechelic polymer according to any one of Implementation Schemes 1 to 4, wherein the polymer chain contains more than 50 mol% ethylene units.

[0128] Implementation Scheme 6: The telechelic polymer according to any one of Implementation Schemes 1 to 5, wherein the polymer chain comprises no more than 15 mol% of 1,2-cyclohexane units of Formula (II).

[0129]

[0130] Implementation Scheme 7: The telechelic polymer according to any one of Implementation Schemes 1 to 6, wherein the polymer chain is a statistical copolymer chain.

[0131] Implementation Scheme 8: The telechelic polymer according to any one of Implementation Schemes 1 to 7, wherein Z1 and Z2 represent groups containing alcohol, amine, halogen, carbonyl, alkoxysilane or silanol functional groups.

[0132] Implementation Scheme 9: The teleclaw polymer according to any one of Implementation Schemes 1 to 8, wherein the macroscopic structure is defined by a number-average molecular weight greater than 10,000 g / mol, preferably greater than 20,000 g / mol.

[0133] Implementation Scheme 10: The teleclaw polymer according to Implementation Scheme 9, wherein the macrostructure is defined by a dispersion of less than 1.5.

[0134] Implementation Scheme 11: According to any one of Implementation Schemes 1 to 10, the telechelic polymer contains a divalent group R within the polymer chain "POLY", the divalent group R being an aliphatic hydrocarbon chain interrupted or not interrupted by one or more oxygen atoms or sulfur atoms or one or more arylene groups, and R is not an ethylene unit, a 1,3-diene unit, an ethylene unit chain, a 1,3-diene unit chain, or a chain of units composed of one or more ethylene units and one or more 1,3-diene units.

[0135] Implementation Scheme 12: The telechelic polymer according to Implementation Scheme 11, wherein the divalent group R is a branched or linear alkyldiyl, cycloalkyldiyl, or xylenediyl group.

[0136] Implementation Scheme 13: The teleclaw polymer according to Implementation Schemes 11 to 12, wherein the divalent group comprises 3 to 10 carbon atoms.

[0137] Implementation Scheme 14: The teleclaw polymer according to any one of Implementation Schemes 11 to 13, wherein the divalent group R comprises 3 to 8 carbon atoms.

[0138] Implementation Scheme 15: The teleclaw polymer according to any one of Implementation Schemes 11 to 14, wherein the divalent group R is an alkyldiyl group.

[0139] Implementation Scheme 16: The teleclaw polymer according to any one of Implementation Schemes 11 to 15, wherein the divalent group R is a linear alkyl diester.

[0140] Implementation Scheme 17: The telechelic polymer according to any one of Implementation Schemes 11 to 16, wherein the divalent group R is 1,3-propanediyl, 1,5-pentanediyl or 1,7-heptanediyl.

[0141] The above and other features of the invention will be more clearly understood by reading the following description of embodiments of the invention given as a non-limiting description.

[0142] Example

[0143] Example 1: Preparation of 1,5-bis(magnesium bromide)pentanediyl (DMBP), a cocatalyst containing two magnesium-carbon bonds involving different magnesium atoms:

[0144] The synthesis used 9.72 g of magnesium (400 mmol, 10 equivalents), 80 mL of 2-methyltetrahydrofuran (MeTHF) (64 mL of which was in a dropping funnel), 60 mg of diiodine (0.23 mmol, 0.006 equivalents), and 5.45 mL of 1,5-dibromopentane (40 mmol, 1 equivalent). The glassware used included a 200 mL flask and a 100 mL dropping funnel. After the Grignard reagent synthesis was complete, the solution was transferred to a second inert 200 mL flask through a filter sleeve. This solution was concentrated under vacuum and then diluted in 55 mL of toluene. The concentration of pentanediyl was estimated to be 0.43 mol / L. -1 This oil is immiscible with methylcyclohexane.

[0145] Equal portions of concentrated oil: 1 ¹H NMR (toluene-D8-500 MHz-298 K) δ: ppm = 2.21 (quint, J = 7.2 Hz, “b”), 1.88 (quint, J = 7.0 Hz, “c”), 0.11 (t, J = 7.4 Hz, “a”); quint indicates a quintet.

[0146]

[0147] Example 2: Synthesis of 2-trimethylmethylmagnesium bromide:

[0148] 4.15 g (170 mmol, 3.4 equivalents) of magnesium was inertized in a 250 mL flask fitted with magnetized olivine and a 10 mL dropping funnel. 10 mg of diiodine beads were added to the magnesium. 47.5 mL of MeTHF was added to the flask with stirring, and 2.5 mL was added to the dropping funnel. 7.65 mL of degassed 2-bromotrimethylbenzene (50 mmol, 1 equivalent) dried over activated molecular sieves was added to the dropping funnel. The flask was heated to 60 °C, and 2-bromotrimethylbenzene was added dropwise to the magnesium over 1 hour. Stirring was maintained at 60 °C for 3 hours, followed by 12 hours at 20 °C.

[0149] Equal portions of concentrated oil in Young's test tubes: 1 H NMR (C6D6-400MHz-298K) δ: ppm=7.01 (s, "a"), 2.74 (s, "b"), 2.36 (s, "c")

[0150]

[0151] Synthesis of telechelic polymers:

[0152] The copolymer of ethylene and butadiene is composed of the complex {(Me2Si(C)} 13 The polymer was prepared using H8)2)Nd(-BH4)[(-BH4)Li(THF)]}2 and the cocatalyst 1,5-bis(magnesium bromide)pentanediyl (DMBP) prepared according to the steps in Example 1 above. The polymer was characterized using the methods described below.

[0153] THF size exclusion chromatography (THF-SEC). Size exclusion chromatography analysis was performed using a Viscotek TDA305 instrument (Malvern Instruments). The instrument was equipped with three columns (SDVB (styrene-divinylbenzene column), 5 μm, 300 × 7.5 mm, from the polymer standard service), a guard column, and three detectors (differential refractometer and viscometer, and light scattering).

[0154] The polymer to be analyzed was administered at 3 mg / mL. -1 The concentration was dissolved in THF (elution solvent) to prepare a sample solution. 3 mL of THF was filtered through a 0.45 μm PTFE membrane to obtain a concentration of 3 mg / mL. -1 The sample solution. At 35°C, use 1 mL min... -1 The solution was eluted in THF at a flow rate of [value missing]. OmniSEC software was used for data acquisition and analysis. Standard polystyrene (peak molar mass M) was used as a reference from Polymer Standard Service (Mainz). p : 1306 to 2520000 g mol-1 The universal calibration curve is determined by measuring the number-average molecular weight and mass-average molecular weight of the synthesized polymer using a "molar" calibration. The dispersity is calculated by dividing the mass-average molecular weight (Mw) by the number-average molecular weight (Mn).

[0155] Nuclear magnetic resonance (NMR). A Brüker 400 Avance III spectrometer equipped with a 5 mm BBFO probe was used for protons, operating at 400 MHz, and a 10 mm PSEX probe was used for carbon. 13 High-resolution NMR spectra of the polymer were performed on a Brüker 400 Avance II spectrometer operating at 400 MHz using a C probe. Acquisition was performed at 363 K. A mixture of tetrachloroethylene (TCE) and deuterated benzene (C6D6) (2 / 1 volume / volume) was used as the solvent. Samples were analyzed at concentrations of 1 wt% (for protons) and 5 wt% (for carbon). Chemical shifts are given in ppm relative to the deuterated benzene proton signal set at 7.16 ppm and the TCE carbon signal set at 120.65 ppm. [The last sentence appears to be incomplete and possibly refers to a different method or technique.] 13 The C-spectral sequence is: a "power threshold decoupling" (NOE proton decoupling spectrum) with a pulse angle of 70°, DT = 64K, and a pulse delay of 4.5s. The number of samples was set to 5120.

[0156] Example EBR-A:

[0157] 310 mL of toluene purified on an activated alumina column (also known as a solvent fountain) was placed into a 750 mL Steinie flask. After bubbling with nitrogen for approximately 10 minutes, 300 mL of toluene was recovered. In a glove box, 46 mg (72 μmol of neodymium) of {(Me₂Si(C)} was weighed into a 250 mL Steinie flask. 13 H8)2)Nd(-BH4)[(-BH4)Li(THF)]}2 complex. Approximately 100 mL of the contents of a 750 mL bottle was transferred to a 250 mL bottle using a double-ended needle system. 2.3 mL of 1,5-bis(magnesium bromide)pentanediyl (DMBP) (0.43 mol / L in toluene) prepared according to the same method described in Example 1 was added. -1 Add to a 250mL bottle.

[0158] Add another 100 mL of the contents from the 750 mL bottle to the inert 500 mL reactor while stirring (400 rpm) and heat to 77°C. Then, transfer the contents of the 250 mL bottle to the reactor, and fill the reactor with the remaining contents (approximately 100 mL) from the 750 mL bottle. Degas the reactor under vacuum until bubbles form, then pressurize it to 3 bar using an 80 / 20 molar ratio ethylene / butadiene mixture.

[0159] When the desired amount of monomer is consumed, the reactor is degassed. Functionalization is performed using 2 equivalents of 4,4'-bis(diethylamino)benzophenone (DEAB) dissolved in toluene relative to the total amount of magnesium.

[0160] The medium was stirred at 77°C for 1 hour, then cooled and deactivated with ethanol. The polymer was dried under vacuum at 50°C for 24 hours and then weighed.

[0161] Approximately 2 g of the polymer was dissolved in 20 mL of methylcyclohexane, and then the polymer was precipitated from approximately 150 mL of acetone. This procedure was repeated three times to wash the polymer. The washed and dried polymer was recovered for analysis.

[0162] Example EBR-B:

[0163] 310 mL of toluene from the solvent fountain was introduced into a 750 mL Steinie flask. After bubbling with nitrogen for approximately 10 minutes, 300 mL of toluene was recovered. 46 mg (72 μmol of neodymium) of {(Me₂Si(C)} was weighed into a 250 mL Steinie flask in a glove box. 13 H8)2)Nd(-BH4)[(-BH4)Li(THF)]}2. 1 mL of 2-trimethylmethyl magnesium bromide (0.5 mol / L in toluene) prepared according to Example 2 was used. -1 Add to a 750 mL bottle. Transfer approximately 100 mL of the contents from the 750 mL bottle to a 250 mL bottle using a double-ended needle system. Add 2.3 mL of 1,5-bis(magnesium bromide)pentanediyl (DMBP) (0.43 mol / L in toluene) prepared according to the same method described in Example 1. -1 Add to a 250mL bottle.

[0164] Add another 100 mL of the contents from the 750 mL bottle to the inert 500 mL reactor while stirring (400 rpm) and heat to 77°C. Then, transfer the contents from the 250 mL bottle to the reactor, and fill the reactor with the remaining contents (approximately 100 mL) from the 750 mL bottle. Degas the reactor under vacuum until bubbles form, then pressurize it to 3 bar using an 80 / 20 molar ratio ethylene / butadiene mixture.

[0165] When the desired amount of monomer is consumed, the reactor is degassed. Functionalization is performed using 2 equivalents of 4,4'-bis(diethylamino)benzophenone (DEAB) dissolved in toluene relative to the total amount of magnesium.

[0166] The medium was stirred at 77°C for 1 hour, then cooled and deactivated with ethanol. The polymer was dried under vacuum at 50°C for 24 hours and then weighed.

[0167] Approximately 2 g of the polymer was dissolved in 20 mL of methylcyclohexane, and then the polymer was precipitated from approximately 150 mL of acetone. This procedure was repeated three times to wash the polymer. The washed and dried polymer was recovered for analysis.

[0168] Table 1 gives the conditions for copolymerization of ethylene and 1,3-butadiene.

[0169] Tables 2 and 3 show the characteristics of the synthesized copolymers.

[0170] The microstructure of the polymer and the functionalization at both polymer chain ends were determined by NMR. The contents of ethylene units, 1,2-configured 1,3-butadiene units (1,2-units), 1,4-configured 1,3-butadiene units (1,4-units), and 1,2-cyclohexane units (cyclic units) are expressed as molar percentages relative to the total units of the polymer.

[0171] result:

[0172] The results show that the telechelic polymer according to the present invention can be synthesized in the copolymerization of ethylene and 1,3-butadiene using a catalytic system based on rare earth metallocene and containing two magnesium-carbon bonds involving different magnesium atoms (e.g., DMBP). The polymer is a copolymer of ethylene and 1,3-butadiene, wherein the copolymer contains 1,2-cyclohexane units in its polymer chain. The functional groups at the ends of the polymer chains are identical. The macroscopic structure of the polymer is well defined by a dispersion of less than 1.5 or a number-average molecular weight greater than 10,000 g / mol.

[0173] Table 1

[0174] polymer co-catalyst molar ratio Mg / Nd Time (min) EBR-A DBMP 28 127 EBR-B DBMP 35 110

[0175] Table 2

[0176]

[0177] Table 3

[0178] polymer Ethylene unit Units 1 and 2 Units 1 and 4 Ring unit EBR-A 79.3 5.1 4.1 11.5 EBR-B 80.8 4.2 3.5 11.5

Claims

1. Teleclaw polymer of formula (I) Z1-POLY-Z2(I) The term "POLY" refers to a polymer chain containing 1,3-diene units, ethylene units, and 1,2-cyclohexane units of formula (II). Z1 and Z2 represent functional groups. Z1 and Z2 are the same. The polymer has a macroscopic structure defined by a dispersity of less than 1.5 or a number-average molecular weight of greater than 10,000 g / mol. in, Z1 and Z2 represent groups containing alcohol, amine, halogen, carbonyl, alkoxysilane, or silanol functional groups.

2. The telechelicer polymer according to claim 1, wherein, The polymer chain is a copolymer chain formed by the polymerization of 1,3-diene and ethylene.

3. The telechelicer polymer according to any one of claims 1 and 2, wherein, The 1,3-diene is a mixture of 1,3-dienes or 1,3-butadiene, wherein one of the mixtures of 1,3-dienes is 1,3-butadiene.

4. The telechelicer polymer according to claim 1, wherein, The polymer chain contains more than 50 mol% ethylene units.

5. The telechelicer polymer according to claim 1, wherein, The polymer chain contains no more than 15 mol% of 1,2-cyclohexane units.

6. The telechelicer polymer according to claim 1, wherein, The polymer chain is a statistical copolymer chain.

7. The telechelicer polymer according to claim 1, wherein, The macroscopic structure is defined by a number-average molecular weight greater than 10,000 g / mol.

8. The telechelicer polymer according to claim 1, wherein, The macroscopic structure is defined by a number-average molecular weight greater than 20,000 g / mol.

9. The telechelicer polymer according to claim 7 or 8, wherein, The macrostructure is defined by a dispersion of less than 1.

5.

10. The telechelic polymer according to claim 1, wherein the polymer contains a divalent group R within the polymer chain "POLY", the divalent group R being an aliphatic hydrocarbon chain interrupted or not interrupted by one or more oxygen atoms or sulfur atoms or one or more arylene groups, and R is not an ethylene unit, a 1,3-diene unit, an ethylene unit chain, a 1,3-diene unit chain, or a chain of units composed of one or more ethylene units and one or more 1,3-diene units.

11. The telechelicer polymer according to claim 10, wherein, The divalent group R is a branched or linear alkyldiyl, cycloalkyldiyl, or xylenediyl group.

12. The telechelic polymer according to claim 10, wherein, The divalent group R is an alkyl diester.

13. The telechelicer polymer according to claim 10, wherein, The divalent group R contains 3 to 10 carbon atoms.

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