Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/12—Hydrolysis
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/18—Introducing halogen atoms or halogen-containing groups
  • C08F8/20—Halogenation
  • C08F8/22—Halogenation by reaction with free halogens
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
  • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains

Definitions

• the present invention relates to copolymers of conjugated diene and monoolefin, which copolymer carries at least one functional group, as well as to a process for their preparation.
• the modifications of polymers already known may consist of a post-polymerization modification, which modification takes place on the previously synthesized polymer, such as, for example, the hydrogenation reaction or the functional grafting along the polymer chain, in the copolymerization of polymers.
• a functional monomer in the use of a functionalizing agent in the polymer chain termination reaction or in the polymer chain initiation reaction.
• This method which uses a functional transfer agent, allows not only the synthesis of conjugated diene copolymer and monoolefin, which copolymer carries a function on one end of the copolymer chain, but also opens the way to the synthesis of diene copolymers. conjugate and telechelic or hetero-telechelic monoolefin.
• a first subject of the invention is a copolymer comprising a copolymer chain A carrying a function B selected from the group consisting of the functions Bl and B2,
• the copolymer chain A being a copolymer chain comprising monomer units M1 and monomer units M2, M1 being a conjugated diene and M2 being a monomer chosen from the group consisting of ⁇ -monoolefins, ethylene and their mixtures,
• B1 is selected from the group consisting of N (SiMe 3 ) 2 ; N (SiMe 2 CH 2 CH 2 SiMe 2 ); para-C 6 H 4 (NMe 2 ); para-C 6 H 4 (OMe); para-C 6 H 4 (N (SiMe 3 ) 2); ortho-CH 2 -C 6 H 4 NMe 2; ortho-CH 2 -C 6 H 4 OMe; C 6 F 5 ; C 3 F 7 ; C 6 F 13 ; CH (OCH 2 CH 2 0);
• Another object of the invention is a process for preparing the copolymer according to the invention.
• Another subject of the invention is the use of a transfer agent of formula (III) in the copolymer synthesis according to the invention,
• od is an integer of 0 to 50, preferably 0 to 11; wherein B1 is selected from the group consisting of N (SiMe 3 ) 2 ;
• the invention also relates to a compound of formula (II), an intermediate compound in the synthesis of the copolymer according to the invention,
• the invention also relates to a rubber composition comprising the copolymer according to the invention.
• 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., terminals a and b excluded) while any interval of values denoted by “from a to b” means the range from “a” to "b” (i.e., including the strict limits a and b).
• base-based composition in the present description a composition comprising the mixture and / or the reaction product in situ of the different constituents used, some of these basic constituents (for example the elastomer, the filler or other additive conventionally used in a rubber composition intended for the manufacture of a tire) being capable of or intended to react with one another, at least in part during the various phases of manufacture of the composition intended for the manufacture of a tire.
• the copolymer according to the invention has the essential characteristic of comprising a copolymer chain A.
• the copolymer chain A comprises monomer units M1 and monomer units M2, M1 being a conjugated diene and M2 being a monomer chosen from the group consisting of ⁇ -monoolefins, ethylene and mixtures thereof.
• M1 being a conjugated diene
• M2 being a monomer chosen from the group consisting of ⁇ -monoolefins, ethylene and mixtures thereof.
• the respective molar percentage of the monomer units M1 and monomer units M2 in the copolymer chain A is strictly greater than 0.
• the monomer units M1 result from the insertion of the monomer M1, a conjugated diene, in the growing copolymer chain A, in particular by a 1,2 or 1,4 addition.
• conjugated diene means one or more conjugated dienes.
• M 1 represents a mixture of conjugated dienes
• the monomer units M 1 designate the monomeric units resulting from the insertion of each of the conjugated dienes.
• the monomer units M2 result from the insertion of the monomer M2 into the growing copolymer chain A, M2 being preferably ethylene or a monomer mixture of an ⁇ -monoolefin and ethylene.
• ⁇ -monoolefin is understood to mean one or more ⁇ -monoolefins.
• M2 represents a monomer mixture, that is to say a mixture of several monomers
• the monomer units M2 designate the monomer units resulting from the insertion of each of the monomers of the monomer mixture.
• conjugated diene mention may be made of 1,3-dienes, particularly a conjugated diene selected from the group consisting of 1,3-butadiene, isoprene and their mixture.
• M1 is 1,3-butadiene.
• ⁇ -monoolefins aliphatic or aromatic ⁇ -monoolefins, especially aliphatic ⁇ -monoolefins having preferably 3 to 18 carbon atoms, such as propene, 1-butene, 1-hexene, octene, 1-hexadecene or mixtures thereof.
• the monomer units M 1 represent more than 40%, preferably more than 60 mol% of the monomer units of the copolymer.
• the monomer units M1 represent less than 35 mol% of the monomer units of the copolymer.
• the ethylene units represent more than 50%, preferably more than 65 mol% of the monomer units of the copolymer.
• the monomer units M 1 contain more than 80 mol% of unit resulting from a 1,4-trans insertion of M 1 in the copolymer chain.
• the copolymer preferably contains less than 0.5 mol% of aliphatic hydrocarbon cyclic units, more preferably is free of such units, the cyclic unit containing a 5 or 6 carbon atoms.
• the copolymer according to the invention is a copolymer of M 1 and M 2, in particular a copolymer of 1,3-butadiene and ethylene or a terpolymer of 1,3-butadiene. , ethylene and an ⁇ -monoolefin as defined above.
• the copolymer preferably has a number-average molar mass (M n) of at least 5000 g / mol, more preferably at least 60 000 g / mol. mol, a particularly advantageous minimum value for use of the copolymer as an elastomer for example in a tire rubber composition.
• M n number-average molar mass
• its average molar mass in number does not exceed 1 500 000 g / mol; beyond this value, the viscosity of the copolymer can make the use of the copolymer difficult.
• It preferably has a polydispersity index D equal to Mw / Mn (Mw being the weight average molar mass) of between 1.20 and 3.00.
• M n, M w and D are measured according to the method described in paragraph 11.1.
• the copolymer chain A has another essential characteristic of carrying a function B.
• the function B can be attached to the copolymer chain directly by a covalent bond or by means of a divalent group of formula (I)
• w is an integer from 1 to 50, preferably from 1 to 11.
• w is equal to 3.
• the function B is carried at the end of the copolymer chain A.
• the function B is chosen from the group constituted by the functions B1 and B2.
• B1 is selected from the group consisting of N (SiMe 3 ) 2 ; N (SiMe 2 CH 2 CH 2 SiMe 2 ); para-C 6 H 4 (NMe 2 ); para- C 6 H 4 (OMe); para-C 6 H 4 (N (SiMe 3 ) 2 ); ortho-CH 2 -C 6 H 4 NMe 2 ; ortho-CH 2 -C 6 H 4 OMe; C 6 F 5 ; C 3 F 7 ; C 6 F 13; CH (OCH 2 CH 2 0).
• B2 is a function derived from Bl.
• function deriving from B1 is meant a function which is obtained by modifying the function B1 according to the reactions known to those skilled in the art.
• Function B1 is advantageously N (SiMe 2 CH 2 CH 2 SiMe 2 ) or N (SiMe 3 ) 2 .
• the function B2 is advantageously chosen from the group consisting of amines, ammoniums and ketones. When B2 is an amine, it is typically obtained by deprotection of the N (SiMe 2 CH 2 CH 2 SiMe 2 ) or N (SiMe 3 ) 2 group , optionally followed by alkylation, according to reactions well known to humans. of career.
• B2 When B2 is an ammonium, it can be obtained by modification of the same N (SiMe 2 CH 2 CH 2 SiMe 2 ) or N (SiMe 3 ) 2 groups , for example by quaternization reaction according to methods well known to the human being. job.
• B2 When B2 is a ketone, it is advantageously obtained by deprotection of the acetal functional group CH (OCH 2 CH 2 0), a process also well known to those skilled in the art.
• B2 is an amine, primary, secondary or tertiary, preferably a primary amine.
• the function B is the function B1.
• the copolymer carries a second function, function Z.
• the function Z is preferably carried on a chain end of the copolymer A.
• the copolymer carries a function B and a function Z both end the two functions are carried respectively by different ends: the copolymer is said telechelic or heterotelechelic in the particular case where Z is different from B.
• the Z function is preferably selected from halogens, groups having a carbon-to-carbon unsaturated bond and heteroatom-containing functions selected from S, N, Si, O, B and P.
• the copolymer is preferably linear.
• the copolymer according to the invention may be prepared by the process described below.
• the process for preparing the copolymer has the essential characteristic of comprising the following steps (a) and (b), and optionally the following step (c): (A) the preparation of a compound of formula (II)
• o 2 or 3
• Y is aluminum
• d is an integer from 0 to 50, advantageously from 0 to 11;
• B1 is selected from the group consisting of N (SiMe 3 ) 2 ; N (SiMe2CH2CH2SiMe2); para-C 6 H 4 (NMe 2 ); para-C 6 H 4 (OMe); para-C 6 H 4 (N (SiMe 3 ) 2); ortho-CH 2 -
• step (b) is a reaction of the compound of formula (II) with a compound having an acid proton, said stopper (or stopper agent).
• stopper may be mentioned water, carboxylic acids including fatty acids, C 2 -C 8, such as acetic acid, stearic acid, aliphatic or aromatic alcohols, such as methanol, ethanol, isopropanol, phenolic antioxidants, primary or secondary amines such as antioxidants having the diaminophenylene unit.
• This variant of the process makes it possible to synthesize a copolymer comprising a monofunctional copolymer chain, since the copolymer chain A of the copolymer carries the B1 function at the end of the chain provided by step (a) of the process.
• step (b) is a reaction of the compound of formula (II) with a functionalising agent.
• the functionalization reaction involves the breaking of the bond formed by Y and the carbon both adjacent to Y and belonging to the copolymer chain A.
• the functionalizing agent is chosen by those skilled in the art for its reactivity vis-à-vis -vis this connection and for the chemical nature of the Z function it carries. Since step (b) is then a functionalization reaction, the method makes it possible to access, according to this other variant, a telechelic or hetero-telechelic copolymer, since one end of the copolymer chain A bears the function Bl brought by step (a), and the other end the Z function provided by step (b).
• the termination reaction is conducted by bringing the polymerization reaction medium into contact with a terminating agent, whether it is a stopper or a functionalizing agent, at a monomer conversion ratio chosen by those skilled in the art according to the desired macrostructure of the copolymer.
• Step (c) is an optional step depending on whether or not it is desired to transform the function B1, in particular into the function B2.
• the embodiment of the method which comprises step (c) can be applied to the two variants of the method described above. In some very particular embodiments, step (c) can be conducted simultaneously with step (b).
• step (b) and (c) are concomitant, mention may be made of the case where step (b) is a termination reaction with an acidic compound and step (c) is a reaction. deprotection of the B1 function under acidic conditions.
• step (c) is a deprotection reaction of the B1 function in B2, conducted in an acidic or basic medium depending on the chemical nature of the function B1 to be deprotected.
• the trimethylsilyl group which protects the amine function can be hydrolysed in an acidic or basic medium.
• the choice of the deprotection conditions is judiciously made by those skilled in the art taking into account the chemical structure of the substrate to be deprotected.
• copolymer prepared according to the process according to the invention can be separated from the reaction medium of step (b) or (c) according to processes well known to those skilled in the art, for example by an operation of evaporation of the solvent under reduced pressure or by a stripping operation with steam.
• Step (a) of the process according to the invention requires the preparation of the compound of formula (II).
• the compound of formula (II) may be prepared by the copolymerization of a monomer mixture containing the monomer M1 and the monomer M2 in the presence of a catalytic system comprising a transfer agent of formula (III) and a metallocene catalyst,
• Y, B1, d and y being as defined above, in particular in the various described embodiments of the invention.
• copolymerization of a monomer mixture containing a conjugated diene and a monoolefin such as ethylene, ⁇ -monoolefins or a mixture thereof can be carried out in accordance with patent applications EP I 092 731, WO 2004035639, WO2005028526, WO 2007054223 and WO 2007054224. knowing that the co-catalyst of the catalyst systems described in these documents is replaced in this case by the transfer agent. Furthermore, those skilled in the art adapt the polymerization conditions described in these documents so as to achieve the desired microstructure and macrostructure of the copolymer chain A.
• the molar ratio of the transfer agent on the metal Met constituting the metallocene catalyst is preferably in a range from 1 to 100, more preferably is greater than or equal to 1 and less than 10.
• the range of values from 1 to less than 10 is particularly favorable for obtaining copolymers of high molar masses.
• those skilled in the art adapt the polymerization conditions and the concentrations in each of the reagents (components of the catalyst system, monomers, stopper), depending on the equipment (tools, reactors) used to conduct the polymerization and the various chemical reactions.
• the copolymerization as well as the handling of the monomers, the catalyst system and the polymerization solvent or solvents are carried out under anhydrous conditions and under an inert atmosphere.
• the polymerization solvents are typically hydrocarbon, aliphatic or aromatic solvents.
• the monomer M1 is preferably a monomer selected from the group consisting of 1,3-butadiene, isoprene and their mixture, more preferably 1,3-butadiene.
• the monomer M2 is preferably ethylene or a mixture of ethylene and an ⁇ -monoolefin.
• Suitable ⁇ -monoolefins are those mentioned above, namely the aliphatic or aromatic ⁇ -monoolefins, particularly the aliphatic ⁇ -monoolefins having preferably 3 to 18 carbon atoms, such as propene, 1-butene, 1- hexene, 1-octene, 1-hexadecene or mixtures thereof.
• the transfer agent is preferably of formula (III-a) or (III-b), with d ranging from 1 to 11, preferably being equal to 3.
• d is equal to 3 is advantageous. in particular from the point of view of the accessibility of the transfer agent, since the reagent necessary for its synthesis is a commercial product or a product also easily accessible by synthesis.
• the transfer agent may be prepared by reaction of the metal Y-shaped, said reagent with a substrate of formula X- (CH 2 ) d -B1, B1 and d being as defined above, X being a halogen, preferably a bromine atom.
• the transfer agent of formula (III) is preferably prepared by reacting AICI 3 with a derivative of a compound of formula X- (CH 2 ) d -B 1 described above, which derivative may be an ionic salt based on lithium or potassium, for example of the respective formula Li (CH 2 ) d -Bl or K (CH 2 ) d -Bl or their complexed form with a solvent, as is well known in the compounds organometallic compounds based on lithium or potassium.
• the transfer agent is typically synthesized under operating conditions generally used in the synthesis of organometallic compounds, i.e.
• the metallocene catalyst is a metallocene comprising the unit (in English "moiety") of formula (IV-1)
• Met being a Group 4 metal atom or a rare earth metal atom
• Cp 1 and Cp 2 identical or different, being selected from the group consisting of cyclopentadienyl groups, indenyl groups and fluorenyl groups, the groups may be substituted or unsubstituted,
• P being a group bridging the two groups Cp 1 and Cp 2 , and comprising at least one silicon or carbon atom.
• the Met atom is connected to a ligand molecule consisting of two groups Cp 1 and Cp 2 interconnected by the bridge P.
• the metallocene catalyst is a metallocene comprising the unit (in English "moiety") of formula (IV-2)
• Met is a Group 4 metal atom or a rare earth metal atom
• Cp 1 and Cp 2 identical or different, being selected from the group consisting of cyclopentadienyl groups, indenyl groups and fluorenyl groups, the groups may be substituted or not.
• the rare earths are metals and denote the elements scandium, yttrium and lanthanides whose atomic number varies from 57 to 71.
• substituted cyclopentadienyl, fluorenyl and indenyl groups mention may be made of those substituted by alkyl radicals having 1 to 6 carbon atoms or by aryl radicals having 6 to 12 carbon atoms.
• the choice of radicals is also oriented by accessibility to the corresponding molecules that are cyclopentadienes, fluorenes and substituted indenes, because they are commercially available or easily synthesizable.
• a bridged metallocene of formula (IV-1) as a cyclopentadienyl group substituted, there may be mentioned particularly those substituted in the 2 or 3 position, such as tetramethylcyclopentadienyl, 3-trimethylsilylcyclopentadienyl groups.
• Position 2 (or 5) denotes the position of the carbon atom which is adjacent to the carbon atom to which bridge P is attached, as shown in the diagram below.
• substituted fluorenyl groups that may be mentioned more particularly include 2,7-ditertiobutyl-fluorenyl and 3,6-di-tert-butyl-fluorenyl groups.
• the positions 2, 3, 6 and 7 respectively denote the position of the carbon atoms of the rings as shown in the diagram below, the position 9 corresponding to the carbon atom in which the bridge P. is attached.
• substituted cyclopentadienyl group there may be mentioned 3-trimethylsilylcyclopentadienyl, tetramethylcyclopentadienyl groups; as the substituted indenyl group, mention may be made of methylindenyl and phenylindenyl groups; substituted fluorenyl groups that may be mentioned are 2,7-di-tert-butyl-fluorenyl and 3,6-di-tert-butyl-fluorenyl.
• Cp 1 represents a substituted or unsubstituted cyclopentadienyl group and Cp 2 represents a substituted or unsubstituted fluorenyl group. More preferably, Cp 1 is unsubstituted cyclopentadienyl and Cp 2 is unsubstituted fluorenyl.
• the symbol P corresponds to the formula MR 1 R 2 , M representing a silicon or carbon atom, preferably a silicon atom, R 1 and R 2 , which may be identical or different, representing an alkyl group comprising from 1 to 20 carbon atoms. More preferably, the bridge P is of formula SiR 1 R 2 , R 1 and R 2 , being as defined above. Even more preferably, it meets the SiMe 2 formula.
• the Met symbol preferably represents a rare earth metal atom, more preferably a lanthanide atom (Ln) whose atomic number is from 57 to at 71, even more preferably a neodymium atom (Nd).
• the metallocene catalyst is of formula (IV-la) or (IV-2b)
• Met represents a rare earth metal atom
• the Met symbol preferably represents a lanthanide atom (Ln) whose atomic number ranges from 57 to 71, more preferably a neodymium atom ( nd).
• Ln lanthanide atom
• nd neodymium atom
• the metallocene may be in the form of crystallized powder or not in the form of single crystals.
• the metallocene may be in a monomeric or dimer form, these forms depending on the mode of preparation of the metallocene, as for example this is described in the applications WO 2007054223 and WO 2007054224.
• the metallocene can be prepared in a traditional manner by a process analogous to that described in documents EP I 092 731, WO 2007054223 and WO 2007054224, in particular by reaction under inert and anhydrous conditions of the alkali metal salt of the ligand with a rare earth salt such as a rare earth halide or borohydride, or a salt of a Group 4 metal in a suitable solvent, such as an ether, such as diethyl ether or tetrahydrofuran or any other solvent known to man of the 'art.
• a suitable solvent such as an ether, such as diethyl ether or tetrahydrofuran or any other solvent known to man of the 'art.
• the metallocene is separated from the reaction by-products by techniques known to those skilled in the art, such as filtration or precipitation in a second solvent.
• the metallocene is finally dried and isolated in solid form.
• Cp 1 represents a substituted or unsubstituted cyclopentadienyl group and Cp 2 represents a substituted or unsubstituted fluorenyl group. More preferably, Cp 1 is unsubstituted cyclopentadienyl and Cp 2 is unsubstituted fluorenyl.
• the unsubstituted fluorenyl group has the formula Ci 3 H 8 .
• the metallocene catalyst is preferably a metallocene lanthanide borohydride or a lanthanide metallocene halide, especially a metallocene lanthanide chloride.
• the symbol G denotes chlorine or the group of formula (IV)
• L represents an alkali metal selected from the group consisting of lithium, sodium and potassium
• N represents a molecule of an ether
• x integer or not, is equal to or greater than 0,
• c integer, is equal to or greater than 0.
• ether any ether which has the power to complex the alkali metal, including diethyl ether and tetrahydrofuran.
• the metallocene catalyst is of formula (IV-3a) or (IV-3b) or (IV-3c).
• the use of the transfer agent provides access to the copolymers according to the invention, whether they are monofunctional end chain or telechelic.
• Such copolymers correspond in particular to the following formulas (V) and (VI) HA- (CH 2 ) d (V)
• Another subject of the invention is the compound of formula (II), the preparation of which is required in step (a) of the process according to the invention,
• d is an integer of 0 to 50, preferably 0 to 11;
• B1 being selected from the group consisting of N (SiMe 3 ) 2 ; N (SiMe 2 CH 2 CH 2 SiMe 2 ); para- C 6 H 4 (NMe 2 ); para-C 6 H 4 (OMe); para-C 6 H 4 (N (SiMe 3 ) 2 ); ortho-CH 2 -C 6 H 4 NMe 2 ; ortho-CH 2 -C 6 H 4 OMe; C 6 F 5 ; C 3 F 7 ; C 6 F 13 ; CH (OCH 2 CH 2 0). More particularly, the compound of formula (II) is such that Y is Mg, B1 is N (SiMe 2 CH 2 CH 2 SiMe 2 ) or N (SiMe 3 ) 2 and d is 1 to 11 or equal at 3.
• the copolymer according to the invention especially when it is an elastomer, can be used in a rubber composition, in particular in a semi-finished tire product.
• the rubber composition according to the invention may contain in addition to the copolymer any ingredient traditionally used in a tire rubber composition, such as, for example, a reinforcing filler such as a carbon black or a silica, a plasticizer system, a system crosslinking, in particular vulcanization, one or more antioxidants.
• SEC analyzes were performed at high temperature (HT-SEC) using a Viscotek (Malvern I nstruments) instrument equipped with 3 columns (PLgel Olexis 300mm x 7mm ID from Agilent Technologies) and 3 detectors (refractometer, viscometer and light scattering). 200 ⁇ l of a solution of the sample at a concentration of 5 mg ml 1 were eluted in 1,2,4-trichlorobenzene using a flow rate of 1 ml min -1 at 150 ° C. The mobile phase was stabilized with 2,6-di (tert-butyl) -4-methylphenol (200 mg L 1 ). OmniSEC software was used for data acquisition and analysis. The number-average molar masses M n and the polydispersity index D were calculated by universal calibration using polystyrene standards.
• High resolution NMR spectroscopy was performed on a Bruker DRX 400 spectrometer operating at 400 M Hz for the proton and 101 M Hz for the carbon 13. The acquisitions were made at 363 K using a 5 mm Q.NP probe for 1 H and a 10 mm PSEX probe for 13 C NMR. The samples were analyzed at a concentration of 5-15% by weight. A mixture of tetrachlorethylene (TCE) and deuterated benzene (C6D6) (2/1 v / v) was used as the solvent. The chemical shifts are given in ppm units, relative to tetramethylsilane as internal reference for the RM N 1H and the methylene signal at 30 ppm of the chain of ethylene units for 13 C.
• TCE tetrachlorethylene
• C6D6D6D6 deuterated benzene
• microstructure of the ethylene / butadiene copolymers is determined by NMR 13 C according to the method described in Macromolecules 2001, 34, 6304-6311. II.2-Example of preparation of a transfer agent:
• 2,5-disilacyclopentane having the formula - (CH 2 ) 3 -N (SiMe 2 CH 2 CH 2 SiMe 2 ))
• the solution is transferred under an argon atmosphere to a 250 mL reactor.
• Argon is removed under vacuum and the reactor is pressurized to 4 bar using a gaseous mixture of ethylene / 1,3-butadiene monomer of constant composition (5 mol% of 1,3-butadiene) at 70 ° C.
• the reactor is degassed after 2 hours of polymerization and the temperature is reduced to 20 ° C.
• the polymerization medium is poured into 1M methanol / HCl solution and stirred for 1 hour.
• the precipitated polymer is solubilized in toluene and is then precipitated in a methanol solution to be washed. The polymer is finally dried.
• the composition of the copolymer is 95.6 mol% of ethylene.
• the 1,3-butadiene is inserted at 24.7% mol 1,4-trans, 11.0% mol 1,2 and 64.3% mol in the form of rings.
• Example 2 The same procedure as in Example 2 is followed for the synthesis of this copolymer but with a mixture of 20% mol monomer of 1,3-butadiene.
• composition of the copolymer is 80.0 mol% of ethylene. 1,3-butadiene is inserted at
• composition of the copolymer is 80.1 mol% of ethylene.
• the 1,3-butadiene is inserted at 17.5% mol 1,4-trans, 45,2% mol 1,2 and 37,3% mol in the form of rings.
• Example 4 The same procedure as in Example 4 is followed for the synthesis of this copolymer, but the polymerization this time lasts 4 hours.
• composition of the copolymer is 79.3 mol% of ethylene. 1,3-butadiene is inserted at
• Example 2 The same procedure as in Example 2 is followed for the synthesis of this copolymer but with a monomer mixture containing 30 mol% of 1,3-butadiene.
• the composition of the copolymer is 75.3 mol% of ethylene.
• the 1,3-butadiene is inserted at 25.7% mol 1,4-trans, 44.2% mol 1,2 and 30.1% mol in the form of rings.
• the argon is removed under vacuum and the reactor is pressurized to 4 bars using a gaseous mixture of monomer ethylene / 1,3-butadiene of constant composition (20 mol% of
• 1,3-butadiene at 80 ° C.
• the reactor is degassed after 90 minutes of polymerization and the temperature is reduced to 20 ° C.
• the polymerization medium is poured into 1M methanol / HCl solution and stirred for 1 hour.
• the precipitated polymer is solubilized in toluene, then precipitated in a methanol solution to be washed.
• the polymer is finally dried.
• composition of the copolymer is 67.6 mol% of ethylene and 32.4% of butadiene.
• 1,3-butadiene is inserted in two forms, 97.4 mol% of 1,4-trans units and 2,6 mol% of 1,2 units.
• Example 8 II.3-Examples of preparation of monofunctional copolymers, involving a step (c) of modification of the function:
• step (c) being a hydrolysis reaction in a basic medium:
• Example 2 A fraction of the polymer of Example 2 is taken (10 g). The polymer is solubilized in toluene and then precipitated with a methanol / NaOH solution (1M) and stirred for 1 hour at room temperature.
• the polymer is recovered and then washed with methanol and dried under vacuum at 60 ° C.
• step (c) being a hydrolysis reaction in a basic medium:
• a fraction of the polymer of Example 3 is taken (8 g).
• the polymer is solubilized in toluene and then precipitated with a methanol / NaOH solution (1M) and stirred for 1 hour at room temperature.
• the polymer is recovered and then washed with methanol and dried under vacuum at 60 ° C.
• step (c) being a hydrolysis reaction in a basic medium
• a fraction of the polymer of Example 4 is taken (7 g).
• the polymer is solubilized in toluene and then precipitated with a methanol / NaOH solution (1M) and stirred for 1 hour at room temperature.
• the polymer is recovered and then washed with methanol and dried under vacuum at 60 ° C.
• step (c) being a hydrolysis reaction in a basic medium
• Example 5 A fraction of the polymer of Example 5 is taken (13 g). The polymer is solubilized in toluene and then precipitated with a methanol / NaOH solution (1M) and stirred for 1 hour at room temperature.
• the polymer is recovered and then washed with methanol and dried under vacuum at 60 ° C.
• step (c) being a hydrolysis reaction in a basic medium
• a fraction of the polymer of Example 6 is taken (3 g).
• the polymer is solubilized in toluene and then precipitated with a methanol / NaOH solution (1M) and stirred for 1 hour at room temperature.
• the polymer is recovered and then washed with methanol and dried under vacuum at 60 ° C.
• the solution is transferred under an argon atmosphere to a 250 mL reactor.
• the argon is removed under vacuum and the reactor is pressurized to 4 bars by means of a gaseous mixture of monomer ethylene / 1,3-butadiene of constant composition (20% molar 1,3-butadiene) at 70 ° C.
• the reactor is degassed after 2 hours of polymerization and the temperature of the reaction medium is maintained at 70 ° C.
• a 100 ml sample of the reaction medium is then carried out. This sample is poured into a 1M methanol / HCl solution and stirred for 1 hour. The precipitated reference polymer is solubilized in toluene and is then precipitated in a methanol solution to be washed.
• the polymer is finally dried.
• the composition of the reference copolymer is 80.8 mol% of ethylene. 1,3-butadiene is inserted at 18.7% mol 1,4-trans, 39.9% mol 1,2 and 41.4% mol in the form of rings.
• the temperature is reduced to 20 ° C.
• the polymerization medium is poured into a 1M methanol / HCl solution and stirred for 1 hour.
• the precipitated polymer is solubilized in toluene and is then precipitated in a methanol solution to be washed. The polymer is finally dried.

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