Process for the continuous synthesis of modified diene elastomer with lithium amide initiator

Description

[0001] The present invention relates to a process for the continuous synthesis, using several reactors in series, of a modified diene elastomer, making it possible to obtain, in the case of initiation with a lithium amide, a high level of functions in the elastomer other than those provided by the initiator.

[0002] Since fuel savings and the need to protect the environment have become a priority, it is desirable to produce polymers with good mechanical properties and as low a hysteresis as possible in order to be able to implement them in the form of rubber compositions usable for the manufacture of various semi-finished products used in the constitution of tire casings such as, for example, underlayers, rubbers for bonding between rubbers of different natures or for coating metallic or textile reinforcements, sidewall rubbers or treads and to obtain tires with improved properties, in particular having reduced rolling resistance.

[0003] Reducing mixture hysteresis is a constant objective of the tire industry in order to limit fuel consumption and thus preserve the environment.

[0004] To achieve the objective of reducing hysteresis, many solutions have already been tested. In particular, we can cite the modification of the structure of polymers and diene copolymers at the end of polymerization by means of functionalization, coupling or star-forming agents in order to obtain a good interaction between the polymer thus modified and the filler, whether it is carbon black or a reinforcing inorganic filler. We can also cite the use of a functional initiator having a functional group interactive with the filler.

[0005] As an illustration of this prior art, mention may be made of the use of diene elastomers functionalized by alkoxysilane compounds and amine compounds.

[0006] We can cite patent JP4655706B2 which proposes to combine the functionalization of the living chain end with a compound of the alkoxysilane type carrying an amine function at initiation with an amine functional alkyllithium in order to minimize hysteresis. Similarly, in patent application US20120245275A1, it is proposed to combine the functionalization of the living chain end with a compound of the alkoxysilane type carrying an amine function at initiation with a lithium amide but also with a functional monomer of the vinylaminosilane type. We can also cite document WO 2016 / 162528 which discloses a process for synthesizing a modified diene elastomer with the use of different functionalization agents, in particular lithium amides but also n-butyl lithium.Finally, in patent applications WO2015063161A1, WO2015044225A1, WO2015018772A1 and WO2015018600A1, it is proposed to combine initiation with a lithium amide with the reaction of the living chain end with alkoxysilane type compounds carrying different groups having an affinity towards silica.

[0007] As illustrated above, the use of functional initiators possessing an interactive group towards silica such as amine-functional alkyllithium or lithium amides is of interest for reducing rolling resistance by reducing the energy dissipation linked to free chain ends. It therefore seems interesting to be able to use them on an industrial scale in competitive elastomer synthesis processes.

[0008] It is known to those skilled in the art that continuous synthesis processes are more competitive than batch synthesis processes for which frequent stops and restarts are necessary. While the use of lithium amide initiator leads to the joint obtaining of high monomer conversions (greater than 85%) and high levels of living polymer chains in C -< Li +< form in a batch process (greater than or equal to 90%), a high monomer conversion (greater than 85%) is associated with a low level of living polymer chains and therefore with a low level of functionalizable chains (less than 60%) and a high level of living polymer chains, therefore functionalizable (greater than or equal to 90%), is associated with a low monomer conversion (less than 70%) in the case of a conventional continuous process with a reactor.

[0009] The aim of the invention is therefore to identify a continuous synthesis process allowing the joint obtaining of a high conversion into monomers (greater than 70% by mass) and a high rate of living polymer chains (greater than or equal to 90% by number) and therefore a high rate of functionalizable polymer chains at the end of the polymerization step in the case of initiation with a lithium amide. A high rate of living polymer at the end of the polymerization step is desirable in order to be able to functionalize, couple or star the polymer chains as desired.

[0010] The inventors have now surprisingly discovered that the aims of the invention could be obtained by a continuous synthesis process comprising several reactors in series, the mass conversion in the first reactor being less than 70%, the polymerization being continued in such a way that the total mass conversion at the outlet of the last reactor is greater than 70%.

[0011] The subject of the invention is therefore a process for the continuous synthesis of a modified diene elastomer comprising at least one silicon atom directly linked to the elastomer chain comprising: a) a polymerization step using n reactors r1 to rn, equipped with an internal stirring system, assumed to be perfectly stirred, arranged in series, n varying from 2 to 15, preferably from 2 to 9, the reactor r1 being fed with an input solution comprising a solvent, one or more monomers, an anionic polymerization initiator chosen from lithium amides and a polar agent, the mass conversion C1 in the first reactor being less than 70%, one or more of the reactors r2 to rn being optionally further fed by reinjection of a solution, preferably purified, comprising solvent and / or monomers and / or the polar agent, the mass conversion C1 in the first reactor being less than 70%, where C 1 = P 1 / M 1 where P1 is the mass of polymer formed at the outlet of reactor r1, where M1 is the mass quantity of monomer(s) introduced into reactor r1, the total mass conversion Cn at the outlet of reactor rn being greater than or equal to 70%, where Cn = Pn ∑ 1 n Mi where Pn is the mass of polymer formed at the outlet of reactor rn, where Mi is the mass quantity of monomer(s) introduced into reactor ri, i varying from 1 to n, b) a step of modification of the living diene elastomer obtained in the previous step by means of a functionalization, coupling or star-forming agent, which makes it possible to introduce into the elastomer a functional group comprising at least one silicon atom directly linked to the elastomer chain, the functionalizing, coupling or star-forming agent, which makes it possible to introduce into the elastomer a functional group comprising at least one silicon atom directly linked to the elastomer chain, is at least one compound corresponding to formula II: SiR4 n (GOLD') 4-pack (R3-X) c , (Formula II) in which, R3 is a divalent aliphatic, saturated or unsaturated, cyclic or non-cyclic, C 1 -C 18, aromatic C 6 -C 18 hydrocarbon radical; X is a hydrogen atom or a function capable of interacting with a reinforcing filler comprising at least one heteroatom chosen from N, S, O, P; the radicals R', substituted or unsubstituted, identical or different, represent a C 1 -C 10 alkyl group; the radicals R4, substituted or unsubstituted, identical or different, represent a C 1 -C 10 alkyl group; p represents an integer with a value ranging from 0 to 2, q represents an integer with a value 0 or 1, provided that p+q ≤ 2.

[0012] In the context of the present application, the term "possible reinjection" refers to the fact of repeating the injection action into a reactor ri', different from the reactor r1, already supplied with the flow from ri'-1. The reinjection can be done directly into one or more of the reactors, or, advantageously, by mixing with the flow from ri'-1. The reinjection can be done with flows of identical or different composition from the feed flow of r1. When the reinjection takes place in at least two reactors, the natures of these reinjections can be identical or different. The term "reinjected monomer" refers to the monomer injected into ri' not originating from the flow coming from ri'-1.

[0013] Thus, by mass quantity Mi of monomer(s) introduced into the reactor ri, we mean, when i=1, the quantity of monomer(s) contained in the input solution and introduced as such into the reactor 1, and when i=2 to n, the quantity of monomer(s) possibly reinjected into the reactor i.

[0014] Conversion control in all reactors, particularly in the first and last reactors, is ensured by the temperature, residence time, quantity of polar agent and quantity of monomer entering these reactors, as well as the concentration of living polymer. A person skilled in the art knows how to vary these different parameters to control conversions in the different reactors.

[0015] The temperature of each reactor advantageously varies from 20 to 150°C.

[0016] The method according to the invention makes it possible to obtain at the outlet of the last reactor at the end of step a) a rate of living chains greater than or equal to 90% in number relative to the total number of living chains initiated in reactor r1. However, when a solution is reinjected as explained previously, this solution is advantageously purified so as not to degrade the living polymer.

[0017] In the case of anionic polymerization, the living chain is a carbanion. The carbanion is a very reactive species. It reacts with protic species or electrophilic species.

[0018] Also, if the feedstock of the first reactor contains protic impurities (alcohols, water, acids, etc.) or electrophilic impurities (carbonyls, etc.), the initiator will first react with these impurities to produce inactive species (alcoholates, etc.) incapable of initiating the polymerization of the monomers. The difference between the quantity of initiator introduced at the inlet of reactor r1 and the quantity of initiator having reacted with the impurities in reactor r1 constitutes the quantity of active initiator. The number of living chains initiated in reactor r1 is equivalent to this quantity of active initiator in reactor r1.

[0019] Preferably, the number of reactors is 2 or 3, preferably 2.

[0020] Preferably, the mass conversion C1 in the reactor r1 is less than 65%, preferably less than 60%.

[0021] Preferably, the total mass conversion Cn at the outlet of the reactor rn is greater than or equal to 80%, more preferably greater than or equal to 85%.

[0022] Preferably, the residence time in the reactor ri, i varying from 1 to n, is between 1 and 60 minutes, preferably between 5 and 60 minutes, more preferably between 10 and 50 minutes. It is calculated as follows: τ i = V i Q Vi With : Vi, volume of reactor ri, i varying from 1 to n QVi = volume flow rate leaving reactor i.

[0023] As explained previously, according to a particular embodiment, one or more of the reactors r2 to rn is further supplied by reinjection of a solution, preferably purified, comprising solvent and / or monomers and / or polar agent.

[0024] Since the polymer carbanion is a highly reactive species, as explained above, the neutralization of impurities brought by reinjection will be done by the polymer carbanion. This neutralization prevents the polymer chain from continuing to propagate because the chain becomes inactive towards polymerization but also towards functionalization. This species is therefore no longer reactive with any stopping, functionalization, coupling or star-forming agents.

[0025] This is why, apart from the charge of the first reactor, it may be necessary to control the purity of each solution possibly reinjected in order to contribute to the lowest possible rate of dead polymer at the outlet of reactor rn, i.e. less than 10% in number, compared to the total number of chains initiated in reactor r1.

[0026] The purity of a reinjected solution means the mass proportion of any monomer(s), any solvent and any polar agent, relative to the total mass of the reinjected solution.

[0027] The purification step consists of eliminating from the reinjected solution the protic compounds (water, alcohol, acids, etc.) and electrophilic compounds (carbonyl, etc.) which can deactivate the living chain end so as to reduce their quantity in this reinjected solution to a content less than or equal to 5 mol.% of the active initiator, preferably less than or equal to 2 mol.% of the active initiator. By active initiator, we mean the quantity of starting lithium amide type product used as an initiator and not to neutralize the impurities.

[0028] Each re-injected solution contains purified solvent if necessary and / or purified monomers if necessary and / or purified polar agent if necessary.

[0029] The constituent or each constituent of the reinjected solution(s) may, before reinjection, be purified independently by any means of purification usually used to purify constituents, for example by adsorption, liquid / liquid extraction, gas / liquid extraction or distillation.

[0030] The solution to be reinjected, comprising all or part of all of its constituents, may be, before reinjection, purified by any means of purification usually used to purify the constituents, for example by adsorption, liquid / liquid extraction, gas / liquid extraction or distillation.

[0031] By diene elastomer, is meant in a known manner one (meaning one or more) elastomers derived at least in part (i.e., a homopolymer or a copolymer) from diene monomers (monomers bearing two carbon-carbon double bonds, conjugated or not). More particularly, by diene elastomer, is meant any homopolymer obtained by polymerization of a conjugated diene monomer having 4 to 12 carbon atoms, or any copolymer obtained by copolymerization of one or more conjugated dienes with each other or with one or more vinylaromatic monomers having 8 to 20 carbon atoms. In the case of copolymers, these contain from 20% to 99% by weight of diene units, and from 1 to 80% by weight of vinylaromatic units.

[0032] Suitable conjugated dienes which can be used in the process according to the invention are, in particular, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di(C 1 to C 8 alkyl)-1,3-butadiene such as, for example, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene, phenyl-1,3-butadiene, 1,3-pentadiene and 2,4-hexadiene, etc.

[0033] Suitable vinylaromatic monomers include styrene, ortho-, meta-, para-methylstyrene, the commercial mixture "vinyltoluene", para-tert-butylstyrene, methoxystyrenes, vinylmesitylene, divinylbenzene and vinylnaphthalene, etc.

[0034] The diene elastomer is preferably selected from the group of highly unsaturated diene elastomers consisting of polybutadienes (BR), synthetic polyisoprenes (IR), butadiene copolymers, in particular copolymers of butadiene and a vinyl aromatic monomer, isoprene copolymers and mixtures of these elastomers. Such copolymers are more particularly butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR) and isoprene-butadiene-styrene copolymers (SBIR). Among these copolymers, butadiene-styrene copolymers (SBR) are particularly preferred.

[0035] The diene elastomer is prepared by anionic polymerization in the presence of a lithium amide polymerization initiator included in the input solution.

[0036] Lithium amides are the reaction products of an organolithium compound, preferably alkyllithium, and an acyclic or cyclic secondary amine, preferably cyclic.

[0037] As secondary amines which can be used to prepare the initiators, mention may be made of dimethylamine, diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, dipentylamine, dihexylamine, di-n-octylamine, di-(2-ethylhexyl)amine, di-cyclohexylamine, N-methylbenzylamine, diallylamine, morpholine, piperazine, 2,6-dimethylmorpholine, 2,6-dimethylpiperazine, 1-ethylpiperazine, 2-methylpiperazine, 1-benzylpiperazine, piperidine, 3,3-dimethylpiperidine, 2,6-dimethylpiperidine, 1-methyl-4-(methylamino)piperidine, 2,2,6,6-tetramethylpiperidine, pyrrolidine, 2,5-dimethylpyrrolidine, azetidine, hexamethyleneimine, heptamethyleneimine, 5-benzyloxyindole, 3-azaspiro[5,5]undecane, 3-aza-bicycle[3.2.2]nonane, carbazole, bistrimethylsilylamine, pyrrolidine and hexamethyleneimine.

[0038] The secondary amine, when cyclic, is preferably chosen from pyrrolidine and hexamethyleneimine.

[0039] The alkyllithium compound is preferably ethyllithium, n-butyllithium (n-BuLi), isobutyllithium, etc.

[0040] Polymerization is carried out in the presence of a solvent included in the input solution.

[0041] The solvent used in the process according to the invention is preferably an inert hydrocarbon solvent which may be, for example, an aliphatic or alicyclic hydrocarbon such as pentane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane or an aromatic hydrocarbon such as benzene, toluene, xylene.

[0042] As explained above, the input solution, as well as possibly one or more of the reinjected solutions, used in the method according to the invention comprises / comprise a polar agent.

[0043] Suitable polar chelating agents which can be used in the process according to the invention are in particular agents comprising at least one tertiary amine function or at least one ether function and preferably agents of the tetrahydrofurfuryl ethyl ether or tetramethyl ethylenediamine type.

[0044] According to the invention, the living diene elastomer included in the flow leaving the polymerization reactor rn is then reacted with at least one functionalization, coupling or star-forming agent, as defined above, and which makes it possible to introduce into the elastomer a functional group comprising at least one silicon atom directly linked to the elastomer chain.

[0045] The functionalizing, coupling or star-forming agent according to the invention is at least one compound corresponding to formula (II): SiR4 p (OR') 4-pq (R3-X) q , Formula (II) in which, R3 is a divalent aliphatic hydrocarbon radical, saturated or unsaturated, cyclic or not, C 1 -C 18 , aromatic C 6 -C 18 , preferably a divalent, linear or branched, aliphatic hydrocarbon radical, more preferably a linear aliphatic divalent hydrocarbon radical, more preferably still the linear C 2 or C 3 hydrocarbon radical; X is a hydrogen atom or a function capable of interacting with a reinforcing filler comprising at least one heteroatom chosen from N, S, O, P; the radicals R', substituted or unsubstituted, identical or different, represent a C 1 -C 10 alkyl group, or even a C 1 -C 8 alkyl group, preferably a C 1 -C 4 alkyl group, more preferably methyl and ethyl; the radicals R4, substituted or unsubstituted, identical or different, represent a C 1 -C 10 alkyl group, or even a C 1 -C 8 alkyl group;p represents an integer with a value ranging from 0 to 2, q represents an integer with a value of 0 or 1, provided that p+q ≤ 2. ;

[0046] The different aspects concerning formula (II), preferential or not, which precede can be combined with each other.

[0047] According to variants of the invention, the functionalizing agent of formula (II) does not comprise any function other than that comprising the silicon atom of alkoxysilane type. It is then a tetraalkoxysilane, a monoalkyl trialkoxysilane, or a dialkyl dialkoxysilane.

[0048] According to other variants of the invention, the functionalizing agent of formula (II) comprises a function other than the function comprising the silicon atom, in particular capable of interacting with a reinforcing filler. This name does not, however, exclude the possibility for the function comprising the silicon atom to also interact with a reinforcing filler.

[0049] By function capable of interacting with a reinforcing filler, we preferably mean functions comprising at least one heteroatom chosen from N, S, O, P. We can, by way of example, cite among these functions protected or unprotected primary, protected or unprotected secondary or tertiary, cyclic or not amines, isocyanates, imines, cyano, the protected or unprotected thiol function, carboxylates, epoxides, protected or unprotected primary, protected or unprotected secondary or tertiary phosphines.

[0050] Thus, according to variants of the invention, the function capable of interacting with a reinforcing filler is a primary amine, protected or not, secondary amine, protected or not, or tertiary. The nitrogen atom can then be substituted by two groups, identical or different, which can be a trialkyl silyl radical, the alkyl group having 1 to 4 carbon atoms, or a C1-C10 alkyl radical, preferably C1-C4 alkyl, more preferably a methyl or ethyl radical, or the two substituents of the nitrogen form with it a heterocycle containing a nitrogen atom and at least one carbon atom, preferably from 2 to 6 carbon atoms,

[0051] Examples of functionalizing agents whose function capable of interacting with a reinforcing filler is an amine include (N,N-dialkylaminopropyl)trialkoxysilanes, (N,N-dialkylaminopropyl)alkyldialkoxysilanes, (N-alkylaminopropyl)trialkoxysilanes and (N-alkylaminopropyl)alkyldialkoxysilanes whose secondary amine function is protected by a trialkyl silyl group and aminopropyltrialkoxysilanes and aminopropylalkydialkoxysilanes whose primary amine function is protected by two trialkyl silyl groups. The alkyl substituents present on the nitrogen atom are linear or branched and advantageously have from 1 to 10 carbon atoms, preferably 1 to 4, more preferably 1 or 2.For example, suitable alkyl substituents are methylamino-, dimethylamino-, ethylamino-, diethylamino-, propylamino-, dipropylamino-, butylamino-, dibutylamino-, pentylamino-, dipentylamino, hexylamino, dihexylamino, hexamethyleneamino groups, preferably diethylamino and dimethylamino groups. The alkoxy substituents are linear or branched and generally have from 1 to 10 carbon atoms, or even 1 to 8, preferably from 1 to 4, more preferably 1 or 2.

[0052] Preferably, the functionalizing agent may be chosen from 3-(N,N-dialkylaminopropyl)trialkoxysilanes and 3-(N,N-dialkylaminopropyl)alkyldialkoxysilanes, the alkyl group on the silicon atom being the methyl or ethyl group and the alkoxy group being the methoxy or ethoxy group.

[0053] Preferably, the functionalizing agent may be chosen from 3-(N,N-alkyltrimethylsilylaminopropyl)trialkoxysilanes and 3-(N,N-alkyltrimethylsilylaminopropyl)alkyldialkoxysilanes, the alkyl group on the silicon atom being the methyl or ethyl group and the alkoxy group being the methoxy or ethoxy group.

[0054] Preferably, the functionalizing agent may be chosen from 3-(N,N-bistrimethylsilylaminopropyl)trialkoxysilanes and 3-(N,N-bistrimethylsilylaminopropyl)alkyldialkoxysilanes, the alkyl group on the silicon atom being the methyl or ethyl group and the alkoxy group being the methoxy or ethoxy group.

[0055] According to variants of the invention, the function capable of interacting with a reinforcing filler is an isocyanate function. Preferably, the functionalizing agent may be chosen from 3-(isocyanatopropyl)trialkoxysilanes and 3-(isocyanatopropyl)alkyldialkoxysilanes, the alkyl group being the methyl or ethyl group and the alkoxy group being the methoxy or ethoxy group.

[0056] According to variants of the invention, the function capable of interacting with a reinforcing filler is an imine function. Preferably, the functionalizing agent may be chosen from N-(1,3-dimethylbutylidene)-3-(trimethoxysilyl)-1-propanamine, N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine, N-(1,3-methylethylidene)-3-(trimethoxysilyl)-1-propanamine, N-(1,3-methylethylidene)-3-(triethoxysilyl)-1-propanamine, N-ethylidene-3-(trimethoxysilyl)-1-propanamine, N-ethylidene-3-(triethoxysilyl)-1-propanamine, N-(1-methylpropylidene)-3-(trimethoxysilyl)-1-propanamine, N-(1-methylpropylidene)-3-(triethoxysilyl)-1-propanamine, N-(4-N,N-dimethylaminobenzylidene)-3-(trimethoxysilyl)-1-propanamine, N-(4-N,N-dimethylaminobenzylidene)-3-(triethoxysilyl)-1-propanamine, N-(cyclohexylidene)-3-(trimethoxysilyl)-1-propanamine, N-(cyclohexylidene)-3-(triethoxysilyl)-1-propanamine, N-(3-trimethoxysilylpropyl)-4,5-dihydroimidazole,N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole, N-(3-trimethoxysilylpropyl)-4,5-imidazole and N-(3-triethoxysilylpropyl)-4,5-imidazole.,

[0057] According to variants of the invention, the function capable of interacting with a reinforcing filler is a cyano function. Preferably, the functionalizing agent may be chosen from 3-(cyanopropyl)trialkoxysilanes and 3-(cyanopropyl)alkyldialkoxysilanes, the alkyl group being the methyl or ethyl group and the alkoxy group being the methoxy or ethoxy group.

[0058] According to variants of the invention, the function capable of interacting with a reinforcing filler is a thiol function, protected or not. Examples that may be mentioned are (S-trialkylsilylmercaptopropyl)trialkoxysilanes, (S-trialkylsilylmercaptopropyl)alkyldialkoxysilanes, (S-trialkylsilylmercaptoethyl)trialkoxysilanes and (S-trialkylsilylmercaptoethyl)alkyldialkoxysilanes, the alkyl group on the silicon atom bearing the alkoxysilane groups being the methyl or ethyl group and the alkoxy group being the methoxy or ethoxy group. The alkyl group on the silicon linked to the sulfur atom is the methyl or tert-butyl group.

[0059] According to variants of the invention, the function capable of interacting with a reinforcing filler is a carboxylate function. As a carboxylate function, mention may be made of acrylates or methacrylates. Such a function is preferably a methacrylate. Preferably, the functionalizing agent may be chosen from 3-(methacryloyloxypropyl)trialkoxysilanes and 3-(methacryloyloxypropyl)alkyldialkoxysilanes, the alkyl group being the methyl or ethyl group and the alkoxy group being the methoxy or ethoxy group.

[0060] According to variants of the invention, the function capable of interacting with a reinforcing filler is an epoxide function. Preferably, the functionalizing agent may be chosen from 3-(glycidyloxypropyl)trialkoxysilanes and 3-(glycidyloxypropyl)alkyldialkoxysilanes, the alkyl group being the methyl or ethyl group and the alkoxy group being the methoxy or ethoxy group.

[0061] According to variants of the invention, the function capable of interacting with a reinforcing filler is a primary phosphine function, protected or not, secondary, protected or not, or tertiary. Preferably, the functionalizing agent may be chosen from 3-(P,P-bistrimethylsilylphosphinopropyl)trialkoxysilanes, 3-(P,P-bistrimethylsilylphosphinopropyl)alkyldialkoxysilanes, 3-(P,P-alkyltrimethylsilylphosphinopropyl)trialkoxysilanes, 3-(P,P-alkyltrimethylsilylphosphinopropyl)alkyldialkoxysilanes, 3-(P,P-dialkylphosphinopropyl)trialkoxysilanes and 3-(P,P-dialkylphosphinopropyl)alkyldialkoxysilanes, the alkyl group on the phosphorus atom being the methyl, ethyl or phenyl group, the alkyl group on the silicon atom being the methyl or ethyl group and the alkoxy group being the methoxy or ethoxy group.

[0062] The various aspects, preferential or not, which precede and which concern the functionalizing agent of formula (II), in particular as regards the nature of the other function capable of interacting with the reinforcing filler, the nature of the spacer group R3 and the nature of the alkoxysilane group are combinable with each other. According to the process of the invention, it is possible to use a single silicon-based functionalizing, coupling or star-forming agent, as defined above, or a mixture of at least two of these agents.

[0063] The silicon-based functionalizing, coupling or star-forming agent is advantageously in solution in a solvent compatible with that included in the flow from the polymerization reactor rn and feeding the functionalization device. By compatible solvent, we generally mean a solvent miscible with the polymerization solvent. Preferably, this solvent is identical to the polymerization solvent.

[0064] The silicon-based functionalizing, coupling or star-forming agent is added in proportions such that the molar ratio of this silicon-based functionalizing, coupling or star-forming agent to the polymerization initiator depends essentially on the type of modified diene elastomer desired and the number of sites of the functionalizing, coupling or star-forming agent reactive with respect to the living elastomer. By reactive sites, in the context of the invention, is essentially meant Si-OR bonds in formula (II).

[0065] Thus, with a ratio ranging from 0.40 to 0.75, preferably from 0.45 to 0.65 and even more preferably from 0.45 to 0.55, the formation of coupled species within the modified elastomer is favored if the agent of formula (II) has at least two reactive sites with respect to the living elastomer. In the same way, with a ratio ranging from 0.15 to 0.40, preferably from 0.20 to 0.35, star species (3 and / or 4 branches) are mainly formed within the modified elastomer if the agent of formula (II) has at least three reactive sites with respect to the living elastomer. With a ratio greater than or equal to 0.75, preferably greater than 1, we mainly form functionalized species at the end of the chain if the agent has at least one reactive site with respect to the living elastomer.With an excess of agent of formula (II), in particular with a molar ratio of this functionalizing agent to the initiator of at least 2, the levels of species other than the functionalized species at the end of the chain are negligible.

[0066] The molar ratio of this silicon-based functionalizing agent to the polymerization initiator uniquely defines the proportions of end-functionalized chains and non-functional chains in the modified elastomer.

[0067] The silicon-based functionalizing, coupling or star-forming agent is advantageously continuously injected homogeneously into a functionalizing device fed at the inlet of the device by the flow at the outlet of the polymerization reactor rn comprising the living diene elastomer carrying an active site. The term "functionalizing device" means one or more reactors in series. These reactors may be of the same or different nature, in particular tubular, tubular with axial dispersion, stirred or assumed to be perfectly stirred. The continuous injection of at least one functionalizing, coupling or star-forming agent is carried out in at least one of these reactors.

[0068] The residence time in each tubular reactor, or axially dispersed tubular reactor, is preferably between 0 and 120 minutes, in particular between 0.1 and 60 minutes, more preferably between 0.1 and 5 minutes.

[0069] The residence time in each continuous, perfectly stirred reactor or stirred reactor is preferably between 0 and 60 minutes, more preferably between 5 and 50 minutes.

[0070] The functionalization temperature generally varies from 30 to 150°C. Preferably, the functionalization temperature is equal to the temperature within the polymerization reactor immediately preceding the functionalization device.

[0071] With the silicon-based functionalizing, coupling or star-forming agent in accordance with formula (II), a particularly advantageous implementation of the invention consists in using a device for the functionalization of the living diene elastomer in accordance with that described in application FR 3 009 556 A1, the content of which must be considered as forming part of the present application. It is thus possible to proceed in a competitive, economical and flexible manner, adaptable to industrial production, to the synthesis of modified diene elastomers with control of the distribution of functional species (functionalized at the end of the chain and / or coupled and / or star-formed) within the elastomer.

[0072] The functionalization device of this advantageous implementation of the invention with the silicon-based functionalization, coupling or star-forming agent in accordance with formula (II) may have one of the following models: a tubular reactor with axial dispersion, or alternatively, a tubular reactor with axial dispersion in series with at least one continuous stirred reactor, assumed to be perfectly stirred, or alternatively, at least one tubular reactor with axial dispersion, in series with a continuous stirred reactor, assumed to be perfectly stirred, or alternatively, several tubular reactors with axial dispersion in series with several continuous stirred reactors, assumed to be perfectly stirred, or alternatively, at least two continuous stirred reactors, assumed to be perfectly stirred, in series.

[0073] According to a particular embodiment, the living diene elastomer included in the flow at the outlet of the polymerization reactor rn can be reacted with at least two different agents in accordance with formula (II). Mention may be made, for example, of the combination of a trialkoxysilane and an alkyldialkoxysilane, each carrying a function capable of interacting with a preferably identical reinforcing filler, the latter being advantageously chosen from protected or unprotected primary, protected or unprotected secondary or tertiary, cyclic or non-cyclic amines, the protected or unprotected thiol function.

[0074] According to another particular embodiment, possibly combinable with the preceding embodiment, the living diene elastomer included in the flow at the outlet of the polymerization reactor rn can be reacted with, in addition, a coupling or star-forming agent based on silicon or tin. Among these, mention may be made of tin or silicon derivatives of formula MR x Y 4-x , M represents an Sn or Si atom, x represents an integer of value 0 to 2, preferably of value 0 to 1, R represents an alkyl radical of 1 to 10 carbon atoms, preferably an alkyl radical having 1 to 4 carbon atoms, and Y is a halogen atom, preferably chlorine. Examples include compounds such as tin tetrachloride, methyl tin trichloride, dimethyl tin dichloride, tetrachlorosilane, methyltrichlorosilane, and dimethyldichlorosilane.

[0075] The reaction with this complementary coupling or star-forming agent can be carried out in a manner known per se.

[0076] According to the invention, the preferred aspects of this particular embodiment of the process for synthesizing the modified diene elastomer can be combined with the different aspects, preferred or not, of the other embodiments or variants of the process that it completes.

[0077] The process for synthesizing the modified diene elastomer according to the invention can continue in a manner known per se.

[0078] According to variants of the invention, the method may comprise a conventional stopping step using, for example, methanol or water.

[0079] According to the variants of the invention in which the functionalizing agent carries a protected primary or secondary amine function, the synthesis process can continue with a step of deprotection of the primary or secondary amine. This step is carried out after the modification reaction. For example, the chains functionalized by the protected amine group can be reacted with an acid, a base, a fluorinated derivative such as tetrabutylammonium fluoride, a silver salt such as silver nitrate, etc. to deprotect this amine function. These different methods are described in the work "Protective Groups in Organic Synthesis, TW Green, PGM Wuts, Third Edition, 1999". This deprotection step can have the effect of hydrolyzing all or part of the hydrolyzable alkoxysilane functions of the modified diene elastomer to transform them into silanol functions.

[0080] According to the variants of the invention in which the functionalizing agent carries a protected thiol function, the synthesis process can continue with a step of deprotection of the thiol. This step is carried out after the modification reaction. For example, the chains functionalized by the protected thiol group can be reacted with water, an alcohol, or an acid (hydrochloric acid, sulfuric acid, carboxylic acid). This deprotection step can have the effect of hydrolyzing all or part of the hydrolyzable alkoxysilane functions of the modified diene elastomer to transform them into silanol functions.

[0081] According to the variants of the invention in which the functionalizing agent carries a protected primary or secondary phosphine function, the synthesis process can continue with a step of deprotection of the phosphine. This step is carried out after the modification reaction. For example, the chains functionalized by the protected phosphine group can be reacted with water, an alcohol, or an acid (hydrochloric acid, sulfuric acid, carboxylic acid). This deprotection step can have the effect of hydrolyzing all or part of the hydrolyzable alkoxysilane functions of the modified diene elastomer to transform them into silanol functions.

[0082] According to variants of the invention, the synthesis process may comprise a step of hydrolysis of the hydrolyzable alkoxysilane functions, by addition of an acidic, basic or neutral compound as described in document EP 2 266 819 A1. The hydrolyzable functions are then transformed into silanol functions.

[0083] The process for synthesizing the modified diene elastomer according to the invention can continue in a manner known per se with the steps of recovering the modified elastomer.

[0084] According to variants of this process, these steps include a stripping step in order to recover the elastomer from the previous steps in dry form. This stripping step can have the effect of hydrolyzing all or part of the hydrolyzable functions of the modified diene elastomer, in particular the hydrolyzable alkoxysilane functions, transforming them into silanol functions. At least 50 to 70 mol% of the hydrolyzable functions can thus be hydrolyzed.

[0085] The diene elastomers modified according to the process of the invention can be advantageously used in rubber compositions in a mixture with one or more other compounds. Due to the high level of functions, whether they come from the polymerization initiator or from the post-polymerization modification, the diene elastomers thus modified are particularly suitable for optimizing the interactions between the elastomer and the reinforcing filler within a reinforced rubber composition, regardless of the nature of the reinforcing filler.

[0086] The above-mentioned characteristics of the present invention, as well as others, will be better understood upon reading the following description of several exemplary embodiments of the invention, given for illustrative and non-limiting purposes. Measures and tests used Conversion

[0087] Conversions are measured by weighing the dry extract of the solution containing the polymer. In this method, the solution containing the polymer is taken from the reactor outlet. This solution is placed in a previously tared container. The mass of the solution is then weighed.

[0088] The sample is dried at 140°C, under a reduced pressure of 200 mmHg for 15 minutes. The tray is then placed in a desiccator containing silica gel for 2 minutes. Weighing the tray then allows the mass of polymer in the sample taken to be determined. The conversion at the reactor outlet is then calculated via the monomer concentration. C = m extrait sec m échantillon ∑ 1 n Mi ∑ 1 n Qi ⋅ 100 with Σ 1 n Mi which represents the sum of all monomer mass inputs in the total process (reactors 1 to n) Σ 1 n Qi and which represents the sum of all mass inputs in the total process (reactors 1 to n). (Solvent, monomers, catalysts etc.), the report ∑ 1 n Mi ∑ 1 n Qi corresponding to the mass % of monomers Glass transition temperature

[0089] In these examples, the glass transition temperatures (Tg) of the elastomers are determined using a differential scanning calorimeter. Microstructure of elastomers

[0090] The microstructure of elastomers is characterized by the near infrared spectroscopy (NIR) technique.

[0091] Near infrared (NIR) spectroscopy is used to quantitatively determine the mass content of styrene in the elastomer as well as its microstructure (relative distribution of 1,2-, 1,4-trans and 1,4-cis butadiene units). The principle of the method is based on the Beer-Lambert law generalized to a multicomponent system. Since the method is indirect, it uses a multivariate calibration [Vilmin, F.; Dussap, C.; Coste, N. Applied Spectroscopy 2006, 60, 619-29] carried out using standard elastomers of composition determined by 13< C NMR. The styrene content and microstructure are then calculated from the NIR spectrum of an elastomer film of approximately 730 µm thickness. The spectrum acquisition is carried out in transmission mode between 4000 and 6200 cm -1< with a resolution of 2 cm -1< , using a Bruker Tensor 37 Fourier transform near infrared spectrometer equipped with a Peltier-cooled InGaAs detector. Number-average molar mass and polymolecularity index

[0092] The number-average molar mass and the polydispersity index of the polymer are determined using SEC (size exclusion chromatography).

[0093] The SEC (Size Exclusion Chromatography) technique separates macromolecules in solution according to their size through columns filled with a porous gel. The macromolecules are separated according to their hydrodynamic volume, with the largest being eluted first.

[0094] SEC allows the average molar masses and molar mass distributions of a polymer to be understood. From commercial standard products, the different number-average (Mn) and weight-average (Mw) molar masses can be determined and the polydispersity index (Ip = Mw / Mn) calculated via a so-called MOORE calibration.

[0095] There is no special treatment of the polymer sample before analysis. It is simply solubilized in the elution solvent at a concentration of approximately 1 gL -1< . Then the solution is filtered through a 0.45µm porosity filter before injection.

[0096] The equipment used is a "WATERS alliance" chromatographic chain. The elution solvent is either tetrahydrofuran or tetrahydrofuran + 1% vol. diisopropylamine + 1% vol. triethylamine, the flow rate is 1 mL.min -1< , the system temperature is 35° C and the analysis time is 30 min. A set of two WATERS columns with the trade name "STYRAGEL HT6E" is used. The injected volume of the polymer sample solution is 100 µL. The detector is a "WATERS 2410" differential refractometer and the chromatographic data processing software is the "WATERS EMPOWER" system.

[0097] The calculated average molar masses are relative to a calibration curve produced for SBRs with the following microstructure: 28% by mass of styrene-type units, 18% by mass of 1-2-type units, 31% by mass of 1-4-trans-type units and 23% by mass of 1-4-cis-type units. Rate of functionalized chains (CH 3 ) 2 SiOH at the chain end

[0098] The determination of the rate of functionalized chains (CH 3 ) 2 SiOH at the end of the chain is carried out by NMR analysis.

[0099] 2D 1< H- 29< Si NMR allows the nature of the function to be verified using the chemical shift values ​​of the silicon nuclei and protons in the vicinity of 2< J (via 2 bonds). It uses a coupling constant value of 2< J 1< H- 29< Si of 8 Hz. The silicon chemical shift of the SBR(CH 3 ) 2 SiOH species at the chain end is approximately 11-12 ppm.

[0100] 1H NMR allows the quantification of methyl groups carried by silicon (SiCH 3 ) by integration of the corresponding signal, located around δ = 0 ppm. The samples are solubilized in carbon disulfide (CS 2 ). 100 µL of deuterated cyclohexane (C 6 D 12 ) are added for the lock signal. NMR analyses are carried out on a 500 MHz BRUKER spectrometer equipped with a BBIz 5 mm “broadband” probe. For the quantitative 1< H NMR experiment, the sequence uses a 30° pulse and a 2 second repetition delay.

[0101] Thus, knowing the total quantity of chains by the value of Mn obtained by SEC analysis, it is possible to determine the rate of functionalized chains (CH 3 ) 2 SiOH at the end of the chain. Rate of chains functionalized at the chain end with the compound 3-(N,N-dimethylaminopropyl)trimethoxysilane (DMAPTMS)

[0102] The determination of the rate of chains functionalized at the chain end with the compound 3-(N,N-dimethylaminopropyl)trimethoxysilane (DMAPTMS) is carried out by NMR analysis.

[0103] The spectra were acquired on a BRUKER Avance III HD 500 MHz spectrometer equipped with a BBIz-grad mm “broadband” cryoprobe. The quantitative 1< H NMR experiment used a single 30° pulse sequence and a 5-second repetition delay between each acquisition. 64 to 256 accumulations were performed.

[0104] The two-dimensional experiments 1< H / 13< C and 1< H / 29< Si are used to determine the structure of functional polymers.

[0105] The samples are solubilized in carbon disulfide (CS 2 ). 100 µL of deuterated cyclohexane is added to the solution for Lock.

[0106] The final chemical structure of the functional polymer is identified by 1< H, 13< C and 29< Si NMR.

[0107] The 1D 1< H NMR spectrum recorded under quantitative conditions allows the calculation of the rate of 3-(N,N-dimethylaminopropyl)trimethoxysilane grafted onto the polymer. The characteristic signals of the grafted function are observable at 1< H chemical shifts located between 3.25 ppm and 3.40 ppm for the methoxy group (Si-OCH 3 ) and 0.58 ppm to 0.35 ppm for the methylene unit in alpha of silicon (Si-CH 2 -R). The quantification of the rate of function is carried out from the integration of the NMR signals of the methylene protons in alpha of silicon.

[0108] The position of the function on the polymer is confirmed by a two-dimensional 1< H / 29< Si correlation map. The 29< Si NMR signals of 3-(N,N-dimethylaminopropyl)trimethoxysilane grafted at the end of the polymer chain correspond to a block whose chemical shift is between - 10 ppm and - 8 ppm. The 29< Si NMR signals of 3-(N,N-dimethylaminopropyl)trimethoxysilane grafted in the middle of the polymer chain correspond to a block whose chemical shift is between 10 ppm and 9 ppm.

[0109] Thus, knowing the total quantity of chains by the Mn value obtained by SEC analysis, it is possible to determine the rate of 3-(N,N-dimethylaminopropyl)trimethoxysilane functionalized chains at the chain end. Hexamethyleneimine (HMN) initiated chain rate

[0110] The determination of the rate of initiated hexamethyleneimine (HMN) chains is carried out by NMR analysis.

[0111] Samples (approximately 200 mg) are solubilized in approximately 1 mL of carbon disulfide (CS 2 ). 100 µL of deuterated cyclohexane (C 6 D 12 ) are added to the solution for the spectrometer lock.

[0112] The spectra are acquired on a BRUKER Avance 500 MHz spectrometer equipped with a BBIz-grad 5 mm “broadband” cryoprobe.

[0113] The quantitative 1< H NMR experiment uses a single 30° pulse sequence and a 5-second repetition delay between each acquisition. 64 to 1024 accumulations are performed. Two-dimensional 1< H / 13< C experiments were performed to determine the structure of functional polymers. Proton chemical shifts are calibrated against the protonated impurity of CS 2 at 7.18 ppm.

[0114] In the case of a butadiene homopolymer, i.e. a polybutadiene, the quantitative single-pulse 1D 1< H NMR measurement allows the observation of two clusters (2.8 ppm to 3.0 ppm and 2.3 ppm to 2.5 ppm) corresponding respectively to protons 1 and 2.

[0115] The integration of the 2 protons allows to estimate the quantity of HMN units grafted onto a 1,4 butadiene and the integration of the 1 protons allows to estimate the total quantity of HMN units grafted onto the polybutadiene chains.

[0116] In the case of a copolymer of butadiene and styrene, the quantitative single-pulse 1D 1< H NMR measurement allows the observation of a single cluster (2.8 ppm to 3.0 ppm) corresponding to the 2 protons. The integration of the 2 protons allows the estimation of the quantity of HMN units grafted onto a 1,4-butadiene only. The signal of the 1 protons is masked by the aliphatic signal of the SBR matrix. In the case of an SBR, only the quantity of HMN units grafted onto a 1,4-butadiene can therefore be estimated.

[0117] Thus, knowing the total quantity of chains by the value of Mn obtained by SEC analysis, it is possible to determine the rate of HMN initiated chains (only the HMN units linked to a 1,4-butadiene unit are quantifiable in the case of butadiene and styrene copolymers). Examples of elastomer preparation

[0118] In a continuous polymerization pilot plant containing one or more continuous stirred reactors, assumed to be perfectly stirred according to those skilled in the art, methylcyclohexane, butadiene, styrene and tetrahydrofurfuryl ethyl ether are continuously introduced in the proportions described in each example. n-Butyllithium is introduced in sufficient quantity to neutralize the protic impurities brought by the various constituents present in the line inlet and then lithiated hexamethyleneimine is introduced to initiate the polymer chains. The synthesis of lithiated hexamethyleneimine is carried out in situ continuously by reacting one equivalent of hexamethyleneimine and 1.02 equivalents of butyllithium in a perfectly stirred reactor.

[0119] The residence times and concentrations indicated as examples are calculated from the flow rates of the different constituents entering the polymerization process.

[0120] For examples A, B, D, E and G, a sample is taken at the outlet of the reactor rn to determine the polydispersity index of the polymer before modification. The sample of living polymer is stopped by introducing methanol in large molar excess relative to the initiator. The polydispersity index is then measured by size exclusion chromatography.

[0121] Furthermore, at the outlet of the reactor rn, the living elastomer flow is continuously introduced into an axial dispersion tubular reactor continuously supplied with an excess of hexamethylcyclotrisiloxane in cyclohexane to functionalize the living polymer.

[0122] For examples C and F, a sample is taken at the outlet of the reactor rn to determine the polymolecularity index of the polymer before modification. The sample of living polymer is stopped by introducing methanol in large molar excess relative to the initiator. The polymolecularity index is then measured by size exclusion chromatography.

[0123] Furthermore, at the outlet of the reactor rn, the flow of living elastomer is continuously introduced into an axial dispersion tubular reactor continuously supplied with an excess of 3-(N,N-dimethylaminopropyl)trimethoxysilane in solution in methylcyclohexane (molar ratio n(DMAPTMS) / n(living polymer) = 2) to functionalize the elastomer at the chain end. Example A - Comparison - Continuous process with 1 reactor and functionalization of chains with hexamethylcyclotrisiloxane

[0124] A synthesis of butadiene / styrene polymer is carried out according to a comparative process using a single stirred reactor, assumed to be perfectly stirred.

[0125] The operating conditions are specified in Table 1. Table 1 Operating conditions Value Unit Reactor Number of reactors 1 - - Reactor volume 14 L 1 %Styrene (1) 33 % 1 % mass of monomers (2) 12 % 1 Polar agent (tetrahydrofurfuryl ethyl ether) 3,51.10 -4< Mol / L 1 Active initiator (lithium hexamethyl eneimine) 6,45.10 -4< Mol / L 1 Stay time 30 Min 1 Temperature 90 °C 1 Mass conversion (3) 86 % 1 (1) by weight relative to the sum of all mass inputs of monomers in the process (2) by weight relative to the sum of all mass inputs of the process (3) mass conversion into monomers in the reactor

[0126] The characteristics of the polymer obtained at the reactor outlet are given in Table 2. Table 2 Vinyl rate (4) 25,5 % Styrene rate (5) 28 % Tg -45 °C Ip 2,0 - Mn 124,0 kg / mol Quantity of HMN functions 6,0 mmol / kg HMN initiated chain rates (6) 75 % Quantity of functions (CH 3 ) 2 SiOH 4,3 mmol / kg Rate of functionalized chains (CH 3 ) 2 SiOH (7) 54 % (4) by weight relative to the butadiene units present in the polymer chains (5) by weight relative to the butadiene and styrene units (6) molar ratio between the quantity of HMN functions determined by NMR and the number of chain ends calculated from the Mn value measured on the elastomer recovered at the end of the functionalization step with hexamethylcyclotrisiloxane. (7) molar ratio between the quantity of (CH 3 ) 2 SiOH functions determined by NMR and the number of chain ends calculated from the Mn value measured on the elastomer recovered at the end of the functionalization step with hexamethylcyclotrisiloxane. Example B - According to the invention - Continuous process with 2 reactors in series with 50% conversion in the 1st reactor and functionalization of the chains with hexamethylcyclotrisiloxane

[0127] A synthesis of styrene / butadiene polymer is carried out according to a process according to the invention using 2 stirred reactors, assumed to be perfectly stirred in series.

[0128] The operating conditions are specified in Table 3. Table 3 Operating conditions Value Unit Reactor Number of reactors 2 - - Reactor volume 14 L 1 14 2 %Styrene (1) 38 % 1 % mass of monomers (2) 12 % 1 Polar agent (tetrahydrofurfuryl ethyl ether) 8,8.10 -5< Mol / L 1 Active initiator (lithium hexamethyleneimine) 5,43.10 -4< Mol / L 1 Stay time 30 Min 1 30 Min 2 Temperature 55 °C 1 75 °C 2 Mass conversion (3) 45 % 1 88 % 2 (1) by weight relative to the sum of all mass inputs of monomers in the process (2) by weight relative to the sum of all mass inputs of the process (3) mass conversion into monomers at the outlet of the reactor

[0129] The characteristics of the polymer obtained at the outlet of reactor 2 are given in Table 4. Table 4 Vinyl rate (4) 25 % Styrene rate (5) 28 % Tg -45 °C Mn 150,5 kg / mol IP 1,6 - Quantity HMN functions 4,9 mmol / kg HMN initiated chain rates (6) 73 % Quantity functions (CH 3 ) 2 SiOH 6,5 mmol / kg Rate of functionalized chains (CH 3 ) 2 SiOH (7) 97 % (4) by weight relative to the butadiene units present in the polymer chains (5) by weight relative to the butadiene and styrene units (6) molar ratio between the quantity of HMN functions determined by NMR and the number of chain ends calculated from the Mn value measured on the elastomer recovered at the end of the functionalization step with hexamethylcyclotrisiloxane. (7) molar ratio between the quantity of (CH 3 ) 2 SiOH functions determined by NMR and the number of chain ends calculated from the Mn value measured on the elastomer recovered at the end of the functionalization step with hexamethylcyclotrisiloxane.

[0130] Thus, this example shows that it is possible to obtain, concomitantly with the continuous process according to the invention, a high conversion and a high rate of functionalized chains. Example C - According to the invention - Continuous process with 2 reactors in series with 50% conversion in the 1st reactor and functionalization of the chains with 3-(N,N-dimethylaminopropyl)trimethoxysilane

[0131] A synthesis of styrene / butadiene polymer is carried out according to a process according to the invention using 2 stirred reactors, assumed to be perfectly stirred in series.

[0132] The operating conditions are specified in Table 5. Table 5 Operating conditions Value Unit Reactor Number of reactors 2 - - Reactor volume 14 L 1 14 2 %Styrene (1) 38 % 1 % mass of monomers (2) 12 % 1 Polar agent (tetrahydrofurfuryl ethyl ether) 8,8.10 -5< Mol / L 1 Active initiator (lithium hexamethyleneimine) 5,43.10 -4< Mol / L 1 Stay time 30 Min 1 30 Min 2 Temperature 55 °C 1 75 °C 2 Mass conversion (3) 45 % 1 88 % 2 (1) by weight relative to the sum of all mass inputs of monomers in the process (2) by weight relative to the sum of all mass inputs of the process (3) mass conversion into monomers at the reactor outlet

[0133] The characteristics of the polymer obtained at the outlet of reactor 2 are given in table 6. Table 6 Vinyl rate (4) 25 % Styrene rate (5) 28 % Tg -45 °C Mn 148,5 kg / mol IP 1,6 - Quantity HMN functions 4,8 mmol / kg HMN initiated chain rates (6) 72 % Quantity of DMAPTMS functions 6,5 mmol / kg DMAPTMS functionalized chain rates (7) 95 % (4) by weight relative to the butadiene units present in the polymer chains (5) by weight relative to the butadiene and styrene units (6) molar ratio between the quantity of HMN functions determined by NMR and the number of chain ends calculated from the Mn value measured on the elastomer recovered at the end of the functionalization step with DMAPTMS. (7) molar ratio between the quantity of DMPATMS functions determined by NMR and the number of chain ends calculated from the Mn value measured on the elastomer recovered at the end of the functionalization step with DMAPTMS.

[0134] Thus, this example shows that it is possible to obtain, concomitantly with the continuous process according to the invention, a high conversion and a high rate of functionalized chains. Example D - Comparison - Continuous process with 2 reactors in series with 75% conversion in the 1st reactor and functionalization of the chains with hexamethylcyclotrisiloxane

[0135] A synthesis of styrene / butadiene polymer is carried out according to a process according to the invention using 2 stirred reactors, assumed to be perfectly stirred in series.

[0136] The operating conditions are specified in Table 7. Table 7 Operating conditions Value Unit Reactor Number of reactors 2 - - Reactor volume 14 L 1 14 2 %Styrene (1) 30 % 1 % mass of monomers (2) 12 % 1 Polar agent (tetrahydrofurfuryl ethyl ether) 1,9.10 -4< Mol / L 1 Active initiator (lithium hexamethyleneimine) 6,01.10 -4< Mol / L 1 Stay time 30 Min 1 30 Min 2 Temperature 75 °C 1 90 2 Mass conversion (3) 74 % 1 95 % 2 (1) by weight relative to the sum of all mass inputs of monomers in the process (2) by weight relative to the sum of all mass inputs of the process (3) mass conversion into monomers at the reactor outlet

[0137] The characteristics of the polymer obtained at the outlet of reactor 2 are given in table 8. Table 8 Vinyl rate (4) 25,5 % Styrene rate (5) 28 % Tg -45 °C Mn 145,0 kg / mol IP 1,8 - Quantity HMN functions 5,1 mmol / kg HMN initiated chain rates (6) 75 % Quantity functions (CH 3 ) 2 SiOH 3,9 mmol / kg Rate of functionalized chains (CH 3 ) 2 SiOH (7) 58 % (4) by weight relative to the butadiene units present in the polymer chains (5) by weight relative to the butadiene and styrene units (6) molar ratio between the quantity of HMN functions determined by NMR and the number of chain ends calculated from the Mn value measured on the elastomer recovered at the end of the functionalization step with hexamethylcyclotrisiloxane. (7) molar ratio between the quantity of (CH 3 ) 2 SiOH functions determined by NMR and the number of chain ends calculated from the Mn value measured on the elastomer recovered at the end of the functionalization step with hexamethylcyclotrisiloxane.

[0138] Thus, this comparative example shows that if the conversion into monomers is too high in reactor 1 then the rate of functionalized chains is less than 90% at the outlet of reactor 2. Example E - According to the invention - Continuous process with 2 reactors in series with 60% conversion in the first reactor and functionalization of the chains with hexamethylcyclotrisiloxane

[0139] A synthesis of styrene / butadiene polymer is carried out according to a process according to the invention using 2 stirred reactors, assumed to be perfectly stirred in series.

[0140] The operating conditions are specified in Table 9. Table 9 Operating conditions Value Unit Reactor Number of reactors 2 - - Reactor volume 14 L 1 14 2 %Styrene (1) 33 % 1 % mass of monomers (2) 12 % 1 Polar agent (tetrahydrofurfuryl ethyl ether) 1,2.10 -4< Mol / L 2 Active initiator (lithium hexamethyleneimine) 5,6.10 -4< Mol / L 2 Stay time 30 Min 1 30 Min 2 Temperature 65 °C 1 80 2 Mass conversion (3) 61 % 1 93 % 2 (1) by weight relative to the sum of all mass inputs of monomers in the process (2) by weight relative to the sum of all mass inputs of the process (3) mass conversion into monomers at the reactor outlet

[0141] The characteristics of the polymer obtained at the outlet of reactor 2 are given in table 10. Table 10 Vinyl rate (4) 25 % Styrene rate (5) 28 % Tg -46 °C Mn 152,5 kg / mol IP 1,7 - Quantity HMN functions 4,9 mmol / kg HMN initiated chain rates (6) 75 % Quantity functions (CH 3 ) 2 SiOH 6,0 mmol / kg Rate of functionalized chains (CH 3 ) 2 SiOH (7) 90 % (4) by weight relative to the butadiene units present in the polymer chains (5) by weight relative to the butadiene and styrene units (6) molar ratio between the quantity of HMN functions determined by NMR and the number of chain ends calculated from the Mn value measured on the elastomer recovered at the end of the functionalization step with hexamethylcyclotrisiloxane. (7) molar ratio between the quantity of (CH 3 ) 2 SiOH functions determined by NMR and the number of chain ends calculated from the Mn value measured on the elastomer recovered at the end of the functionalization step with hexamethylcyclotrisiloxane.

[0142] Thus, this example shows that it is possible to obtain, concomitantly with the continuous process according to the invention, a high conversion and a high rate of functionalized chains. Example F - According to the invention - Continuous process with 2 reactors in series with 60% conversion in the first reactor and functionalization of the chains with 3-(N,N-dimethylaminopropyl)trimethoxysilane

[0143] A synthesis of styrene / butadiene polymer is carried out according to a process according to the invention using 2 stirred reactors, assumed to be perfectly stirred in series.

[0144] The operating conditions are specified in Table 11. Table 11 Operating conditions Value Unit Reactor Number of reactors 2 - - Reactor volume 14 L 1 14 2 %Styrene (1) 33 % 1 % mass of monomers (2) 12 % 1 Polar agent (tetrahydrofurfuryl ethyl ether) 1,2.10 -4< Mol / L 2 Active initiator (lithium hexamethyleneimine) 5,6.10 -4< Mol / L 2 Stay time 30 Min 1 30 Min 2 Temperature 65 °C 1 80 2 Mass conversion (3) 63 % 1 95 % 2 (1) by weight relative to the sum of all mass inputs of monomers in the process (2) by weight relative to the sum of all mass inputs of the process (3) mass conversion into monomers at the reactor outlet

[0145] The characteristics of the polymer obtained at the outlet of reactor 2 are given in table 12. Table 12 Vinyl rate (4) 25 % Styrene rate (5) 28 % Tg -46 °C Mn 154,2 kg / mol IP 1,7 - Quantity HMN functions 5,1 mmol / kg HMN initiated chain rates (6) 77 % Quantity functions DMAPTMS 6,0 mmol / kg DMAPTMS functionalized chain rates (7) 92 % (4) by weight relative to the butadiene units present in the polymer chains (5) by weight relative to the butadiene and styrene units (6) molar ratio between the quantity of HMN functions determined by NMR and the number of chain ends calculated from the Mn value measured on the elastomer recovered at the end of the functionalization step with DMAPTMS. (7) molar ratio between the quantity of DMAPTMS functions determined by NMR and the number of chain ends calculated from the Mn value measured on the elastomer recovered at the end of the functionalization step with DMAPTMS.

[0146] Thus, this example shows that it is possible to obtain, concomitantly with the continuous process according to the invention, a high conversion and a high rate of functionalized chains. Example G - According to the invention - Continuous process with 3 reactors in series and functionalization of the chains with hexamethylcyclotrisiloxane

[0147] A synthesis of butadiene / styrene polymer is carried out according to a process according to the invention using 3 stirred reactors, assumed to be perfectly stirred in series.

[0148] The operating conditions are specified in Table 13. Table 13 Operating conditions Value Unit Reactor Number of reactors 3 - - Reactor volume 14 L 1 14 2 14 3 %Styrene (1) 28 % 1 % mass of monomers (2) 12 % 1 Polar agent (tetrahydrofurfuryl ethyl ether) 8,8.10 -5< Mol / L - Active initiator (lithium hexamethyleneimine) 5,81.10 -4< Mol / L 1 Stay time 30 Min 1 30 Min 2 30 Min 3 Temperature 50 °C 1 70 °C 2 80 °C 3 Conversion 41 % 1 mass (3) 72 % 2 94 % 3 (1) by weight relative to the sum of all mass inputs of monomers in the process (2) by weight relative to the sum of all mass inputs of the process (3) mass conversion into monomers at the reactor outlet

[0149] The characteristics of the polymer obtained at the outlet of reactor 3 are given in table 14. Table 14 Vinyl rate (4) 25,5 % Styrene rate (5) 27,5 % Tg -46 °C Ip 1,45 - Mn 147,4 kg / mol Quantity HMN functions 5,1 mmol / kg HMN initiated chain rates (6) 76 % Quantity functions (CH 3 ) 2 SiOH 6,6 mmol / kg Functionalized chain rates (CH 3 ) 2 SiOH (7) 96 % (4) by weight relative to the butadiene units present in the polymer chains (5) by weight relative to the butadiene and styrene units (6) molar ratio between the quantity of HMN functions determined by NMR and the number of chain ends calculated from the Mn value measured on the elastomer recovered at the end of the functionalization step with hexamethylcyclotrisiloxane. (7) molar ratio between the quantity of (CH 3 ) 2 SiOH functions determined by NMR and the number of chain ends calculated from the Mn value measured on the elastomer recovered at the end of the functionalization step with hexamethylcyclotrisiloxane.

[0150] Thus, this example shows that it is possible to obtain, concomitantly with the continuous process according to the invention, a high conversion and a high rate of functionalized chains.

Claims

1. Process for the continuous synthesis of a modified diene elastomer comprising at least one silicon atom directly connected to the elastomer chain, comprising: a) a stage of polymerization by means of n reactors r1 to rn which are equipped with an internal stirring system, which are assumed perfectly stirred and which are arranged in series, n varying from 2 to 15, the reactor r1 being fed by an input solution comprising a solvent, one or more monomer(s), an anionic polymerization initiator chosen from lithium amides and a polar agent, the conversion by weight C1 in the first reactor being less than 70%, where C1 = P1 / W1 where P1 is the weight of polymer formed at the outlet of the reactor r1, where W1 is the amount by weight of monomer(s) introduced into the reactor r1, the total conversion by weight Cn at the outlet of the reactor rn being greater than or equal to 70%, where: C n = P n ∑ 1 n W i where Pn is the weight of polymer formed at the outlet of the reactor rn, and Wi is the amount by weight of monomer(s) introduced into the reactor ri, i varying from 1 to n, b) a stage of modification of the living diene elastomer obtained in the preceding stage by means of a functionalization, coupling or star-branching agent, which makes it possible to introduce, into the elastomer, a functional group comprising at least one silicon atom directly connected to the elastomer chain, the functionalization, coupling or star-branching agent which makes it possible to introduce, into the elastomer, a functional group comprising at least one silicon atom directly connected to the elastomer chain, is at least one compound corresponding to the formula (II):         SiR4p(OR')4-p-q(R3-X)q,     (Formula II) in which: - R3 is a saturated or unsaturated, cyclic or non-cyclic, divalent C1-C18 aliphatic hydrocarbon radical or divalent C6-C18 aromatic hydrocarbon radical, preferably a linear or branched, divalent aliphatic hydrocarbon radical, more preferably a linear divalent aliphatic hydrocarbon radical and more preferably still the linear C2 or C3 hydrocarbon radical; - X is a hydrogen atom or a functional group capable of interacting with a reinforcing filler comprising at least one heteroatom chosen from N, S, O or P; - the R' radicals, which are substituted or unsubstituted and identical or different, represent a C1-C10, indeed even C1-C8, alkyl group, preferably a C1-C4 alkyl group, more preferably methyl and ethyl; - the R4 radicals, which are substituted or unsubstituted and identical or different, represent a C1-C10 alkyl group, indeed even a C1-C8 alkyl group; - p represents an integer with a value ranging from 0 to 2 and q represents an integer with the value 0 or 1, with the proviso that p + q ≤ 2.

2. Process according to Claim 1, characterized in that n varies from 2 to 3.

3. Process according to either one of the preceding claims, characterized in that the conversion by weight C1 in the reactor r1 is less than 65%.

4. Process according to any one of the preceding claims, characterized in that the total conversion by weight Cn at the outlet of the reactor rn is greater than or equal to 80%.

5. Process according to any one of the preceding claims, characterized in that the diene elastomer is a copolymer of butadiene and of a vinylaromatic monomer.

6. Process according to any one of the preceding claims, characterized in that the residence time in the reactor ri, i varying from 1 to n, is between 1 and 60 minutes.

7. Process according to any one of the preceding claims, characterized in that the functionalization, coupling or star-branching agent does not comprise another functional group than that comprising the silicon atom of alkoxysilane type.

8. Process according to any one of claims 1 to 6, characterized in that the functional group capable of interacting with a reinforcing filler is a protected or unprotected primary amine, a protected or unprotected secondary amine or a tertiary amine which is cyclic or non-cyclic, an isocyanate, an imine, a cyano, the protected or unprotected thiol functional group, a carboxylate, an epoxyde or a protected or unprotected primary phosphine, a protected or unprotected secondary phosphine or a tertiary phosphine.

9. Process according to claim 8, characterized in that the functional group capable of interacting with a reinforcing filler is an amine chosen from (3-N,N-dialkylaminopropyl)trialkoxysilanes, (3-N,N-dialkylaminopropyl)alkyldialkoxysilanes, (3-N,N-alkyltrimethylsilylaminopropyl)trialkoxysilanes, (3-N,N-alkyltrimethylsilylaminopropyl)alkyldialkoxysilanes, (3-N,N-bistrimethylsilylaminopropyl)trialkoxysilanes or (3-N,N-bistrimethylsilylaminopropyl)alkyldialkoxysilanes, the alkyl groups being methyl or ethyl and the alkoxy groups being methoxy or ethoxy.

10. Process according to Claim 8, characterized in that the functional group capable of interacting with a reinforcing filler is a protected or unprotected thiol functional group chosen from (S-trialkylsilylmercaptopropyl)trialkoxysilanes, (S-trialkylsilylmercaptopropyl)alkyldialkoxysilanes, (S-trialkylsilylmercaptoethyl)trialkoxysilanes and (S-trialkylsilylmercaptoethyl)alkyldialkoxysilanes, the alkyl group on the silicon atom bearing the alkoxysilane groups being the methyl or ethyl group, the alkoxy group being the methoxy or ethoxy group and the alkyl group on the silicon bonded to the sulfur atom being the methyl or tert-butyl group.

11. Process according to any one of Claims 1 to 10, characterized in that it comprises a complementary stage of coupling or star-branching by means of a coupling or star-branching agent based on tin or silicon derivatives of formula MRxY4-x, in which M represents a Sn or Si atom, x represents an integer with a value from 0 to 2, preferably with a value from 0 to 1, R represents an alkyl radical of 1 to 10 carbon atoms, and Y is a halogen atom.

12. Process according to any one of the preceding Claims, characterized in that, at stage a), one or more of the reactors r2 to rn additionally being optionally fed by reinjection of a preferably purified solution comprising solvent and / or monomers and / or polar agent.