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    • 专利摘要:
    The invention relates to a modified diene elastomer comprising: a) at least 70% by weight, based on the total weight of the modified diene elastomer, of a diene elastomer functionalized at one end of the chain by a silanol function or a block polysiloxane having a silanol end and having a polymolecularity index before functionalization less than or equal to 1.6, b) more than 0 and up to 30% by weight, relative to the total weight of the modified diene elastomer, of a diene diene elastomer having a polymolecularity index before staring less than or equal to 1.6, the Mooney viscosity of said modified diene elastomer ranging from 30 to 80.
    公开号:FR3023293A1
    申请号:FR1456373
    申请日:2014-07-03
    公开日:2016-01-08
    发明作者:Charlotte Dire；Florent Vaultier；Margarita Dorato；Jean Marc Marechal
    申请人:Michelin Recherche et Technique SA Switzerland ；Compagnie Generale des Etablissements Michelin SCA；Michelin Recherche et Technique SA France；
    IPC主号:
    专利说明:

    [0001] The invention relates to a modified diene elastomer comprising at least 70% by weight of a specific diene elastomer functionalized at the end of the chain with a silanol function or with a silanol function. a polysiloxane block having a silanol end and at most 30% by weight of a specific star-diene elastomer, the Mooney viscosity of said modified diene elastomer ranging from 30 to 80. Since the fuel savings and the need to preserve the environment are become a priority, it is desirable to produce mixtures having a hysteresis as low as possible so as to be able to implement them in the form of rubber compositions that can be used for the manufacture of various semi-finished products used in the composition of tire casings such as, for example, underlays, flanks, and to obtain tires with reduced rolling resistance. The reduction of the hysteresis of the mixtures is a permanent objective which must, however, be carried out while preserving intact the processability, particularly the green, of the mixtures, while maintaining the creep resistance of the elastomers.
    [0002] To achieve the goal of lower hysteresis, many solutions have already been tested. In particular, mention may be made of modifying the structure of the diene polymers and copolymers at the end of polymerization by means of functionalising, coupling or starring agents in order to obtain a good interaction between the polymer thus modified and the load, be it carbon black or a reinforcing inorganic filler.
    [0003] In the context of mixtures containing a reinforcing inorganic filler, it has been proposed to use diene copolymers functionalized with silanol groups. We can cite the patents FR2951178B1 and EP778311B1 which describe the use of diene polymers functionalized with a silanol group at the chain end. In the patent FR2951178B I, the functional polymers are described as associated with star polymers using tin-based compounds. More recently, patent application WO2009077837A1 describes elastomers functionalized with a silanol group at one chain end and with an amino group at the other chain end. These elastomers are also described as being capable of being associated with star-shaped elastomers, in particular with silicon or tin. The associations illustrated, however, lead to a reinforced rubber composition whose compromise implementation of the composition / hysteresis of the composition / creep of the elastomer is not satisfactory for pneumatic application. It turns out that the compositions described in the prior art do not always have a satisfactory hysteresis and an acceptable implementation for use in tread. There is therefore a need to provide a chain-end silanol functionalized elastomer for obtaining rubber compositions having improved raw / hysteresis compromise while maintaining the creep resistance of the elastomer. The object of the present invention is therefore to provide such a composition. One objective is in particular to provide a functionalized elastomer satisfactorily interacting with the reinforcing filler of a rubber composition containing it in order to reduce the hysteresis thereof, while maintaining an acceptable raw implementation and creep resistance. satisfactory elastomer, especially for use in tread for tires.
    [0004] This object is achieved in that the inventors have surprisingly discovered in the course of their research that a modified diene elastomer comprising at least 70% by weight, relative to the total weight of the modified diene elastomer, of an elastomer diene functionalized at the chain end by a silanol function or a polysiloxane block having a silanol end, having a narrow molecular weight distribution before functionalization, and at most 30% by weight, relative to the total weight of the modified diene elastomer, d a star-diene elastomer having a narrow molecular weight distribution prior to staring, the Mooney viscosity of said modified diene elastomer ranging from 30 to 80, gives the rubber compositions containing it an improvement in the compromise implemented in raw / hysteresis while retaining intact the creep resistance of the elastomer. The subject of the invention is therefore a modified diene elastomer comprising: a) at least 70% by weight, relative to the total weight of the modified diene elastomer, of a diene elastomer functionalized at one end of a chain by a silanol function or a polysiloxane block having a silanol chain end, and having a polymolecularity index before functionalization less than or equal to 1.6, b) more than 0 and up to 30% by weight, relative to the total weight of the elastomer modified diene, of a star-diene elastomer and having a polymolecularity index before staring less than or equal to 1.6, the Mooney viscosity of said modified diene elastomer ranging from 30 to 80.
    [0005] The invention also relates to a reinforced rubber composition based on at least one reinforcing filler and an elastomeric matrix comprising at least said modified diene elastomer. In the present description, unless expressly indicated otherwise, all the percentages (%) indicated are% by weight.
    [0006] On the other hand, any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e. terminals a and b excluded) while any range of values designated by the term "from a to b" means the range from a to b (i.e., including the strict limits a and b). By the term "composition-based" is meant a composition comprising the mixture and / or the reaction product of the various constituents used, some of these basic constituents being capable of or intended to react with one another, less in part, during the various phases of manufacture of the composition, in particular during its crosslinking or vulcanization. In the present description, the term "diene elastomer" is understood to mean a diene elastomer which comprises a group comprising one or more heteroatoms. This grouping can be at the end of the chain. It will then be said that the diene elastomer is functionalized at the end or end of the chain. This is generally an elastomer obtained by reacting a living elastomer with a functionalizing agent, that is to say any molecule that is at least monofunctional, the function being any type of chemical group known to those skilled in the art for reacting with a piece of living chain. This grouping can be in the linear main elastomeric chain. It will be said that the diene elastomer is coupled or functionalized in the middle of the chain, as opposed to the position "at the end of the chain" and although the group is not precisely in the middle of the elastomeric chain. It is generally an elastomer obtained by reaction of a living elastomer on a coupling agent, that is to say any molecule at least difunctional, the function being any type of chemical group known to those skilled in the art to react. with a piece of living chain. This group can be central to which n elastomer chains (n> 2) are linked forming a star structure. It will then be said that the diene elastomer is starred. It is generally an elastomer obtained by reaction of a living elastomer on a starzing agent, that is to say any multifunctional molecule, the function being any type of chemical group known to those skilled in the art to react with a piece of living chain.
    [0007] By diene elastomer, it is to be understood in a known manner (is meant one or more) elastomer derived at least in part (ie, a homopolymer or a copolymer) of monomers dienes (monomers bearing two carbon-carbon double bonds, conjugated or not ). More particularly, diene elastomer is 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 one another or with one or more vinylaromatic compounds. having from 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. Conjugated dienes which can be used in the process according to the invention are especially suitable for 1,3-butadiene, 2-methyl-1,3-butadiene and 2,3-di (C 1 -C 5 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-1-butadiene, 3-isopropyl-1,3-butadiene, phenyl-1,3-butadiene, 1,3-pentadiene and 2,4-hexadiene, etc. Examples of suitable vinylaromatic compounds are styrene, ortho-, meta, para-methylstyrene, the commercial "vinyltoluene" mixture, para-tert-butylstyrene, methoxystyrenes, vinylmesitylene, divinylbenzene and vinylnaphthalene, and the like. The diene elastomer is preferably chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (BR), synthetic polyisoprenes (IR) and butadiene copolymers, in particular copolymers of butadiene and of a vinyl aromatic monomer, copolymers of isoprene and mixtures of these elastomers. Such copolymers are more particularly copolymers of butadiene-styrene (SBR), copolymers of isoprene-butadiene (BIR), copolymers of isoprene-styrene (SIR) and copolymers of isoprene-butadiene-styrene (SBIR) . Among these copolymers, butadiene-styrene copolymers (SBR) are particularly preferred.
    [0008] The diene elastomer may have any microstructure which is a function of the polymerization conditions used. The elastomer may be block, random, sequence, microsequential, etc. and be prepared in dispersion or in solution. In the case of anionic polymerization, the microstructure of these elastomers may be determined by the presence or absence of a randomizing agent and the amounts of randomizing agent employed. For the purposes of the invention, the term "polymolecularity index" means the ratio of average molecular weight to number average molecular weight. The weight and number average molecular weights are measured by size exclusion chromatography. According to a preferred embodiment, the modified diene elastomer according to the invention comprises at least 80% by weight, relative to the total weight of the modified diene elastomer, of the functionalized diene elastomer a). According to another preferred embodiment, the modified diene elastomer according to the invention comprises at most 20% by weight, relative to the total weight of the modified diene elastomer, of the diene diene elastomer b).
    [0009] According to a particularly preferred embodiment, the modified diene elastomer according to the invention comprises at least 80% by weight, relative to the total weight of the modified diene elastomer, of the functionalized diene elastomer a) and at most 20% by weight, based on the total weight of the modified diene elastomer, of the diene diene elastomer b). The polysiloxane block having a silanol end of the diene functionalized end-group diene elastomer may have the following general formula: [- (SiRiR 2 O) '- H] in which: R 1 and R 2, identical or different, represent a group alkyl, cycloalkyl, aryl, alkaryl, aralkyl, vinyl having 1 to 10 carbon atoms. x is an integer ranging from 1 to 1500 and preferably from 1 to 50, more preferably x is 1. Preferably, R 1 and R 2 represent an alkyl group having from 1 to 6 carbon atoms. More preferably, R 1 and R 2 each represent a methyl radical. According to the invention, the functionalized diene elastomer bearing at the chain end a silanol function or a polysiloxane block having a silanol end is monofunctional. In other words, the diene elastomer is functionalized at one end of the chain. The other end of the chain is free and has no function. The diene diene elastomer b) is preferably a stellar diene elastomer based on tin or silicon. The diene diene elastomer b) is preferably a four-branched diene diene elastomer. The functionalized diene elastomer a) carrying at the chain end a silanol function or a polysiloxane block having a silanol end and the diene diene elastomer b) may have before functionalization and starring the same microstructure or a different microstructure. Preferably, the functionalized diene elastomer a) and the diene diene elastomer b) have before functionalization and starring the same microstructure. More preferably, the functionalized diene elastomer a) and the diene diene elastomer b) have before functionalization and starring the same microstructure and the same macrostructure. The modified diene elastomer according to the invention can be obtained by a process as described below.
    [0010] The first step of a process for preparing the modified diene elastomer is the anionic polymerization of at least one conjugated diene monomer in the presence of a polymerization initiator.
    [0011] As a polymerization initiator, any known monofunctional anionic initiator can be used. However, an initiator containing an alkali metal such as lithium is used in a preferred manner. Suitable organolithium initiators include those having a carbon-lithium bond. Preferably, use will be made of an organolithium hydrocarbon initiator having no heteroatom. Representative compounds are aliphatic organoliths such as ethyllithium, isobutyl lithium, etc.
    [0012] The polymerization is preferably n-butyllithium (n-BuLi), carried out in the presence of 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.
    [0013] The polymerization can be carried out continuously or discontinuously. The polymerization is generally carried out at a temperature of between 20 ° C. and 120 ° C. and preferably in the region of 30 ° C. to 110 ° C. It is of course also possible to add at the end of the polymerization a transmetallation agent for modifying the reactivity of the living-chain end. The living diene elastomer resulting from the polymerization is then functionalized to prepare the modified diene elastomer according to the invention. According to a first variant of the preparation of the modified diene elastomer according to the invention, the end-chain functionalized diene elastomer is mixed with a silanol function or a polysiloxane block having a silanol chain end and the star-diene elastomer, in the appropriate proportions.
    [0014] The diene elastomer functionalized at the chain end by a silanol function or a polysiloxane block having a silanol end can advantageously be obtained according to the procedures described in the patent application EP-A-0 778 311.
    [0015] The starchy diene elastomer can be obtained in a manner known per se by reacting the living end of chain with a staring agent, that is to say any multifunctional molecule, the function being any type of chemical group known by the human the art to react with a piece of living chain. Preferably, the starch agents are agents based on tin or silicon with a functionality greater than 2, and which can be represented by the formulas SnRX3, Sn1-1X3, SnX4, SiRX3, SiHX3, SiX4, SiR (OR ) 3, Si (OR) 4 with R being an alkyl, araikyl or vinyl group having 1 to 20 carbon atoms and X a halogen.
    [0016] The two elastomers can be mixed in an inert solvent, for example an aliphatic or alicyclic hydrocarbon such as pentane, hexane, heptane, isooctane, cyclohexane or an aromatic hydrocarbon such as benzene or toluene. xylene, which may be the same as the polymerization solvent. The mixing will then be carried out at a temperature of between 20 ° C. and 120 ° C. and preferably in the region of 30 ° C. to 110 ° C. According to a second variant of preparation of the modified diene elastomer according to the invention, the living diene elastomer resulting from the polymerization stage is subjected to the reaction of a starch agent and to that of a functionalizing agent. capable of introducing at the end of the polymer chain the silanol function or the polysiloxane block having a silanol end. As a functionalization agent capable of introducing, at the end of the polymer chain, the silanol function or the polysiloxane block having a silanol end, mention may be made of the agents of cyclic polysiloxane type in order to obtain an elastomer having an SiO- end and this in a medium that does not allow the polymerization of said cyclopolysiloxane.
    [0017] Cyclic polysiloxanes which may be mentioned are those corresponding to the formula: R 1 - Si-O-m R 2 in which: R 1 and R 2, which may be identical or different, represent an alkyl, cycloalkyl, aryl, alkaryl, aralkyl or vinyl group having from 1 to 10 carbon atoms, m represents an integer of value 3 to 8.
    [0018] Preferred cyclic polysiloxane compounds include hexamethylcyclotrisiloxane, trimethyltriethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and mixtures thereof. Preferred starch agents include tin tetrachloride or tetrachlorosilane. Thus, for example, the functionalization of the living diene elastomer resulting from the polymerization step can be carried out at a temperature ranging from 20 to 120 ° C., in the presence initially of an appropriate amount of an agent starring for starring at most 30% by weight of the living diene elastomer. Then, in a second step, the remaining living chains of the diene elastomer obtained after the first step are functionalized by adding a functionalizing agent capable of introducing at the end of the polymer chain the silanol function or the polysiloxane block having one end. silanol and reaction with this agent. The functionalization reaction of the diene elastomer is then stopped by deactivation of the remaining living chains and by reaction of the SiO- chain ends with a proton-donating compound to yield the modified diene elastomer according to the invention.
    [0019] The modified diene elastomer according to the invention has satisfactory creep resistance, which induces a good resistance during storage and transport of this rubber. The modified diene elastomer according to the invention may advantageously be used, for pneumatic application, in a rubber composition reinforced with at least one inorganic filler such as silica, the compromise of which is advantageously implemented in green / hysteresis. This rubber composition is also the subject of the invention.
    [0020] As explained above, another subject of the invention is a reinforced rubber composition based on at least one reinforcing filler and an elastomeric matrix comprising at least one modified diene elastomer as described above. It should be understood that the rubber composition may comprise one or more of these modified diene elastomers according to the invention. The reinforced rubber composition according to the invention may be in the crosslinked state or in the uncrosslinked state, that is to say crosslinkable. The diene elastomer modified according to the invention can be, according to different variants, used alone in the composition or in blending with at least one other conventional diene elastomer, whether star-shaped, coupled, functionalized or not. Preferably, this other diene elastomer used in the invention is chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (BR) synthetic polyisoprenes (IR), natural rubber (NR), butadiene copolymers, copolymers isoprene and mixtures of these elastomers. Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR) and isoprene-copolymers. butadiene-styrene (SBIR). It is also possible to cut with any synthetic elastomer other than diene, or with any other polymer other than elastomer, for example a thermoplastic polymer.
    [0021] When the conventional elastomer used in cutting is natural rubber and / or one or more diene polymers such as polybutadienes, polyisoprenes, butadiene-styrene or butadiene-styrene-isoprene copolymers, this elastomer or these elastomers, modified or otherwise can then be present from 1 to 70 parts by weight per 100 parts of modified diene elastomer according to the invention. It will be noted that the improvement in the properties of the composition according to the invention will be all the greater as the proportion of the elastomer (s) different from the modified diene elastomers of the invention in this composition will be reduced. Thus, preferably, the elastomer matrix substantially comprises in bulk the modified diene elastomer according to the invention.
    [0022] More preferably, the elastomeric matrix consists solely of the modified diene elastomer according to the invention. The rubber composition of the invention comprises, in addition to at least one elastomeric matrix as described above, at least one reinforcing filler.
    [0023] It is possible to use any type of reinforcing filler known for its ability to reinforce a rubber composition that can be used for manufacturing tire treads, for example carbon black, a reinforcing inorganic filler such as silica with which it is associated with known manner a coupling agent, or a mixture of these two types of load. Suitable carbon blacks are all carbon blacks, used individually or in the form of mixtures, in particular blacks of the HAF, ISAF, SAF type conventionally used in tire treads (so-called pneumatic grade blacks). Among the latter, there will be mentioned more particularly the reinforcing carbon blacks of the series 100, 200 or 300 (ASTM grades), such as, for example, the blacks N115, N134, N234, N326, N330, N339, N347 and N375. The carbon blacks could for example already be incorporated into the isoprene elastomer in the form of a masterbatch (see for example WO 97/36724 or WO 99/16600). As reinforcing inorganic filler, is meant by the present application, by definition, any inorganic or mineral filler regardless of its color and its origin (natural or synthetic), capable of reinforcing on its own, without other means than an agent intermediate coupling, a rubber composition for the manufacture of tires; such a filler is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface. Suitable reinforcing inorganic fillers are, in particular, mineral fillers of the siliceous type, in particular silica (SiO 2), or aluminous type, in particular alumina (Al 2 O 3). The silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g, especially between 60 and 300 m2 / g. Mention may also be made of mineral fillers of the aluminous type, in particular alumina (Al 2 O 3) or aluminum (oxide) hydroxides, or reinforcing titanium oxides, for example described in US 6,610,261 and US 6,747,087. Reinforcing fillers of another nature, in particular carbon black, are also suitable as reinforcing fillers, provided that these reinforcing fillers are covered with a siliceous layer, or else comprise at their surface functional sites, in particular hydroxyl sites, which require use of a coupling agent to establish the bond between the filler and the elastomer. By way of example, mention may be made, for example, of carbon blacks for tires as described for example in documents WO 96/37547 and WO 99/28380. The physical state in which the reinforcing inorganic filler is present is indifferent whether in the form of powder, microbeads, granules, beads or any other suitable densified form. Of course, the term "reinforcing inorganic filler" also refers to mixtures of different reinforcing fillers, in particular highly dispersible siliceous fillers as described above. Preferably, the content of total reinforcing filler (carbon black and / or other reinforcing filler such as silica) is between 30 and 200 phr, more preferably between 30 and 150 phr, and even more preferably between 70 and 130 phr, the optimum being in a known manner different according to the particular applications concerned.
    [0024] According to a variant of the invention, the reinforcing filler is predominantly other than carbon black, that is to say it comprises more than 50% by weight of the total weight of the reinforcing filler, of one or of several fillers other than carbon black, especially a reinforcing inorganic filler such as silica, or it consists exclusively of such a filler. According to this variant, when carbon black is also present, it may be used at a level of less than 20 phr, more preferably less than 10 phr (for example between 0.5 and 20 phr, in particular from 1 to 10 phr).
    [0025] According to another variant of the invention, a reinforcing filler comprising predominantly carbon black and optionally silica or other inorganic filler is used. When the reinforcing filler comprises a filler requiring the use of a coupling agent to establish the bond between the filler and the elastomer, the rubber composition according to the invention further comprises, in a conventional manner, an agent capable of effectively provide this link. When the silica is present in the composition as reinforcing filler, it is possible to use as coupling agents organosilanes, in particular polysulfide alkoxysilanes or mercaptosilanes, or at least bifunctional polyorganosiloxanes. In the composition according to the invention, the level of coupling agent is advantageously less than 20 phr, it being understood that it is generally desirable to use as little as possible. Its rate is preferably between 0.5 and 12 phr. The presence of the coupling agent depends on that of the reinforcing inorganic filler. Its rate is easily adjusted by the skilled person according to the rate of this charge; it is typically of the order of 0.5% to 15% by weight relative to the amount of reinforcing inorganic filler other than carbon black. The rubber composition according to the invention may also contain, in addition to the coupling agents, coupling activators, charge-recovery agents or, more generally, processing aid agents which can be used in known manner, thanks to an improvement of the dispersion of the filler in the rubber matrix and a lowering of the viscosity of the composition, to improve its ability to use in the green state, these agents being for example hydrolysable silanes such as alkylalkoxysilanes, polyols, polyethers, primary, secondary or tertiary amines, hydroxyl or hydrolyzable polyorganosiloxanes. The rubber compositions in accordance with the invention may also contain reinforcing organic fillers which may replace all or part of the carbon blacks or other reinforcing inorganic fillers described above. Examples of reinforcing organic fillers that may be mentioned include functionalized polyvinyl organic fillers as described in applications WO-A-2006/069792, WO-A-2006/069793, WO-A-2008/003434 and WO-A 2008/003435. The rubber composition according to the invention may also comprise all or part of the usual additives usually used in elastomer compositions intended for the manufacture of tires, for example pigments, non-reinforcing fillers, protective agents such as waxes anti-ozone, anti-chemical ozonants, anti-oxidants, anti-fatigue agents, plasticizing agents, reinforcing or plasticizing resins, acceptors (for example phenolic novolac resin) or methylene donors (for example HMT or H3M) as described for example in the application WO 02/10269, a crosslinking system based on either sulfur, or sulfur and / or peroxide donors and / or bismaleimides, vulcanization accelerators, vulcanization activators.
    [0026] The composition is manufactured in appropriate mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or thermomechanical mixing (so-called "non-productive" phase) at high temperature, up to a maximum of maximum temperature between 110 ° C and 190 ° C, preferably between 130 ° C and 180 ° C, followed by a second phase of mechanical work (so-called "productive" phase) to a lower temperature, typically less than 110 ° C, for example between 40 ° C and 100 ° C, finishing phase during which is incorporated the crosslinking system.
    [0027] The process for preparing a composition according to the invention generally comprises: (i) the production, at a maximum temperature of between 130 ° C. and 180 ° C., of a first thermomechanical working time of the constituents of the composition comprising the modified diene elastomer according to the invention and a reinforcing filler, with the exception of a crosslinking system, and then (ii) the production, at a temperature below said maximum temperature of said first time, of a second mechanical working time during which said crosslinking system is incorporated. This process may also comprise, prior to carrying out steps (i) and (ii) above, the steps for preparing the modified diene elastomer according to the method described above. The invention also relates to a semi-finished rubber article for a tire, comprising a rubber composition according to the invention, crosslinkable or crosslinked or consisting of such a composition. The final composition thus obtained can then be calendered, for example in the form of a sheet, a plate or extruded, for example to form a rubber profile usable as a semi-finished rubber product for the tire. Because of the improved hysteresis / raw-working implementation compromise while maintaining the creep resistance of the elastomer which characterizes a reinforced rubber composition according to the invention, it should be noted that such a composition can constitute any semi-finished product of the invention. pneumatic and especially the tread, particularly decreasing its rolling resistance. The invention therefore finally relates to a tire comprising a semi-finished article according to the invention, in particular a tread. The aforementioned features of the present invention, as well as others, will be better understood on reading the following description of several embodiments of the invention, given by way of illustration and not limitation. Examples Measurements and tests used Size Exclusion Chromatography The Size Exclusion Chromatography (SEC) technique separates macromolecules in solution by size through columns filled with a porous gel. The macromolecules are separated according to their hydrodynamic volume, the larger ones being eluted first. Without being an absolute method, the SEC allows to apprehend the distribution of the molar masses of a polymer. From commercial standard products, the various average molar masses (Mn) and weight (Mw) can be determined and the polymolecularity index (Ip = Mw / Mn) calculated via a so-called calibration of MOORE.
    [0028] There is no particular treatment of the polymer sample before analysis. This is simply solubilized in the eluting solvent at a concentration of about 1 g / L. Then the solution is filtered through a 0.451 μm porosity filter before injection.
    [0029] The equipment used is a chromatographic chain "WATERS alliance". The elution solvent is either tetrahydrofuran or tetrahydrofuran + 1% vol. of diisopropylamine + 1% vol. of triethylamine, the flow rate of 1 mL.min-1, the temperature of the system of 35 ° C and the analysis time of 30 min. A set of two WATERS columns with the trade name "STYRAGEL HT6E" is used. The injected volume of the solution of the polymer sample is 100 μl. The detector is a differential refractometer "WATERS 2410" and the chromatographic data exploitation software is the "WATERS EMPOWER" system.
    [0030] The average molar masses calculated are relative to a calibration curve produced for SBR microstructure following: 25% by weight (relative to the weight of the polymer) of styrene type units, 23% by weight (relative to the butadiene part) of type 1-2 and 50% by weight (with respect to the butadiene moiety) of type 1-4 trans units. High Resolution Steric Exclusion Chromatography The high resolution SEC technique is used to determine the mass percentages of the different chain populations present in a polymer sample. There is no particular treatment of the polymer sample before analysis. This is simply solubilized in the eluting solvent at a concentration of about 1 g / L. Then the solution is filtered on a porosity filter 0.45 i.tm before injection. The equipment used is a chromatographic chain "WATERS alliance 2695". The elution solvent is tetrahydrofuran, the flow rate 0.2 ml.min-1, the system temperature 35 ° C. A set of three identical columns in series is used (Shodex, length 300 mm, diameter 8 mm). The number of theoretical plates in the set of columns is greater than 22,000. The injected volume of the solution of the polymer sample is 50 μL. The detector is a differential refractometer "WATERS 2414" and the chromatographic data exploitation software is the "WATERS EMPOWER" system. The molar masses calculated are relative to a calibration curve produced for SBR microstructure following: 25% by weight (relative to the weight of the polymer) of styrene type units, 23% by weight (relative to the butadiene part) of patterns type 1,2 and 50% by weight (with respect to the butadiene part) of 1,4-trans type units. Mooney Viscosity For polymers and rubber compositions, Mooney ML (i + 4) viscosities of 100 ° C are measured according to ASTM D-1646. An oscillatory consistometer is used as described in ASTM D-1646. The Mooney plasticity measurement is carried out according to the following principle: the elastomer or composition in the green state (i.e., before firing) is molded in a cylindrical chamber heated to 100 ° C. After one minute preheating, the rotor rotates within the specimen at 2 rpm and the torque needed to maintain this movement after 4 minutes of rotation is measured. The Mooney plasticity ML (i + 4) is expressed in "Mooney unit" (UM, with 1 UM = 0.83 Nm). The difference between the Mooney viscosity of the composition and the Mooney viscosity of the elastomer makes it possible to measure the processability or implementation in the raw state. The lower this difference, the better the implementation is raw.
    [0031] Differential calorimetry The glass transition temperatures (Tg) of the elastomers are determined using a differential scanning calorimeter. Near Infrared Spectroscopy (NIR) The microstructure of elastomers is characterized by the technique of near infrared spectroscopy (NIR). Near-infrared spectroscopy (NIR) is used to quantitatively determine the mass content of styrene in the elastomer as well as its microstructure (relative distribution of 1,2-butadiene 1,4-trans and 1,4-cis units). The principle of the method is based on the Beer-Lambert law generalized to a multicomponent system. The method being 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 NMR HC. The styrene content and the microstructure are then calculated from the NIR spectrum of an elastomer film about 730 μm thick. The acquisition of the spectrum 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 infrared near-infrared spectrometer equipped with a cooled InGaAs detector. by Peltier effect. Inherent Viscosity The inherent viscosity of the elastomers at 25 ° C is determined from a solution of elastomer at 0.1 g.dL-1 in toluene, according to the following principle: The inherent viscosity is determined by the measurement of time flow rate of the polymer solution and the flow time to toluene, in a capillary tube.
    [0032] In a Ubbelhode tube (capillary diameter 0.46 mm, capacity 18 to 22 ml), placed in a bath thermostated at 25 ± 0.1 ° C, the flow time of toluene and that of the polymer solution at 0, 1 g.dL-1 are measured.
    [0033] The inherent viscosity is obtained by the following relationship: = cm 1 [(t) - inh (t0 with: concentration of the polymer solution in toluene in g.dL-1, t: flow time of the solution of polymer in toluene in second, to: toluene flow time in second,: inherent viscosity expressed in dL.g-1.
    [0034] Cold-Flow (CF (1 + 6) 100 ° C) It is a question of measuring the extruded elastomer mass through a calibrated die for a given time (6 hours) and under fixed conditions (T = 100 ° C ). The die has a diameter of 6.35 mm, a thickness of 0.5 mm and is located at the bottom and the center of a cylindrical cut-out cut of 52 mm in diameter. In this device are placed 40 ± 4 g of elastomer previously formed into a pellet (2 cm thick and 52 mm in diameter). On the elastomer pellet is positioned a calibrated piston of 1 kg (± 5 g). The assembly is then placed in an oven at 100 ± 0.5 ° C. The conditions are not stabilized during the first hour in the oven, the extruded product at t = 1 hour is cut and then discarded.
    [0035] The measurement is then continued for 6 hours ± 5 minutes, during which the product is left in the oven. After 6 hours, the extruded product sample is cut and weighed. The result of the measurement is the weighted elastomer mass. The lower this result, the more the elastomer is resistant to cold creep. Nuclear Magnetic Resonance (NMR) 1E1 NMR makes it possible to quantify the methyl groups carried by silicon (SiCH3) by integrating the corresponding signal, located around S = 0 ppm. The samples are solubilized in carbon disulfide (CS2). 100 μl of deuterated cyclohexane (C6D12) are added for the lock signal. The NMR analyzes are carried out on a BRUKER 500 MHz spectrometer equipped with a BBIz 5 mm broadband probe. For the quantitative 1E1 NMR experiment, the sequence uses a 30 ° pulse and a 2 second repetition time.
    [0036] Dynamic properties The dynamic properties, and in particular tan δ max, are measured on a viscoanalyzer (Metravib VA4000), according to the ASTM D 5992-96 standard. The response of a sample of vulcanized composition (cylindrical specimen with a thickness of 2 mm and a section thickness of 79 mm 2) is recorded, subjected to a sinusoidal stress in alternating simple shear, at a frequency of 10 Hz, under normal temperature conditions. (40 ° C) according to ASTM D 1349-99. A strain amplitude sweep is performed from 0.1% to 50% peak-to-peak (forward cycle), then from 50% to 0.1% peak-to-peak (return cycle). The most particularly exploited result is the loss factor tan Ô. For the return cycle, the maximum value of tan δ observed, denoted tan ô max, is indicated. This value is representative of the hysteresis of the material and in this case the rolling resistance: the lower the value of tan δ max, the lower the rolling resistance. In the examples, the results of the dynamic properties are given in base 100.
    [0037] Preparation of the Polymers Preparation of the Polymer A: Functional Silanol SBR at the Chain End According to the Invention In a 90 liter reactor, maintained under a nitrogen pressure of approximately 2 bars, containing 46 kg of methylcyclohexane, 2 kg of styrene and 4.7 kg of butadiene and 260 ml of a solution of tetrahydrofurfuryl ethyl ether at 0.1 mol.L-1 in methylcyclohexane. After neutralization of the protic impurities in the solution to be polymerized by the addition of n-butyllithium, 770 ml of 0.05 mol.L-1 n-butyllithium (n-BuLi) in methylcyclohexane are added. The polymerization is conducted at 40 ° C. After 80 minutes, the conversion rate of the monomers reaches 88%. This level is determined by weighing a dried extract at 140 ° C., under the reduced pressure of 200 mmHg. A control sample is then taken from the reactor and then stopped with an excess of methanol relative to lithium. The inherent viscosity ("initial" viscosity) which is measured at 25 ° C. at 0.1 g.L -1 in toluene is 1.26 dL.g -1. The number average molecular weight, Mn, determined by the SEC technique, is 139,000 g.mol -1 and the polydispersity index, Ip, is 1.04. 481 ml of a solution of 0.004 mol·l-1 tin tetrachloride in methylcyclohexane are then added (SnCl 4 / Li = 0.050).
    [0038] After 1 minute at 40 ° C, 825 ml of a solution of hexamethylcyclotrisiloxane 0.021 mol.L-1 are added (0.45 eq / Li). The solution is then antioxidized by the addition of 0.4 parts per hundred parts elastomer (phr) of 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol) and 0.2 phr of N- ( 1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine. The polymer thus treated is separated from its solution by a stripping operation with steam and then dried on a roll tool at 100 ° C.
    [0039] The "final" inherent viscosity measured is 1.45 dL.g -1. The viscosity jump, defined as the ratio of said "final" viscosity to said "initial" viscosity, is here 1.15. The Mooney viscosity of this polymer A is 57.
    [0040] The number-average molecular weight, Mn, determined by the SEC technique, is 150,500 g.mol -1 and the polymolecularity index, Ip, is 1.20. The mass percentages of species functionalized with a silanol group at the chain end and star-shaped, determined by the SEC HR technique, are 80% and 20%, respectively. The microstructure of this polymer is determined by the NIR method. The level of 1,2 units is 58.5% relative to the butadiene units. The mass content of styrene is 25.8%. The glass transition temperature of this polymer is -25 ° C. The function ratio (CH 3) 2 Si determined by 1 H NMR for polymer A is 3.3 mmol.kg-1. The CF (i + 6) 100 ° C cold flow of the polymer is 2.1.
    [0041] Preparation of the Polymer B: Functional Silanol SBR at the End of a Control Chain In a stirred continuous reactor of 32.5 L, presumably perfectly stirred according to those skilled in the art, are continuously introduced methylcyclohexane, butadiene, styrene and tetrahydrofurfuryl ethyl ether, in the following proportions: butadiene mass flow rate = 1.49 kg.h-1, styrene mass flow rate = 0.511 kg.h-1, mass concentration of monomer = 12.5 wt%, 350 ppm tetrahydrofurfuryl ethyl ether. N-Butyllithium (n-BuLi) is introduced in sufficient quantity to neutralize the protic impurities provided by the various constituents present in the line inlet. At the inlet of the reactor, 645 μg of n-BuLi per 100 g of monomer are introduced.
    [0042] The different flow rates are calculated so that the average residence time in the reactor is 40 min. The temperature is maintained at 80 ° C. At the outlet of the polymerization reactor, a sample of polymer solution is made. The polymer is then subjected to an antioxidant treatment with addition of 0.4 phr of 2,2'-methylene-bis (4-methyl-6-tert-butylphenol) and 0.2 phr of N- (1,3-dimethylbutyl) ) -N'-phenyl-p-phenylenediamine. The polymer thus treated is separated from its solution by a stripping operation with steam, and then dried on a roll tool at 100 ° C. The "initial" inherent viscosity measured is 1.86 dL.g -1. The number-average molecular weight, Mn, determined by the SEC technique, is 121,000 g.mol -1 and the polydispersity index, Ip, is 1.90 (which does not satisfy the definition of the elastomer functionalized diene a) according to the invention).
    [0043] At the outlet of the polymerization reactor, 19 iamol per 100 g of tin tetrachloride monomer dissolved in methylcyclohexane are added to the living polymer solution (SnCl.sub.4 / Li = 0.029) and then 245 iamol per 100 g of hexamethylcyclotrisiloxane monomer. (0.38 eq / Li) in solution in methylcyclohexane are added. The polymer is then subjected to an antioxidant treatment with addition of 0.4 phr of 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol) and 0.2 phr of N- (1,3-methylene). dimethylbutyl) -N'-phenyl-pphénylènediamine.
    [0044] The polymer thus treated is separated from its solution by a stripping operation with steam, and then dried on a roll tool at 100 ° C. The "final" inherent viscosity measured is 1.98 dL.g -1. The viscosity jump, defined as the ratio of said "final" viscosity to said "initial" viscosity, is here 1.06. The Mooney viscosity of this polymer B is 57. The number-average molecular weight, Mn, determined by the SEC technique, is 130,000 g.mol -1 and the polymolecularity index, Ip, is 1.9. .
    [0045] The microstructure of this polymer is determined by the NIR method. The level of 1,2 units is 58.3% relative to the butadiene units. The mass content of styrene is 25.1%. The glass transition temperature of this polymer is -24 ° C. The function ratio (CH 3) 2 Si determined by 1 H NMR for polymer B is 5.3 mmol.kg -1. The cold flow CF (i + 6) 100 ° C of the polymer is 1.9.
    [0046] Preparation of the polymer C: SBR functional silanol at the end of control chain In a reactor of 90 liters, maintained under a nitrogen pressure of about 2 bars, containing 46 kg of methylcyclohexane, are injected 2 kg of styrene and 4.7 kg of butadiene and 260 ml of a solution of tetrahydrofurfuryl ethyl ether at 0.1 mol.L-1 in methylcyclohexane. After neutralization of the protic impurities in the solution to be polymerized by addition of n-butyllithium, 500 ml of 0.05 mol·l-1 n-butyllithium (n-BuLi) in methylcyclohexane are added. The polymerization is conducted at 40 ° C. After 80 minutes, the conversion rate of the monomers reaches 88%. This level is determined by weighing a dried extract at 140 ° C., under the reduced pressure of 200 mmHg. A control sample is then taken from the reactor and then stopped with an excess of methanol relative to lithium. The inherent viscosity ("initial" viscosity) which is measured at 25 ° C. at 0.1 g.L -1 in toluene is 1.86 dL.g -1. The number average molecular weight, Mn, determined by the SEC technique, is 205,000 g.mol -1 and the polydispersity index, Ip, is 1.05. 311 ml of a solution of 0.004 mol·l-1 tin tetrachloride in methylcyclohexane are then added (SnCl 4 / Li = 0.050). After 1 minute at 40 ° C., 474 ml of a solution of hexamethylcyclotrisiloxane at 0.021 mol.l -1 are added (0.4 eq / Li). The solution is then antioxidized by the addition of 0.4 parts per hundred parts elastomer (phr) of 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol) and 0.2 phr of N- ( 1,3-dimethylbutyl) -N'-phenyl-pphénylènediamine. The polymer thus treated is separated from its solution by a stripping operation with steam and then dried on a roll tool at 100 ° C. The "final" inherent viscosity measured is 2.15 dL.g -1. The viscosity jump, defined as the ratio of said "final" viscosity to said "initial" viscosity, is here of 1.16.
    [0047] The Mooney viscosity of this polymer C is 100 (which does not meet the definition of the invention). The number-average molecular weight, Mn, determined by the SEC technique, is 222,200 g.mol -1 and the polydispersity index, Ip, is 1.20.
    [0048] The mass percentages of species functionalized with a silanol group at the chain end and star-shaped, determined by the SEC HR technique, are 80% and 20%, respectively. The microstructure of this polymer is determined by the NIR method. The level of 1,2 units is 58.5% relative to the butadiene units. The mass content of styrene is 25.8%. The glass transition temperature of this polymer is -25 ° C. The function ratio (CH 3) 2 Si determined by 1 H NMR for polymer A is 3.1 mmol.kg -1.
    [0049] The CF (i + 6) 100 ° C cold flow of the polymer is 2.1. Comparative Examples of Rubber Compositions Three compositions are compared reported in Table 1 below. Composition 1 is in accordance with the invention. Compositions 2 and 3 are comparative compositions which do not conform to the invention. The formulations are expressed in percent by weight per 100 parts by weight of elastomer (phr).
    [0050] Table 1 Example Comparative Examples 1 2 3 Polymer A 80 0 0 Polymer B 0 80 0 Polymer C 0 0 80 BR-Nd ML44 (1) 20 20 Silica (2) 73 73 73 N234 3 3 3 Oil MES (3) 6 6 6 Resin (4) 20 20 20 Coupling agent (5) 6 6 6 ZnO 1 1 1 Stearic acid 2 2 2 Antioxidant (6) 2 2 2 Anti-ozone wax "C32ST" (7) 1.6 1 1,6 1,6-Diphenylguanidine 1,3 1,3 1,3 Sulfenamide (1) Sulfenamide (8) 1,6 1,6 1,6 (1) 1,4-cis polybutadiene obtained by neodymium catalyzed polymerization; Mooney elastomer = 44 (2) Rhodia "Zeosil 1165MP" silica. (3) Catenex® SBR from Shell. (4) Polylimonene. (5) "Si69" from Degussa. (6) N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine. (7) Repsol Anti-Ozone. (8) N-cyclohexyl-2-benzothiazylsulphenamide. For the following tests, the procedure is as follows: Each of the compositions is carried out initially by a thermomechanical work, then, in a second finishing time, by mechanical work. The elastomer, two-thirds of the silica, is introduced into a "Banbury" laboratory type internal mixer, which is 400 cm 2, which is 72% filled and whose initial temperature is 90 ° C. the coupling agent, diphenylguanidine and carbon black. The thermomechanical work is performed by means of pallets whose average speed is 50 rpm and whose temperature is 90 ° C. After one minute, the last third of silica, the antioxidant, stearic acid and anti-ozone wax, the MES oil and the resin, still under thermomechanical work, are introduced. After two minutes, the zinc oxide is introduced, the speed of the pallets being 50 rpm. The thermomechanical work is again conducted for two minutes, up to a maximum fall temperature of about 160 ° C. The mixture thus obtained is recovered, cooled and then, in an external mixer (homo-finisher), the sulfur and sulfenamide are added at 30 ° C., mixing again for a period of 3 to 4 minutes (second time). mechanical work). The compositions thus obtained are then calendered, either in the form of plates (with a thickness ranging from 2 to 3 mm) or thin rubber sheets, for the measurement of their physical or mechanical properties, or in the form of directly usable profiles, after cutting and / or assembly to the desired dimensions, for example as semi-finished products for tires, in particular for treads.
    [0051] The crosslinking is carried out at 150 ° C for 40 min. The results are shown in Table 2.
    [0052] Table 2 Rubber Results (Tan S max 40 ° C, ML (i + 4) 100 ° C Composition, Cold-Flow): Example Comparative Examples 1 2 3 ABC ML (i + 4) 100 ° C Elastomer 57 57 100 Tan O max 40 ° C 110 100 105 ML (i + 4) 100 ° C composition 92.4 97.3 NM * ML (i + 4) 100 ° C composition - ML (i + 4) 100 ° C elastomer 35.4 40 , 3 - Cold-Flow (g / 6h) 2.1 1.9 2.1 * Value not measurable because too high. The results presented in Table 2 show an improved hysteresis of the composition 1 according to the invention compared to that of the control composition 2 (Polymer B having a polymolecularity index before functionalization and high starch) and that of the control composition 3 ( Mooney high viscosity polymer C). The processability of the composition 1 according to the invention is better than that of the control compositions 2 and 3. Finally, the creep resistance of the composition 1 is comparable to that of the control compositions 2 and 3. Thus, the results presented in the Table 2 show an improvement in the compromise hysteresis / green implementation of the composition containing the polymer according to the invention while maintaining the creep resistance of the elastomer.
    权利要求:
    Claims (15)
    [0001]
    REVENDICATIONS1. A modified diene elastomer comprising: a) at least 70% by weight, based on the total weight of the modified diene elastomer, of a diene elastomer functionalized at one end of a chain by a silanol function or a polysiloxane block having a silanol end and having a polymolecularity index before functionalization less than or equal to 1.6, b) more than 0 and up to 30% by weight, based on the total weight of the modified diene elastomer, of a diene diene elastomer and having a polymolecularity index before or lower than or equal to 1.6, the Mooney viscosity of said modified diene elastomer ranging from 30 to 80.
    [0002]
    2. Elastomer according to claim 1, characterized in that the polysiloxane block having a silanol end corresponds to the formula: [- (SiRiR20), (41) in which: - R1 and R2, which may be identical or different, represent an alkyl group, cycloalkyl, aryl, alkaryl, aralkyl, vinyl having 1 to 10 carbon atoms, - x is an integer ranging from 1 to 1500.
    [0003]
    3. Elastomer according to claim 2, characterized in that R1 and R2, identical or different, represent an alkyl group having 1 to 6 carbon atoms, preferably the methyl radical.
    [0004]
    4. Modified diene elastomer according to claim 1, characterized in that it comprises at least 80% by weight, relative to the total weight of the modified diene elastomer, of the functionalized diene elastomer a).
    [0005]
    5. Modified diene elastomer according to any one of claims 1 to 4, characterized in that it comprises at most 20% by weight, relative to the total weight of the modified diene elastomer, the diene diene elastomer b) .
    [0006]
    6. Elastomer according to claim 1, characterized in that the star-diene elastomer is a star-shaped elastomer based on tin or silicon.
    [0007]
    7. Modified diene elastomer according to any one of the preceding claims, characterized in that the diene diene elastomer b) is a star-branched diene elastomer with four branches.
    [0008]
    8. Modified diene elastomer according to any one of the preceding claims, characterized in that the diene elastomer is a copolymer of butadiene and a vinylaromatic monomer, preferably a butadiene-styrene copolymer.
    [0009]
    9. Modified diene elastomer according to any one of the preceding claims, characterized in that the diene elastomers a) and b) have before functionalization and starring the same microstructure and the same macrostructure.
    [0010]
    10. Reinforced rubber composition based on at least one reinforcing filler and an elastomeric matrix comprising at least one modified diene elastomer as defined in any one of claims 1 to 9.
    [0011]
    11. Composition according to claim 10, characterized in that the reinforcing filler (s) comprises more than 50% by weight, relative to the total weight of the reinforcing filler (s), of reinforcing inorganic filler.
    [0012]
    12. Composition according to claim 10 or 11, characterized in that the reinforcing inorganic filler consists of silica.
    [0013]
    13. Semi-finished rubber tire article, characterized in that it comprises a crosslinkable or crosslinked rubber composition according to any one of claims 10 to 12.
    [0014]
    14. Semi-finished article according to claim 13, characterized in that said article is a tread.
    [0015]
    15. Pneumatic tire, characterized in that it comprises a semi-finished article as defined in claim 14.
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    同族专利:
    公开号 | 公开日
    WO2016001372A1|2016-01-07|
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    JP2017521547A|2017-08-03|
    PL3164270T3|2019-06-28|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP1122281A1|2000-02-07|2001-08-08|Société de Technologie Michelin|Tyres for heavy loads and use of a rubber composition for retarding the irregular wear of those tyres|
    FR2951178A1|2009-10-08|2011-04-15|Michelin Soc Tech|FUNCTIONALIZED DIENIC ELASTOMER AND RUBBER COMPOSITION CONTAINING SAME.|WO2019115470A1|2017-12-11|2019-06-20|Compagnie Generale Des Etablissements Michelin|Method for synthesising a functional or non-functional polymer having a specific structure|
    FR3037586A1|2015-06-17|2016-12-23|Michelin & Cie|PROCESS FOR CONTINUOUS POLYMERIZATION OF DIENE ELASTOMER|
    WO2018088483A1|2016-11-14|2018-05-17|日本ゼオン株式会社|Method for producing modified conjugated diene rubber|
    FR3060579A1|2016-12-21|2018-06-22|Compagnie Generale Des Etablissements Michelin|PROCESS FOR THE CONTINUOUS SYNTHESIS OF MODIFIED DIENIC ELASTOMER WITH LITHIUM AMIDIDE INITIATOR|
    FR3060581A1|2016-12-21|2018-06-22|Compagnie Generale Des Etablissements Michelin|PROCESS FOR THE CONTINUOUS POLYMERIZATION OF MODIFIED DIENIC ELASTOMER WITH LITHIUM AMIDIDE INITIATOR|
    FR3061187B1|2016-12-22|2019-02-01|Compagnie Generale Des Etablissements Michelin|RUBBER COMPOSITION WITH GOOD DISPERSION OF HIGH QUANTITIES OF INORGANIC REINFORCING LOAD|
    KR101865796B1|2017-01-03|2018-06-11|주식회사 엘지화학|Modified conjugated diene polymer and rubber composition comprising the same|
    KR20180084603A|2017-01-03|2018-07-25|주식회사 엘지화학|Modified conjugated diene polymer and rubber composition comprising the same|
    WO2019220627A1|2018-05-18|2019-11-21|Compagnie Generale Des Etablissements Michelin|A composition for a tire tread|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1456373A|FR3023293B1|2014-07-03|2014-07-03|DIENIC ELASTOMER WITH REDUCED IP HAVING SILANOL FUNCTION IN THE END OF THE CHAIN AND COMPOSITION CONTAINING SAME|FR1456373A| FR3023293B1|2014-07-03|2014-07-03|DIENIC ELASTOMER WITH REDUCED IP HAVING SILANOL FUNCTION IN THE END OF THE CHAIN AND COMPOSITION CONTAINING SAME|
    JP2017519996A| JP6539731B2|2014-07-03|2015-07-02|Low PI diene elastomer having silanol functional group at chain end and composition containing the same|
    PL15734134T| PL3164270T3|2014-07-03|2015-07-02|Diene elastomer with a reduced pi having a silanol function at the chain end and composition containing same|
    EP15734134.8A| EP3164270B1|2014-07-03|2015-07-02|Diene elastomer with a reduced pi having a silanol function at the chain end and composition containing same|
    PCT/EP2015/065123| WO2016001372A1|2014-07-03|2015-07-02|Diene elastomer with a reduced pi having a silanol function at the chain end and composition containing same|
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