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    • 专利摘要:
    Functionalized diene elastomer, reinforced rubber composition, semi-finished rubber article, pneumatic, and cold creep reduction process of a monofunctional diene elastomer The present invention relates to a specific functionalized diene elastomer. This functionalized elastomer exhibits reduced cold creep without, however, degrading the properties of a reinforced rubber composition containing it, notably the performance properties and the hysteretic properties. This di-chain-functionalized diene elastomer has a silanol function or a polysiloxane block having a silanol end and is partially copulated or starred with tin.
    公开号:BR112012008027B1
    申请号:R112012008027
    申请日:2010-10-07
    公开日:2019-08-13
    发明作者:Jean-Marc Marechal；Stéphanie De Landtsheer；Jean-Michel Favrot
    申请人:Compagnie Generale Des Etablissements Michelin；
    IPC主号:
    专利说明:

    “FUNCTIONALIZED DIENE ELASTOMER, REINFORCED RUBBER COMPOSITION, SEMI-FINISHED RUBBER ARTICLE, PNEUMATIC, AND COLD FLUENCE REDUCTION PROCESS OF A MONOFUNCTIONAL DIENE ELASTOMER”
    The present invention relates to a specific functionalized dienic elastomer. This functionalized elastomer has a reduced cold creep without, however, degrading the properties of a reinforced rubber composition containing it, notably its hysteretic properties.
    Since fuel savings and the need to protect the environment have become a priority, it is desirable to produce polymers that have good mechanical properties and as low a hysteresis as possible in order to be able to use them in the form of usable rubber compositions for the manufacture of various semi-finished products entering the constitution of tire covers, such as sub-layers, gums connecting different types of rubber or coating metallic or textile reinforcements, flanks or tread gums and obtaining tires with improved properties, notably having reduced rolling resistance.
    Reducing the hysteresis of mixtures is a permanent objective that must, however, be done while maintaining the aptitude for mixing.
    To achieve the goal of low hysteresis, numerous solutions have already been tried. In particular, it is possible to mention the modification of the structure of polymers and dienic copolymers at the end of polymerization by means of functionalization, copulation or star formation agents in order to obtain a good interaction between the polymer thus modified and the charge, whether it is carbon black or a reinforcing inorganic charge.
    In the context of mixtures containing a reinforcing inorganic filler, it has been proposed notably to use dienic polymers functionalized by alkoxysilanes derivatives.
    By way of illustration of this prior art relating to reinforcing inorganic fillers, for example, US patent US-5 066,721, which describes a rubber composition comprising a dienic polymer functionalized by an alkoxysilane having at least one alkoxyl residue not hydrolyzable when mixed with silica. Reference can also be made to patent applications EP-A-0 299,074 and EP-A-0 447,066 which describe functionalized polymers having alkoxysilane functions. These functionalized polymers have been described in the prior art as effective for reducing hysteresis and improving abrasion behavior, however their properties remain insufficient to allow the realization of these polymers in compositions intended to constitute tire treads. On the other hand, the formulation of these polymers poses problems of evolution of the macrostructures when the polymerization solvent is eliminated, which leads to a severe degradation of the potentially interesting properties. On the other hand, this evolution is very little controllable.
    Patent applications EP 0.778 311, EP 0.786.493 or WO 9850462 describe a reinforced rubber composition based on a chain end functionalized dienic polymer by a silanol function or a polysiloxane block having at least one silanol end. This functionalized elastomer is not subjected to structural modifications that harm it in the context of its later use in tires. The composition comprising such a functionalized elastomer, on the other hand, has good hysteresis properties.
    More recently, patent application WO 2009/077837 describes elastomers functionalized at one end of the chain by a silanol function or a polysiloxane block having at least one silanol end, and functionalized at the other end of the chain. These elastomers are also described as being able to be associated with starred elastomers, particularly by silicon. However, the illustrated associations lead to a reinforced rubber composition whose compromise of properties employed and hysteresis is not satisfactory for a pneumatic design.
    When using an elastomer functionalized at the end of the chain by a silanol function or a polysiloxane block having at least one silanol end in mixture with silica as a reinforcing filler, the mixture becomes stiff. This stiffening that translates into a degradation of the manufacture and / or the ability to carry out the composition, leading to a decrease in productivity. To remedy this stiffening of the mixtures, it is noticeably possible to readjust the Mooney of the elastomer to obtain in fine a mixture with acceptable performance properties, notably in view of the extrusion of the mixture to manufacture semi-finished products intended for tires, such as treads for example. However, Mooney's drop in the elastomer does not occur without effect on the properties of the elastomer and more particularly leads to a tendency for the elastomer to have a high cold creep. This creep or cold flow (i.e., cold flow) reflects the ability of elastomers to flow under a load equal to their own weight, notably when the samples or balls of these elastomers are stacked on top of each other in storage boxes. Thus, cold creep can cause major inconveniences when transporting and storing elastomers.
    The purpose of the present invention is to provide an elastomer that gives a reinforced rubber composition good hysteresis and performance properties with a view to application in pneumatics, while presenting a reduced cold creep in terms of better performance when storing of rubber. It results in a minimization of the risk so that the samples or balls of elastomers leak from the boxes, causing them to collapse and opposing the extraction of the elastomers.
    The inventors have just discovered during their investigations that a functionalized dienic elastomer composed of a functionalized dienic elastomer at one end of the chain solely for a silanol function or a polysiloxane block having a silanol end and, to a certain extent, a copulated dienic elastomer or star-based tin, gives a rubber composition containing the same rubber properties, and in particular hysteretic and realization properties, completely satisfactory and acceptable for use in tires, while presenting significantly improved cold creep resistance . The rubber properties of this composition are thus maintained at a level equivalent to that of the prior art compositions based on a single elastomer functionalized at the end of the chain by a silanol function. This is even more unexpected because an increase in hysteresis and application of the rubber composition could be expected to benefit from the significant increase in cold creep resistance observed for the functionalized dienic elastomer it comprises.
    The invention therefore relates to a dienic elastomer functionalized at the end of the chain by a silanol function or a polysiloxane block having a silanol end and, to a certain extent, stellated or copulated with tin.
    Another object of the invention is a rubber composition reinforced by at least one inorganic filler such as silica, comprising such a functionalized dienic elastomer.
    The invention also relates to a tire that incorporates in at least one of its constituent elements a reinforced rubber composition according to the invention
    The invention also has for its object the processes of reducing the cold creep of a monofunctional dienic elastomer carrying a silanol function or a polysiloxane block on one single chain end having one silanol end, the other end being free from any functionalization.
    By the expression "based on", it is necessary to understand a composition comprising the mixture and / or the reaction product of the different constituents used, some of these basic constituents susceptible, or destined, to react with each other, at least in part, when different stages of the manufacture of the composition, in particular during its cross-linking or vulcanization.
    In the present description, except for different express indication, all percentages (%) indicated are% by weight. On the other hand, any range of values designated by the expression “between a and b” represents the range of values ranging from more than aa to less than b (ie, excluded limits a and b) whereas any range of values designated by the expression “from a to b” means the domain of values ranging from a to b (that is, including the strict limits a and b).
    In the present description, functionalized dienic elastomer is understood to mean a dienic elastomer comprising a group comprising one or more heteroatoms.
    This group can be located at the end of the chain. The dienic elastomer is then said to be functionalized at the end of the chain. It is generally an elastomer obtained by reacting a live elastomer on a functionalizing agent, that is, any molecule at least monofunctional, the function being any type of chemical group known to the person skilled in the art to react with a live chain end.
    This group can be located on the linear main elastomer chain. It is said then that the dienic elastomer is copulated or functionalized in a chain medium, as opposed to the “end of chain” position and although the group is not located precisely in the middle of the elastomer chain. It is generally an elastomer obtained by reacting a live elastomer on a copulating agent, that is, any molecule at least difunctional, the function being of any type of chemical group known to the person skilled in the art to react with a live chain end.
    This group can be central to which n elastomeric chains (n> 2) are attached forming a star structure of the elastomer. The dienic elastomer is then said to be stellate. It is generally an elastomer obtained by reacting a live elastomer on a star-forming agent, that is, any multifunctional molecule, the function being any type of chemical group known to the person skilled in the art to react with a live chain end.
    A first object of the invention is, therefore, a functionalized dienic elastomer characterized by the fact that it is composed of 75 to 95% by weight of functionalized dienic elastomer at the end of the chain by a silanol function or a polysiloxane block having a silanol end and 5 to 25% by weight of dienic elastomers stellated or copulated with tin. These percentages are understood in relation to the total weight of the functionalized dienic elastomer.
    According to the invention, the functionalized dienic elastomer carrying a silanol function at the end of the chain or a polysiloxane block having a silanol end is present in the functionalized dienic elastomer according to proportions ranging from 75% to 95% by weight of the total weight of the elastomer functionalized, preferably from
    75% to 90% by weight, more preferably from 75% to 85% by weight, for example, from 80% to 85% by weight.
    Preferably, a polysiloxane block having a silanol end is suitable for those who respond to the following general formula:
    - (SiRiR 2 OJp-H where:
    -Rj and R 2 , identical or different, represent an alkyl, cycloalkyl, aryl, alkaryl, aralkyl, vinyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, more preferably still Ri and R 2 each represents a methyl radical.
    -x is an integer ranging from 1 to 1500 and preferably from 1 to 50, more preferably x is worth 1.
    According to a preferred variant of the invention, the functionalized dienic elastomer carrying a silanol end at the chain end or a polysiloxane block having a silanol end is monofunctional. In other words, according to this variant, the dienic elastomer is functionalized at a single chain end. The other end of the chain is free and carries no function.
    According to the invention, the stellate or copulated tinic dienic elastomer is present in the functionalized elastomer according to an amount of 5% to 25% by weight of the total weight of the functionalized elastomer, preferably ranging from 10% to 25% by weight, more preferably still 15 to 25% by weight, for example, 15 to 20% by weight. In fact, a significant improvement in the storage behavior of the functionalized dienic elastomer according to the invention is observed for a proportion of at least 5% by weight of starry or copulated tinic dienic elastomer. In addition to 25% by weight of stellate or copulated tin-containing dienic elastomer, the cold creep compromise of the elastomer / rubber properties of the rubber composition is impaired due to increased hysteresis.
    According to a preferred variant of the invention and for better resistance to cold creep, the dienic elastomer is advantageously stellated with tin, that is, that the tin atom is attached to elastomeric chains (n> 2) forming a structure in elastomer star. Most preferably, four elastomeric chains are linked with tin; which results in a starred elastomer with four branches.
    By dienic elastomer capable of being made according to the invention, is meant any homopolymer obtained by polymerizing a conjugated diene monomer having from 4 to 12 carbon atoms, any copolymer obtained by copolymerizing one or more dienes conjugated together or with one or more vinilaromatic compounds having 8 to 20 carbon atoms
    As conjugated dienes, butadiene-1,3, 2-methyl-1,3-butadiene, 2,3-di (C 1 to C 5 alcohol) -l, 3-butadiene, such as 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, 2,4-hexadiene, etc.
    Styrene, ortho-, meta-, para-methylstyrene, the commercial mixture “viniltoluene”, para-tertiarybutylstyrene, methoxy styrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene, etc., are notably suitable as vinyl-aromatic compounds.
    Copolymers can contain between 99% and 20% by weight of dienic units and from 1% to 80% by weight of vinylaromatic units.
    The functionalized dienic elastomer according to the invention is preferably chosen from the group of strongly unsaturated dienic elastomers consisting of polybutadienes (b), polyisoprene (IR) synthesis, butadiene copolymers, isoprene copolymers and mixtures of these elastomers. Such copolymers are preferably chosen from butadiene-styrene (SBR) copolymers.
    The functionalized dienic elastomer can have any microstructure that is a function of the polymerization conditions used. The elastomer can be in blocks, statistical, sequenced, micro sequenced, etc. and be prepared in dispersion or solution. When it comes to anionic polymerization, the microstructure of these elastomers can be determined by the presence or absence of a modifying and / or randomizing agent and the amounts of modifying and / or randomizing agent used. The functionalized dienic elastomer carrying a silanol function at the end of the chain or a polysiloxane block having a silanol end and the starry or copulated tinic dienic elastomer may have the same microstructure or a different microstructure.
    Especially suitable are polybutadienes having a content (molar%) in units-1,2 of between 4% and 80% or having a content (molar%) in cis-1,4 greater than 80%, polyisoprene, copolymers of butadiene-styrene and in particular having a Tg (glass transition temperature, measured according to ASTM D3418) between -80 ° C and ° 0C and more particularly between -70 ° C and -10 ° C, a styrene content comprised between 5% and 60% by weight and more particularly between 20% and 50%, a content (molar%) in 1,2-bonds of the butadiene part comprised between 4% and 75%, a content (molar%) in trans bonds -1.4 comprised between 10% and 80%, butadiene-isoprene copolymers and notably having an isoprene content comprised between 5% and 90% by weight and a Tg-80 ° Ca 40 ° C, isoprene copolymers -styrene and notably having a styrene content comprised between 5% and 50% by weight and a Tg comprised between -50 ° C and 0 ° C.
    In the case of butadiene-styrene-isoprene copolymers, it is particularly useful to have a styrene content between 5% and 50% by weight and more particularly between 10% and 40%, an isoprene content between 15% and 60% in weight and more particularly between 20% and 50%, a butadiene content between 5% and 50% by weight and more particularly between 20% and 40%, a content (molar%) of 1,2-units of the butadiene part between 4% and 85%, a content (mol%) of trans-1,4 units of the butadiene part comprised between 6% and 80%, a content (molar%) of units-1,2 plus-3,4 of the isoprene part comprised between 5% and 70% and a content (molar%) in trans-1,4 units of the isoprene part comprised between 10% and 50%, and more generally any butadiene-styrene-isoprene copolymer having a Tg comprised between -70 ° C and 0 ° C.
    According to the invention, the dienic elastomer functionalized at the end of the chain and the dienic elastomers stellated or copulated with tin are, before their functionalization, of the same nature. However, it should be noted that non-identical elastomers, but which are considered in the tire domain as similar elastomers due to comparable technical effects, also fall within the scope of the invention.
    The polymerization of dienic monomers is initiated by an initiator. As a polymerization initiator, any known monofunctional anionic initiator can be used. However, a primer containing an alkali metal such as lithium is used preferentially.
    Organolithium initiators are particularly suitable for those with a carbon-lithium bond. Preferably, a hydrocarbon organolithium initiator that does not contain a heteroatom is used. Representative compounds are aliphatic organolithes such as ethyl lithium, nbutyl lithium (n-BuLi), isobutyl lithium, polymethylenes dilithium such as 1, 411 dilithiobutane, etc.
    Polymerization, as it is known per se, is preferably carried out in the presence of an inert solvent which can, for example, be an aliphatic or alicyclic hydrocarbon such as pentane, hexane, heptane, isooctane, cyclohexane or a hydrocarbon aromatics such as benzene, toluene, xylene.
    Polymerization can be carried out continuously or batchwise. Polymerization is generally carried out at a temperature between 20 ° C and 120 ° C and preferably around 30 ° C to 90 ° C. Of course, a transmetallation agent can also be added at the end of the polymerization to modify the reactivity of the live chain end.
    The live dienic elastomer from polymerization is then functionalized to prepare the functionalized dienic elastomer according to the invention.
    According to a first preparation variant of the functionalized dienic elastomer according to the invention, the functionalized dienic elastomer at the end of the chain is mixed by a silanol function or a polysiloxane block having a silanol end and the starry or copulated dienic elastomer with tin , in the appropriate proportions.
    The dienic elastomer functionalized at the end of the chain by a silanol function or a polysiloxane block having a silanol end can be advantageously obtained according to the operational modes described in patent application EP-A-0 778 31 1, the description of which is integrated by reference.
    The dienic elastomer stellated or copulated with tin, can be obtained in a manner known per se by reacting a tin derivative on the live dienic elastomer from polymerization. The preparation of such a starry dienic elastomer is, for example, described in US3,393,182.
    The mixture of two elastomers can be carried out 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, toluene , xylene, which can be the same as the polymerization solvent. The mixture is then carried out at a temperature between 20 ° C and 120 ° C and preferably around 30 ° Ca90 ° C.
    According to a second variant of preparation of the functionalized dienic elastomer according to the invention, the live dienic elastomer from the polymerization stage is subjected to the reaction of a copulation or star-forming agent based on tin and that of an agent of functionalization capable of introducing at the end of the polymer chain the silanol function or the polysiloxane block having a silanol end.
    As a functionalizing agent capable of introducing at the end of the polymer chain the silanol function or the polysiloxane block having a silanol end, cyclic polysiloxane type agents can be cited to obtain an elastomer having a SiO-end and this in a medium which does not allow the polymerization of said cyclopolysiloxane. As cyclic polysiloxanes, one can quote those responding to the formula:
    -Rj and 2 identical or different, represents an alkyl, cycloalkyl, aryl, alkaryl, aralkyl, vinyl group having from 1 to 10 carbon atoms,
    -m represents an integer from 3 to 8.
    As preferred cyclic polysiloxane compounds, hexamethylcyclotrisiloxane, trimethyltriethylcyclotrisiloxane, octamethylcyclotetrassiloxane, decamethylcyclopentassiloxane and mixtures thereof can be mentioned.
    Tin-like copulating or star-forming agents include tin derivatives of the formula SnRxX4-x, x representing an integer of 0 to 2, R representing an alkyl, cycloalkyl, aryl, alkaryl radical , aralkyl, vinyl having 1 to 10 carbon atoms, preferably an alkyl radical having 1 to 4 carbon atoms, and X is a halogen atom, preferably chlorine. Preferred tin derivatives include dibutyl tin dichloride or tin tetrachloride, the latter being particularly preferred. Likewise, functionalization can be achieved with a tin-derived functionalizing agent that can respond to the general formula (X R ] 2 Snj-O-CSnR ^ -yX ^) or (Χ R 1 2Sn) -O- (CH2) n -O- (SnR 1 3.yX 1 y), where y represents an integer of value 0 or 1, Ri represents an alkyl, cycloalkyl, aryl, alkaryl or vinyl radical having from 1 to 12 carbon atoms, preferably a butyl, X 1 is a halogen atom, preferably chlorine, and n represents an integer from 1 to 20, preferably 4.
    Thus, for example, the functionalization of the live dienic elastomer from the polymerization step can be carried out at a temperature ranging from 30 to 120 ° C, in the presence of an appropriate amount of a tin-based agent in the first instance to form star or copulate 5% to 25% by weight of the live dienic elastomer. Then, in a second time, the remaining live chains of the dienic elastomer obtained after the first step are functionalized by adding a functionalizing agent capable of introducing the silanol function or the polysiloxane block having a silanol end at the polymeric chain end. reaction with this agent. The functionalization reaction of the dienic elastomer is then stopped by deactivating the remaining living chains and by reacting the ends of chains in SiO'with a proton donor compound to lead to the functionalized dienic elastomer according to the invention.
    The functionalized dienic elastomer according to the invention has an improved cold creep resistance. What induces a better behavior when storing and transporting this rubber.
    The functionalized dienic elastomer according to the invention can be used advantageously in a rubber composition reinforced by at least one inorganic filler such as silica, from which it maintains the dynamic and performance properties at a satisfactory level for a pneumatic application. This rubber composition is also the subject of the invention.
    According to the invention, the rubber composition is based on at least reinforcing filler comprising an inorganic filler, and an elastomeric matrix comprising the functionalized dienic elastomer described above.
    The functionalized dienic elastomer according to the invention is present in the rubber composition in proportions ranging from 10 to 100 pce (parts by weight to one hundred parts by weight of elastomer).
    According to a variant of the invention, the functionalized dienic elastomer is present in the elastomeric matrix according to a major weight fraction. Within the scope of the invention, the majority weight fraction is understood as the highest weight fraction of the matrix, preferably a weight fraction of at least 50%. The weight fraction is understood in relation to the total weight of the elastomeric matrix. The functionalized dienic elastomer according to the invention is then present in the elastomeric matrix in an amount ranging from 50 to 100 pce, preferably 60 to 100 pce.
    The elastomeric matrix can also comprise, in addition to the functionalized dienic elastomer defined above, at least one dienic elastomer conventionally used in tires as natural rubber or a synthetic elastomer, or yet another functionalized, copulated or stellated dienic elastomer. This or these other dienic elastomers are present in the matrix in proportions ranging from 0 to 90 pce, or even, according to the above variant, proportions ranging from 0 to 50 pce.
    The rubber composition according to the invention comprises, in addition to the elastomeric matrix, at least one reinforcing filler comprising an inorganic filler. By "inorganic filler", in this application, by definition, any inorganic or mineral filler regardless of its color and its origin (natural or synthetic), still called "white", "clear" or even " non-black filler ”as opposed to carbon black, capable of reinforcing it alone, without other means than an intermediate copulating agent, a rubber composition intended for the manufacture of tires, in other words apt to replace, in its reinforcement function, a conventional pneumatic carbon black; such a charge is generally characterized, in a known manner, by the presence of hydroxyl groups (-OH) on its surface. "Inorganic filler" means any mixture of these fillers.
    Preferably, the reinforcing inorganic filler is, in whole or at least mostly, silica (SiO2). The silica used can be any reinforcing silica known to the person skilled in the art, notably any precipitated or pyrogenic silica having a BET surface as well as a specific CTAB surface, all of which are less than 450 m 2 / g, even though highly dispersible precipitated silicas are preferred. As an inorganic reinforcing filler, mineral fillers of the aluminous type are also mentioned, in particular alumina (AI2O3) (oxide), aluminum hydroxides, or even reinforcing titanium oxides.
    The physical state under which the reinforcing inorganic charge is present is indifferent, whether in the form of powder, microperolas, granules, or spheres. Naturally, inorganic reinforcing filler also means mixtures of different inorganic reinforcing fillers, in particular highly dispersible silicas as described above.
    It is noted that the reinforcing inorganic filler can be cut (mixed) with an organic filler, such as carbon black, thus constituting the reinforcing filler of the composition according to the invention.
    According to a preferred embodiment of the invention, this reinforcing filler is mainly constituted of the inorganic reinforcing filler, that is, that the proportion of inorganic filler is greater than 50% by weight of the total weight of the filler, the maximum being 100%. Preferably, the reinforcing filler consists of 70% to 100% by weight of the inorganic filler.
    As carbon blacks, all carbon blacks are suitable, notably carbon blacks of the HAF, ISAF, SAF, FF, FEF, GPF and SRF types conventionally used in the rubber composition for tires (so-called carbon blacks of the pneumatic type). These include more particularly reinforcing carbon blacks of the 100, 200 or 300 series (ASTM types), such as, for example, NI 15, N134, N234, N326, N330, N339, N347, N375 carbon blacks, but also the coarser carbon blacks, for example, the N550 or N683 blacks. Carbon blacks could, for example, have already been incorporated into rubber in the form of a standard mixture.
    As examples of organic fillers other than carbon blacks, we can cite the organic fillers of functionalized polyvinylaromatics such as described in applications WO-A-2006/069792 and WO-A-2006/069793, or even organic loads of non-aromatic polyvinyl functionalized as described in applications WO-A-2008/003434 and WO-A-2008/003435.
    In the case where the reinforcing filler contains an inorganic reinforcing filler and carbon black, the weight fraction of this carbon black in said reinforcing filler is preferably chosen less than or equal to 30% in relation to the total weight of the reinforcing filler, more preferably less than 20%.
    The person skilled in the art will understand that as an equivalent load to the inorganic reinforcing charge described in this paragraph, a reinforcing charge of another nature, notably organic, could be used, provided that this reinforcing charge is partially or integrally covered with an inorganic layer such as silica, or it contains functional sites on its surface, notably hydroxyls, requiring the use of a copulation agent to establish the connection between the load and the elastomer. Carbon blacks modified by silica are also suitable, as, without limitation, the cargoes that are marketed by the company CABOT under the name “CRX 2000”, and which are described in the international patent document WO-A-96/37547.
    Advantageously, the composition according to the invention comprises from 35 to 200 parts of reinforcing charge. Preferably, the rate of reinforcement load is comprised between 40 and 140 pce, more preferably between 50 and 130 pce, the optimal situation being, in a known way, different according to the specific applications envisaged; notably in tires, the level of reinforcement expected on a bicycle tire, for example, is certainly lower than that required for a tire capable of rotating at high speed in a sustained manner, for example, a motorcycle tire, a tire for a passenger vehicle or for utility vehicle as for heavy load.
    To copulate the reinforcing inorganic filler with the dienic elastomer, a copulation agent (or binding agent) at least bifunctional is used in a known manner to ensure a sufficient connection, of a chemical and / or physical nature, between the inorganic filler and the dienic elastomer, in particular organosilanes or bifunctional polyorganosiloxanes.
    Polysulfurized silanes, known as “symmetrical” or “asymmetric” according to their particular structure, are used, as described, for example, in orders W003 / 002648 (or US 2005/016651) and W003 / 002649 (or US 2005 / 016650).
    In particular, without the following definition being limiting, polysulfurized silanes called “symmetrical” responding to the following general formula (I):
    - (i) Z-A'-Sx-A'-Z, where:
    -x is an integer from 2 to 8 (preferably from 2 to 5);
    -A 'is a divalent hydrocarbon radical (preferably
    Clusters Ci-Cig alkylene groups or arylene C 6 -C 12, more particularly alkylene -C Cio, especially C1 -C4 alkyl, in particular propylene);
    -Z responds to one of the following formulas:
    R'1 • Si — R ' 1
    R’2
    R'2 • Si — R'2
    R’2 where:
    -R'1 radicals, substituted or unsubstituted, identical or different from each other, represent a Cj-Cig alkyl group, C 5 Cis cycloalkyl or C 6 -Ci 8 aryl group (preferably C 1 -C 6 alkyl groups; cyclohexyl or phenyl, notably C1-C4 alkyl groups, more particularly methyl and / or ethyl).
    -R'2 radicals, substituted or unsubstituted, identical or different from each other, represent a C 1 -C 8 alkoxy group or C 5 -C 8 cycloalkoxy group (preferably a group chosen from C 1 -C 8 alkoxyl groups and C 5 cycloalkoxyl groups) C 8 , more preferably still a group chosen from C1-C4 alkoxyls, in particular methoxy and ethoxy).
    As examples of polysulfurized silanes, bis (3-trimethoxysilylpropyl) or bis (3triethoxysilylpropyl) polysulfides are particularly mentioned. Among these compounds, bis (3-triethoxysilylpropyl) tetrasulfide, abbreviated TESPT, or bis (triethoxysilylpropyl) disulfide, abbreviated TESPD, are used in particular. Preferred examples are also the polysulfides (notably bisulfides, trisulfides or tetrasulfides) of bis (monoalkoxy (C] -C 4 ) -dialkyl (C1-C4) silylpropyl), more particularly bis-monoethoxydimethylsilyl propyl tetrasulfide patent application WO 02/083782 (or US 2004/132880).
    As a copulation agent other than polysulfuric alkoxysilane, mention is made of bifunctional POSS (polyorganosiloxanes) or hydroxysilane polysulfides as described in patent applications WO 02/30939 (or US 6,774,255) and WO 02/31041 ( or US 2004/051210), or silanes or POSS with azo-dicarbonyl functional groups, as described, for example, in patent applications WO 2006/125532, WO 2006/125533, WO 2006/125534.
    In the compositions according to the invention, the rate of copulation agent is advantageously less than 20 pce, it being understood that it is generally desirable to use as little as possible. Its rate is preferably between 0.5 and 12 pce, more preferably 3 to 10 pce. Typically, the rate of copulating agent represents at least 0.5% and at most 15% by weight relative to the amount of inorganic filler, preferably at most 12% and more particularly at most 10%.
    The rubber compositions according to the invention may also contain, in addition to the copulating agents, copulating activators, inorganic fillers, or more generally, agents of realization which are known to be susceptible, thanks to an improvement in the dispersion of the load on the rubber matrix and a reduction in the viscosity of the compositions, to improve their ability to perform to the non-vulcanized state.
    The rubber compositions according to the invention may also include all or part of the usual additives commonly used in the elastomer compositions for the manufacture of tires, such as, for example, pigments, non-reinforcing fillers, protective agents such as ozone, chemical anti-ozonants, antioxidants, anti-fatigue agents, plasticizers, reinforcing or plasticizing resins, receptors (for example, novolac phenolic resin) or methylene donors (for example, HMT or H3M) as they were described, for example, in WO 02/10269, a crosslinking system based on either sulfur, sulfur and / or peroxide and / or bismaleimide donors, vulcanization accelerators, vulcanization activators.
    The compositions of the invention may also contain, as a preferred non-aromatic or very slightly aromatic plasticizer, at least one compound chosen from the group consisting of naphthenic, paraphoric oils, MES oils, TDAE oils, ester plasticizers (for example, trioleates) glycerol), hydrocarbon resins having a high Tg, preferably above 30 ° C, as described, for example, in WO 2005/087859, WO 2006/061064 and WO 2007/017060, and mixtures of such compounds . The overall rate in plasticizer is preferably at least 10 and at most 100 pce, more preferably at most 80 pce, or even over 70 pce. According to another preferred aspect, the composition comprises a plasticizer system composed of at least one MES or TDAE oil and at least one high Tg resin, each of the components being present, for example, in amounts ranging from 5 to 35 pce.
    The rubber composition according to the invention can be prepared according to a process comprising at least the following steps:
    (i) the realization, at a maximum temperature between 130 ° C and 200 ° C, of a first thermomechanical working time (sometimes called “non-productive” phase) of the necessary basic constituents, with the exception of the cross-linking system , of said composition comprising the elastomeric matrix and a reinforcing load, then (ii) performing, at a temperature below the said maximum temperature of said first time, preferably below 120 ° C, of a second mechanical working time in the course of into which said crosslinking system is incorporated.
    The rubber composition thus obtained can then advantageously be extruded or calendered in a manner known per se, in the desired form, to manufacture semi-finished products as tread.
    This process may also comprise, prior to carrying out the steps (i) and (ii) above, the steps of preparing the elastomeric matrix and more particularly those of preparing the functionalized dienic elastomer according to the invention.
    The invention also relates to a tire that incorporates in at least one of its constituent elements a reinforced rubber composition according to the invention, and more particularly the invention concerns semi-finished articles of one comprising this composition.
    Due to the cold creep resistance that characterizes the functionalized dienic elastomer according to the invention, it is noted that the storage and transport of this elastomer are significantly improved in relation to a star-free elastomer.
    On the other hand, due to a good compromise of rubber properties and more particularly of a satisfactory realization and hysteresis, it is understood that the use of the rubber composition comprising the functionalized dienic elastomer according to the invention, for the manufacture of a tread seeks the tire containing a rolling resistance of a convenient level. The invention therefore has, more particularly, a tire tread which is such that it comprises a reinforced rubber composition according to the invention or is such that it consists exclusively of this composition.
    The invention also has as its object a process of reducing the cold creep of a monofunctional dienic elastomer carrying a silanol function or a polysiloxane block having a silanol end at one end of the chain, the other end being free from any functionalization. This process consists previously of the conditioning of the elastomer, to modify it by adding a copulated or starry diene elastomer with tin in a proportion of 5 to 35% by weight in relation to the weight of the monofunctional dienic elastomer, in order to obtain a dienic elastomer functionalized of which 75% to 95% by weight carry on a single chain end a silanol function or a polysiloxane block having one silanol end, the other end being free from any functionalization, and 5% and 25% by weight is stellated or copulated with tin.
    The invention also has as its object a process of reducing the cold creep of a monofunctional dienic elastomer carrying a silanol function or a polysiloxane block having a silanol end at one end of the chain, the other end being free from any functionalization. This process consists of synthesizing the dienic elastomer, proceeding from the polymerization stage, in carrying out a copulation or star formation of 5 to 25% by weight of the live elastomer with a tin-based compound, then in functionalizing 75 to 95% by weight of the remaining live elastomer with a functionalizing agent capable of introducing the silanol function or the polysiloxane block having a silanol end.
    The aforementioned characteristics of the present invention, as well as others, will be better understood by reading the following description of the various examples of carrying out the invention, given by way of illustration and not limitation.
    EXAMPLES
    I Preparation of an elastomeric matrix according to the invention.
    1) Measures and tests used - Experimental techniques used for the characterization before cooking the obtained polymers:
    (a) Determination of the molar mass distribution by the stereochemical exclusion chromatography technique (conventional SEC)
    The SEC technique (size exclusion chromatography) was used to determine the molecular mass distributions for samples of these polymers. From standard products whose characteristics are described in example 1 of the European patent document EP-A-692 493, this technique allowed to evaluate for a sample a numerical molecular mass (Mn) having a relative value, contrary to that determined by osmometry, as well as a weight average molecular mass (Mw). The polydispersity index (Ip = Mw / Mn) of this sample was then “deducted”, calculated via a so-called MOORE calibration.
    According to this technique, the macromolecules are physically separated according to their dimensions corresponding to the swollen state, in columns filled with a porous stationary phase. Before carrying out this separation, the polymer sample is solubilized in tetrahydrofuran at a concentration of about 1 g / 1. Then the solution is filtered through a 0.45 pm porosity filter before injection.
    A chromatograph sold under the name “WATERS Alliance 2690” with an in-line degasser is used for the separation mentioned above. The eluting solvent is tetrahydrofuran, the flow rate is 1 ml / min, the system temperature is 35 ° C and the analysis duration is 30 min. A set of two “WATERS” columns mounted in series is used of which the type is “STYRAGEL HT6E”.
    Number Brand Domain of molar masses(g / mol) Length (mm) Inner diameter (mm) Particle size (pm) Trade name References(indicative) Column 1 WATERS 2,000-10 7 300 7.8 10 STYRAGEL HT6E WAT044219 Column 2 WATERS 2,000-10 7 300 7.8 10 STYRAGEL HT6E WAT044219
    The injected volume of the polymer sample solution is 100 μΐ. The detector is a “WATERS” differential reffactometer whose model is “2410”. Chromatographic data exploration software is used, the trade name is “WATERS EMPOWER”.
    The calculated average molar masses are relative to a calibration curve performed for the following microstructure SBR: 25% mass of styrene-like motifs, 23% mass of type-1.2 motifs and 50% mass of type-1.4 trans motifs.
    (b) For polymers and rubber compositions, the Mooney ML (1 + 4) viscosities at 100 ° C are measured according to the ASTMD-1646 standard.
    An oscillating consistometer is used as described in the ASTM D-1646 standard. The Mooney plasticity measure is made according to the following principle: the composition in the non-vulcanized state (ie before cooking) is modeled in a cylindrical enclosure heated to 100 ° C.
    After one minute of preheating, the rotor rotates within the specimen at 2 rpm and the useful torque is measured to maintain this movement after 4 minutes of rotation. Mooney plasticity (ML 1 + 4) is expressed in “Mooney unit” (UM, with 1 UM = 0.83 N.m).
    (c) The glass transition temperatures Tg of the polymers are measured using a differential calorimeter Çdifferential scanning calorimeter ”).
    (d) CH 3 Si (SBR) 2 OH functionalization in chain medium or SBR (CH 3 ) 2 SiOH in chain end is characterized by 2D 'H 29 Si NMR and quantified by 1 H NMR.
    The 2D NMR spectrum 1 H- 29 Si allows to verify the nature of the function thanks to the chemical displacement values of the Silicon nuclei and the protons in the vicinity J (via 2 connections). It uses a copulation constant value 2 J m -29Si of 8 Hz. The chemical displacement of the silicon of the species SBR (CH 3 ) 2 SiOH at the end of the chain is about 11-12 ppm.
    The NMR 'Η spectrum allows to quantify the function by integrating the characteristic signal of the protons of the methyl group carried by silicon CH 3 Si, located around δ = 0 ppm. The samples are solubilized in carbon sulfide (CS 2 ). 100 pL of delusional cyclohexane (CôDi 2 ) is added for the blocking signal. NMR analyzes are performed on a 500 MHz BRUKER spectrometer equipped with a BBI 5 mm “broadband” probe. For NMR] M quantitative experiment, the sequence uses a 30 ° pulse and a repetition delay of 2 seconds.
    (e) the 13 C NMR technique (Beebe, DH Polymer 1978, 19, 23133 or Bradbury, JH; Elix, JA; Perera, MCS Journal of Polymer science 1988, 26, 615-26) are used to determine the microstructure of the elastomers obtained. NMR 13 C analyzes are performed on a 250 MHz BRUKER spectrometer equipped with a DUAL 13 C- 1 H 10 mm probe. The elastomer is solubilized in CDC1 3 at a concentration of about q β g / L. The quantitative C NMR experiment uses a sequence with 'H decopulation and suppression of the Overhauser effect (inverse gated ! Hdecoupling), a 90 ° pulse and a repetition delay = 6 s. The spectral width is 200 ppm, the number of scans is 8192. The spectra are calibrated on the central peak of the triplet CDC1 3-77 ppm.
    (f) For polymers, the viscosity inherent at 25 ° C of a 0.1 g / dl polymer solution in toluene, is measured from a dry polymer solution:
    PRINCIPLE:
    The inherent viscosity is determined by measuring the flow time t of the polymer solution and the flow time t of the toluene in a capillary tube. In a Ubbelhode tube (capillary diameter 0.46 mm, capacity 18 to 22 ml), placed in a bath with a thermostat at 25 ± 0.1 ° C, the flow time of toluene and that of the polymer solution from 0 , 1 g / dl are measured.
    The inherent viscosity is obtained by the following ratio:
    with:
    C: concentration of the toluene polymer solution in g / dl; t: flow time of the toluene polymer solution in seconds;
    t 0 : flow time of toluene in seconds;
    q jnh : inherent viscosity expressed in dl / g.
    (g) for polymers, coldflaw: CF 100 (1 + 6) comes from the following measurement process:
    It is about measuring the weight of extruded gum through a calibrated die for a given time (6 hours), under fixed conditions (at
    100 ° C). The die has a diameter of 6.35 mm for a thickness of 0.5 mm.
    The cold-flow rig is a cylindrical cut, drilled at the bottom. About 40g ± 4g of Gina previously prepared in the form of a tablet (2 cm thick and 52 mm in diameter) are placed in this device. A calibrated piston of 1 kg (± 5 g) is placed on the gum tablet. The set is then placed in an oven, thermally stabilized at 100 ° C ± 0.5 ° C.
    During the first hour in the greenhouse, the measurement conditions are not stabilized. After an hour, therefore, cut the product that is extruded and cast it.
    The measurement after 6 hours ± 5 min, during which the product is left in the oven. At the end of 6 hours, it is necessary to recover the extruded product sample by cutting the same flush on the bottom surface. The test result is the gum weight weighed in grams.
    2) Preparation of a functionalized SiOH copolymer at the chain end:
    It is continuously introduced into a 32.5 1 reactor equipped with a turbine, cyclohexane, butadiene, styrene and tetrahydrofurfuryl ethyl ether agitator, according to the respective mass flow rates of 100/11 / 3.2 / 0.037 . 200 micromols of n-butyl lithium (n-BuLi) to 100 g of monomers are introduced into the line in order to neutralize the protic impurities brought by the different constituents present in the line inlet. At the reactor inlet, 530 pmol of n-BuLi is introduced for 100 g of monomers.
    The different flow rates are adjusted so that the average residence time in the reactor is 40 min. The temperature is maintained at 80 ° C.
    The conversion rate, which is measured on a sample carried out at a reactor output, is 98%.
    Finally, at the exit of the reactor, add the live polymer solution (static in-line mixer) 265 micromoles to 100 g of hexamethylcyclotrisiloxane monomers in solution in cyclohexane. Then the copolymer is subjected to an antioxidant treatment, with the help of 0.8 pce of 2,2 '-methylene-bis (4-methyl-6-terciobutylphenol) and 0.2 pce of N- (1,3-dimethylbutyl) ) -N'-phenyl-p-phenylenediamine.
    The copolymer thus treated is separated from its solution by a water vapor extraction operation, then dried on an instrument with cylinders at 100 ° C for 20 min, to obtain the functionalized SiOH end-of-chain copolymer.
    The ML viscosity of this copolymer A is 53. The molecular weight of the copolymer, determined by conventional SEC, is 123,000 g / mol, the Ip is 2.0.
    The microstructure of this copolymer Á is determined by rmn 13 c.
    The SBR block of this copolymer A contains 25% styrene (by weight) and, for its butadiene part, 58% vinyl motifs, 21% 1.4 cis motifs and 21% 1.4 trans motifs.
    The 2D H-Si NMR analysis allows to conclude the existence of a SBR (CH 3 ) 2 SiOH chain end function. The function rate (CH 3 ) 2 Si determined by 1 H NMR for copolymer A is 5.85 mmol / kg.
    3) Preparation of a copolymer B starring with tin:
    The synthesis of copolymer B is carried out according to the operational conditions described in test 1, except that tin tetrachloride is added instead of hexamethylcyclotrisiloxane, 265 micromoles to 100 g of tin tetrachloride monomers in solution in cyclohexane.
    The ML viscosity of copolymer B is 104. The molecular weight of the copolymer, determined by conventional SEC, is 209,000 g / mol, the Ip is 2.1.
    The microstructure of this copolymer B is determined by NMR , 3 C.
    The SBR block of this copolymer B contains 25% styrene (by weight) and, for its butadiene part, 58% vinyl motifs, 21% 1.4 cis motifs and 21% 1.4 trans motifs.
    4) Preparation of elastomeric matrices, mixtures of copolymer A and copolymer B:
    In a 10 liter reactor, 5 kg of cyclo10 hexane, 285 g of polymer A and 15 g of polymer B are added, this mixture is placed at 60 ° C for 5 hours. The copolymer thus treated is separated from its solution by a water vapor extraction operation, then dried over a tool with cylinders at 100 ° C for 20 min, to obtain copolymer C.
    Copolymer CopolymerA (g) CopolymerB (g) Mn SEC Ip Cold flow Ç 285 15 119000 2.0 1.83 D 270 30 119000 2.1 1.40 AND 240 60 125000 2.0 0.84 F 210 90 129000 2.1 0.41
    II-Comparative examples of rubber compositions
    1) Measurements and tests used (h) Mooney ML (large) and MS (small) (1 + 4) viscosity at 100 ° C: measured according to ASTM: D-1646, entitled “Mooney” in the tables. The results are relative data: an increase over the core at 100 indicates an increase in viscosity and therefore an altered performance.
    (i) SHORE A hardness: measurements made according to DIN 53505. The results are in relative data: an increase in relation to the core at 100 indicates an increased stiffness.
    (j) The dynamic properties AG * and tan (ô) max are measured on a viscoanalyzer (Metravib VA4000), according to ASTM D 5992-96. The response of a sample of vulcanized composition (cylindrical specimen 2 mm thick and 79 m 2 section) is recorded, submitted to a sinusoidal request in alternating simple shear, at a frequency of 10 Hz, under normal temperature conditions (23 ° C) according to ASTM D 1349-99. A sweep in a crest-crest amplitude range of 0.1% to 50% (cycle going) is performed, after 50% to 0.1% (cycle return). The results explored are the complex dynamic shear modulus (G *) and the loss factor tan δ. For the return cycle, the maximum observed tan δ value (tan (6) max) is indicated, as well as the deviation of the complex modulus (AG *) between the values at 0.1% and 50% deformation (Payne effect ). The results are relative data: an increase over the 100 core test indicates an increase in hysteresis.
    Example 1 (Tg = -25 ° C)
    The elastomers SBR C, SBR D, SBR E and SBR F were used for the preparation of rubber compositions C, D, E and F of tread type, each comprising silica as a reinforcing filler.
    Each of these compositions C, D, E and F has the following formulation (expressed in pce: parts for one hundred parts of elastomer):
    BR (1) 23 SBR 77 Silicon (2) 85 Carbon black (3) 4 Plasticizer (4) 12 Plasticizer (5) 18 Silane (6) 6.8 Stearic acid 2 DPG (7) 1.6 Anti ozone wax 1.5 ZnO 1.5
    6PPD (8) 1.9 Sulfur 1.2 Accelerator 1.9
    (1) = BR with 4.3% of 1-2; 2.7% trans-1-4; 93% cis 1-4 (Tg = -106 ° C) (2) = Silica "Zeosil 1165 MP" from Rhodia (3) = N234 (4) = MES oil (Shell "Catenex SNR") (5) = polyilimonene resin (“Dercolyte LI20” from DRT) (6) = TESPT copulating agent (“Si69” from Degussa) (7) = diphenylguanidine (“Perkacit DPG” from Flexsys) (8) = N 1, 3 -dimethylbutyl-N-phenylparaphenylenediamine (“Santoflex 6-PPD” from Flexsys) (9) = CBS (“Santocure” from Flexsys)
    Each of the following compositions is performed, first, by thermomechanical work, then, in a second finishing time, by mechanical work.
    Successively, in an internal mixer of the “Banbury” type laboratory, whose capacity is 400 cm, which is filled to 70% and whose initial temperature is about 90 ° C, the elastomer, the two thirds of silica, carbon black, copulating agent and diphenylguanidine, then, about a minute later, the rest of the reinforcing filler, MES oil, resin, antioxidant, stearic acid and anti-ozone wax, then, about two minutes later, zinc monoxide.
    The thermomechanical work step is carried out for 4 to 5 minutes, until a maximum drop temperature of about 160 ° C.
    The first time mentioned above of thermomechanical work is performed like this, being necessary that the average speed of the reeds when this first time is 50 rpm.
    The mixture thus obtained is recovered, then cooled in an external mixer (homo-finisher), the sulfur and accelerator are added at 30 ° C, mixing the whole for a duration of 3 to 4 minutes (second time) above mentioned of 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 sheets of rubber, 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.
    Cross-linking is carried out at 150 ° C for 40 min
    Table 1:
    € Omission (% stars) -A <0%) C (5%) ..... Εφα%) And (20%) .... F (30%) ...... Elastomer SBRA SBRC SBRD SBRE SBRF ML 1 + 4 elastomer at 100 ° C 50 53 53 56 59 Cold flow elastomer 2.17 1.83 1.4 0.84 0.41 Properties in the non-crosslinked state ML (1 + 4) at 100 ° C 100 99 105 104 101 Properties in the reticulated state Shore A 100 103 106 104 102 Dynamic properties as a function of deformation Tan (δ) max 23 ° C 100 105 105 106 107
    It is found that the cold flow resistance of the functionalized dienic elastomer significantly improves by increasing the rate of tin-starred copolymer in the rubber composition compared to a composition A that does not contain it. On the other hand, for the C, D and E compositions, tan (δ) Max is maintained at acceptable values, despite the increase in the rate of copolymer stellated with tin to the detriment of the copolymer functionalized at the end of the chain by a silanol function. .
    The cold flow commitment of the elastomers-hysteresis of the composition is completely satisfactory for compositions C, D and E according to the invention comprising, respectively, in their elastomeric matrix 5%, 10% and 20% of a stellate copolymer with tin.
    权利要求:
    Claims (16)
    [1]
    1. Functionalized dienic elastomer, characterized by the fact that:
    - 75% to 95% by weight of the elastomer is monofunctional bearing, at only one end of the chain, a silanol function or a polysiloxane block having one silanol end, the other end without any functionalization and
    - 5% to 25% by weight of the elastomer are coupled or starred with tin.
    [2]
    2. Elastomer according to claim 1, characterized by the fact that the polysiloxane block having a silanol end corresponds to the formula:
    - (SiR ^ Ol * —H where
    - R1 and R2, being identical or different, represent an alkyl, cycloalkyl, aryl, alkaryl, aralkyl or vinyl group having from 1 to 10 carbon atoms,
    - x is an integer ranging from 1 to 1500.
    [3]
    Elastomer according to claim 2, characterized by the fact that R1 and R2, identical or different, represent an alkyl group with 1 to 5 carbon atoms.
    [4]
    4. Elastomer according to claim 1, characterized by the fact that the functionalized dienic elastomer is composed of 10% to 25% by weight of a dienic elastomer coupled or starred with tin.
    Petition 870190040312, of 29/04/2019, p. 10/31
    2/3
    [5]
    Elastomer according to any one of claims 1 to 4, characterized in that the dienic elastomer coupled with, or stellar with tin is a star-branched elastomer with tin.
    [6]
    6. Elastomer according to claim 5, characterized in that the star-branched dienic elastomer with tin is an elastomer comprising four branches.
    [7]
    An elastomer according to any one of claims 1 to 6, characterized in that the dienic elastomer is a butadiene / styrene copolymer.
    [8]
    8. Reinforced rubber composition based on at least one reinforcement filler comprising an inorganic filler and an elastomer matrix, characterized in that the elastomer matrix comprises at least one functionalized dienic elastomer as described in any one of claims 1 to 7.
    [9]
    Composition according to claim 8, characterized in that the elastomer matrix also comprises at least one conventional dienic elastomer.
    [10]
    Composition according to claim 8 or 9, characterized in that the proportion of inorganic filler in the reinforcing filler is greater than 50% by weight, in relation to the total weight of the reinforcing filler.
    [11]
    Composition according to any one of claims 8 to 10, characterized in that the inorganic reinforcing filler is composed of silica.
    [12]
    12. Semi-finished rubber article for tires, characterized in that it comprises a crosslinkable or crosslinked rubber composition as defined in any one of claims 8 to 11.
    [13]
    13. Semi-finished article according to claim 12, characterized by the fact that said article is a band.
    Petition 870190040312, of 29/04/2019, p. 11/31
    3/3
    [14]
    Tire characterized in that it comprises a semi-finished article as defined in claim 12 or 13.
    [15]
    15. Process to reduce the cold flow of a monofunctional dienic elastomer carrying, on only one end of the chain, a silanol function, or a polysiloxane block having one silanol end, the other end having no functionalization, characterized by the fact that , before conditioning, it is modified by the addition of a dienic elastomer coupled with or stellated with tin, in a proportion of 5 to 35% by weight, in relation to the weight of the monofunctional dienic elastomer.
    [16]
    16. Process to reduce the cold flow of a monofunctional dienic elastomer carrying, on only one end of the chain, a silanol function or a polysiloxane block having one silanol end, the other end having no functionalization, characterized by the fact that, during the process for its synthesis, at the conclusion of the polymerization stage, from 5 to 25% by weight of the live elastomer is coupled by or branched in star by a tin-based compound and then the process is continued by the functionalization of the 75 to 95% by weight of the remaining live elastomer with a functionalizing agent capable of introducing the silanol functional group or the polysiloxane block having a silanol end.
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    同族专利:
    公开号 | 公开日
    CN102549019B|2014-12-24|
    KR20170045369A|2017-04-26|
    FR2951178B1|2012-08-17|
    JP6026279B2|2016-11-16|
    EP2486065B1|2014-12-24|
    US20120252928A1|2012-10-04|
    PL2486065T3|2015-06-30|
    RU2565706C2|2015-10-20|
    BR112012008027A2|2016-03-15|
    KR20120093269A|2012-08-22|
    WO2011042507A1|2011-04-14|
    RU2012118621A|2013-11-20|
    US9670291B2|2017-06-06|
    EP2486065A1|2012-08-15|
    JP2013507468A|2013-03-04|
    CN102549019A|2012-07-04|
    FR2951178A1|2011-04-15|
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    WO2021089958A1|2019-11-06|2021-05-14|Compagnie Generale Des Etablissements Michelin|Tyre having a tread|
    WO2021089959A1|2019-11-06|2021-05-14|Compagnie Generale Des Etablissements Michelin|Tire comprising a tread|
    法律状态:
    2016-07-12| B25A| Requested transfer of rights approved|Owner name: MICHELIN RECHERCHE ET TECHNIQUE S.A. (CH) , COMPAG |
    2018-01-02| B25A| Requested transfer of rights approved|Owner name: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN (FR |
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-02-26| B06T| Formal requirements before examination|
    2019-07-16| B09A| Decision: intention to grant|
    2019-08-13| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/10/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/10/2010, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    FR0957030A|FR2951178B1|2009-10-08|2009-10-08|FUNCTIONALIZED DIENIC ELASTOMER AND RUBBER COMPOSITION CONTAINING SAME.|
    PCT/EP2010/065030|WO2011042507A1|2009-10-08|2010-10-07|Functionalized diene elastomer, and rubber composition containing same|
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