Catalytic systems comprising metallocene for synthesis of polyethylene and ethylene and 1, 3-diene copolymers

Abstract

The present invention relates to a catalytic system based on at least a neodymium borohydride-ferrocene, a dialkylzinc compound and an organomagnesium halide of formula RB-Mg-X, in which RB comprises a benzene ring with two carbon atoms substituted, one of which is substituted with methyl, ethyl or isopropyl, or forms a ring with its closest carbon atom, and the other one of which is substituted with methyl, ethyl or isopropyl, or forms a ring with its closest carbon atom. The second carbon atom is substituted by methyl, ethyl or isopropyl, the magnesium atom is located at the ortho-position of each of the two carbon atoms, and X is a halogen atom. The catalytic system can be used in the homopolymerization of ethylene and the copolymerization of ethylene and 1, 3-diene.

Description

Technical Field

[0001] The present invention pertains to catalytic systems that can be used to prepare polyethylene and ethylene-1,3-diene copolymers (more particularly polyethylene and ethylene-1,3-diene copolymers with ketone functional groups). Background Technology

[0002] Highly saturated polymers (such as polyethylene and diene copolymers rich in ethylene units) are inherently hydrocarbon polymers and have a weak affinity for polar materials, which limits the application range of these highly saturated hydrocarbon polymers. To improve this affinity, in the case of polyethylene, the introduction of one or more ketone functional groups has been described. For example, the synthesis of copolymers of ethylene and carbon monoxide has been widely described, but such synthetic methods are not applicable to copolymers of ethylene with α-olefins (e.g., 1,3-diene) or mixtures of 1,3-diene with vinyl aromatic compounds. Furthermore, such synthetic methods cannot selectively lead to the introduction of terminal ketone functional groups. The introduction of a single ketone functional group at the chain end of polyethylene has also been described. For example, Polymer Science, Ser. B, Vol. 46, Nos. 9-10, 2004, 308-311 describes the reaction between nitrous oxide and polyethylene with vinyl groups at the chain end. The introduction of a ketone functional group at the chain end of polyethylene originates from the oxidation reaction of the vinyl double bond with nitrous oxide. Therefore, it can be seen that the synthetic method is not suitable for the selective functionalization of copolymers of ethylene and 1,3-diene containing double bonds outside the chain ends.

[0003] For example, the applicant describes catalytic systems comprising neodymium metallocene and organomagnesium compounds for the synthesis of ethylene-1,3-butadiene copolymers in documents WO 2007054223 and WO 2007054224. The organomagnesium compound acts as a co-catalyst in the catalytic system, thereby activating the metallocene for polymerization. The catalytic system is useful in the synthesis of polyethylene and ethylene-1,3-diene copolymers. The applicant also describes variations of these catalytic systems in document WO 2021123589, wherein the organomagnesium compound is of formula R. B -Mg-R A The compound, R A R is a substituted or unsubstituted alkyl, cycloalkyl, or benzyl group. B A benzene ring comprising two substituted carbon atoms, one of which is substituted by a methyl, ethyl, or isopropyl group, or forms a ring with its nearest neighbor carbon atom, the second carbon atom being substituted by a methyl, ethyl, or isopropyl group, and a magnesium atom located adjacent to each of the two carbon atoms.

[0004] In continuing its efforts, the applicant has developed a novel catalytic system capable of synthesizing not only polyethylene with copolymers containing ethylene and 1,3-diene units, but also selectively synthesizing polymers with ketone functional groups, which are copolymers of polyethylene with ethylene and 1,3-diene units. The ketone functional groups are introduced through the reaction of acidic halides with polymer chains prepared in the presence of the catalytic system according to the invention. Summary of the Invention

[0005] Therefore, the first subject of this invention is a catalytic system, said catalytic system being based on at least: Metallocenes of formula (Ia), Organomagnesium halides of formula (IIa), Dialkylzinc compounds, {P(Cp 1 (Cp) 2 Nd(BH4) (1+y)- L y -N x}(Ia) R B -Mg-X(IIa) Cp 1 and Cp 2 The groups may be the same or different, and are selected from fluorenyl, cyclopentadienyl, and indene, wherein the groups are substituted or unsubstituted. P is a bridging group between two Cp groups. 1 and Cp 2 And contains groups that contain silicon or carbon atoms, Nd represents a neodymium atom. L indicates an alkali metal selected from lithium, sodium, and potassium. N represents an ether molecule. x is an integer equal to or greater than 0, or a non-integer. y is an integer equal to or greater than 0. R B A benzene ring comprising two substituted carbon atoms, one of which is substituted by a methyl, ethyl, or isopropyl group, or forms a ring with its nearest neighbor carbon atom, the second carbon atom being substituted by a methyl, ethyl, or isopropyl group, and a magnesium atom located adjacent to each of the two carbon atoms. X is a halogen atom.

[0006] The present invention also relates to a method for preparing a polymer, the method comprising polymerizing ethylene or a mixture of monomers comprising ethylene and 1,3-diene in the presence of a catalytic system according to the invention, followed by modification with an acidic halide where appropriate. Detailed Implementation

[0007] 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).

[0008] The compounds described in the specification can be fossil-derived compounds or bio-based compounds. In the case of bio-based compounds, they can be partially or wholly derived from biomass or obtained from renewable raw materials derived from biomass. Similarly, the compounds can also be derived from the recycling of already used materials, i.e., they can be partially or wholly derived from recycling processes or obtained from raw materials that are themselves derived from recycling processes.

[0009] The expression “based on” used to define the components of a catalytic system or catalytic composition is understood to mean a mixture of these components, or the reaction products of some or all of these components with each other.

[0010] In this patent application, metallocene is understood to mean an organometallic complex in which a metal (in this case, a rare earth metal atom) is bonded to a ligand molecule, the ligand molecule being composed of two Cp groups linked together by a bridge P. 1 and Cp 2 Composition. These Cp 1 and Cp 2 The groups may be the same or different and are selected from fluorenyl, cyclopentadienyl and indene, which may be substituted or unsubstituted.

[0011] As substituted cyclopentadienyl, fluorenyl, and indole groups, references may be made to cyclopentadienyl, fluorenyl, and indole groups substituted with alkyl groups having 1 to 6 carbon atoms or aryl or trialkylsilyl groups having 6 to 12 carbon atoms (e.g., SiMe3 groups). The choice of groups also depends on the availability of the parent molecules (which are substituted cyclopentadiene, fluorenyl, and indole groups), as these molecules are commercially available or readily synthesized.

[0012] 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 connected by bridge P. Substituted cyclopentadienyl groups include those substituted at position 2 (or 5) or position 3 (or 4), particularly those substituted at position 2, and even more particularly tetramethylcyclopentadienyl groups. Position 2 (or 5) indicates the position of the carbon atom adjacent to the carbon atom connected to bridge P, as shown in the diagram below. As for substituted indenyl groups, those substituted at position 2 are particularly noteworthy, especially 2-methylindenyl or 2-phenylindenyl. Position 2 indicates the position of the carbon atom adjacent to the carbon atom connected to bridge P, as shown in the diagram below. 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 The unsubstituted fluorene group of H8.

[0013] Any ether capable of complexing alkali metals (especially diethyl ether and tetrahydrofuran) is suitable as an ether.

[0014] Linking group Cp 1 and Cp 2 The bridge P preferably 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.

[0015] Metallocenes used in the synthetic catalytic system can be in the form of crystalline or amorphous powders, or in single-crystal form. Metallocenes can be in monomeric or dimer form, depending on the method of metallocene preparation described, for example, in patent applications WO 2007054224 or WO 2007054223. Metallocenes can be conventionally prepared by methods similar to those described in patent applications WO 2007 / 054224 or WO 2007 / 054223, particularly by reacting an alkali metal salt of a ligand with a rare earth metal borohydride under inert and anhydrous conditions 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 from a second solvent). Finally, the metallocene is dried and separated in solid form.

[0016] According to particularly preferred embodiments, metallocenes have formulas (III-1), (III-2), (III-3), (III-4), or (III-5): [Me2Si(Flu)2Nd(µ-BH4)2Li(THF)] (III-1) [{Me2SiFlu2Nd(µ-BH4)2Li(THF)}2] (III-2) [Me2SiFlu2Nd(µ-BH4)(THF)] (III-3) [{Me2SiFlu2Nd(µ-BH4)(THF)}2] (III-4) [Me2SiFlu2Nd(µ-BH4)] (III-5) Where Flu represents C 13 H8 group.

[0017] Another essential component of the catalytic system is an organomagnesium halide of formula (IIa). R B -Mg-X(IIa) R B A benzene ring comprising two substituted carbon atoms, one of which is substituted by a methyl, ethyl, or isopropyl group, or forms a ring with its nearest neighbor carbon atom, the second carbon atom being substituted by a methyl, ethyl, or isopropyl group, and a magnesium atom located adjacent to each of the two carbon atoms. X is a halogen atom. In formula (IIa), X preferably represents a bromine atom or a chlorine atom, more preferably a bromine atom.

[0018] The organomagnesium compound of formula (IIa) is used as a cocatalyst in the catalytic system. Preferably, the two substituents of the two carbon atoms adjacent to the magnesium atom are identical. More preferably, they are methyl or ethyl. Advantageously, they are methyl.

[0019] Preferably, the organomagnesium compound of formula (IIa) has formula (IIb), wherein X represents a halogen atom, R1 and R5 are the same or different and represent methyl or ethyl, and R2, R3 and R4 are the same or different and represent hydrogen atoms or alkyl groups. Preferably, R1 and R5 represent methyl groups. Preferably, R2 and R4 represent hydrogen atoms. In formula (IIb), X preferably represents a bromine atom or a chlorine atom, more preferably a bromine atom. According to a preferred variant, R3 is the same as R1 and R5. According to a more preferred variant, R2 and R4 represent hydrogen, and R1, R3, and R5 are the same. In an even more preferred variant, R2 and R4 represent hydrogen, and R1, R3, and R5 represent methyl groups.

[0020] Another essential component of the catalytic system is a zinc compound. The zinc compound is a dialkylzinc compound. In other words, the zinc compound has the formula R2Zn, where each of the symbols R represents an alkyl group. The alkyl group of the dialkylzinc compound is preferably an alkyl group containing 2 to 10 carbon atoms, more preferably ethyl, butyl, or octyl. Advantageously, the dialkylzinc compound has the formula (IIIa). ZnR 5 R 6 (IIIa) Among them, the symbol R 5 and R 6 The alkyl groups are the same. More advantageously, they are represented by the symbol R. 5 and R 6 The alkyl groups are the same, and are either ethyl or octyl.

[0021] Preferably, the ratio N Zn / (N Zn +N Mg (This refers to the number of moles of Zn (N) in the dialkylzinc compound.) Zn The molar number of Zn in the dialkylzinc compound (N) Zn ) and the number of moles of Mg (N) in organomagnesium halides. Mg The ratio of the sum of the two groups is greater than 0.05 and less than 0.99. More preferably, the ratio is greater than 0.30 and less than 0.99.

[0022] The catalytic system can be conventionally prepared by a method similar to that described in patent applications WO 2007054224 or WO 2007054223, wherein the organomagnesium halide and dialkylzinc compound claimed in this invention serve as co-catalysts. For example, in a hydrocarbon solvent, the organomagnesium halide and zinc compound are typically contacted with the metallocene for a time between 5 and 60 minutes at a temperature ranging from 20°C to 80°C. The amounts of the organomagnesium halide, zinc compound, and metallocene reacted to form the catalytic system are such that the ratio (N...)... Mg +N Zn ) / N Nd (It is the number of moles of Mg in the organomagnesium halide (N)) Mg ) and the number of moles of Zn in zinc compounds (N) Zn The sum of the total and the number of moles of rare earth metals in the metallocene (N) Nd The ratio of () is preferably in the range of 2 to 500, more preferably 2 to less than 40. The range of values ​​from 2 to less than 40 is particularly advantageous for obtaining polymers with high molar mass.

[0023] The catalytic system is typically in the form of a solution in a hydrocarbon solvent. The hydrocarbon solvent can be an aliphatic hydrocarbon solvent (e.g., methylcyclohexane) or an aromatic hydrocarbon solvent (e.g., toluene). The hydrocarbon solvent is preferably an aliphatic hydrocarbon solvent, more preferably methylcyclohexane. Typically, the catalytic system is stored as a solution in a hydrocarbon solvent before use in polymerization. This can be referred to as a catalytic solution, which comprises the catalytic system and the hydrocarbon solvent. The concentration of the catalytic solution is typically defined by the metallocene content in the solution. The metallocene concentration is preferably in the range of 0.0001 mol L. -1 Up to 0.2 mol / L -1 More preferably 0.001 mol L -1 Up to 0.03 mol L -1 .

[0024] As with any synthesis in the presence of organometallic compounds, the catalytic system was synthesized under an inert atmosphere and anhydrous conditions. Typically, the reaction was initiated with anhydrous solvents and compounds under anhydrous nitrogen or argon.

[0025] The catalytic system according to the invention is intended for use in methods of synthesizing polymers, particularly in the synthesis of polymers containing ethylene, and even more particularly in the synthesis of polymers containing more than 50 mol% ethylene.

[0026] The first method for preparing polymers (which is particularly capable of preparing polyethylene) includes polymerizing ethylene in the presence of a catalytic system according to the invention.

[0027] A second method for preparing polymers (which is particularly capable of preparing copolymers of ethylene and 1,3-diene, preferably statistical copolymers of ethylene and 1,3-diene) includes polymerizing a mixture of monomers comprising ethylene and 1,3-diene in the presence of a catalytic system according to the invention.

[0028] The common polymerization reaction in both methods according to the invention is a polymerization reaction of monomers, said monomers being ethylene or a mixture of monomers comprising ethylene and 1,3-diene. The monomer mixture comprising ethylene and 1,3-diene preferably contains more than 50 mol% ethylene, the molar percentage being calculated relative to all monomers constituting the monomer mixture comprising ethylene and 1,3-diene. The monomer mixture comprising ethylene and 1,3-diene is preferably a mixture of ethylene and 1,3-diene, or a mixture of ethylene, 1,3-diene, 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. α-monoolefin is preferably styrene. 1,3-diene is a single compound (i.e., a single 1,3-diene) or a mixture of 1,3-dienes with different chemical structures. 1,3-dienes having 4 to 20 carbon atoms are particularly suitable as 1,3-dienes. Preferably, the 1,3-diene is 1,3-butadiene, isoprene, myrcene, β-farnesene, or a mixture thereof (e.g., a mixture of at least two of them). A mixture of at least two of them is advantageously a mixture containing 1,3-butadiene. The 1,3-diene is preferably 1,3-butadiene or a mixture of 1,3-dienes containing 1,3-butadiene.

[0029] Polymerization is preferably carried out continuously or batchwise in solution. The polymerization solvent can be an aromatic hydrocarbon solvent or an 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 presence of an optional inert gas. The polymerization temperature is typically varied from 40°C to 150°C, preferably from 40°C to 120°C. Those skilled in the art adjust polymerization conditions, such as polymerization temperature, the concentration of each reactant, and the pressure in the reactor, according to the composition of the monomer mixture, the polymerization reactor, and the desired micro and macroscopic structure of the polymer chains. Polymerization is preferably carried out at a constant monomer pressure, particularly at a constant ethylene pressure.

[0030] In 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 particularly suitable for the synthesis of statistical copolymers.

[0031] According to one embodiment of the present invention, the polymer prepared is polyethylene.

[0032] According to another embodiment of the invention, the prepared polymer is a copolymer of ethylene and 1,3-diene, preferably a statistical copolymer of ethylene and 1,3-diene.

[0033] According to another embodiment of the present invention, the polymer prepared is an ethylene-1,3-butadiene copolymer, preferably a statistical copolymer of ethylene-1,3-butadiene.

[0034] According to any embodiment of the present invention, the prepared polymer preferably contains more than 50 mol% ethylene.

[0035] According to a particularly preferred embodiment of the invention (wherein the monomer is a mixture of monomers comprising ethylene and 1,3-butadiene, and is composed of Cp...), 1 and Cp 2 The ligands in the catalytic systems represented are all of formula C 13 The unsubstituted fluorene group of H8), the polymer prepared not only contains ethylene monomer units and butadiene units, but also cyclic units (1,2-cyclohexane units of the following formula): In addition to the conventional ethylene and 1,3-butadiene units (-(CH2-CH2)-, -(CH2-CH=CH-CH2)-, and -(CH2-CH(C=CH2))-, respectively), the cyclic units originate from specific insertions of ethylene and 1,3-butadiene monomers into the polymer chain. The mechanisms used to obtain this microstructure are described, for example, in Macromolecules 2009, 42, 3774-3779. When the polymer according to the invention contains 1,2-cyclohexane units, it preferably contains up to 15 mol% of 1,2-cyclohexane units, the percentage being expressed relative to all repeating units constituting the polymer.

[0036] According to a first variant of the invention, polymerization is terminated, for example, by cooling the polymerization medium or by adding an alcohol (preferably an alcohol containing 1 to 3 carbon atoms, such as ethanol). The polymer can be recovered using conventional techniques known to those skilled in the art (e.g., by precipitation, by evaporation of the solvent under reduced pressure, or by steam stripping).

[0037] According to the second variant, a modification reaction using an acidic halide is carried out after the polymerization reaction to introduce ketone functional groups into the polymer. In a known manner, an acidic halide (also called an acyl halide) is a halogenated derivative of a carboxylic acid, wherein the OH group of the carboxylic acid functional group COOH is replaced by a halogen atom. Therefore, an acidic halide is a compound containing one or more COX groups. 1 Compound X 1 This represents a halogen atom.

[0038] Prior to the addition of the acid halide, the reactor is preferably degassed and inertized. Degassed reactor removes residual gaseous monomers and facilitates the addition of the acid halide. Alternatively, the acid halide can be injected into the reactor under positive pressure. Inertizing the reactor, for example, with nitrogen, avoids the deactivation of carbon-metal bonds present in the reaction medium, which are essential for the reaction of the acid halide with the polymer chains formed during the polymerization reaction. The acid halide can be added in pure form or diluted in a hydrocarbon solvent (preferably an aliphatic hydrocarbon solvent (e.g., methylcyclohexane) or an aromatic hydrocarbon solvent (e.g., toluene)). The contact time between the acid halide and the polymer chains is the time required for the reaction between the acid halide and the polymer chains generated in the previous stage (i.e., the polymerization reaction). The reaction between the acid halide and the polymer chains can typically be monitored by chromatographic analysis to monitor the consumption of the acid halide. The reaction is preferably carried out with stirring at a temperature ranging from 23°C to 120°C for 1 to 60 minutes. The modification reaction is preferably carried out with 1 molar equivalent of the group COX, relative to the total number of carbon-magnesium bonds per mole of magnesium compound and carbon-zinc bonds per mole of zinc compound in the catalytic system. 1 The process is carried out. However, depending on the desired proportion of polymers with ketone functional groups in the prepared polymer, the COX group... 1 The ratio of the molar equivalent number to the total number of carbon-magnesium bonds per mole of cocatalyst and carbon-zinc bonds per mole of zinc compound can vary considerably, for example, from 0.1 to 10. A ratio close to 1 (typically ranging from 0.85 to 1.05) is favorable for obtaining the highest proportion of ketone functional groups.

[0039] Acidic halides may contain one or more COX groups. 1 X 1 This represents a halogen atom. Acidic halides can be aliphatic or aromatic compounds. Aromatic acidic halides are preferred from the perspective of characterizing modified polymers (especially those confirming the presence of aromatic rings in the modified polymers via NMR analysis). Preferably, the acidic halide has the formula Ar-(COX). 1 ) n Where Ar represents an aromatic ring, preferably a benzene ring, n is an integer equal to 1, 2 or 3, and X 1Halogen atoms are present. Aromatic rings (especially benzene rings) can contain groups other than COX. 1 One or more substituents other than those listed above. Suitable such halides may include 4-methoxybenzoyl chloride, p-toluyl chloride, 4-iodobenzoyl chloride, 4-bromobenzoyl chloride, 4-nitrobenzoyl chloride, 4-methoxybenzoyl chloride, 4-(methoxymethyl)benzoyl chloride, 3-methoxybenzoyl bromide, 4-(dimethylamino)benzoyl chloride, 4-[(dimethylamino)methyl]benzoyl chloride, 4-[2-(dimethylamino)ethyl]benzoyl chloride, trimesoyl chloride, 5-methoxy-1,3-benzoyl dichloride, benzoyl bromide, isophthaloyl dichloride, and terephthaloyl chloride.

[0040] Having a single COX group 1 Acidic halides are formed in polymers with ketone functional groups at the chain ends. These polymers contain two COX groups. 1 Acidic halides can form coupling polymers by the coupling between two polymer chains. COX groups have more than two groups. 1 Acidic halides can generate star polymers formed by coupling between at least three polymer chains.

[0041] According to any embodiment of the invention, the acidic halide is advantageously an acidic chloride, in which case the COX group 1 It is a COCl group.

[0042] After modifying the polymer chain, an additive step (which deactivates the reaction sites remaining in the reaction medium) can be performed, for example, by adding a terminator to the reaction medium or pouring the reaction medium into a solution containing a terminator. The terminator is typically in stoichiometric excess. Terminators are usually protonated compounds (compounds containing relatively acidic protons). Terminators include water, carboxylic acids (especially C2-C...). 18 Fatty acids, such as acetic acid or stearic acid, aliphatic alcohols or aromatic alcohols (such as methanol, ethanol or isopropanol), or phenolic antioxidants. The modified polymer can be separated from the reaction medium by methods known to those skilled in the art, such as by solvent evaporation under reduced pressure, by precipitation or by steam stripping.

[0043] The polymer prepared according to the second variant carries one or more ketone functional groups, preferably located at the chain ends. The modification reaction for introducing ketone functional groups into the polymer prepared in the presence of the catalytic system according to the invention is highly selective. With respect to ketone functional groups, the selectivity of the modification reaction reaches 100% or almost 100%.

[0044] Furthermore, the proportion of modified chains is also very high, typically at least 50%. They are usually much higher than 50%, typically at least 80% in the case of preparing modified polyethylene.

[0045] In summary, the present invention is advantageously implemented according to any one of the following embodiments 1 to 28: Implementation Scheme 1: A catalytic system, said catalytic system being based on at least: Metallocenes of formula (Ia), Organomagnesium halides of formula (IIa), Dialkylzinc compounds, {P(Cp 1 (Cp) 2 Nd(BH4) (1+y)- L y -N x}(Ia) R B -Mg-X(IIa) Cp 1 and Cp 2 The groups may be the same or different, and are selected from fluorenyl, cyclopentadienyl, and indene, wherein the groups are substituted or unsubstituted. P is a bridging group between two Cp groups. 1 and Cp 2 And contains groups that contain silicon or carbon atoms, Nd represents a neodymium atom. L indicates an alkali metal selected from lithium, sodium, and potassium. N represents an ether molecule. x is an integer equal to or greater than 0, or a non-integer. y is an integer equal to or greater than 0. R B A benzene ring comprising two substituted carbon atoms, one of which is substituted by a methyl, ethyl, or isopropyl group, or forms a ring with its nearest neighbor carbon atom, the second carbon atom being substituted by a methyl, ethyl, or isopropyl group, and a magnesium atom located adjacent to each of the two carbon atoms. X is a halogen atom.

[0046] Implementation Scheme 2: According to the catalytic system described in Implementation Scheme 1, wherein Cp 1 and Cp 2 The same, and selected from substituted fluorene groups and formula C 13 The unsubstituted fluorene group of H8.

[0047] Implementation Scheme 3: The catalytic system according to Implementation Scheme 1 or 2, wherein Cp 1 and Cp 2 Each expression C 13 The unsubstituted fluorene group of H8.

[0048] Implementation Scheme 4: The catalytic system according to any one of Implementation Schemes 1 to 3, wherein the linking group Cp 1 and Cp 2 The bridge P has a ZR type 1 R 2 Where Z represents a silicon atom or a carbon atom, and R 1 and R 2 The same or different, and each refers to an alkyl group containing 1 to 20 carbon atoms.

[0049] Implementation Scheme 5: The catalytic system according to Implementation Scheme 4, wherein R 1 and R 2 Each represents a methyl group.

[0050] Implementation Scheme 6: The catalytic system according to Implementation Scheme 4 or 5, wherein Z represents a silicon atom.

[0051] Implementation Scheme 7: A catalytic system according to any one of Implementation Schemes 1 to 6, wherein the metallocene has the formula (III-1), (III-2), (III-3), (III-4), or (III-5): [Me2Si(Flu)2Nd(µ-BH4)2Li(THF)] (III-1) [{Me2SiFlu2Nd(µ-BH4)2Li(THF)}2] (III-2) [Me2SiFlu2Nd(µ-BH4)(THF)] (III-3) [{Me2SiFlu2Nd(µ-BH4)(THF)}2] (III-4) [Me2SiFlu2Nd(µ-BH4)] (III-5) Where Flu represents C 13 H8 group.

[0052] Implementation Scheme 8: The catalytic system according to any one of Implementation Schemes 1 to 7, wherein the alkyl group of the dialkylzinc compound is an alkyl group containing 2 to 10 carbon atoms.

[0053] Implementation Scheme 9: A catalytic system according to any one of Implementation Schemes 1 to 8, wherein the dialkylzinc compound has formula (IIIa). ZnR 5 R 6 (IIIa) Among them, the symbol R 5 and R 6 The alkyl groups are the same.

[0054] Implementation Scheme 10: The catalytic system according to Implementation Scheme 9, wherein, by the symbol R 5 and R 6 The alkyl group represented is ethyl or octyl.

[0055] Implementation Scheme 11: A catalytic system according to any one of Implementation Schemes 1 to 10, wherein the organomagnesium halide has formula (IIb). Where X represents a halogen atom, R1 and R5 are the same or different and represent methyl or ethyl, and R2, R3 and R4 are the same or different and represent hydrogen atoms or alkyl groups.

[0056] Implementation Scheme 12: The catalytic system according to Implementation Scheme 11, wherein R3 is the same as R1 and R5.

[0057] Implementation Scheme 13: The catalytic system according to Implementation Scheme 11 or 12, wherein R1 and R5 represent methyl groups.

[0058] Implementation Scheme 14: The catalytic system according to any one of Implementation Schemes 11 and 13, wherein R2 and R4 represent hydrogen atoms.

[0059] Implementation Scheme 15: The catalytic system according to any one of Implementation Schemes 1 to 14, wherein X is a chlorine atom or a bromine atom.

[0060] Implementation Scheme 16: The catalytic system according to any one of Implementation Schemes 1 to 15, wherein X is a bromine atom.

[0061] Implementation Scheme 17: According to any one of Implementation Schemes 1 to 16, the ratio of the number of moles of Zn in the dialkylzinc compound to the sum of the number of moles of Zn in the dialkylzinc compound and the number of moles of Mg in the organomagnesium halide compound is greater than 0.05 and less than 0.99.

[0062] Implementation Scheme 18: According to any one of Implementation Schemes 1 to 17, the ratio of the number of moles of Zn in the dialkylzinc compound to the sum of the number of moles of Zn in the dialkylzinc compound and the number of moles of Mg in the organomagnesium halide compound is greater than 0.3 and less than 0.99.

[0063] Implementation Scheme 19: According to any one of Implementation Schemes 1 to 18, the ratio of the sum of the number of moles of Mg in the organomagnesium halide and the number of moles of Zn in the zinc compound to the number of moles of rare earth metals in the metallocene ranges from 2 to 500.

[0064] Implementation Scheme 20: According to any one of Implementation Schemes 1 to 19, the ratio of the sum of the number of moles of Mg in the organomagnesium halide and the number of moles of Zn in the zinc compound to the number of moles of rare earth metals in the metallocene ranges from 2 to less than 40.

[0065] Implementation Scheme 21: A method for preparing a polymer, the method comprising polymerizing ethylene or a mixture of monomers comprising ethylene and 1,3-diene in the presence of a catalytic system defined in any one of Implementation Schemes 1 to 20.

[0066] Implementation Scheme 22: The preparation method according to Implementation Scheme 21, wherein an acidic halide is used for modification reaction after the polymerization reaction.

[0067] Implementation Scheme 23: The preparation method according to Implementation Scheme 22, wherein the acidic halide has the formula Ar-(COX) 1 ) n Where Ar represents an aromatic ring, preferably a benzene ring, n is an integer equal to 1, 2 or 3, and X 1 It is a halogen atom.

[0068] Implementation Scheme 24: The preparation method according to any one of Implementation Schemes 22 to 23, wherein the acidic halide is an acidic chloride.

[0069] Implementation Scheme 25: The preparation method according to any one of Implementation Schemes 21 to 24, wherein the polymer is polyethylene or a copolymer of ethylene and 1,3-diene.

[0070] Implementation Scheme 26: According to the preparation method described in Implementation Scheme 25, wherein the copolymer of ethylene and 1,3-diene is a statistical copolymer of ethylene and 1,3-diene.

[0071] Implementation Scheme 27: The preparation method according to any one of Implementation Schemes 21 to 26, wherein the 1,3-diene is 1,3-butadiene, isoprene, myrcene, β-farnesene, or a mixture thereof.

[0072] Implementation Scheme 28: The preparation method according to any one of Implementation Schemes 21 to 27, wherein the 1,3-diene is 1,3-butadiene or a mixture of 1,3-dienes containing 1,3-butadiene.

[0073] The above and other features of the invention will be more clearly understood by reading the following description of embodiments of the invention given in an illustrative but not limiting manner.

[0074] Example Both the ethylene homopolymer and the copolymer of ethylene and butadiene were prepared using metallocene {(Me₂Si(C)₂} prepared according to the steps described in patent application WO 2007054224. 13 The preparation method is H8)2)Nd(µ-BH4)[(µ-BH4)Li(THF)]}2. Both the organomagnesia and zinc compounds are commercial products. Unless otherwise stated: Obtained from Chemtura at 0.88 mol L -1 Butyloctyl magnesium used in solution in heptane; Obtained from Sigma-Aldrich at 1 mol L -1 Diethylzinc used in solution in hexane; Obtained from Sigma-Aldrich at 1 mol L -1 Trimethylbenzene magnesium bromide used in diethyl ether.

[0075] The polymer was characterized using the methods described below.

[0076] N35 grade ethylene is obtained from Air Liquide and can be used without prior purification.

[0077] 1,3-Butadiene was purified using an alumina protective tube.

[0078] Toluene solvent from BioSolve is dried and purified on an alumina column in a solvent fountain from mBraun and used in an inert atmosphere.

[0079] All reactions were carried out under an inert atmosphere.

[0080] High-Temperature Size Exclusion Chromatography (HT-SEC) Analysis of Polyethylene: High-temperature size exclusion chromatography (HT-SEC) analysis was performed using a Viscotek (Malvern Instruments) instrument equipped with three columns (PLgel Olexis 300 mm × 7 mm ID from Agilent Technologies) and three detectors (differential refractometer, differential viscometer, and light scattering detector). A concentration of 200 µL was obtained at 8 mg / mL. -1 The sample solution was used at 150℃ for 1 mL min -1 The elution was carried out in 1,2,4-trichlorobenzene at a flow rate of [missing information]. The mobile phase used was 2,6-di(tert-butyl)-4-methylphenol (400 mg / L). -1 Stabilization was performed. Data acquisition and analysis were conducted using OmniSEC software. Standard polyethylene (PE) was obtained from Polymer Standards Service (Mainz).M p 338 g mol -1 507g mol -1 770 g mol -1 1890 g mol -1 17000 g mol -1 27300 g mol -1 43400 g mol -1 53100g mol -1 65700 g mol -1 78 400g mol -1 The number-average molar mass of the synthesized polyethylene was calculated from the calibration curve obtained. M n ) and weight-average molar mass ( M w ).

[0081] THF size exclusion chromatography (THF-SEC) of ethylene-1,3-butadiene copolymer: Size exclusion chromatography analysis was performed using a Viscotek (Malvern Instruments) instrument equipped with three columns (SDVB, 5 µm, 300 × 7.5 mm, from Polymer Standard Service), one guard column, and three detectors (differential refractometer, differential viscometer, and light scattering detector). 1 mL of the solution was 5 mg / mL. -1 The sample solution in THF was filtered through a 0.45 µm PTFE membrane. 100 µL of this solution was used at 35 °C with 0.8 mL / min. -1 Elution was performed in THF at a flow rate of [missing information]. OmniSEC software was used for data acquisition and analysis. Standard polystyrene (PS) was obtained from Polymer Standard Service (Mainz). M p 1306 g mol -1 Up to 2,520,000 g mol -1 The number-average molar mass of the synthesized ethylene-butadiene copolymer was calculated using a universal calibration curve obtained from the standard calibration curve. M n ) and weight-average molar mass ( M w ).

[0082] Nuclear magnetic resonance (NMR): A Bruker 400 Avance III spectrometer (for protons) operating at 400 MHz and equipped with a 5 mm BBFO probe, and a 10 mm PSEX probe operating at 400 MHz. 13 High-resolution NMR spectra of polymers were performed on a Bruker 400 Avance II spectrometer (for carbon) using a C-probe. Acquisitions were performed at 363 K in a mixture of tetrachloroethylene (TCE) and deuterated benzene (C6D6) (2 / 1 volume / volume) (for ethylene homopolymer) and at 298 K in deuterated chloroform (CDCl3) (for ethylene-butadiene copolymer). Samples were analyzed at 1% by mass (for protons) and 5% by mass (for carbon). Chemical shifts are given in ppm relative to the deuterated benzene proton signal set at 7.16 ppm (or the deuterated chloroform signal set at 7.26 ppm, respectively) and the TCE carbon signal set at 120.65 ppm.

[0083] Example 1: Synthesis of polyethylene (using butyloctylmagnesium as a co-catalyst and functionalization with 4-methoxybenzoyl chloride) (not according to an example of the invention): 192 mL of toluene, taken from the solvent fountain (SPS800 MBraun), was placed into an inert 250 mL round-bottom flask equipped with a magnetic olive. While stirring, 2.27 mL of 0.88 mol / L butyloctyl magnesium from heptane was introduced into the flask. -1 ) and 4 mL of diethyl ether (38.5 mmol). Then 8.3 mg (13 µmol of neodymium) of {(Me2Si(C)} was introduced into the flask. 13 H8)2)Nd(µ-BH4)[(µ-BH4)Li(THF)]}2. Under an inert atmosphere, the catalyst solution was transferred to a 250 mL reactor via a sleeve. The pressure in the reactor was reduced to 0.5 bar, and then the reactor was pressurized to 4 bar (absolute pressure) using ethylene while the temperature was raised to 80 °C. The pressure in the reactor was kept constant through a storage tank containing ethylene. When the desired amount of ethylene was consumed (in this case, after 26 min), the reactor was degassed, and 10 mL (5%) of the polymer solution was drawn from the reactor. The polymer was then precipitated from methanol, recovered by filtration, and dried.

[0084] 10 mL of a degassed solution of 4-methoxybenzoyl chloride in 0.57 M toluene (stored using molecular sieves) (5.7 mmol, 2 equivalents / Mg) was added to the residual polymer solution in the reactor. After stirring at 80 °C for 1 h, the polymer solution was poured into methanol with stirring to precipitate the polymer. The polymer with the modifier was filtered, washed with methanol, dried, and characterized. 4.3 g of polyethylene (activity 750 kg / mol / h) was recovered, with a number-average molar mass of 1400 g mol. -1 The dispersion was 1.4, and 55% of the chains were functionalized. The 55% functionalized chains decomposed into 11% secondary alcohols and 44% tertiary alcohols.

[0085] Example 2: Synthesis of polyethylene (using diethylzinc and mesitylene-methylmagnesium bromide as co-catalysts, followed by functionalization with 4-methoxybenzoyl chloride) (according to an embodiment of the present invention): 196 mL of toluene taken from the solvent fountain (SPS800 MBraun) was placed into an inert 250 mL round-bottom flask equipped with a magnetic olive. While stirring, 0.5 mL of trimethylbenzyl magnesium bromide (0.5 mol L) in diethyl ether was introduced into the flask. -1 ) and 1 mL of diethylzinc in hexane (1 mol L) -1 Then 7.7 mg (12 µmol of neodymium) of {(Me2Si(C)} was introduced into the flask. 13 H8)2)Nd(µ-BH4)[(µ-BH4)Li(THF)]}2. Under an inert atmosphere, the catalyst solution was transferred to a 250 mL reactor via a sleeve. The pressure in the reactor was reduced to 0.5 bar, and then the reactor was pressurized to 4 bar using ethylene while the temperature was raised to 80 °C. The pressure in the reactor was kept constant via a storage tank containing ethylene. When the desired amount of ethylene was consumed (in this case, after 31 min), the reactor was degassed, and 10 mL (5%) of the polymer solution was transferred from the reactor via a sleeve. The polymer was then precipitated from methanol, recovered by filtration, and dried.

[0086] 10 mL of a degassed solution of 4-methoxybenzoyl chloride in 0.23 M toluene (stored using molecular sieves) (2.3 mmol, 1 equivalent / Mg + 2 equivalent / Zn) was added to the residual polymer solution in the reactor. After stirring at 80 °C for 1 hour, the polymer solution was poured into methanol with stirring to precipitate the polymer. The polymer was filtered, washed with methanol, dried, and characterized. 4.2 g of polyethylene (activity 690 kg / mol / h) was recovered, with a number-average molar mass of 2000 g mol. -1The dispersion was 1.1, and 79% of the chains were functionalized and contained ketones, indicating that the selectivity of the functionalization reaction was 100%.

[0087] Example 3: Synthesis of polyethylene (using diethylzinc and mesitylene-methylmagnesium bromide as co-catalysts, followed by functionalization with 4-dimethylaminobenzoyl chloride) (according to an example of the present invention): 196 mL of toluene taken from the solvent fountain (SPS800 MBraun) was placed into an inert 250 mL round-bottom flask equipped with a magnetic olive. While stirring, 0.4 mL of 0.5 mol / L trimethylbenzene magnesium bromide in diethyl ether was introduced into the flask. -1 ) and 1 mL of heptane containing diethylzinc (1 mol L) -1 Then 7.7 mg (12 µmol of neodymium) of {(Me2Si(C)} was introduced into the flask. 13 H8)2)Nd(µ-BH4)[(µ-BH4)Li(THF)]}2. Under an inert atmosphere, the catalyst solution was transferred to a 250 mL reactor via a sleeve. The pressure in the reactor was reduced to 0.5 bar, and then the reactor was pressurized to 4 bar using ethylene while the temperature was raised to 80 °C. The pressure in the reactor was kept constant via a storage tank containing ethylene. When the desired amount of ethylene was consumed (in this case, after 17 min), the reactor was degassed, and 10 mL (5%) of the polymer solution was transferred from the reactor via a sleeve. The polymer was then precipitated from methanol, recovered by filtration, and dried.

[0088] 7.8 mL of a degassed solution of 4-dimethylaminobenzoyl chloride in 0.23 M toluene (stored using molecular sieves) (1.8 mmol, 1 equivalent / Mg + 2 equivalent / Zn) was added to the residual polymer solution in the reactor. After stirring at 80 °C for 1 hour, the polymer solution was poured into methanol with stirring to precipitate the polymer. The polymer was filtered, washed with methanol, dried, and characterized. 3.7 g of polyethylene (activity 980 kg / mol / h) was recovered, with a number-average molar mass of 2100 g mol. -1 The dispersion was 1.1. 50% of the chains were functionalized and contained ketones, indicating that the selectivity of the functionalization reaction was 100%.

[0089] Example 4: Poly(ethylene-) jointly Synthesis of 1,4-butadiene (using diethylzinc and mesitylene-methylmagnesium bromide as co-catalysts, followed by functionalization with 4-methoxybenzoyl chloride) (according to an embodiment of the invention): 198 mL of toluene taken from the solvent fountain (SPS800 MBraun) was placed into an inert 250 mL round-bottom flask equipped with a magnetic olive. While stirring, 0.8 mL of trimethylbenzyl magnesium bromide (0.5 mol L) in diethyl ether was introduced into the flask. -1 ) and diethylzinc in 0.5 mL of heptane (1 mol L ) -1 Then 32 mg (50 µmol) of {(Me₂Si(C)} was introduced into the flask. 13 H8)2)Nd(µ-BH4)[(µ-BH4)Li(THF)]}2. Under an inert atmosphere, the catalyst solution was transferred to a 250 mL reactor via a sleeve. The pressure in the reactor was reduced to 0.5 bar, and then the reactor was pressurized to 4 bar using ethylene while the temperature was raised to 80 °C. The pressure in the reactor was kept constant by a tank containing an 80 / 20 mol / mol ethylene / butadiene gas mixture. When the desired amount of monomer was consumed (in this case, after 115 min), the reactor was degassed, and 10 mL (5%) of the polymer solution was transferred from the reactor via a sleeve. The polymer was then precipitated from methanol, recovered by filtration, and dried.

[0090] 10 mL of a degassed solution of 4-methoxybenzoyl chloride in 0.14 M toluene (stored using molecular sieves) (1.4 mmol, 1 equivalent / Mg + 2 equivalent / Zn) was added to the residual polymer solution in the reactor. After stirring at 80 °C for 1 hour, the polymer solution was poured into methanol with stirring to precipitate the polymer. The polymer was filtered, washed with methanol, dried, and characterized. 7.2 g of poly(ethylene-) was recovered. Co- Butadiene (activity 75 kg / mol / h), with a number-average molar mass of 12600 g mol -1 The dispersion was 1.3. 38% of the chains were functionalized and contained ketones, indicating that the selectivity of the functionalization reaction was 100%.

[0091] Example 5: Poly(ethylene-) jointly Synthesis of 1,4-butadiene (using diethylzinc and mesitylene magnesium bromide as co-catalysts, followed by functionalization with 4-dimethylaminobenzoyl chloride) (according to an embodiment of the invention): 198 mL of toluene taken from the solvent fountain (SPS800 MBraun) was placed into an inert 250 mL round-bottom flask equipped with a magnetic olive. While stirring, 1.6 mL of 0.5 mol / L trimethylbenzene magnesium bromide in diethyl ether was introduced into the flask. -1 ) and 1 mL of heptane containing diethylzinc (1 mol L) -1Then 32 mg (50 µmol) of {(Me2Si(C)} was introduced into the flask. 13 H8)2)Nd(µ-BH4)[(µ-BH4)Li(THF)]}2. Under an inert atmosphere, the catalytic solution was introduced into a 250 mL reactor through a sleeve. The pressure in the reactor was reduced to 0.5 bar, and then the reactor was pressurized to 4 bar using ethylene while the temperature was raised to 80 °C. The pressure in the reactor was kept constant through a tank containing an 80 / 20 mol / mol ethylene / butadiene gas mixture. When the desired amount of monomer was consumed (in this case, after 174 min), the reactor was degassed, and 10 mL (5%) of the polymer solution was transferred from the reactor through a sleeve. The polymer was then precipitated from methanol, recovered by filtration, and dried.

[0092] 20 mL of a degassed solution of 4-dimethylaminobenzoyl chloride in 0.14 M toluene (stored using molecular sieves) (2.8 mmol, 1 equivalent / Mg + 2 equivalent / Zn) was added to the residual polymer solution in the reactor. After stirring at 80 °C for 1 hour, the polymer solution was poured into methanol with stirring to allow the polymer to precipitate. The polymer was filtered, washed with methanol, dried, and characterized. 10.3 g of poly(ethylene- Co- Butadiene (activity 70 kg / mol / h), with a number-average molar mass of 16400 g mol -1 The dispersion was 1.3. 35% of the chains were functionalized and contained ketones, indicating that the selectivity of the functionalization reaction was 100%.

[0093] Examples show that the catalytic system containing organomagnesium halides and dialkylzinc compounds of formula (IIa) can not only synthesize polyethylene and copolymers containing ethylene units and 1,3-diene units, but also selectively synthesize polyethylene and copolymers containing ethylene units and 1,3-diene units, which have ketone functional groups.

[0094] The catalytic system according to the invention is as versatile as the zinc-free catalytic system: like the zinc-free catalytic system, it can not only produce polyethylene, but also copolymers of ethylene with 1,3-diene (especially 1,3-butadiene).

Claims

1. A catalytic system, said catalytic system being based on at least: Metallocenes of formula (Ia), Organomagnesium halides of formula (IIa), Dialkylzinc compounds, {P(Cp 1 )(Cp 2 )Nd(BH4) (1+y)- L y -N x }(Ia) R B -Mg-X(IIa) Cp 1 and Cp 2 The groups may be the same or different, and are selected from fluorenyl, cyclopentadienyl, and indene, wherein the groups are substituted or unsubstituted. P is a bridging group between two Cp groups. 1 and Cp 2 And contains groups that contain silicon or carbon atoms, Nd represents a neodymium atom. L indicates an alkali metal selected from lithium, sodium, and potassium. N represents an ether molecule. x is an integer equal to or greater than 0, or a non-integer. y is an integer equal to or greater than 0. R B A benzene ring comprising two substituted carbon atoms, one of which is substituted by a methyl, ethyl, or isopropyl group, or forms a ring with its nearest neighbor carbon atom, the second carbon atom being substituted by a methyl, ethyl, or isopropyl group, and a magnesium atom located adjacent to each of the two carbon atoms. X is a halogen atom.

2. The catalytic system according to claim 1, wherein, Cp 1 and Cp 2 The same, and selected from substituted fluorene groups and formula C 13 The unsubstituted fluorene group of H8, preferably Cp 1 and Cp 2 Each expression C 13 The unsubstituted fluorene group of H8.

3. The catalytic system according to any one of claims 1 to 2, wherein, Linking group Cp 1 and Cp 2 The bridge P has a ZR type 1 R 2 Where Z represents a silicon atom or a carbon atom, R 1 and R 2 The same or different, and each refers to an alkyl group containing 1 to 20 carbon atoms, preferably methyl.

4. The catalytic system according to any one of claims 1 to 3, wherein, The alkyl group in the dialkylzinc compound is an alkyl group containing 2 to 10 carbon atoms.

5. The catalytic system according to any one of claims 1 to 4, wherein, The dialkylzinc compound has formula (IIIa). ZnR 5 R 6 (IIIa) Among them, the symbol R 5 and R 6 The alkyl groups are the same, preferably ethyl or octyl.

6. The catalytic system according to any one of claims 1 to 5, wherein, The organomagnesium halide has the formula (IIb). ， Where X represents a halogen atom, R1 and R5 are the same or different and represent methyl or ethyl, and R2, R3 and R4 are the same or different and represent hydrogen atoms or alkyl groups.

7. The catalytic system according to claim 6, wherein, R3 is the same as R1 and R5.

8. The catalytic system according to claim 6 or 7, wherein, R1 and R5 represent methyl groups.

9. The catalytic system according to any one of claims 6 to 8, wherein, R2 and R4 represent hydrogen atoms.

10. The catalytic system according to any one of claims 1 to 9, wherein, X is a bromine atom or a chlorine atom, preferably a bromine atom.

11. The catalytic system according to any one of claims 1 to 10, wherein, The ratio of the number of moles of Zn in the dialkylzinc compound to the sum of the number of moles of Zn in the dialkylzinc compound and the number of moles of Mg in the organomagnesium halide compound is greater than 0.05 and less than 0.99, more preferably greater than 0.3 and less than 0.

99.

12. A method for preparing a polymer, the method comprising polymerizing ethylene or a mixture of monomers comprising ethylene and 1,3-diene in the presence of a catalytic system as defined in any one of claims 1 to 11.

13. The preparation method according to claim 12, wherein, Following the polymerization reaction, an acidic halide, preferably an acidic chloride, is used for modification.

14. The preparation method according to claim 12 or 13, wherein, The polymer is polyethylene or a copolymer of ethylene and 1,3-diene, preferably a statistical copolymer of ethylene and 1,3-diene.

15. The preparation method according to any one of claims 12 to 14, wherein, The 1,3-diene is 1,3-butadiene, isoprene, myrcene, β-farnesene or a mixture thereof, preferably 1,3-butadiene or a mixture of 1,3-dienes containing 1,3-butadiene.

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