Triblock polymers having a poly(1,3-cyclohexadiene) block and a polyethylene block linked together by a random copolymer based on ethylene and a 1,3-diene

Abstract

The invention relates to a triblock polymer of formula A-B-C, where symbol A represents a thermoplastic poly(1,3-cyclohexadiene) block, symbol B represents an elastomeric block which is a random copolymer comprising units of a 1,3-diene and more than 50 mol% of ethylene units, and symbol C represents a polyethylene having a melting temperature greater than 90°C, the 1,3-diene being an α-olefin, in particular 1,3-butadiene.

Description

[0001] Triblock polymers having a poly(1,3-cyclohexadiene) block and a polyethylene block linked together by a random copolymer based on ethylene and a 1,3-diene

[0002] The field of the invention is that of thermoplastic elastomers containing two terminal hard blocks connected to each other by a central elastomer block consisting of an ethylene-rich diene copolymer chain.

[0003] Statistical 1,3-diene and ethylene elastomers containing more than 50 mole percent ethylene units are known in the prior art, particularly in the field of tire treads. To impart thermoplastic elastomeric properties to elastomers, it is known to introduce hard blocks at each end. Thus, documents WO 2019077235 and WO 2021123590 describe triblock polymers containing a polystyrene block and a polyethylene block as the hard blocks, linked together by a soft central block consisting of a statistical 1,3-diene and ethylene elastomer chain. Although these triblock polymers have thermoplastic elastomer properties, there is a need to offer thermoplastic elastomers with improved mechanical properties, in particular improved elongation at break, while having a static 1,3-diene and ethylene elastomer as their soft block.

[0004] The inventors discovered that substituting a poly(l,3-cyclohexadiene) thermoplastic block for the polystyrene block in the thermoplastic elastomers described above improves their elongation at break.

[0005] A first object of the invention is a triblock polymer of formula ABC, the symbol A representing a thermoplastic poly(l,3-cyclohexadiene) block, the symbol B representing an elastomer block which is a statistical copolymer comprising units of a 1,3-diene and more than 50% by mole of ethylene units, the symbol C representing a polyethylene with a melting temperature above 90°C, the 1,3-diene being an α-olefin.

[0006] A second object of the invention is a composition comprising a triblock polymer according to the invention and another ingredient.

[0007] Detailed description:

[0008] Any range of values ​​designated by the expression "between a and b" represents the range of values ​​greater than "a" and less than "b" (i.e., bounds a and b excluded) while any range of values ​​designated by the expression "from a to b" means the range of values ​​from "a" to "b" (i.e., including the strict bounds a and b).

[0009] The compounds mentioned in the description can be of fossil origin or bio-based. In the latter case, they may be derived, partially or entirely, from biomass or obtained from renewable raw materials derived from biomass. Similarly, the compounds mentioned may also come from the recycling of previously used materials; that is, they may be derived, partially or entirely, from a process

[0010] 2024PAT00105WO from recycling, or obtained from raw materials themselves derived from a recycling process.

[0011] The block represented by the symbol B in the ABC formula represents an elastomer block containing ethylene units and 1,3-diene units. The elastomer block is a statistical copolymer, meaning that the monomer units constituting the elastomer block are statistically distributed within the block.

[0012] An ethylene unit is known to be a unit with the repeating pattern -(CH2-CH2)-. The ethylene units present in the elastomer block represent more than 50% by mole of the monomer units constituting the elastomer block. In this application, the proportion of ethylene units in the elastomer block, that is, the number of moles of ethylene units in the elastomer block, is expressed as a mole percentage relative to the number of moles of monomer units constituting the elastomer block.

[0013] According to any one embodiment of the invention, the elastomer block is preferably a random copolymer of ethylene and a 1,3-diene, in which case the monomer units of the elastomer block are those resulting from the copolymerization of ethylene and the

[0014] 1.3-diene and are statistically distributed in the elastomer block.

[0015] The 1,3-diene whose monomeric units constitute the elastomer block is an α-olefin. As is known, an α-olefin is an olefin with a terminal double bond and is therefore distinct from 1,3-cyclohexadiene. "A 1,3-diene" refers to one or more 1,3-dienes, that is, at least two 1,3-dienes. The 1,3-diene is preferably 1,3-butadiene or isoprene, or a mixture of 1,3-dienes, one of which is 1,3-butadiene. More preferably, the 1,3-diene is 1,3-butadiene. Most preferably, the elastomer block is a random copolymer of ethylene and

[0016] 1,3-butadiene.

[0017] As is known, a 1,3-diene can insert itself into a growing polymer chain by a 1,4 or 2,1 or even 3,4 insertion in the case of substituted dienes such as isoprene to give rise respectively to the formation of 1,3-diene units of configuration 1,4, 1,3-diene units of configuration 1,2 or of configuration 3,4. Preferably, the 1,3-diene units in the configuration 1,2 and the 1,3-diene units in the configuration 3,4 represent more than 50% by mole of the 1,3-diene units.

[0018] According to one embodiment of the invention, the elastomer block contains units of 1,3-diene in the 1,4 configuration, preferably Al cin. Preferably, the units of 1,3-diene in the 1,4-trans configuration represent more than 50% by mole of the units of 1,3-diene in the 1,4 configuration. More preferably, the units of 1,3-diene in the 1,4-trans configuration represent 100% by mole of the units of 1,3-diene in the 1,4 configuration.

[0019] According to a particularly preferred embodiment of the invention, the elastomer block contains 1,3-diene units which are more than 50% by mole of 1,2 or 3,4 configuration units, the complement to 100% of the 1,3-diene units being ^-trans configuration units.

[0020] 2024PAT00105WO According to another particularly preferred embodiment of the invention, especially when the 1,3-diene is 1,3-butadiene or a mixture of 1,3-dienes, one of which is 1,3-butadiene, the elastomer block further contains 1,2-cyclohexane or 1,4-cyclohexane motifs, preferably 1,2-cyclohexane motifs. The presence of these cyclic structures in the elastomer block results from a very specific insertion of ethylene and 1,3-butadiene during their copolymerization. The mechanism for obtaining such a microstructure is described, for example, in Macromolecules 2009, 42, 3774-3779. The 1,2-cyclohexane and 1,4-cyclohexane motif content of the elastomer block varies according to the respective ethylene and 1,3-butadiene contents of the elastomer block. Preferably, it is less than or equal to 15%, a molar percentage expressed relative to the number of moles of monomer units constituting the elastomer block.The elastomer block typically contains less than 10 mole percent of the 1,2-cyclohexane and 1,4-cyclohexane repeating units at the highest ethylene concentrations in the block, and may contain more than 10 mole percent at the lowest ethylene concentrations, for example, up to 15 mole percent. This percentage is expressed relative to the number of moles of monomer units constituting the elastomer block. The 1,2-cyclohexane repeating unit has the following formula.

[0021] Since the stiffness of the triblock polymer increases with the proportion of ethylene units in the elastomer block, a triblock polymer with a particularly high proportion of ethylene units in the elastomer block may be sought for applications where high material stiffness is required. Preferably, the ethylene units in the elastomer block represent at least 60 mole percent of the units constituting the elastomer block, in which case the elastomer block comprises at least 60 mole percent of ethylene units. Preferably, the ethylene units in the elastomer block represent at most 85 mole percent of the units constituting the elastomer block, in which case the elastomer block contains at most 85 mole percent of ethylene units.

[0022] Preferably, the elastomer block has a glass transition temperature (Tg) below -10°C, preferably between -90°C and -10°C. More preferably, the glass transition temperature of the elastomer block is between -70°C and -20°C, advantageously between -50°C and -20°C. The glass transition temperature of the elastomer block can be adjusted, for example, by the chemical structure of 1,3-diene, specifically the respective proportions of ethylene and 1,3-diene units in the elastomer block.

[0023] The elastomer block has a number-average molar mass preferably greater than or equal to 50,000 g / mol. The elastomer block has a number-average molar mass preferably less than or equal to 150,000 g / mol. According to one embodiment

[0024] 2024PAT00105WO preferred of the invention, the elastomer block has a number average molar mass greater than or equal to 50,000 g / mol and less than or equal to 150,000 g / mol.

[0025] According to another preferred embodiment of the invention, the elastomer block has a number-average molar mass ranging from 50,000 g / mol to 100,000 g / mol.

[0026] The block represented by the symbol A is a thermoplastic polymer, a homopolymer of 1,3-cyclohexadiene, also known as poly(1,3-cyclohexadiene). Preferably, the poly(1,3-cyclohexadiene) thermoplastic block has a number-average molar mass greater than 2000 g / mol and less than 40000 g / mol. More preferably, the poly(1,3-cyclohexadiene) thermoplastic block has a number-average molar mass less than 30000 g / mol. Even more preferably, the thermoplastic block has a number-average molar mass greater than 2000 g / mol and less than 30000 g / mol.

[0027] The poly(l,3-cyclohexadiene) thermoplastic block has a glass transition temperature preferably above 120°C. A glass transition temperature of the poly(l,3-cyclohexadiene) thermoplastic block above 120°C gives the triblock polymer better thermal stability of its properties when exposed to temperatures exceeding 100°C. More preferably, the poly(l,3-cyclohexadiene) thermoplastic block has a glass transition temperature above 140°C.

[0028] The block represented by the symbol C in formula ABC is characterized by being a polyethylene with a melting point above 90°C, specifically above 90°C and below 140°C. The melting point of the polyethylene block is more preferably above 100°C and below 130°C. Preferably, C represents a linear polyethylene. The polyethylene block preferably has a number-average molar mass greater than or equal to 2,000 g / mol and less than or equal to 12,000 g / mol.

[0029] The triblock polymer has a number-average molar mass (Mn) preferably between 50,000 g / mol and 200,000 g / mol, more preferably ranging from 60,000 g / mol to 150,000 g / mol, in particular ranging from 60,000 g / mol to 100,000 g / mol.

[0030] The triblock polymer according to the invention can be prepared by a process which comprises the sequence of steps a), b), c), d) and e):

[0031] - step a) being the reaction in a hydrocarbon solvent of an organolithium compound and a multidentate polar agent to form a complex consisting of a multidentate polar agent and an organolithium compound,

[0032] - step b) being the anionic polymerization of 1,3-cyclohexadiene initiated by the complex consisting of a multidentate polar agent and an organolithium compound in a hydrocarbon solvent, to form a poly(1,3-cyclohexadienyl)lithium,

[0033] - step c) being the reaction between poly(l,3-cyclohexadienyl)lithium and a halide of an organomagnesium compound of formula (I) to form an organomagnesium compound of formula R-Mg-A,

[0034] R-Mg-X (I)

[0035] R comprising a benzene ring in which two carbon atoms are substituted, one of the two is substituted by a methyl, an ethyl or an isopropyl or forms a ring with the atom

[0036] 2024PAT00105WO of carbon which is its nearest neighbor, the second carbon atom being substituted by a methyl, an ethyl or an isopropyl, the magnesium atom being in ortho position with respect to each of said two carbon atoms,

[0037] where X is a halogen atom, and A represents a poly(1,3-cyclohexadiene) polymer chain,

[0038] - step d) being the statistical polymerization of a monomer mixture containing ethylene and 1,3-diene, in the presence of a catalytic system comprising a metallocene of formula (II) and the organomagnesium compound of formula R-Mg-A, P(Cp 1 CP 2 )Nd(BH4)(i +y) .L y -N x (II)

[0039] CP 1 and Cp 2 , identical or different, being chosen from the group consisting of fluorenyl groups, cyclopentadienyl groups and indenyl groups, the groups being substituted or unsubstituted,

[0040] P being a group bridging the two groups Cp 1 and Cp 2 and comprising a silicon or carbon atom,

[0041] L represents an alkali metal chosen from the group consisting of lithium, sodium, and potassium,

[0042] N representing a molecule of an ether, x, an integer or not, being equal to or greater than 0, y, an integer, being equal to or greater than 0

[0043] - step e) being the subsequent homopolymerization of ethylene.

[0044] Step a) consists of preparing a complex of a multidentate polar agent and an organolithium compound by reacting the organolithium compound and the multidentate polar agent in a hydrocarbon solvent. In the complex of a multidentate polar agent and an organolithium compound, the lithium ion is chelated by the multidentate polar agent. For example, it is well known that multidentate polar agents have the property of chelating the lithium ion from organolithium compounds, thereby enhancing the nucleophilicity of the organolithium compounds.

[0045] Organolithium compounds are commonly defined as compounds consisting of a carbon chain, preferably a hydrocarbon chain, with a carbon-lithium bond. Organolithium compounds are most commonly alkyllithium compounds. The alkyl group of an alkyllithium compound may contain one or more carbon atoms, that is, at least two. Organolithium compounds are most commonly butyllithium compounds, and even more commonly n-butyllithium compounds.

[0046] The multidentate polar agent is preferably a bidentate polar agent such as N,N,N',N'-tetramethylenediamine, 1,2-dipiperidinoethane, 1,4-diazabicyclo[2,2,2]octane (DABCO), more preferably N,N,N',N'-tetramethylenediamine.

[0047] Preferably, the ratio of the number of moles of the multidendate polarizing agent to the number of moles of the organolithium compound in step a) is greater than 0.5 and less than 1. Using a ratio both greater than 0.5 and less than 1 is advantageous for obtaining a thermoplastic block with a glass transition temperature well above 100°C, particularly above 120°C. Furthermore, the preferred range of the ratio between the number of moles of the multidendate polarizing agent and the number of moles of the organolithium compound in step a) is also favorable for accurately controlling the respective molar masses of the thermoplastic block and the elastomer block.

[0048] The hydrocarbon solvent in step a) is preferably an aliphatic solvent, more preferably cyclohexane, methylcyclohexane or a mixture thereof.

[0049] 2024PAT00105WO Step b) consists of preparing a poly(1,3-cyclohexadienyl)lithium by anionic polymerization of 1,3-cyclohexadiene in a hydrocarbon solvent in the presence of the complex consisting of the polar agent and the organolithium compound which was prepared in step a). The complex consisting of the polar agent and the organolithium compound acts as a initiator in the polymerization of 1,3-cyclohexadiene.

[0050] Poly(1,3-cyclohexadienyl)lithium is known to be a homopolymer of 1,3-cyclohexadiene whose polymer chains possess a reactive center with respect to polymerization, in this case a carbon-lithium bond, particularly at the end of the polymer chain.

[0051] The hydrocarbon solvent in step b) is preferably an aliphatic solvent, more preferably cyclohexane, methylcyclohexane, or a mixture thereof. Advantageously, the hydrocarbon solvent in step b) is the same as that used in step a).

[0052] The ratio of hydrocarbon solvent to 1,3-cyclohexadiene required for the formation of poly(1,3-cyclohexadienyl)lithium is determined by a person skilled in the art based on the desired viscosity of the poly(1,3-cyclohexadienyl) polymer solution. This viscosity depends not only on the concentration of the polymer solution but also on numerous other factors, such as the length of the poly(1,3-cyclohexadienyl) chains, the intermolecular interactions between the poly(1,3-cyclohexadienyl)lithium chains, and the temperature of the polymer solution. Therefore, a person skilled in the art adjusts the amount of solvent on a case-by-case basis.

[0053] The polymerization temperature for forming poly(l,3-cyclohexadienyl)lithium can vary widely. Generally, it is above -20°C and below 80°C. Preferably, it is above 0°C and below 60°C.

[0054] Step c) consists of reacting poly(l,3-cyclohexadienyl)lithium with a halide of an organomagnesium compound of formula R-Mg-X to form an organomagnesium compound of formula R-Mg-A, R comprising a benzene ring with two substituted carbon atoms, one of the two being substituted by a methyl, an ethyl or an isopropyl or forming a ring with the carbon atom which is its nearest neighbor, the second carbon atom being substituted by a methyl, an ethyl or an isopropyl, the magnesium atom being in ortho position with respect to each of said two carbon atoms, X being a halogen atom, A representing a poly(l,3-cyclohexadiene) polymer chain.

[0055] The halide of an organomagnesium compound of formula R-Mg-X is preferably of formula (la) in which Ri and Rs, identical or different, represent a methyl or an ethyl, R2, R3 and R4, identical or different, being a hydrogen atom or an alkyl, X being a halogen atom.

[0056] X preferentially represents a chlorine atom or a bromine atom, more preferably a bromine atom. Preferably, Ri and Rs each represent a

[0057] 2024PAT00105WO methyl. Preferably, R2 and R4 each represent a hydrogen atom. Advantageously, Ri and R5 each represent a methyl atom, and R2 and R4 each represent a hydrogen atom. Even more advantageously, X represents a bromine atom, Ri and R5 each represent a methyl atom, and R2 and R4 each represent a hydrogen atom. In step c), the reaction between poly(1,3-cyclohexadienyl)lithium and the halide of an organomagnesium compound can be carried out by adding the polymer solution obtained at the end of step b) to a solution of the halide of an organomagnesium compound R-Mg-X, but it is preferably carried out by adding a solution of the halide of an organomagnesium compound R-Mg-X to the polymer solution obtained at the end of step b). The solution of the halide of an organomagnesium compound R-Mg-X is generally a solution in an ether, preferably diethyl ether or dibutyl ether.The concentration of poly(1,3-cyclohexadienyl)lithium is preferably 0.001 to 1 mol lithium equivalent / L, more preferably 0.01 to 0.2 mol lithium equivalent / L, while that of the organomagnesium compound solution R-Mg-X is preferably 1 to 5 mol / L, more preferably 2 to 3 mol / L. The reaction between poly(1,3-cyclohexadienyl)lithium and the halide of the organomagnesium compound R-Mg-X is typically carried out at a temperature ranging from 0°C to 60°C. Contact is preferably made at a temperature between 0°C and 23°C. As with any synthesis carried out in the presence of organometallic compounds, contact and the reaction take place under anhydrous conditions in an inert atmosphere. Typically, solvents and solutions are used under anhydrous nitrogen or argon. The various stages of the process are generally carried out under agitation.

[0058] Once formed and without being separated from the reaction medium of step c), organomagnesium T of formula R-Mg-A can be stored in airtight containers, for example capped bottles, at a temperature between -25°C and 23°C, under an inert and anhydrous atmosphere, before it is used in step d).

[0059] Step d) consists of forming a statistical copolymer block comprising 1,3-diene units and more than 50 mol% ethylene units. Step d) is the statistical polymerization of a monomer mixture containing ethylene and 1,3-diene in the presence of a catalytic system (or catalytic composition) comprising a metallocene and the reaction product of step c), in this case, the organomagnesium compound R-Mg-A. The organomagnesium compound R-Mg-A obtained in step c) is used as a cocatalyst for the catalytic system in step d). It is generally used in step d) without being separated from the reaction mixture of step c).

[0060] The metallocene used in the catalytic system has the formula (II) P(Cp 1 CP 2 )Nd(BH4)(i+ y) -L y -Nx (II)

[0061] CP 1 and Cp 2 , identical or different, being chosen from the group consisting of fluorenyl groups, cyclopentadienyl groups and indenyl groups, the groups being substituted or unsubstituted,

[0062] P being a group bridging the two groups Cp 1 and Cp 2 and comprising a silicon or carbon atom,

[0063] L represents an alkali metal chosen from the group consisting of lithium, sodium, and potassium,

[0064] N representing a molecule of an ether, x, an integer or not, being equal to or greater than 0, y, an integer, being equal to or greater than 0.

[0065] 2024PAT00105WO In formula (II), the neodymium atom is linked to a ligand molecule consisting of the two Cp groups 1 and Cp 2 connected to each other by bridge P. Preferably, the symbol P, designated as bridge, corresponds to the formula ZRjR 2 , Z representing a silicon or carbon atom, R 1 and R 2 , identical or different, representing an alkyl group comprising 1 to 20 carbon atoms, preferably methyl. More preferably, the P bridge has the formula SiR x R 2 , R 1 and R 2 , being identical and as defined previously. Even more preferably, P satisfies the formula SiMe?.

[0066] Examples of substituted cyclopentadienyl and fluorenyl groups include those substituted with alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 12 carbon atoms, or trialkylsilyl groups such as SiMes. The choice among alkyl, aryl, and trialkylsilyl groups is also influenced by the availability of the corresponding molecules, namely the substituted cyclopentadienes and fluorenes, because these are either commercially available or easily synthesized.

[0067] Examples of substituted cyclopentadienyl groups include those substituted at both position 2 (or 5) and position 3 (or 4), particularly those substituted at position 2, more specifically the tetramethylcyclopentadienyl group. In the present application, for the cyclopentadienyl group, position 2 (or 5) refers to the position of the carbon atom adjacent to the carbon atom to which the P-bridge is attached, as shown in the diagram below.

[0068] Examples of substituted fluorenyl groups include those substituted at positions 2,7, 3, or 6, particularly the 2,7-ditertiobutyl-fluorenyl and 3,6-ditertiobutyl-fluorenyl groups. Positions 2, 3, 6, and 7 respectively designate the positions of the carbon atoms in the rings, as shown in the diagram below, with position 9 corresponding to the carbon atom to which the P-bridge is attached.

[0069] Preferably, Cp 1 and Cp 2 are chosen from the group consisting of substituted fluorenyl groups and the unsubstituted fluorenyl group of formula CBHS. More preferably, Cp 1 and Cp 2 are identical and are chosen from the group consisting of the substituted fluorenyl groups and the fluorenyl group. Advantageously, in formula (I) Cp 1 and Cp 2 Each represents a substituted fluorenyl group or a fluorenyl group, preferably a fluorenyl group. The fluorenyl group has the formula CBHS.

[0070] 2024PAT00105WO Preferably, the metallocene has the formula (II-1), (II-2), (II-3), (II-4) or (II-5): [Me2Si(Flu)2Nd(p-BH4)2Li(THF)] (II-1) [{Me2SiFlu2Nd(p-BH4)2Li(THF)}2] (II-2) [Me2SiFlu2Nd(p-BH4)(THF)] (II-3) [{Me2SiFlu2Nd(p-BH4)(THF)}2] (II-4) [Me2SiFlu2Nd(p-BH4)] (II-5) the symbol Flu representing the CBHS group.

[0071] The metallocene used to prepare the catalytic system can be in the form of a crystalline or non-crystalline powder, or as single crystals. The metallocene can be monomeric or dimeric, depending on the method of preparation, as described, for example, in patent application WO 2007054224. The metallocene can be prepared conventionally by a process analogous to that described in patent application WO 2007054224, specifically by reacting the salt of an alkali metal of the ligand with a rare-earth borohydride under inert and anhydrous conditions in a suitable solvent, such as an ether like 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 byproducts by techniques known to those skilled in the art, such as filtration or precipitation in a second solvent.The metallocene is ultimately dried and insulated in solid form.

[0072] Like all syntheses carried out in the presence of organometallic compounds, the synthesis of metallocene takes place under anhydrous conditions in an inert atmosphere. Typically, the reactions are conducted using solvents and anhydrous compounds under anhydrous nitrogen or argon.

[0073] The catalytic system can be prepared conventionally by a process analogous to that described in patent applications WO 2007054224 or WO 2007054223. For example, the co-catalyst and the metallocene are reacted in a hydrocarbon solvent, typically at a temperature of 20 to 80°C for a duration of 5 to 60 minutes. The amounts of co-catalyst and metallocene reacted are such that the ratio of the number of moles of Mg in the co-catalyst to the number of moles of rare-earth metal in the metallocene is preferably from 1 to 100, and more preferably from 1 to less than 10. The range of values ​​from 1 to less than 10 is particularly favorable for obtaining polymers with high molar masses. The catalytic system is generally prepared in a hydrocarbon solvent, either aliphatic such as methylcyclohexane or aromatic such as toluene.Generally, after its synthesis, the catalytic system is used as is in the polymer synthesis process according to the invention.

[0074] The catalytic system is generally in the form of a solution in a hydrocarbon solvent. The hydrocarbon solvent can be aliphatic, such as methylcyclohexane, or aromatic, such as toluene. The hydrocarbon solvent is preferably aliphatic, most commonly methylcyclohexane. Generally, the catalytic system is stored as a solution in the hydrocarbon solvent before being used in polymerization. This is referred to as a catalytic solution, which includes both the catalytic system and the hydrocarbon solvent. The concentration of the catalytic solution is typically defined by the metallocene content in the solution.

[0075] 2024PAT00105WO in metallocene metal has a value preferably ranging from 0.0001 to 0.2 mol / L, more preferably from 0.001 to 0.03 mol / L.

[0076] As with any synthesis carried out in the presence of organometallic compounds, the synthesis of the catalytic system takes place under anhydrous conditions in an inert atmosphere. Typically, the reactions are conducted using solvents and anhydrous compounds under anhydrous nitrogen or argon.

[0077] The catalytic system is typically introduced into the reactor containing the polymerization solvent and the monomer mixture containing ethylene and 1,3-diene. To achieve the desired macrostructure of the statistical copolymer block, those skilled in the art adjust the polymerization conditions, particularly the molar ratio of magnesium in the cocatalyst to the Nd metal constituting the metallocene. The molar ratio can reach 100, although a molar ratio below 10 is more favorable for obtaining polymers with high molar masses.

[0078] In step d), the monomer mixture containing ethylene and 1,3-diene generally contains more than 50 mol% ethylene and is preferably a mixture of ethylene and 1,3-diene, in which case the block represented by the symbol B is a statistical copolymer of ethylene and 1,3-diene, that is, a block whose constituent monomer units are those resulting from the statistical copolymerization of ethylene and 1,3-diene. Preferably, the monomer mixture containing ethylene and 1,3-diene contains less than 90 mol% ethylene. More preferably, the monomer mixture containing ethylene and 1,3-diene contains at most 85 mol% ethylene.

[0079] Preferably, a continuous addition of ethylene and 1,3-diene is carried out in the polymerization reactor, in which case the polymerization reactor is a fed reactor. This embodiment is particularly suitable for the statistical incorporation of ethylene and 1,3-diene.

[0080] The polymerization temperature generally varies from 30 to 160°C, preferably from 30 to 120°C. During the preparation of the statistical copolymer block, the temperature of the reaction medium is advantageously kept constant throughout the copolymerization process, and the total pressure in the reactor is also advantageously kept constant. The preparation of the statistical copolymer block is completed by stopping the monomer feed and then degassing the reactor to reduce the reactor pressure to approximately 0 to 0.5 bar (relative).

[0081] Step e) consists of preparing a polyethylene block following the preparation of the statistical copolymer block by the subsequent polymerization of ethylene. The subsequent polymerization of ethylene continues by applying ethylene pressure in the reactor, the ethylene pressure being maintained constant until the desired ethylene consumption is reached to achieve the desired number-average molar mass of the polyethylene block. The ethylene polymerization temperature is preferably kept at the same temperature as that of the preparation of the statistical copolymer block. The polymerization temperature for preparing the polyethylene block generally varies in the range of 30 to 160°C, preferably from 30 to 120°C. The pressure for preparing the polyethylene block generally varies in the range of 1 bar to 150 bar.

[0082] 2024PAT00105WO preferably from 1 bar to 10 bar. The synthesis of the polyethylene block is complete when the polyethylene block reaches the desired number-average molar mass.

[0083] At the end of step e), polymerization is stopped by deactivating the active polymerization sites, for example by cooling the polymerization medium or by adding an alcohol, preferably one containing 1 to 3 carbon atoms, such as ethanol. The triblock polymer can be recovered using conventional techniques known to those skilled in the art, such as precipitation, evaporation of the solvent under reduced pressure, or steam stripping.

[0084] Advantageously, the sequence of steps a), b), c), d) and e) is carried out without separating the reaction products of each of the intermediate steps a), b), c) and d). The polymerizations of steps a), b), c), d) and e) can be carried out continuously or discontinuously.

[0085] The triblock polymer according to the invention can be used in a composition, another object of the invention, which typically comprises another ingredient. The other ingredient may be a filler such as carbon black or silica, a plasticizer such as oil, a crosslinking agent such as sulfur or a peroxide, an antioxidant, or a polymer other than the triblock polymer according to the invention. The composition may be a rubber composition.

[0086] In summary, the invention is preferably implemented according to any one of the following embodiments 1 to 19:

[0087] Mode 1: Triblock polymer of formula ABC, the symbol A representing a thermoplastic poly(l,3-cyclohexadiene) block, the symbol B representing an elastomer block which is a statistical copolymer comprising units of a 1,3-diene and more than 50 mole percent of ethylene units, the symbol C representing a polyethylene with a melting temperature above 90°C, the 1,3-diene being an α-olefin.

[0088] Mode 2: Triblock polymer according to mode 1 in which the elastomer block comprises at most 85 mole percent of ethylene units.

[0089] Mode 3: Triblock polymer according to mode 1 or 2 in which the elastomer block comprises at least 60 mole percent of ethylene units.

[0090] Mode 4: Triblock polymer according to any one of modes 1 to 3 in which the elastomer block is a statistical copolymer block of ethylene and a 1,3-diene.

[0091] Mode 5: Triblock polymer according to any one of modes 1 to 4 in which the 1,3-diene is 1,3-butadiene or isoprene or a mixture of 1,3-dienes of which one is 1,3-butadiene.

[0092] Mode 6: Triblock polymer according to any one of modes 1 to 5 in which the 1,3-diene is 1,3-butadiene.

[0093] Mode 7: Triblock polymer according to any one of modes 1 to 6 in which the elastomer block is a random copolymer of ethylene and 1,3-butadiene.

[0094] 2024PAT00105WO Mode 8: Triblock polymer according to any one of modes 5 to 7 in which the elastomer block further contains 1,2-cyclohexane motifs or 1,4-cyclohexane motifs, preferably 1,2-cyclohexane motifs.

[0095] Mode 9: Triblock polymer according to mode 8 in which the content of 1,2-cyclohexane motif and 1,4-cyclohexane motif of the elastomer block is less than or equal to 15%, molar percentage expressed in relation to the number of moles of monomer units constituting the elastomer block.

[0096] Mode 10: Triblock polymer according to any one of modes 1 to 9 in which the elastomer block has a number-average molar mass greater than or equal to 50000 g / mol.

[0097] Mode 11: Triblock polymer according to any one of modes 1 to 10 in which the elastomer block has a number-average molar mass less than or equal to 150000 g / mol.

[0098] Mode 12: Triblock polymer according to any one of modes 1 to 11 in which the thermoplastic block poly(l,3-cyclohexadiene) has a number-average molar mass greater than 2000 g / mol and less than 40000 g / mol.

[0099] Mode 13: Triblock polymer according to any one of modes 1 to 12 in which the thermoplastic poly(l,3-cyclohexadiene) block has a number-average molar mass less than 30000 g / mol.

[0100] Mode 14: Triblock polymer according to any one of modes 1 to 13 in which the thermoplastic poly(l,3-cyclohexadiene) block has a glass transition temperature greater than 120°C.

[0101] Mode 15: Triblock polymer according to any one of modes 1 to 14 in which the thermoplastic poly(l,3-cyclohexadiene) block has a glass transition temperature greater than 140°C.

[0102] Molded: Triblock polymer according to any one of modes 1 to 15 which has a number-average molar mass between 50,000 g / mol and 200,000 g / mol, more preferably ranging from 60,000 g / mol to 150,000 g / mol.

[0103] Mode 17: Triblock polymer according to any one of modes 1 to 16 in which the polyethylene block has a number-average molar mass greater than or equal to 2,000 g / mol and less than or equal to 12,000 g / mol.

[0104] Mode 18: Triblock polymer according to any one of modes 1 to 17 in which the melting temperature of the polyethylene block is greater than 100°C and less than 130°C.

[0105] Mode 19: Composition which comprises a triblock polymer according to any one of modes 1 to 18 and another ingredient.

[0106] The aforementioned features of the present invention, as well as others, will be better understood upon reading the following description of several examples of embodiments of the invention, given by way of illustration and not limitation.

[0107] 2024PAT00105WO Examples

[0108] The name EBR is used to designate a statistical copolymer of ethylene and 1,3-butadiene; the name PCHD is used to designate a homopolymer of 1,3-cyclohexadiene; the name PE is used to designate a homopolymer of ethylene; the name Mes is used to designate the mesityl group.

[0109] Size exclusion chromatography (SEC-HT):

[0110] Size-exclusion chromatography analyses of the entire PCHD group and the PCHD-Z>-EBR-Z>-PE triblock copolymers were performed using a Tosoh Bioscience Instrument (HLC-8321-GPC (HT-GPC)) equipped with two columns (TSKgel ultra-high-temperature columns with mixed pore size) and coupled to a refractometer detector. The exclusion limit of the columns was 4.0 x 10⁻⁴. 8 Da. The samples were prepared at a concentration of 3-5 mg mL' 1in 1,2,4-trichlorobenzene. The columns and detectors were maintained at 150°C. Sample volumes of 100 pL were injected and eluted with 1,2,4-trichlorobenzene (TCB) using a flow rate of 1 mL min⁻¹ 1 at a temperature of 150°C. The mobile phase was stabilized with 2,6-di(tert-butyl)-4-methylphenol (BHT) (0.2 g L 1 Online detection was performed using a refractive index (RI) detector to obtain the absolute molar mass. The dispersity D and the average molar masses by number and by mass (respectively M n etM^) of the polymers were determined from a conventional calibration using polystyrene standards using Tosoh's GPC Analysis software for data acquisition.

[0111] Differential scanning calorimetry (DSC):

[0112] DSC analyses are performed on a DSC 3+ instrument (Mettler Toledo) with sealed aluminum crucibles (40 pL) and under nitrogen flow (30 mL min' 1 The temperature programs are as follows:

[0113] PCHD thermograms are obtained according to the following program: • step 1: ramp from 25 °C to 220 °C (10 °C min' 1 ), • step 2: isothermal at 220 °C for 5 min, • step 3: ramp from 220 °C to -80 °C (10 °C min) 1 ), • step 4: isothermal at -80 °C for 5 min, • step 5: ramp from -80 °C to 220 °C (10 °C min' 1 ), • step 6: isothermal at 220 °C for 5 min, • step 7: ramp from 220 °C to -80 °C (10 °C min' 1 ), • step 8: isothermal at -80 °C for 5 min, • step 9: ramp from -80 °C to 220 °C (10 °C min' 1). For example 1, the program goes up to step 5. The glass transition temperatures (Tg) of the PCHDs reported in Table 1 were determined for all examples at step 5 (ramp -80 °C to 220 °C at 10 °C min' 1 ).

[0114] The thermograms of the triblock copolymers PCHD-Z>-EBR-Z>-PE are obtained according to the following program: • step 1: ramp from 25 °C to 220 °C (10 °C min' 1 ), • step 2: 5 min isotherm at 220 °C, • step 3: ramp from 220 °C to -80 °C (10 °C min' 1 ), • step 4: isothermal 5 min at -80 °C, • step 5: ramp from -80 °C to 220 °C (10 °C min' 1 ), • step 6: 5 min isotherm (220 °C), • step 7: ramp from 220 °C to -80 °C (10 °C min' 1 ), • step 8: 5-minute isothermal temperature at -80 °C • step 9: ramp from -80 °C to 220 °C (10 °C min' 1For example 1, the program goes up to step 5. The glass transition temperatures (Tg) and melting temperatures (Tf) of the EBR and PE blocks are respectively reported in the table.

[0115] 2024PAT00105WO 1 were determined in step 5 (ramp -80 °C to 220 °C at 10 °C min' 1 ) for example 1; at step 9 (ramp -80 °C to 220 °C at 10 °C min' 1 ) for example 2.

[0116] The thermogram of the triblock copolymer PS-Z>-EBR-Z>-PE (example 3) is obtained according to the following program: • step 1: ramp from 25 °C to 180 °C (10 °C min' 1 ), • step 2: 5 min isotherm at 180 °C, • step 3: ramp from 180 °C to -80 °C (10 °C min' 1 ), • step 4: isothermal 5 min at -80 °C, • step 5: ramp from -80 °C to 180 °C (10 °C min' 1 ), • step 6: 5 min isotherm (180 °C), • step 7: ramp from 180 °C to -80 °C (10 °C min' 1), • step 8: 5-minute isothermal temperature at -80 °C • step 9: ramp from -80 °C to 180 °C (10 °C min' 1 ). The glass transition temperatures (7g) and melting temperatures (7f) of the EBR and PE blocks respectively reported in Table 1 were determined in step 9.

[0117] Tensile tests:

[0118] Tensile testing is performed on an MTS Criterion C42 tensile tester at the temperature of the sample being analyzed (20-25°C), equipped with a 50 N load cell and a cross-sectional speed of 500 mm / min. The materials are pressed at 150°C under 4-5 tons in an 80 mm x 60 mm x 1.5 mm mold. Standard H2 type specimens (usable dimensions 30 mm x 4 mm) are cut at room temperature using a suitable die.

[0119] Preparation of triblock polymers:

[0120] All reactions sensitive to air and / or humidity are carried out under an argon atmosphere.

[0121] The dry polymerization solvents (methylcyclohexane and cyclohexane) are drawn from the solvent fountain (SPS800 MBraun). The cyclohexane was stored in a glove box on a molecular sieve (3 A°) before use.

[0122] 1,3-Cyclohexadiene (abcr) is dried for 24 hours on CaEE under an argon atmosphere and then distilled under vacuum. Ethylene (grade N35, Air Liquide) is used without purification. 1,3-Butadiene, previously purified on an "Axens" alumina purification column and stabilized with 60 ppm TBC, is purified by contact with trioctylaluminium for 30 minutes before use.

[0123] γ-Butyllithium (1.6M in hexane, Sigma-Aldrich) is used as received. Tetramethylethylenediamine (TMEDA) is dried for 24 h on CaEE under an argon atmosphere, then distilled under vacuum and stored on a molecular sieve (3 Å). 2-Mesityl-magnesium bromide (BMM, IM in Et2Û, Sigma-Aldrich) is used as received. The {Me2Si(Ci3H8)2Nd(BH4)2Li(THF)}2 complex is prepared according to the protocol described in patent application WO 2007054224 A2.

[0124] 2,2'-Methylenebis(6-tert-butyl-4-methylphenol) (bi-BHT, Sigma-Aldrich) is used as received as an antioxidant. Acetone (technical grade) is used to precipitate the polymers.

[0125] Styrene (Sigmal-Aldrich) is dried for 24 hours on CaEE under an argon atmosphere and then distilled under vacuum.

[0126] The reactor used in steps 2 and 3 is a 250 mL glass reactor equipped with a stirring wheel (anchor).

[0127] 2024PAT00105WO In Examples 1 to 3, triblock polymers of formula ABC are prepared, in which A represents a thermoplastic block, B a statistical copolymer elastomer block of ethylene and 1,3-butadiene, and C a polyethylene with a melting point above 90°C. In Examples 1 and 2, the thermoplastic block is poly(1,3-cyclohexadiene); in Example 3, the thermoplastic block is polystyrene. The structure of the triblocks of formula ABC is identified by SEC and DSC analysis. The block represented by the symbol A, or block A, designates the PCHD block for the examples according to the invention (Examples 1 and 2) and the PS block for the example not according to the invention (Example 3). The tensile test results are shown in Table 1.

[0128] Example 1: Triblock polymer PCHD-Z>-EBR-Z>-PE:

[0129] Step 1: Anionic polymerization of 1,3-cyclohexadiene and preparation of the organomagnesium compound with the formula PCHD-MgMes:

[0130] In a conditioned Schlenk tube (3 vacuum-argon cycles), 7.5 mL of cyclohexane (rhs-to-mmonomer ratio = 7.8), 0.156 mL (0.25 mmol, 1 equivalent) of w-BuLi (1.6 M in hexane), and 28 µL (0.1875 mmol, 0.75 equivalent) of TMEDA are introduced. The mixture is stirred at 40 °C for 15 min, then 0.75 g ([CHD] / [w-BuLi] = 38) of 1,3-cyclohexadiene is added. The solution turns yellow instantly. The reaction mixture is stirred at 40 °C for 60 min. The transmetallation reaction is subsequently carried out with the addition of 0.3 mL (0.3 mmol, 1.2 equivalents) of BMM to obtain an organomagnesium compound of formula R-Mg-A, in which A is a poly(1,3-cyclohexadiene) (PCHD) and R is the mesityl group (Mes). An aliquot was taken and precipitated in ethanol. The medium containing the organomagnesium compound of formula PCHD-MgMes is used in step 2 as described below.

[0131] Step 2: Formation of the PCHD-Z-EBR-b-PE triblock copolymer:

[0132] 38.4 mg (60 pmol of Nd) of the Nd complex {Me2Si(Ci3H8)2Nd(BH4)2Li(THF)}2 are weighed in a glove box into a 50 mL flask. 192.5 mL of MCH (VMCH + V cyc 200 mL of iohexane is taken from the solvent fountain into a 250 mL flask. 0.24 mL (0.24 mmol) of BMM is added to the MCH. The (MCH + BMM) solution is stirred for 5 min before the Nd {Me2Si(Ci3H8)2Nd(BH4)2Li(THF)}2 complex is added. The solution containing the organomagnesium compound of formula PCHD-MgMes is added to the catalytic solution before its transfer, using a cannula under argon flow, into the reactor, which has been previously conditioned and heated to 90 °C. The reactor is isolated and the pressure reduced to 0.5 bar before starting stirring (1000 rpm). 1The reactor is then pressurized to 4 bar with an ethylene / 1,3-butadiene mixture with an 80 / 20 molar ratio. The target temperature is considered to be 89 °C. The pressure is maintained constant in the reactor using a reservoir containing the ethylene / 1,3-butadiene mixture. Monomer consumption is monitored by lowering the pressure in the reservoir until the desired consumption is reached. The reactor is then isolated, and the remaining monomers are consumed until the pressure reaches 2.5 bar to obtain the desired EBR copolymer. Simultaneously, the reservoir is conditioned by two vacuum-ethylene cycles and then pressurized with 100% ethylene. The reactor is then pressurized to 4 bar and supplied with ethylene. After consuming the desired amount of ethylene, the reactor is carefully depressurized and degassed under a flow of argon, and the medium is deactivated by adding EtOH (approximately 0.5 mL) and then cooled to room temperature.

[0133] 2024PAT00105WO copolymer is then precipitated in 600 mL of acetone before being collected in an aluminum capsule. 50 mL of a solution (10 g L' 1 ) of the antioxidant 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (di-BHT) are added to the copolymer, and then the solvent is evaporated under vacuum at 70 °C for 7 h. The triblock copolymer PCHD-Z>-EBR-Z>-PE is weighed and analyzed.

[0134] Example 2: Triblock polymer PCHD-Z>-EBR-Z>-PE:

[0135] Step 1: Anionic polymerization of 1,3-cyclohexadiene and preparation of the organomagnesium compound with the formula PCHD-MgMes:

[0136] In a conditioned Schlenk tube (3 vacuum-argon cycles), 25 mL of cyclohexane (rhs-to-mmonomer ratio = 7.8), 0.156 mL (0.25 mmol, 1 equivalent) of w-BuLi (1.6 M in hexane), and 28 µL (0.1875 mmol, 0.75 equivalent) of TMEDA are introduced. The mixture is stirred at 40 °C for 15 min, then 2.5 g ([CHD] / [w-BuLi] = 125) of 1,3-cyclohexadiene are added. The solution turns yellow instantly. The reaction mixture is stirred at 40 °C for 60 min. The transmetallation reaction is subsequently carried out with the addition of 0.3 mL (0.3 mmol, 1.2 equivalents) of BMM to obtain an organomagnesium compound of formula R-Mg-A, in which A is a poly(1,3-cyclohexadiene) (PCHD) and R is the mesityl group. An aliquot was taken and precipitated in ethanol. The medium containing the organomagnesium compound of formula PCHD-MgMes is used in step 2 as described below.

[0137] Step 2: Formation of the PCHD-Z>-EBR-Z>-PE triblock copolymer:

[0138] 38.4 mg (60 pmol of Nd) of the Nd {Me2Si(Ci3H8)2Nd(BH4)2Li(THF)}2 complex are weighed in a glove box in a 50 mL flask. 175 mL of MCH (VMCH + V cyc 200 mL of iohexane is taken from the solvent fountain into a 250 mL flask. 0.24 mL (0.24 mmol) of BMM is added to the MCH. The (MCH + BMM) solution is stirred for 5 min before the Nd {Me2Si(Ci3H8)2Nd(BH4)2Li(THF)}2 complex is added. The solution containing the organomagnesium compound of formula PCHD-MgMes is added to the catalytic solution before its transfer, using a cannula under argon flow, into the reactor, which has been previously conditioned and heated to 90 °C. The reactor is isolated and the pressure reduced to 0.5 bar before starting stirring (1000 rpm). 1The reactor is then pressurized to 4 bar with an 80 / 20 molar ethylene / butadiene mixture. The temperature at which the solution reaches 89 °C is considered complete. The pressure is maintained constant in the reactor using a reservoir containing the ethylene / butadiene mixture. Monomer consumption is monitored by lowering the pressure in the reservoir until the desired level is reached. The reactor is then isolated, and the remaining monomers are consumed until the pressure reaches 2.5 bar to obtain the EBR copolymer of M ndesired quantity and in parallel the reservoir is conditioned by 2 vacuum-ethylene cycles then pressurized with 100% ethylene. The reactor is then pressurized to 4 bar and supplied with ethylene. After consuming the desired quantity of ethylene, the reactor is carefully depressurized and degassed under argon flow and the medium is deactivated by adding EtOH (~0.5 mL) then cooled to room temperature. The copolymer is then precipitated in 600 mL of acetone before being collected in an aluminum capsule. 50 mL of a solution (10 g L 1 ) of the antioxidant 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (di-BHT) are added to the copolymer, and then the solvent is evaporated under vacuum at 70 °C for 7 h. The triblock copolymer PCHD-Z>-EBR-Z>-PE is weighed and analyzed.

[0139] Example 3 not in accordance with the invention:

[0140] 2024PAT00105WO Step 1: Anionic polymerization of styrene and preparation of the organomagnesium compound with formula PS-MgMes:

[0141] In an inert Schlenk tube, 40 mL of dry toluene and 5.5 mL of styrene (5 g, 48 mmol) are introduced. 0.22 mL of ethyltetrahydrofurfuryl ether (0.3 M in toluene) is added, followed by 0.21 mL of n-BuLi (1.6 M in hexane, 0.33 mmol). The solution turns red. The reaction mixture is stirred at 40 °C for 20 min, and then the transmetallation reaction is carried out with 0.4 mL of BMM (0.4 mmol, 1.2 eq.) to obtain a macro-ATC PSisK-MgMes. An aliquot is taken and precipitated in ethanol. This solution is transferred under argon flow to the previously inert reactor.

[0142] Step 2: Formation of the PS-Z>-EBR-Z>-PE triblock copolymer:

[0143] 32 mg (50 pmol Nd) of the Nd {Me2Si(Ci3H8)2Nd(BH4)2Li(THF)}2 complex are weighed into a 50 mL glovebox. 155 mL of toluene are taken from the solvent fountain into a 250 mL flask. 0.20 mL (0.20 mmol) of BMM is added to the toluene. The solution is stirred for 5 min before the Nd {Me2Si(Ci3H8)2Nd(BH4)2Li(THF)}2 complex is added. The catalytic solution is transferred using a cannula under argon flow into the reactor already containing the PS-MgMes solution. The reactor is isolated and the pressure reduced to 0.5 bar before starting stirring (1000 rpm). 1The reactor is then pressurized to 4 bar with an 80 / 20 molar ethylene / l,3-butadiene mixture. The target temperature is considered to be 89 °C. The pressure is maintained constant in the reactor using a reservoir containing the ethylene / l,3-butadiene mixture. Monomer consumption is monitored by lowering the pressure in the reservoir until the desired consumption is reached. The reactor is depressurized, and an aliquot is taken and precipitated in ethanol. The reservoir is conditioned by two vacuum-ethylene cycles and then pressurized with 100% ethylene. The reactor is then pressurized to 4 bar and fed with ethylene. After the desired amount of ethylene has been consumed, the reactor is depressurized and degassed under argon flow, polymerization is stopped by adding EtOH (approximately 0.5 mL), and the medium is cooled to room temperature.A few milligrams of the antioxidant 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (di-BHT) are added, and the copolymer is precipitated in 400 mL of MeOH. The polymer is washed with methanol, then collected in a crystallizer and dried under vacuum at 80 °C for 4 hours. The PS-Z>-EBR-Z>-PE triblock copolymer is weighed and analyzed.

[0144] Results :

[0145] The characteristics of the polymers in Examples 1 to 3 are shown in Table 1. The Mn and Tg of the HDPE thermoplastic blocks and the PS blocks are measured on a sample taken at the end of the synthesis of said blocks before proceeding to step 2.

[0146] Table 1:

[0147] 2024PAT00105WQ

[0148] The triblock polymers of Example 1 and Example 2 are polymers according to the invention. They differ in particular in their Mn content and in the Mn content of the PCHD block. Despite these differences, they exhibit comparable elongation at break. However, the tensile strength of the triblock polymer of Example 2 is much higher than that of the triblock polymer of Example 1.

[0149] These results show that the length of the blocks in the triblock polymers according to the invention has a strong impact on the breaking strength, but that it has little or no impact on the elongation at break.

[0150] Compared to a PS-EBR-PE triblock polymer not conforming to the invention (example 3), the triblock polymer of example 2 has a much higher elongation at break while exhibiting a comparable tensile strength, whereas the two triblock polymers differ essentially in the nature of one of the two terminal blocks: PCHD for example 2, PS for example 3.

[0151] The triblock polymer of example 1, which has more differences with the triblock polymer of example 3, also has a higher elongation at break than the triblock polymer of example 3.

[0152] Replacing the PS thermoplastic block with a PCHD thermoplastic block in a PS-EBR-PE triblock polymer increases the elongation at break of the triblock polymer, even though the Tg of the PCHD block is higher than that of the PS block. Indeed, one might have expected that the presence of a block with a higher Tg than that of a PS block would lead to a stiffer polymer with a lower capacity for deformation.

[0153] 2024PAT00105WQ

Claims

Demands 1. Triblock polymer of formula ABC, the symbol A representing a thermoplastic poly(l,3-cyclohexadiene) block, the symbol B representing an elastomer block which is a statistical copolymer comprising units of a 1,3-diene and more than 50 mole percent of ethylene units, the symbol C representing a polyethylene with a melting temperature above 90°C, the 1,3-diene being an α-olefin.

2. Triblock polymer according to claim 1 in which the elastomer block comprises at most 85 mole percent of ethylene units.

3. Triblock polymer according to claim 1 or 2 in which the elastomer block comprises at least 60 mole percent of ethylene units.

4. Triblock polymer according to any one of claims 1 to 3 wherein the elastomer block is a statistical copolymer block of ethylene and a 1,3-diene.

5. Triblock polymer according to any one of claims 1 to 4 wherein the 1,3-diene is 1,3-butadiene or isoprene or a mixture of 1,3-dienes of which one is 1,3-butadiene.

6. Triblock polymer according to any one of claims 1 to 5 wherein the 1,3-diene is 1,3-butadiene.

7. Triblock polymer according to any one of claims 1 to 6 wherein the elastomer block has a number-average molar mass greater than or equal to 50000 g / mol.

8. Triblock polymer according to any one of claims 1 to 7 wherein the elastomer block has a number-average molar mass less than or equal to 150000 g / mol.

9. Triblock polymer according to any one of claims 1 to 8 wherein the thermoplastic block poly(l,3-cyclohexadiene) has a number-average molar mass greater than 2000 g / mol and less than 40000 g / mol.

10. Triblock polymer according to any one of claims 1 to 9 wherein the thermoplastic block poly(l,3-cyclohexadiene) has a number-average molar mass of less than 30000 g / mol.

11. Triblock polymer according to any one of claims 1 to 10 wherein the thermoplastic block poly(l,3-cyclohexadiene) has a glass transition temperature greater than 120°C.

12. Triblock polymer according to any one of claims 1 to 11 having a number-average molar mass of between 50,000 g / mol and 200,000 g / mol, more preferably from 60,000 g / mol to 150,000 g / mol.

13. Triblock polymer according to any one of claims 1 to 12 wherein the polyethylene block has a number-average molar mass greater than or equal to 2,000 g / mol and less than or equal to 12,000 g / mol.

14. Composition comprising a triblock polymer according to any one of claims 1 to 13 and another ingredient. 2024PAT00105WO

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