Functional copolymers of ethylene and 1,3-diene

Abstract

The present invention relates to ethylene copolymers and 1,3-diene copolymers of the formula CH2=CR-CH=CH2, said copolymers having amine functionality, where the symbol R represents a hydrocarbon chain having from 3 to 20 carbon atoms, which copolymers offer an improved compromise between the ethylene content in the polymer, the crystallinity of the copolymer, and the stiffness of rubber compositions containing the copolymer.

Description

[Technical field]

[0001] The present invention relates to copolymers of ethylene and 1,3-diene intended for use in rubber compositions for tires. [Background technology]

[0002] The diene copolymers most widely used in tire manufacture are polybutadiene, polyisoprene, especially natural rubber, and copolymers of 1,3-butadiene and styrene. In particular, document WO 2014114607 proposes the use of copolymers of ethylene and 1,3-butadiene in rubber compositions for tires. These copolymers are synthesized by copolymerization of ethylene and 1,3-butadiene in the presence of a catalyst system comprising a rare earth metallocene. Reinforced rubber compositions of ethylene / 1,3-butadiene copolymers are described, in particular for use in tire treads. These diene rubber compositions, when crosslinked, exhibit a much higher stiffness than conventional diene rubber compositions and, as a result, may prove unsuitable for certain applications. There is therefore a need to significantly reduce the cure stiffness of such compositions comprising ethylene-based diene rubbers. The Applicant has discovered copolymers which make it possible to solve the above problems. Summary of the Invention

[0003] Thus, a first subject of the present invention is a compound comprising ethylene and a copolymer of formula (I) CH2=CR-CH=CH2(I) (The symbol R represents a hydrocarbon chain having 3 to 20 carbon atoms.) with 1,3-dienes and having amine functional groups. Another subject of the invention is a rubber composition comprising the copolymer of the invention, a reinforcing filler and a crosslinking system, in which the copolymer is an elastomer. The present invention also relates to a tire comprising the rubber composition of the present invention.

[0004] The present invention relates to a process for the preparation of the copolymer of the present invention, comprising the following steps: a) a metallocene of the following formula (II) and an organomagnesium compound of the following formula (III):

[0005] [ka]

[0006] (Cp 1 and Cp 2 may be the same or different and are cyclopentadienyl groups of the formula C5H4, 13 H8 is selected from the group consisting of unsubstituted fluorenyl groups and substituted fluorenyl groups; P is two Cp 1 and Cp 2 ZR 3 R 4 group, Z represents silicon or carbon atom, R 3 and R 4 are the same or different and each represents an alkyl group containing 1 to 20 carbon atoms, preferably methyl, y is an integer greater than or equal to 0; x, which may or may not be an integer, is equal to or greater than 0; L represents an alkali metal selected from the group consisting of lithium, sodium and potassium; N represents a molecule of an ether, preferably diethyl ether or tetrahydrofuran, R 1 and R 2 may be the same or different and represent a carbon group. and ethylene in the presence of a catalyst system comprising CH2=CR-CH=CH2(I) (The symbol R represents a hydrocarbon chain having 3 to 20 carbon atoms.) Copolymerization with 1,3-dienes, b) Formula (IV) Si(Fc 1 ) 3-g (Rc 2 ) g(Rca) (IV) (Symbol Fc 1 may be the same or different, and represent an alkoxy group or a halogen atom; 2 may be the same or different and represent a hydrogen atom or a hydrocarbon chain, The symbol Rca represents a hydrocarbon chain substituted with an amine functional group; g is an integer ranging from 0 to 1; with the copolymer obtained in step a), c) If necessary, a hydrolysis reaction The present invention also relates to a process comprising: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] Detailed Description Any interval of values ​​indicated by the expression "between a and b" denotes a range of values ​​greater than "a" and less than "b" (i.e. excluding the limits a and b), whereas any interval of values ​​indicated by the expression "a to b" means a range of values ​​extending from "a" to "b" (i.e. including the precise limits a and b). The abbreviation "phr" means parts by weight per 100 parts by weight of elastomer (or of the sum of the elastomers, if several elastomers are present). The expression "based on" used to define components of a catalyst system or composition is intended to mean a mixture of these components or the product of the reaction of some or all of these components with one another. Unless otherwise indicated, the content of units resulting from the incorporation of a monomer into a copolymer is expressed as a molar percentage relative to all of the monomer units of the copolymer. The compounds referred to in this description may be of fossil origin or bio-based. If bio-based, they may be partially or completely derived from biomass or may be obtained from renewable starting materials derived from biomass. Elastomers, plasticizers, fillers, etc. are of particular relevance. The 1,3-dienes of formula (I) as defined above and useful for the purposes of the present invention are substituted 1,3-dienes, which may result in units of 1,2 configuration as represented by formula (1) below, units of 3,4 configuration as represented by formula (2) below, and units of 1,4 configuration whose trans form is represented by formula (3) below.

[0008] [ka]

[0009] As is also well known, an ethylene unit is a unit of the -(CH2-CH2)- moiety. The copolymers useful for the purposes of the present invention are copolymers of ethylene and 1,3-diene, so that the monomer units of the copolymer are the units resulting from the polymerization of ethylene and 1,3-diene. The copolymers therefore comprise ethylene units and 1,3-diene units. According to any one of the embodiments of the present invention, the 1,3-diene is either the only compound, i.e. the only 1,3-diene of formula (I), or a mixture of 1,3-dienes of formula (I), i.e. a mixture of 1,3-dienes in which the groups represented by the symbol R are different from each other. The copolymers useful for the purposes of the present invention are advantageously statistical copolymers according to any one of the embodiments of the present invention. Preferably, the copolymer contains ethylene units that account for more than 50 mol% of the monomer units of the copolymer, i.e., more than 50 mol% of ethylene units and 1,3-diene units. Very preferentially, the copolymer contains ethylene units that account for at least 60 mol% of the monomer units of the copolymer. Even more preferentially, the copolymer contains ethylene units that account for at least 70 mol% of the monomer units of the copolymer. In other words, the copolymer preferentially contains more than 50 mol% of ethylene units, even more preferentially at least 60 mol% of ethylene units, even more preferentially at least 70 mol% of ethylene units. Preferably, the copolymer contains at most 90 mol % ethylene units, in which case the ethylene units in the copolymer account for at most 90 mol % of the monomer units of the copolymer. According to a particular embodiment of the invention, the copolymer contains at most 85 mol % of ethylene units, in which case the ethylene units in the copolymer represent at most 85 mol % of the monomer units of the copolymer. According to one preferential embodiment of the invention, in the copolymer of the invention, ethylene units represent from 60 to 90 mol % of the monomer units of the copolymer, advantageously from 70 to 90 mol % of the monomer units of the copolymer. According to another particular embodiment of the invention, in the copolymer of the invention, ethylene units represent from 65 to 85 mol % of the monomer units of the copolymer, advantageously from 70 to 85 mol % of the monomer units of the copolymer.

[0010] In the formula (I) of the 1,3-dienes, the hydrocarbon chain represented by the symbol R is a hydrocarbon chain of 3 to 20 carbon atoms. Preferably, the symbol R represents a hydrocarbon chain having 6 to 16 carbon atoms. The hydrocarbon chain represented by the symbol R may be a saturated or unsaturated chain. Preferably, the symbol R represents an aliphatic chain. It may be a straight or branched chain, in which case the symbol R represents a straight or branched chain. Preferably, the hydrocarbon chain is acyclic, in which case the symbol R represents an acyclic chain. Better still, the symbol R represents an unsaturated branched acyclic hydrocarbon chain. The hydrocarbon chain represented by the symbol R is advantageously an unsaturated branched acyclic chain containing 3 to 20 carbon atoms, in particular 6 to 16 carbon atoms. Very advantageously, the 1,3-diene is myrcene or β-farnesene. According to one preferential embodiment of the invention, the 1,3-diene is myrcene. According to another preferred embodiment of the invention, the 1,3-diene is β-farnesene.

[0011] Preferably, the copolymer of ethylene and 1,3-diene has a glass transition temperature of less than -35°C, preferably between -90°C and -35°C. According to a first variant of the invention, the copolymer contains 1,3-diene units in 1,2 or 3,4 configuration, the group consisting of 1,3-diene units in 1,2 configuration and 1,3-diene units in 3,4 configuration making up more than 50 mol % of the 1,3-diene units. In other words, according to this first variant, the 1,3-diene units in the copolymer contain more than 50 mol % of units in 1,2 or 3,4 configuration. In this variant, the remainder to 100 mol % of the 1,3-diene units in the copolymer are formed completely or partly by 1,3-diene units in 1,4 configuration. According to this first variant, preferentially, the majority of the 1,3-diene units in 1,4 configuration are in trans-1,4 configuration, and even more preferentially, all of the 1,3-diene units in 1,4 configuration are in trans-1,4 configuration. According to a second variant of the invention, the copolymer contains more than 50% of 1,3-diene units in 1,4 configuration. In other words, the 1,3-diene units in 1,4 configuration account for more than 50 mol% of the 1,3-diene units. In this variant, the remainder to 100 mol% of the 1,3-diene units in the copolymer is formed completely or partially by 1,3-diene units in 1,2 or 3,4 configuration. Preferably, the 1,3-diene units in 1,4 configuration account for more than 70 mol% of the 1,3-diene units. Advantageously, the majority of the 1,3-diene units in 1,4 configuration are in trans-1,4 configuration, meaning that the 1,3-diene units in trans-1,4 configuration account for more than 50 mol% of the 1,3-diene units in 1,4 configuration.

[0012] The amine functions carried by the copolymers are protected or unprotected primary amine functions, protected or unprotected secondary amine functions or tertiary amine functions. Protecting groups for amine functions are, for example, silyl groups, in particular trimethylsilyl or tert-butyldimethylsilyl groups. As is well known, the primary amine functional groups of the copolymer have the formula -NH2 and the secondary amine functional groups have the formula -NHR A and the tertiary amine functional group has the formula -N(R A )2, symbol R A may be the same or different and each represents a hydrocarbon chain. In the case of a tertiary amine functional group, the two RA may be linked to form a ring. Preferably, the amine functional groups carried by the copolymer are tertiary amine functional groups. Advantageously, the amine functional groups carried by the copolymer are each R A represents alkyl, preferentially methyl or ethyl; A )2 is a tertiary amine.

[0013] According to a particularly preferred embodiment of the invention, the copolymer further comprises a second functional group other than an amine functional group, which second functional group is preferably a silanol functional group or an alkoxysilane functional group. According to a first variant of the particular embodiment in which the copolymer has a second functional group, the copolymer has the following formula (III-a): Si(OR') 2-f (R'') f (Ra'') (III-a) (the symbols R' may be the same or different and represent alkyl, the symbols R″, which may be the same or different, represent a hydrogen atom or a hydrocarbon chain; The symbol Ra″ represents a hydrocarbon chain substituted with an amine functional group; f is an integer from 0 to 1. It has the functional group According to this first variant, the second functional group is an alkoxysilane functional group. In formula (III-a), the symbol R' is preferentially an alkyl having up to 6 carbon atoms, more preferentially methyl or ethyl, more preferentially methyl. The symbol R'' is advantageously methyl or ethyl, more particularly methyl.

[0014] According to a second variant of the particular embodiment in which the copolymer has a second functional group, the copolymer has the following formula (III-b): Si(OH)(R'') (Ra'') (III-b) (The symbol R'' represents a hydrogen atom or a hydrocarbon chain, The symbol Ra'' represents a hydrocarbon chain substituted with an amine functional group. It has the functional group According to this second variant, the second functional group is a silanol functional group. Among the hydrocarbon chains represented by the symbol R″ in formulae (III-a) and (III-b), mention may be made of alkyl, in particular having 1 to 6 carbon atoms, preferentially methyl or ethyl, and even more preferentially methyl. Preferably, in formulae (III-a) and (III-b), the symbols R″, which may be identical or different, represent alkyl having up to 6 carbon atoms.

[0015] The functional groups carried by the copolymer, including amine and alkoxysilane functional groups, may include 3-(N,N-dimethylamino)propyldimethoxysilyl, 3-(N,N-dimethylamino)propyldiethoxysilyl, 3-aminopropyldimethoxysilyl, 3-aminopropyldiethoxysilyl, 3-(N,N-dimethylamino)propylmethoxymethylsilyl, 3-(N,N-dimethylamino)propylmethoxyethylsilyl, 3-(N,N-dimethylamino)propylethoxymethylsilyl, 3-(N,N-dimethylamino)propylethoxyethylsilyl, 3-aminopropylmethoxymethylsilyl, 3-aminopropylmethoxyethylsilyl, 3-aminopropylethoxymethylsilyl and 3-aminopropylethoxyethylsilyl groups. The functional groups that the copolymers have and that contain amine and silanol functions can also be silanol forms of the above functional groups that contain only ethoxy or methoxy functional groups, which can be obtained by hydrolysis of the ethoxy or methoxy functional groups. In this respect, 3-(N,N-dimethylamino)propylmethylsilanol, 3-(N,N-dimethylamino)propylethylsilanol, 3-aminopropylmethylsilanol and 3-aminopropylethylsilanol groups are suitable.

[0016] According to a very preferred embodiment of the invention, the functional group that the copolymer has and that contains the amine and alkoxysilane functions is of formula (III-a) with f equal to 0. According to this very preferred embodiment, groups in which R' is methyl or ethyl are particularly suitable, such as the 3-(N,N-dimethylamino)propyldimethoxysilyl, 3-(N,N-dimethylamino)propyldiethoxysilyl, 3-aminopropyldimethoxysilyl and 3-aminopropyldiethoxysilyl groups. Also suitable are the protected forms of the amine functions of the functional groups listed above, protected with silyl groups, in particular trimethylsilyl or tert-butyldimethylsilyl groups. According to one further preferred embodiment of the invention, the functional group which the copolymer bears and which contains the amine and alkoxysilane functions is a functional group of formula (III-a) in which f is equal to 0 and R' is methyl. According to this further preferred embodiment, the 3-(N,N-dimethylamino)propyldimethoxysilyl and 3-aminopropyldimethoxysilyl groups, as well as the protected forms of the amine functions 3-aminopropyldimethoxysilyl protected with trimethylsilyl or tert-butyldimethylsilyl, are very particularly suitable.

[0017] The copolymers can be prepared by a process comprising steps a) and b), where step a) is the copolymerization of ethylene with a 1,3-diene useful for the purposes of the present invention in the presence of a catalyst system comprising a metallocene of formula (II) and an organomagnesium compound of formula (III):

[0018] [ka]

[0019] Cp 1 and Cp 2 may be the same or different and are cyclopentadienyl groups of the formula C5H4, 13 H8 is selected from the group consisting of unsubstituted fluorenyl groups and substituted fluorenyl groups. P is two Cp 1 and Cp 2ZR 3 R 4 group, Z represents silicon or carbon atom, R 3 and R 4 are the same or different and each represents an alkyl group containing 1 to 20 carbon atoms, preferably methyl, y is an integer greater than or equal to 0; x, which may or may not be an integer, is equal to or greater than 0; L represents an alkali metal selected from the group consisting of lithium, sodium and potassium; N represents a molecule of an ether, preferably diethyl ether or tetrahydrofuran, R 1 and R 2 may be the same or different and represent a carbon group.

[0020] Substituted fluorenyl groups can include those substituted with an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. The choice of group is also guided by the availability of the corresponding molecule, which is a substituted fluorene, since substituted fluorenes are commercially available or can be easily synthesized. As substituted fluorenyl groups, mention may more particularly be made of the 2,7-di(tert-butyl)fluorenyl and 3,6-di(tert-butyl)fluorenyl groups, in which the 2-, 3-, 6- and 7-positions refer respectively to the positions of the carbon atoms of the ring shown in the diagram below, and the 9-position corresponds to the carbon atom to which the bridge P is attached.

[0021] [ka]

[0022] 2 Cp 1 and Cp 2 The group P bridging the groups preferably denotes SiMe2. The catalyst system can be prepared conventionally by a process similar to that described in patent application WO 2007054224 or WO 2007054223. For example, the organomagnesium compound and the metallocene are reacted in a hydrocarbon solvent, typically at a temperature ranging from 20° C. to 80° C., for a time period between 5 and 60 minutes. The catalyst system is generally prepared in an aliphatic hydrocarbon solvent, such as methylcyclohexane, or an aromatic hydrocarbon solvent, such as toluene. The catalyst system is generally used in this form in the synthesis process of the copolymer of the invention after its synthesis. Alternatively, the catalyst system can be prepared by a process similar to that described in patent application WO 2017093654 A1 or patent application WO 2018020122 A1. According to this alternative, the catalyst system further contains a preformation monomer selected from a conjugated diene, ethylene or a mixture of ethylene and conjugated diene, in which case the catalyst system is based on at least a metallocene, an organomagnesium compound and a preformation monomer. For example, the organomagnesium compound and the metallocene are reacted in a hydrocarbon solvent, typically at a temperature between 20°C and 80°C for 10 to 20 minutes to obtain a first reaction product, and then a preformation monomer selected from a conjugated diene, ethylene or a mixture of ethylene and conjugated diene is reacted with this first reaction product at a temperature in the range of 40°C to 90°C for 1 hour to 12 hours. The catalyst system thus obtained can be used immediately in the process of the invention or stored under an inert atmosphere until it is used in the process of the invention.

[0023] The metallocenes used to prepare the catalytic system can be in the form of crystalline or amorphous powders or in the form of single crystals. The metallocenes can also be provided in the form of monomers or dimers, which form depends on the method of preparation of the metallocenes, for example as described in patent applications WO 2007054224 or WO 2007054223. The metallocenes can be prepared in a process similar to that described in patent applications WO 2007054224 or WO 2007054223, in particular by reaction of the alkali metal salt of the ligand with a rare earth metal borohydride under inert and anhydrous conditions in a suitable solvent, for example an ether, for example 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-products by techniques known to those skilled in the art, for example filtration or precipitation from a second solvent. Finally, the metallocene is dried and isolated in solid form. As with any synthesis carried out in the presence of an organometallic compound, the synthesis of metallocenes and the synthesis of the catalyst system are carried out under anhydrous conditions and in an inert atmosphere. Typically, these reactions are carried out under anhydrous nitrogen or argon starting with anhydrous solvents and compounds.

[0024] The organomagnesium compound used in accordance with the present invention has the formula MgR 1 R 2 wherein R 1 and R 2 may be the same or different and represent a carbon group. A carbon group is intended to mean a group containing one or more carbon atoms. Preferably, R 1 and R 2 Contains 2 to 10 carbon atoms. More preferentially, R 1 and R 2 Each represents an alkyl. The organomagnesium compound is preferably a dialkylmagnesium compound, more preferably butylethylmagnesium or butyloctylmagnesium, and even more preferably butyloctylmagnesium. According to one embodiment of the invention, the molar ratio of the organomagnesium compound to the metal Nd constituting the metallocene is preferably in the range from 1 to 100, more preferably greater than or equal to 1 and less than 10. To obtain copolymers with a high molar mass, a value range of 1 to less than 10 is particularly preferred.

[0025] When the copolymer useful for the purposes of the present invention is a copolymer having a microstructure defined according to the first variant of the invention, it is preferably a copolymer having a metallocene of formula (II) where Cp 1 and Cp 2 may be the same or different, and are a substituted fluorenyl group and a group of formula C 13 For this variant, the metallocene is prepared according to the process described in the present application using a metallocene of the formula: 13 H8) are particularly suitable: [{Me2SiFlu2Nd(μ-BH4)2Li(THF)}2]; [Me2SiFlu2Nd(μ-BH4)2Li(THF)]; [Me2SiFlu2Nd(μ-BH4)(THF)]; [{Me2SiFlu2Nd(μ-BH4)(THF)}2]; [Me2SiFlu2Nd(μ-BH4)]. When the copolymer useful for the purposes of the present invention is a copolymer having a microstructure defined according to the second variant of the invention, it is preferably a copolymer having a metallocene of formula (II) where Cp 1 represents a cyclopentadienyl group Cp of formula C5H4, Cp 2 is the formula C 13 H8) is prepared according to the process described in this application.

[0026] The skilled artisan will also choose the polymerization conditions and the concentrations of each reactant (component of the catalytic system, monomers) depending on the equipment (tools, reactors) used to carry out the polymerization and the various chemical reactions. As known to the skilled artisan, the copolymerization is carried out under anhydrous conditions and in an inert atmosphere, as well as the handling of the monomers, the catalytic system and the polymerization solvent. The polymerization solvent is typically an aliphatic or aromatic hydrocarbon solvent. The polymerization is preferably carried out in solution, continuously or batchwise. The polymerization solvent can be an aromatic or aliphatic hydrocarbon solvent. Examples of polymerization solvents include toluene and methylcyclohexane. The monomers can be introduced into the reactor containing the polymerization solvent and the catalyst system, or conversely, the catalyst system can be introduced into the reactor containing the polymerization solvent and the monomers. The copolymerization is typically carried out under anhydrous conditions and in the absence of oxygen, optionally in the presence of an inert gas. The polymerization temperature generally varies within a range ranging from 30°C to 150°C, preferentially from 30 to 120°C. Preferably, the copolymerization is carried out at constant ethylene pressure. During the polymerization of ethylene and 1,3-diene in a polymerization reactor, ethylene and 1,3-diene may be added continuously to the polymerization reactor, in which case the polymerization reactor is a fed reactor. This embodiment is very particularly suitable for the synthesis of statistical copolymers.

[0027] Step b) consists in functionalizing the copolymer obtained in step a) by reacting a functionalizing agent with the copolymer. The functionalizing agent has the following formula (IV): Si(Fc 1 ) 3-g (Rc 2 ) g (Rca) (IV) (Symbol Fc 1 may be the same or different and represent an alkoxy group or a halogen atom; Symbol Rc 2 may be the same or different and represent a hydrogen atom or a hydrocarbon chain, The symbol Rca represents a hydrocarbon chain substituted with an amine functional group; g is an integer ranging from 0 to 1. It is a compound of the formula: Symbol Fc 1 The alkoxy group represented by the formula (I) is preferably methoxy or ethoxy. According to one preferred embodiment of the invention, the functionalizing agent comprises at least one symbol Fc 1 , in particular methoxy or ethoxy. Advantageously, the functionalizing agent is therefore of formula (IV-1): MeOSi(Fc 1 ) 2-g (Rc 2 ) g (Rca) (IV-1) Symbol Fc 1 , Rc 2 and Rca and g are as defined in formula (IV).

[0028] According to a further preferred embodiment, the functionalizing agent comprises at least two symbols Fc 1 , in particular methoxy or ethoxy. Advantageously, the functionalizing agent is therefore of formula (IV-2): (MeO)2Si(Fc 1 ) 1-g (Rc 2 ) g (Rca) (IV-2) Symbol Fc 1 , Rc 2 and Rca is as defined in formula (IV). According to a further preferred embodiment, the functionalizing agent comprises at least three symbols Fc 1 , in particular methoxy or ethoxy. Advantageously, the functionalizing agent is therefore of formula (IV-3): (MeO)3Si(Rca) (IV-3) The symbol Rca is as defined in formula (IV). In formulas (IV), (IV-1), and (IV-2), the symbol Rc 2 Among the hydrocarbon chains of the formula: embedded image, mention may be made of alkyl, preferably alkyl having up to 6 carbon atoms, and more preferentially methyl or ethyl, and better still methyl. Among the hydrocarbon chains represented by the symbol Rca in formulae (IV), (IV-1), (IV-2) and (IV-3), mention may be made of alkanediyl chains, preferably those containing up to 6 carbon atoms, such as the 1,3-propanediyl group.

[0029] The amine function indicated by the symbol Rca, i.e. the amine function of the functionalizing agent, is a protected primary amine function, a protected secondary amine function or a tertiary amine function. As protecting groups for primary and secondary amine functions, mention may be made of silyl groups, such as trimethylsilyl and tert-butyldimethylsilyl groups. Preferably, the amine function of the functionalizing agent is a tertiary amine function. Advantageously, the amine function of the functionalizing agent is of the formula -N(R B )2(in the formula, each R B represents an alkyl, preferentially methyl or ethyl) tertiary amine. The functionalizing agents include the compounds (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane, (N,N-dimethyl-3-aminopropyl)methyldiethoxysilane, (N,N-dimethyl-3-aminopropyl)ethyldimethoxysilane, (N,N-dimethyl-3-aminopropyl)ethyldiethoxysilane, (N,N-dimethylaminopropyl)trimethoxysilane, (N,N-dimethylaminopropyl)triethoxysilane, (N-(3-trimethoxysilyl)propyl)-N-(trimethylsilyl)silaneamine, (N-(3-triethoxy ... )propyl)-N-(trimethylsilyl)silaneamine, preferably (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane, (N,N-dimethyl-3-aminopropyl)ethyldimethoxysilane, (N,N-dimethylaminopropyl)trimethoxysilane and (N-(3-trimethoxysilyl)propyl)-N-(trimethylsilyl)silaneamine, more preferentially (N,N-dimethylaminopropyl)trimethoxysilane and (N-(3-trimethoxysilyl)propyl)-N-(trimethylsilyl)silaneamine may be mentioned.

[0030] The functionalizing agent is typically added to the polymerization medium resulting from step a). The functionalizing agent is typically added to the polymerization medium at a monomer conversion selected by one skilled in the art depending on the desired macrostructure of the copolymer. Since step a) is generally carried out under ethylene pressure, degassing of the polymerization vessel may be performed prior to the addition of the functionalizing agent. The functionalizing agent is added to the polymerization medium maintained at the polymerization temperature under inert and anhydrous conditions. Typically, 0.25 to 10 moles of functionalizing agent per mole of cocatalyst, preferably 2 to 4 moles of functionalizing agent per mole of cocatalyst, are utilized. The functionalizing agent is contacted with the polymerization medium for a time sufficient to allow the functionalization reaction. This contact time is judiciously selected by the skilled artisan as a function of the concentration of the reaction medium and the temperature of the reaction medium. Typically, the functionalization reaction is carried out with stirring at a temperature ranging from 17° C. to 80° C. for a period of 0.01 to 24 hours. Once functionalized, the copolymer can be recovered, in particular by isolating it from the reaction medium. Techniques for isolating the copolymer from the reaction medium are well known to those skilled in the art and are chosen by them depending on the amount of copolymer to be isolated, its macrostructure and the tools available to them. For example, mention may be made of the coagulation of the copolymer in a solvent such as methanol, or the evaporation of the solvent and residual monomers of the reaction medium, for example under reduced pressure.

[0031] When the functionalizing agent is of formula (IV), (IV-1) or (IV-2) and g is equal to 1, step b) may be followed by a hydrolysis reaction in order to form a copolymer carrying silanol functional groups. The hydrolysis may be carried out in a manner known to those skilled in the art by a step of stripping the solution containing the copolymer at the end of step b). When the functionalizing agent is of formula (IV), (IV-1), (IV-2) or (IV-3) and contains a primary or secondary amine function in protected form, a hydrolysis reaction may also be carried out after step b) to deprotect the functional group. The hydrolysis reaction, which is the deprotection step of the functional group, is generally carried out in an acidic or basic medium. For example, silyl groups protecting amine functions, in particular trimethylsilyl or tert-butyldimethylsilyl groups, can be hydrolyzed in an acidic or basic medium in a manner known to those skilled in the art. The choice of deprotection conditions is judiciously made by those skilled in the art, taking into account the chemical structure of the substrate to be deprotected. Step c) of the process of the invention is an optional step depending on whether it is desired to convert alkoxysilane groups into silanol groups or whether it is desired to deprotect protected functional groups. Preferentially, step c) is carried out before or simultaneously with the separation of the copolymer from the reaction medium at the end of step b).

[0032] According to any one embodiment of the invention, the amine functional groups carried by the copolymers of the invention are preferentially at the chain ends of the copolymer. The copolymers of the invention, as described according to any one of the embodiments of the invention, including their preferred variants, exhibit both a lower stiffness and a lower crystallinity than copolymers of ethylene and 1,3-butadiene, even with the same ethylene content. The replacement of a copolymer of ethylene and 1,3-butadiene with the copolymers of the invention in a rubber composition can give the rubber composition a lower stiffness, even with the same ethylene content. Furthermore, the functionalization of the copolymer with amine functional groups allows an improvement in the interaction between the copolymer and the reinforcing filler, in particular carbon black or silica or a mixture thereof, which helps to improve the mechanical properties of the copolymer and, consequently, of the rubber composition containing the copolymer of the invention and reinforced with the reinforcing filler. The copolymer of the invention is advantageously an elastomer, hereinafter referred to as diene and ethylene elastomer. It is particularly intended for use in rubber compositions, in particular for tires.

[0033] Thus, the rubber composition which is another object of the present invention has the essential feature of comprising the diene and ethylene elastomers of the present invention. Preferably, the rubber composition contains more than 50 phr of diene and ethylene elastomer, and more preferentially at least 80 phr of diene and ethylene elastomer. The remainder to 100 phr may consist, in whole or in part, of diene and ethylene elastomers not having silanol or alkoxysilane functional groups. The rubber composition may also comprise an elastomer selected from the group of diene elastomers consisting of polybutadiene, polyisoprene, butadiene copolymers, isoprene copolymers and mixtures thereof. Advantageously, the content of diene and ethylene elastomer of the present invention is 100 phr. The diene and ethylene elastomer may consist of a mixture of diene and ethylene elastomers that differ from each other because of their microstructure or their macrostructure.

[0034] Another essential feature of the rubber composition is that, in addition to the diene and ethylene elastomers, it contains a reinforcing filler. Any type of "reinforcing" filler known for its ability to reinforce rubber compositions that can be used in particular in the manufacture of tires can be utilized, for example organic fillers such as carbon black, inorganic fillers such as silica, or a mixture of these two types of fillers. According to one embodiment of the present invention, the reinforcing filler comprises carbon black. According to another particular embodiment of the invention, the reinforcing filler comprises silica. According to yet another embodiment of the present invention, the reinforcing filler comprises carbon black and silica. According to any one of the embodiments of the present invention, the reinforcing filler preferably comprises carbon black and silica. All carbon blacks are suitable as carbon blacks, in particular the blacks of the HAF, ISAF, SAF, FF, FEF, GPF and SRF types usually used in tire compositions ("tire grade" blacks). These carbon blacks can be used in the isolated state as they are commercially available or in any other form, for example as carriers for some of the rubber additives used.

[0035] The term "reinforcing inorganic filler" is to be understood in the present patent application to mean any inorganic or mineral filler, by definition also called "white fillers", "clear fillers" or even "non-black fillers" as opposed to carbon black, whatever its color and its origin (natural or synthetic), which is capable of reinforcing, by itself and without any other means than intermediate coupling agents, the rubber compositions intended for the manufacture of tires, in other words capable of replacing the usual tire grade carbon black in its reinforcing role; such fillers are generally characterized, as is known, by the presence of hydroxyl (-OH) groups on their surface. Mineral fillers of the siliceous type, preferentially silica (SiO2), are particularly suitable as reinforcing inorganic fillers. The silica used may be any reinforcing silica known to those skilled in the art, in particular both 450m 2 / g, preferably 30 to 400m 2 / g, especially 60m 2 / g and 300m 2 The silica may be any precipitated or fumed silica that exhibits a BET specific surface area between 0.1 mm and 0.1 mm / g and also a CTAB specific surface area between 0.1 mm and 0.1 mm / g. Highly disperse precipitated silicas ("HDS") include, for example, Ultrasil 7000 and Ultrasil 7005 silicas from Degussa, Zeosil 1165MP, 1135MP and 1115MP silicas from Rhodia, Hi-Sil EZ150G silica from PPG, Zeopol 8715, 8745 and 8755 silicas from Huber or silicas with high specific surface area as described in application WO 03 / 16837.

[0036] In the present description, the BET specific surface area is determined in a known manner (multipoint (5-point) volumetric method - gas: nitrogen - degassing: 1 hour at 160°C - relative pressure p / po range: 0.05 to 0.17) using the Brunauer-Emmett-Teller method described in The Journal of the American Chemical Society, Vol. 60, page 309, February 1938, and more specifically by gas adsorption according to the French standard NF ISO 9277 of November 1996. The CTAB specific surface area value is the external surface area measured according to the French standard NF T 45-007 ISO of November 1987 (Method B). The physical state in which the reinforcing inorganic filler is provided is immaterial, whether in the form of powder, micropearls, granules or beads. Naturally, reinforcing inorganic filler is also intended to mean mixtures of different reinforcing inorganic fillers, in particular the highly dispersible silicas described above. Those skilled in the art will understand that equivalent fillers to the reinforcing inorganic fillers described in this section can also be reinforcing fillers of another nature, in particular organic, such as carbon black, provided that they are covered with an inorganic layer, such as silica, or contain functional sites, in particular hydroxyl sites, on their surface, which require the use of coupling agents to establish a bond between the filler and the elastomer. By way of example, mention may be made of the carbon blacks for tires described, for example, in patent documents WO 96 / 37547 and WO 99 / 28380. Preferentially, the content of reinforcing fillers is between 30 and 200 phr, and more preferentially between 40 and 160 phr. Any one of these ranges of reinforcing filler contents can be applied to any one of the embodiments of the present invention.

[0037] To bond the reinforcing inorganic fillers to the elastomers, known methods are used that utilize at least difunctional coupling agents, in particular silanes, (or bonding agents), intended to form sufficient bonds between the inorganic fillers (the surfaces of their particles) and the elastomers, in particular organosilanes or polyorganosilanes that are at least difunctional. In particular, use is made of so-called "symmetric" or "asymmetric" silane polysulfides, which are determined by their specific structure, as described, for example, in applications WO 03 / 002648 (or US 2005 / 016651) and WO 03 / 002649 (or US 2005 / 016650). Particularly suitable, without being limited to the following definition, are silane polysulfides corresponding to the following formula (V): ZGS x -GZ (V) During the ceremony: -x is an integer from 2 to 8 (preferably from 2 to 5); the symbols G may be the same or different and are divalent hydrocarbon radicals (preferably C1-C 18 Alkylene group or C6-C 12 Arylene groups, more particularly C1-C 10 , in particular C1-C4 alkylene, in particular propylene); the symbols Z, which may be identical or different, correspond to one of the following three formulae:

[0038] [ka]

[0039] During the ceremony: -R a The groups are substituted or unsubstituted, identical or different, and are C-C 18 Alkyl groups, C5-C 18 Cycloalkyl group or C6-C 18 represents an aryl group (preferably a C1-C6 alkyl, cyclohexyl or phenyl group, in particular a C1-C4 alkyl group, more in particular methyl and / or ethyl), -R b The groups are substituted or unsubstituted, identical or different, and are C-C 18 Alkoxy or C5-C 18 It represents a cycloalkoxyl group (preferably a group selected from C1-C8 alkoxyl and C5-C8 cycloalkoxyl, and more preferentially a group selected from C1-C4 alkoxyl and in particular methoxyl and ethoxyl). In the case of mixtures of alkoxysilane polysulfides corresponding to formula (I) above, in particular the usual commercial mixtures, the average value of the "x" index is preferably a fraction between 2 and 5, and more preferentially close to 4. However, the invention can also be advantageously carried out, for example, with alkoxysilane disulfides (x=2).

[0040] As examples of silane polysulfides, mention may more particularly be made of bis((C1-C4)alkoxyl(C1-C4)alkylsilyl(C1-C4)alkyl)polysulfides (especially disulfides, trisulfides or tetrasulfides), such as bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilylpropyl) polysulfides. Among these compounds, in particular, bis(3-triethoxysilylpropyl)tetrasulfide of formula [(C2H5O)3Si(CH2)3S2]2, abbreviated as TESPT, or bis(3-triethoxysilylpropyl)disulfide of formula [(C2H5O)3Si(CH2)3S]2, abbreviated as TESPD, is used. As coupling agents other than alkoxysilane polysulfides, particular mention will be made of difunctional POS (polyorganosiloxanes) or hydroxysilane polysulfides, such as those described in patent applications WO 02 / 30939 (or US 6 774 255) and WO 02 / 31041 (or US 2004 / 051210), or silanes or POS containing azodicarbonyl functions, as described, for example, in patent applications WO 2006 / 125532, WO 2006 / 125533 and WO 2006 / 125534.

[0041] The content of coupling agent is advantageously less than 30 phr, and it is generally understood that it is desirable to use as little as possible. Typically, the content of coupling agent represents 0.5% to 15% by weight, based on the amount of inorganic filler. Its content is preferentially between 0.5 phr and 16 phr, and more preferentially in the range of 3 to 10 phr. This content can be easily adjusted by a person skilled in the art according to the content of inorganic filler used in the composition. The rubber composition of the present invention may contain, in addition to the coupling agent, a coupling activator, an agent for coating the inorganic filler or, more generally, a processing aid which can improve the dispersion of the filler in the rubber matrix and reduce the viscosity of the composition, thereby improving the ability of the rubber composition to be processed in the uncured state.

[0042] The rubber composition comprises a crosslinking system. Chemical crosslinking allows the formation of covalent bonds between the elastomer chains. The crosslinking system may be a vulcanization system or one or more peroxide compounds, preferably a vulcanization system. The vulcanization system is entirely based on sulfur (or a sulfur donor) and a primary vulcanization accelerator. In addition to this basic vulcanization system, various known secondary vulcanization accelerators or vulcanization activators, such as zinc oxide, stearic acid or equivalent compounds, or guanidine derivatives (especially diphenylguanidine), are incorporated during the first non-productive phase and / or during the productive phase, as will be described later. Sulphur is used in a preferential content of 0.5 to 12 phr, in particular 1 to 10 phr. Primary vulcanization accelerators are used in a preferential content of between 0.5 phr and 10 phr, more preferentially between 0.5 phr and 5 phr. As (primary or secondary) accelerators, any compound capable of acting as an accelerator for the vulcanization of diene elastomers in the presence of sulfur can be used, in particular accelerators of the thiazole type and also their derivatives, or accelerators of the thiuram or zinc dithiocarbamate type. Preferably, a primary accelerator of the sulfenamide type is used.

[0043] When chemical crosslinking is carried out using one or more peroxide compounds, the peroxide compound(s) preferably accounts for 0.01 to 10 phr. Peroxide compounds that can be used as chemical crosslinking systems include acyl peroxides, such as benzoyl peroxide or p-chlorobenzoyl peroxide, ketone peroxides, such as methyl ethyl ketone peroxide, peroxyesters, such as t-butyl peroxyacetate, t-butyl peroxybenzoate and t-butyl peroxyphthalate, alkyl peroxides, such as dicumyl peroxide, di(t-butyl) peroxybenzoate and 1,3-bis(t-butylperoxyisopropyl)benzene, or hydroperoxides, such as t-butyl hydroperoxide. The rubber composition of the invention may contain all or some of the usual additives generally used in elastomeric compositions intended to constitute the outer mixture of a finished rubber article, such as a tire, and in particular a tread, such as plasticizers or extender oils, whether aromatic or non-aromatic, in particular very weakly aromatic or non-aromatic oils (for example paraffinic or hydrogenated naphthenic oils, or MES or TDAE oils), vegetable oils, in particular glycerol esters, such as glyceryl trioleate, pigments, protective agents, such as anti-vaccinal waxes, chemical anti-vaccinal agents or antioxidants.

[0044] The rubber compositions of the present invention can be produced in a suitable mixer using two successive preparation stages according to general procedures well known to those skilled in the art: a first thermo-mechanical processing or kneading stage (sometimes called the "non-productive" stage) at high temperatures up to a maximum temperature of between 130°C and 200°C, preferably between 145°C and 185°C, followed by a second mechanical processing stage (sometimes called the "productive" stage) at lower temperatures, typically below 120°C, for example between 60°C and 100°C, during which chemical crosslinking agents, in particular vulcanization systems, are incorporated during the final stage. Generally, all the basic constituents of the composition included in the tire of the invention, except for the crosslinking system, i.e. the reinforcing inorganic fillers and, if applicable, the coupling agents, are intimately incorporated into the elastomer during a first "non-productive" stage by kneading, that is to say at least these various basic constituents are introduced into a mixer and mechanically kneaded, in one or more steps, until a maximum temperature of between 130°C and 200°C, preferably between 145°C and 185°C, is reached. By way of example, the first (non-productive) stage is carried out in a single thermomechanical step, during which all necessary ingredients, except the chemical crosslinking agent, optional supplementary processing aids and various other additives are introduced into a suitable mixer, for example a standard internal mixer. The total duration of the kneading in this non-productive stage is preferably between 1 and 15 minutes. After cooling of the mixture thus obtained during the first non-productive stage, the crosslinking system is then incorporated at low temperature, usually in an external mixer such as an open mill; then everything is mixed for a few minutes, for example between 2 and 15 minutes (productive stage). The final composition thus obtained can be calendered, in particular in the form of sheets or slabs for laboratory characterization, or in the form of rubber profiled elements which can be used as semi-finished tire products for vehicles. Thus, according to a particular embodiment of the present invention, the rubber composition of the present invention may be in an uncured state (before crosslinking or vulcanization) or in a cured state (after crosslinking or vulcanization) and may be a semi-finished product that can be used in tires, in particular as a tire tread.

[0045] In summary, the present invention is advantageously carried out according to any one of the following embodiments 1 to 39. Embodiment 1: A method for producing a compound represented by the following formula (I): CH2=CR-CH=CH2(I) (The symbol R represents a hydrocarbon chain having 3 to 20 carbon atoms.) with 1,3-dienes, which have amine functional groups. Embodiment 2: The copolymer of embodiment 1, wherein the amine functional groups are at the chain ends of the copolymer. Embodiment 3: A copolymer according to any one of embodiments 1 and 2, wherein the copolymer is a statistical copolymer. Embodiment 4: The copolymer of any one of embodiments 1 to 3, wherein the copolymer contains more than 50 mol % ethylene units. Embodiment 5: A copolymer according to any one of embodiments 1 to 4, wherein the copolymer contains at least 60 mol % ethylene units. Embodiment 6: The copolymer of any one of embodiments 1 to 5, wherein the copolymer contains at least 70 mol % ethylene units. Embodiment 7: The copolymer of any one of embodiments 1 to 6, wherein the copolymer contains up to 90 mol % ethylene units. Embodiment 8: The copolymer of any one of embodiments 1 to 6, wherein the copolymer contains up to 85 mol % ethylene units. Embodiment 9: A copolymer according to any one of embodiments 1 to 8, wherein the copolymer contains 1,3-diene units in a 1,2 or 3,4 configuration, and the group consisting of 1,3-diene units in a 1,2 configuration and 1,3-diene units in a 3,4 configuration accounts for more than 50 mol % of the 1,3-diene units.

[0046] Embodiment 10: A copolymer according to any one of embodiments 1 to 9, wherein the symbol R represents an aliphatic chain. Embodiment 11: A copolymer according to any one of embodiments 1 to 10, wherein the symbol R represents a hydrocarbon chain having from 6 to 16 carbon atoms. Embodiment 12: A copolymer according to any one of embodiments 1 to 11, wherein the symbol R represents an acyclic chain. Embodiment 13: A copolymer according to any one of embodiments 1 to 12, wherein the symbol R represents a linear or branched chain. Embodiment 14: A copolymer according to any one of embodiments 1 to 13, wherein the 1,3-diene is myrcene or β-farnesene. Embodiment 15: The copolymer according to any one of embodiments 1 to 14, wherein the copolymer has a glass transition temperature of less than -35°C, preferably between -90°C and -35°C. Embodiment 16: A copolymer according to any one of embodiments 1 to 15, wherein the amine functional group is a tertiary amine functional group. Embodiment 17: The amine functional group is represented by the formula -N(R A ) 2 tertiary amine functional groups, A 17. A copolymer according to any one of the preceding embodiments, wherein represents alkyl, preferentially methyl or ethyl.

[0047] Embodiment 18: The copolymer of any one of embodiments 1 to 17, wherein the copolymer further comprises a second functional group other than an amine functional group. Embodiment 19: The copolymer of embodiment 18, wherein the second functional group of the copolymer is a silanol functional group or an alkoxysilane functional group. Embodiment 20: A rubber composition comprising the copolymer according to any one of embodiments 1 to 19, a reinforcing filler and a crosslinking system, wherein the copolymer is an elastomer.

[0041] Embodiment 21: The rubber composition of embodiment 20, wherein the reinforcing filler comprises carbon black. Embodiment 22: The rubber composition of embodiment 20 or 21, wherein the reinforcing filler comprises silica. Embodiment 23: The rubber composition of any one of embodiments 20-22, wherein the reinforcing filler comprises carbon black and silica. Embodiment 24: The rubber composition according to any one of embodiments 20 to 22, wherein the crosslinking system is a vulcanization system. Embodiment 25: A tire comprising the rubber composition according to any one of embodiments 20 to 24. Embodiment 26: A process for preparing a copolymer according to any one of embodiments 1 to 19, comprising the following steps: a) a metallocene of the following formula (II) or an organomagnesium compound of the following formula (III):

[0048] [ka]

[0049] (Cp 1and Cp 2 may be the same or different and are cyclopentadienyl groups of the formula C5H4, 13 H8 is selected from the group consisting of unsubstituted fluorenyl groups and substituted fluorenyl groups; P is two Cp 1 and Cp 2 ZR 3 R 4 group, Z represents silicon or carbon atom, R 3 and R 4 are the same or different and each represents an alkyl group containing 1 to 20 carbon atoms, preferably methyl, y is an integer greater than or equal to 0; x, which may or may not be an integer, is greater than or equal to 0; L represents an alkali metal selected from the group consisting of lithium, sodium and potassium; N represents a molecule of an ether, preferably diethyl ether or tetrahydrofuran, R 1 and R 2 may be the same or different and represent a carbon group. In the presence of a catalyst system comprising Ethylene and the following formula (I) CH2=CR-CH=CH2(I) (The symbol R represents a hydrocarbon chain having 3 to 20 carbon atoms.) Copolymerization with 1,3-dienes, b) Formula (IV) Si(Fc 1 ) 3-g (Rc 2 ) g (Rca) (IV) (Symbol Fc 1 may be the same or different and represent an alkoxy group or a halogen atom; Symbol Rc 2 may be the same or different and represent a hydrogen atom or a hydrocarbon chain, The symbol Rca represents a hydrocarbon chain substituted with an amine functional group; g is an integer ranging from 0 to 1. with the copolymer obtained in step a), c) Hydrolysis reaction, if necessary The process includes:

[0050] Embodiment 27: The process of embodiment 26, wherein P represents a SiMe2 group. Embodiment 28: Cp 1 and Cp 2 may be the same or different, and a substituted fluorenyl group and a group of formula C 13 28. The process according to any one of embodiments 26 and 27, wherein H8 is selected from the group consisting of unsubstituted fluorenyl groups. Embodiment 29: The metallocene catalyst is of the formula [{Me2SiFlu2Nd(μ-BH4)2Li(THF)}2], [Me2SiFlu2Nd(μ-BH4)2Li(THF)], [Me2SiFlu2Nd(μ-BH4)(THF)], [{Me2SiFlu2Nd(μ-BH4)(THF)}2] or [Me2SiFlu2Nd(μ-BH4)], where the symbol Flu is of the formula C 13 29. The process of any one of embodiments 26 to 28, wherein H represents a fluorenyl group. Embodiment 30: The process according to any one of embodiments 26 to 29, wherein the organomagnesium compound is a dialkylmagnesium compound, preferentially a butyloctylmagnesium compound. Embodiment 31: The functionalizing agent comprises at least one symbol Fc 1 31. The process of any one of embodiments 26 to 30, comprising: Embodiment 32: The functionalizing agent comprises at least two symbols Fc 1 32. The process of any one of embodiments 26 to 31, comprising: Embodiment 33: The functionalizing agent comprises at least three symbols Fc 1 33. The process of any one of embodiments 26 to 32, comprising: Embodiment 34: Symbol Fc 1 The process according to any one of embodiments 26 to 33, wherein the alkoxy group represented by is methoxy or ethoxy, preferably methoxy. Embodiment 35: Symbol Rc 2 The process according to any one of embodiments 26 to 34, wherein represents alkyl having up to 6 carbon atoms, preferably methyl or ethyl. Embodiment 36: The process according to any one of embodiments 26 to 35, wherein the hydrocarbon chain represented by the symbol Rca in formulae (IV), (IV-1), (IV-2) and (IV-3) is an alkanediyl chain preferably containing up to 6 carbon atoms, such as a 1,3-propanediyl group. Embodiment 37: The process of any one of embodiments 26 to 36, wherein the amine functional group represented by the symbol Rca is a primary amine functional group protected by a protecting group, a secondary amine functional group protected by a protecting group, or a tertiary amine functional group. Embodiment 38: The process of embodiment 37, wherein the protecting group is a trimethylsilyl or tert-butyldimethylsilyl group.

[0051] Embodiment 39: The functionalizing agent is selected from the group consisting of (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane, (N,N-dimethyl-3-aminopropyl)methyldiethoxysilane, (N,N-dimethyl-3-aminopropyl)ethyldimethoxysilane, (N,N-dimethyl-3-aminopropyl)ethyldiethoxysilane, (N,N-dimethylaminopropyl)trimethoxysilane, (N,N-dimethylaminopropyl)triethoxysilane, (N-(3-trimethoxysilyl)propyl)-N-(trimethylsilyl)silaneamine, (N-(3-triethoxysilyl)propyl)- The process according to any one of embodiments 26 to 38, wherein the N-(trimethylsilyl)silane amine is preferably (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane, (N,N-dimethyl-3-aminopropyl)ethyldimethoxysilane, (N,N-dimethylaminopropyl)trimethoxysilane, (N-(3-trimethoxysilyl)propyl)-N-(trimethylsilyl)silane amine, more preferentially (N,N-dimethylaminopropyl)trimethoxysilane, (N-(3-trimethoxysilyl)propyl)-N-(trimethylsilyl)silane amine. These and other features of the invention will emerge better from a reading of the following description of some exemplary embodiments of the invention, given by way of illustration and not of limitation. EXAMPLES

[0052] 1) Determination of polymer microstructure: Spectral characterization and determination of the microstructure of copolymers of ethylene and 1,3-myrcene are carried out by nuclear magnetic resonance (NMR) spectroscopy. Spectrometer: A Bruker Avance III HD 400 MHz spectrometer equipped with a Bruker cryo-BBFO z-grad 5 mm probe is used for these measurements. Experiment: Using high frequency pulses at an inclination angle of 30° 1 H experiments were recorded with 128 repetitions and a recycle delay of 5 seconds. HSQC (Heteronuclear Single Quantum Coherence) and HMBC (Heteronuclear Multiple-Bond Correlation) 1 H- 13 C NMR correlation experiments are recorded with 128 repeats and 128 increments. The experiments are carried out at 25° C. Sample preparation: Dissolve 25 mg of sample in 1 ml of deuterated chloroform (CDCl3). Sample Calibration: 1 H and 13 The chemical shift axis of C is δ relative to the protonated impurity (CHCl3) of the solvent. 1H = 7.2 ppm and δ 13C Calibrate at =77ppm.

[0053] Spectral assignments: Signals of the insertion types of 1,3-dienes A, B and C (Scheme 1) were observed in the various spectra recorded. According to S. Georges et al. (S. Georges, M. Bria, P. Zinck and M. Visseaux, Polymer, 55 (2014), 3869-3878), the signal of -CH=group number 8'' of type C is identical to the signal of -CH=group number 3.1 H and 13 C chemical shifts are shown. The chemical shifts of the signals characteristic of moieties A, B and C are presented in Table 1. Moieties A, B and C correspond to units of 3,4 configuration, 1,2 configuration and trans-1,4 configuration, respectively.

[0054] [Table 1]

[0055] [ka]

[0056] 2) Determination of polymer functionalization The functionalized product of the copolymer 1 H, 13 C. 29 Characterized by Si NMR spectroscopy. NMR spectra are recorded on a Bruker Avance III 500 MHz spectrometer equipped with a BBFO z-grad 5 mm "broadband" cryoprobe. Quantitative 1 H NMR experiments use a single pulse sequence of 30° and a repetition delay of 5 seconds between each acquisition. 64 to 256 accumulations are performed. 13 C NMR experiments use a 30° single pulse sequence with proton decoupling and a repeat delay of 10 seconds between each acquisition. 1024-10240 accumulations are performed. Two-dimensional (2D) NMR is performed with the aim of determining the structure of functional polymers. 1 H / 13 C and 1 H / 29 Use Si experiments. 1 The H chemical shift axis is δ relative to the protonated impurity of the solvent (CDCl3). 1H Calibrate at =7.20 ppm. 13 The C chemical shift axis is δ relative to the solvent signal (CDCl3). 13C Calibrate at =77ppm. 29The Si chemical shift axis is calibrated to the TMS signal at 0 ppm (addition of a few microliters of TMS to the NMR tube). The final chemical structure of each functionalized polymer is: 1 H, 13 C and 29 Identification by Si NMR. 1D recorded under quantitative conditions 1 The H NMR spectrum allows the calculation of the content of (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane grafted to the polymer. Proton signals characteristic of the grafted functional groups are observable at chemical shifts of 3.37 ppm for methoxy groups bonded to silicon (CH3-O-Si), 0.11 ppm to 0.02 ppm for methyl groups bonded to silicon ((CH3)2-Si) and 0.66 ppm to 0.45 ppm for methylene units alpha to silicon (Si-CH2-R). The graft structure is supported by a two-dimensional proton / silicon 29 interphase map. Silicon signals of (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane grafted to the polymer at the chain ends are located between 15 and 16 ppm and between 21 and 23 ppm. 29 Two broad unresolved peaks with chemical shifts of 1.25 and 1.4 correspond to the functional groups attached to the diene units and the ethylenic units, respectively.

[0057] 3) Determination of the glass transition temperature of a polymer: The glass transition temperature is measured according to ASTM standard D3418 (1999) using a differential calorimeter (differential scanning calorimeter). 4) Determination of polymer crystallinity: The melting and crystallization temperatures and enthalpies of the polymers used are determined by differential scanning calorimetry (DSC) using ISO standard 11357-3:2011. The reference enthalpy for polyethylene is 277.1 J / g (based on Polymer Handbook, 4th Edition, J. Brandrup, EH Immergut and EA Grulke, 1999).

[0058] 5) Size Exclusion Chromatography (SEC): a) Measurement principle: Size Exclusion Chromatography, or SEC, allows the separation of macromolecules according to their size through a column packed with a porous gel. Macromolecules are separated according to their thermodynamic volume, with the bulkiest being eluted first. Combining three detectors (3D), namely refractometer, viscometer and 90° light scattering detector, SEC allows the absolute molar mass distribution of polymers to be known. It is also possible to calculate the various number-average (Mn) and weight-average (Mw) absolute molar masses as well as the dispersity (D=Mw / Mn). b) Preparation of the polymer: Each sample is dissolved in tetrahydrofuran (+1 vol% diisopropylamine + 1 vol% triethylamine) at a concentration of approximately 1 g / l. The solution is then filtered through a filter with a porosity of 0.45 μm before injection.

[0059] c) 3D SEC analysis of the elastomers of the invention: To determine the number-average molar mass (Mn) and, optionally, the weight-average molar mass (Mw) and the dispersity of the components usable in the composition of the invention, the following method is used. The number-average molar mass (Mn), weight-average molar mass (Mw) and dispersity of the components to be tested (hereinafter samples) are determined in an absolute manner by triple detection size exclusion chromatography (SEC), which has the advantage of measuring the average molar mass directly without calibration. The value of the refractive index increment dn / dc of the sample solution is measured online using the peak area detected by the RI of the liquid chromatography instrument. To apply this method, it must be verified that 100% of the sample mass is injected and eluted through the column. The RI area depends on the concentration of the sample, the RI detector constant and the value of dn / dc. To determine the average molar mass, a previously prepared and filtered solution of 1 g / l is used and injected into the chromatographic system. The equipment used is a Waters Alliance Chromatography Line. The elution solvent is tetrahydrofuran protected against oxidation with 250 ppm BHT (2,6-di(tert-butyl)-4-hydroxytoluene), and the flow rate is 1 ml min -1 The temperature of the system is 35° C. and the analysis time is 60 min. The columns used are a set of three Agilent columns with the trade name PL Gel Mixed B LS. The volume of the sample solution is 100 μl. The detection system consists of a Wyatt differential viscometer with the trade name Viscostar II, a Wyatt differential refractometer with the trade name Optilab T-Rex at a wavelength of 658 nm and a Wyatt multi-angle static light scattering detector with the trade name Dawn Heleos 8+ at a wavelength of 658 nm. For the calculation of the number average molar mass and the dispersity, the values ​​of the refractive index increment dn / dc of the sample solution obtained above are integrated. The software for evaluating the chromatographic data is the Astra system from Wyatt.

[0060] d) 3D SEC analysis of elastomers not according to the invention or control elastomers: The equipment used is a Waters Alliance chromatograph. The elution solvent is tetrahydrofuran (+1 vol% diisopropylamine + 1 vol% triethylamine), the flow rate is 0.5 ml / min, and the system temperature is 35° C. A set of four Polymer Laboratories columns, two with the trade name "Mixed A LS" and two with the trade name "Mixed B LS", is used in series. The volume of the solution of the polymer sample injected is 100 μl. The detection system used is a TDA 302 from Viscotek, which consists of a differential refractometer, a differential viscometer and a 90° light scattering detector. For these three detectors, the wavelength is 670 nm. For the calculation of the average molar mass, the value of the refractive index increment dn / dC of the polymer solution is integrated. Said values ​​are defined beforehand in tetrahydrofuran (+1 vol.% diisopropylamine + 1 vol.% triethylamine) at 35° C. and 670 nm. The software for evaluating the data is the Omnisec system from Viscotek.

[0061] 6) Determination of the stiffness of a (cured) rubber composition: The dynamic properties are measured in accordance with ASTM standard D5992-96 on a viscosity analyzer (Metravib VA4000). Samples of the vulcanized compositions (4 mm thick and 400 mm long) are subjected to a simple alternating sine shear stress according to ASTM standard D 1349-99 at a frequency of 10 Hz and under standard temperature conditions (23°C). 2 The response of a cylindrical specimen with a cross-sectional area of ​​100 mm is recorded. A strain amplification sweep is performed from 0.1% to 100% (outward cycle) and then from 100% to 0.1% (return cycle). The results are the complex dynamic shear modulus (G * ). Stiffness results are expressed on a base 100 basis relative to the control recorded as the baseline. Values ​​below 100 indicate values ​​lower than the control.

[0062] 7) Preparation of polymer: In the synthesis of the copolymers of the invention, the 1,3-diene (myrcene) used is a hydrocarbon group of formula (I) having 6 carbon atoms and of formula CH2-CH2-CH=CMe2. All reagents are obtained commercially, except for the metallocene [{Me2SiFlu2Nd(μ-BH4)2Li(THF)}], which is prepared according to the procedure described in patent application WO 2007054224. Butyloctylmagnesium BOMAG (20% in heptane, 0.88 mol.l -1) is sourced from Chemtura and stored under inert atmosphere in a Schlenk tube. N35 grade ethylene is sourced from Air Liquide and used without prior purification. Myrcene (purity ≥ 95%) is obtained from Sigma-Aldrich. (N,N-Dimethyl-3-aminopropyl)methyldimethoxysilane is obtained from ABCR. Polymerization Procedure: The catalyst, butyloctylmagnesium (BOMAG), is added to the reactor containing the methylcyclohexane, followed by the metallocene [Me2Si(Flu)2Nd(μ-BH4)2Li(THF)]. The alkylation time is 10 minutes and the reaction temperature is 20°C. The amounts of each of the components of the catalyst system are given in Table 2 below. The monomers are then added continuously in their respective amounts given in Table 2. The polymerization is carried out under constant temperature and pressure conditions as given in Table 2. The polymerization reaction is stopped by cooling, degassing the reactor and adding ethanol. An antioxidant is added to the polymer solution. The copolymer is recovered by drying in an oven under vacuum to constant weight. Functionalization procedure: Once the desired monomer conversion has been achieved, the reactor contents are degassed and then the functionalizing agent (N,N-dimethyl-3-aminopropyl)methyldimethoxysilane is introduced by overpressure under an inert atmosphere. The reaction medium is stirred for the time and temperature indicated in Table 3 below. After the reaction, the medium is degassed and then precipitated from methanol. The copolymer is recovered by precipitation from methanol and then dried to constant weight at 60° C. under vacuum. The microstructure and functional group content of the elastomer are shown in Table 4 below, and other properties of the elastomer are shown in Table 5 below.

[0063] 8) Preparation of rubber composition: The rubber compositions, the formulation of which is given in phr (parts by weight per 100 parts of elastomer) in Table 6 below, were prepared according to the following procedure: the copolymer, the silica and also the various other components, except for the vulcanization system, are continuously introduced into an internal mixer (final degree of filling: about 70% by volume), the initial vessel temperature being about 80° C. Then the thermomechanical processing (non-productive phase) is carried out in one step, lasting about 5 minutes in total, until a maximum "dropping" temperature of 150° C. is reached. The mixture thus obtained is then collected and cooled, after which the sulfur and accelerators are incorporated into the mixer (homofinisher) at 40° C., and everything is mixed for about 10 minutes (productive phase). The compositions thus obtained are subsequently calendered in the form of rubber slabs (2-3 mm thick) or thin sheets for the measurement of their physical or mechanical properties.

[0064] 9) Results: Elastomers CE1 and CE2 are elastomers not according to the invention, and elastomers E1 to E3 are elastomers according to the invention. The polymer properties are shown below in Table 4. The stiffness values ​​of the compositions are shown below in Table 7. Elastomers E1, E2 and E3 show a degree of crystallinity close to zero, much lower than elastomer CE1. The results for the rubber compositions show that elastomer E3 has the property of imparting to the carbon black reinforced rubber compositions a stiffness much lower than that imparted by elastomer CE2. These results regarding the crystallinity of the elastomer and the stiffness of the rubber composition are obtained even with elastomers having a very similar content of ethylene units.

[0065] [Table 2]

[0066] [Table 3]

[0067] [Table 4] Eth: ethylene; Bde: 1,3-butadiene; Myr: myrcene

[0068] [Table 5]

[0069] [Table 6] (1) N375 (2) A 2 / 1 weight ratio mixture of N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine ("Santoflex 6-PPD" from Flexsys) and 2,2,4-trimethyl-1,2-dihydroquinoline. (3) Stearine, Pristerene 4931, from Uniquema (4) Zinc Oxide, Industrial Grade, from Umicore (5) N-Cyclohexyl-2-benzothiazole sulfenamide (Santocure CBS, from Flexsys)

[0070] [Table 7]

Claims

1. Ethylene and a cyclic alkylene compound represented by the following formula (I): CH 2 =CR-CH=CH 2 (I) (The symbol R represents a hydrocarbon chain having 3 to 20 carbon atoms.) with a 1,3-diene, said copolymer having an amine functionality.

2. 10. The copolymer of claim 1, wherein the copolymer contains greater than 50 mole percent ethylene units.

3. 3. The copolymer according to claim 1 or 2, wherein the copolymer contains 1,3-diene units in a 1,2 or 3,4 configuration, and the group consisting of the 1,3-diene units in a 1,2 configuration and the 1,3-diene units in a 3,4 configuration accounts for more than 50 mol % of the 1,3-diene units.

4. 4. Copolymer according to claim 1, wherein the symbol R represents an aliphatic hydrocarbon chain having from 6 to 16 carbon atoms.

5. The copolymer according to any one of claims 1 to 4, wherein the 1,3-diene is myrcene or β-farnesene.

6. The copolymer according to any one of claims 1 to 5, wherein the copolymer has a glass transition temperature of less than -35°C.

7. The copolymer of any one of claims 1 to 6, wherein the amine functional groups are at the chain ends of the copolymer.

8. The copolymer of any one of claims 1 to 7, further comprising a second functional group other than the amine functional group that is a silanol functional group or an alkoxysilane functional group.

9. A rubber composition comprising the copolymer according to any one of claims 1 to 8, a reinforcing filler comprising carbon black or silica or carbon black and silica, and a crosslinking system, wherein the copolymer is an elastomer.

10. A tire comprising the rubber composition of claim 9.

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