# Patent

## Title
Functional diene block elastomer with a low PI and improved cold flow, and rubber composition containing same

## Abstract

The invention relates to a functionalized diene elastomer composed a) of a specific block copolymer functionalized, at the chain end or in the middle of the chain, by a tin functional group, b) of a specific block copolymer star-branched by tin and c) of a content of less than 15% by weight, with respect to the total weight of the functionalized diene elastomer, of a specific non-tin-functional block copolymer.

## Background
BACKGROUND
1. Field
The present invention relates to a functionalized diene elastomer composed of a specific functionalized block copolymer, of a specific star-branched block copolymer and of a content of less than 15% by weight of a specific non-tin-functional block copolymer.
2. Description of Related Art
The reduction in the hysteresis of the mixtures is an ongoing objective of the tire industry in order to limit the consumption of petrol and to thus protect the environment. This reduction in hysteresis must, however, be carried out while keeping intact, indeed even while improving, the processability of the mixtures.
Many solutions have already been experimented with in order to achieve the objective of fall in hysteresis. In particular, the functionalization of the polymers by a functional group which interacts with the reinforcing filler has appeared as an advantageous route.
Functional groups which interact with the filler have thus been attached at the chain end at the start or end of polymerization by means of functional initiators or functionalization agents. By way of example, 4,4′-bis(diethylamino)benzophenone, also known as DEAB, or other aminated functional groups which interact with carbon black have been added at the end of polymerization, as described in the patent documents FR 2 526 030 and U.S. Pat. No. 4,848,511. The polymers coupled by or star-branched by tin comprise functional groups capable of interacting with carbon black which are introduced at the end of polymerization. Mention may be made, by way of example, of the European patent document EP 0 709 235. Functional groups which interact with silica have also been attached at the chain end at the end of polymerization, such as functional groups comprising a silanol group which are disclosed in the patent document FR 2 740 778 or functional groups comprising alkoxysilane or aryloxysilane groups which are described in the document U.S. Pat. No. 5,066,721. The majority of these solutions, both for the black and for the silica, genuinely result in a limitation on hysteresis of the corresponding compositions but concomitantly in a greater difficulty in processing these same compositions.
Patent EP 1 278 789 describes a copolymer comprising n blocks (n=2 or 3) intended to form an elastomer matrix of a crosslinkable rubber composition, each of the said blocks comprising an essentially unsaturated diene elastomer and one or each of the said blocks forming a chain end of the said copolymer being composed of a polyisoprene. The number-average molecular weight of the polyisoprene block is between 2 500 and 20 000 g/mol and the number-average molecular weight of the block of the copolymer which is other than the said polyisoprene block is substantially between 80 000 g/mol and 350 000 g/mol. The use of the said block copolymer makes it possible to significantly optimise the results of reduction in hysteresis and processability for the said rubber composition in which it is present.
It is also known that polymers having narrow molecular distributions confer a reduced hysteresis on the rubber compositions in which they are present. In particular, linear functional diene elastomers with narrow molecular distributions before functionalization exhibit improved hysteresis properties. However, these elastomers exhibit an increased cold flow in comparison with the same elastomers exhibiting a broad molecular distribution before functionalization, which is damaging for the storage and transportation of the elastomers.
Many solutions exist in order to reduce the cold flow. The work Nouvelles Recherches dans le Domaine des Composés Macromoléculaires [New Research in the Field of Macromolecular Compounds], editor(s) Ceausescu E, Oxford, Pergamon Press Ltd., 1984, pp. 343-56, 72, mentions methods for reducing cold flow, such as the increase in the molecular weight, the star-branching or the degree of branching. However, the increase in the molecular weight is highly damaging to the use of the mixtures while the branching is accompanied by an increase in the hysteresis of the mixtures. Furthermore, surprisingly, the polymers solely star-branched by tin (3 or 4 branches) exhibit greater hysteresis in comparison with the polymers coupled by tin.
It is also known that, in order to solve the problem of cold flow, the polydispersity index of the elastomer can be increased. However, this is not without effect on the properties of the rubber compositions in which it is present, in particular on the hysteresis or the processability of the mixtures, for example.
SUMMARY
There thus exists a need to provide an elastomer which confers, on a reinforced rubber composition, good properties of hysteresis and of processing for the purpose of a tire application, while exhibiting a reduced cold flow from the perspective of better behaviour during storage and transportation of the rubber.
The Applicant Company has discovered, surprisingly, that a functionalized diene elastomer composed of a block copolymer functionalized at the chain end or in the middle of the chain by a tin functional group, exhibiting a narrow molecular weight distribution before functionalization or coupling, and of a block copolymer star-branched with a tin-comprising compound, exhibiting a narrow molecular weight distribution before star-branching and comprising less than 15% by weight, with respect to the total weight of the functionalized diene elastomer, of non-tin-functional block copolymers, confers, on a rubber composition in which it is present, rubber properties, in particular hysteresis and processing properties, which are entirely acceptable for use in tires, while exhibiting a significantly improved resistance to cold flow.
A subject-matter of the invention is thus a functionalized diene elastomer composed:
a) of a block copolymer functionalized, at the chain end or in the middle of the chain, by a tin functional group and corresponding to the following formula:

[A-BnXB-A]m 

where n and m are integers of greater than or equal to 0 and such that n+m=1 or 2,

b) of a block copolymer star-branched by tin and corresponding to the following formula:

[A-BoYB-A]p 

where o and p are integers of greater than or equal to 0 and such that o+p≧3 and o+p≦6,

c) of a content of less than 15% by weight, with respect to the total weight of the functionalized diene elastomer, of a non-tin-functional block copolymer corresponding to the following formula:

[A-B]

where:

    
    
        all the A blocks are composed of a polyisoprene or all the A blocks are composed of a polybutadiene,
        the B blocks are composed of a diene elastomer, the molar content of units resulting from conjugated dienes of which is greater than 15%, the B blocks being identical to one another,
        X and Y independently represent a tin-comprising group,
        the number-average molecular weight Mn1 of each A block varies from 2 500 to 20 000 g/mol,
        the number-average molecular weight Mn2 of each B block varies from 80 000 to 350 000 g/mol,
        the content of 1,2 linkages in each A block is between 1 and 20% in the case where A is a polybutadiene block,
        the content of 3,4 linkages in each A block is between 1 and 25% in the case where A is a polyisoprene block,
        the A-B copolymer exhibits a monomodal distribution of molecular weights before optional functionalization or optional star-branching and a polydispersity index before optional functionalization or optional star-branching of less than or equal to 1.3.
    
    




DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS
The term “polydispersity index” is understood to mean, within the meaning of the invention, the weight-average molecular weight/number-average molecular weight ratio.
Preferably, the functionalized diene elastomer according to the invention comprises from 5% to 45% by weight, preferably from 10% to 30% by weight, with respect to the total weight of the functionalized diene elastomer, of the said block copolymer star-branched by tin b).
Preferably, the functionalized diene elastomer according to the invention comprises a content strictly of greater than 0% by weight and of less than 10% by weight, with respect to the total weight of the functionalized diene elastomer, of the said non-tin-functional block copolymer c). Preferably, the functionalized diene elastomer according to the invention comprises a content of less than 5% by weight, with respect to the total weight of the functionalized diene elastomer, of the said non-tin-functional block copolymer c).
In the present description, the term “functionalized diene elastomer” is understood to mean a diene elastomer which comprises a group comprising one or more heteroatoms.
This group can be located at the end of the chain formed by the B block other than the polyisoprene or polybutadiene block A (m+n=1, m and n being defined as above). It will then be said that the diene elastomer is functionalized at the end of the said chain. It is generally an elastomer obtained by reaction of a living elastomer with a functionalization agent, that is to say any at least monofunctional molecule, the functional group being any type of chemical group known by a person skilled in the art to react with a living chain end.
This group can be located in the linear main elastomer chain between two B blocks other than the polyisoprene or polybutadiene blocks A (m+n=2, m and n being defined as above). It will then be said that the diene elastomer is coupled or alternatively functionalized in the middle of the said chain, in contrast to the position “at the end of the chain”, although the group is not located precisely at the middle of the said elastomer chain. It is generally an elastomer obtained by reaction of a living elastomer with a coupling agent, that is to say any at least difunctional molecule, the functional group being any type of chemical group known by a person skilled in the art to react with a living chain end.
This group can be central, to which o+p elastomer or branched chains A-B (o, p and A-B being defined as above) are bonded, forming a star-branched structure of the elastomer. It will then be said that the diene elastomer is star-branched. It is generally an elastomer obtained by reaction of a living elastomer with a star-branching agent, that is to say any polyfunctional molecule, the functional group being any type of chemical group known by a person skilled in the art to react with a living chain end.
As explained above, the block copolymer a) is functionalized at the end or in the middle of the chaine formed by a tin functional group. The functionalization can be obtained with a monohalotin functionalization agent or a dihalotin coupling agent which can correspond to the general formula R4-xSnX0x, where x represents an integer having the value 1 or 2, R represents an alkyl, cycloalkyl, aryl, alkaryl or vinyl radical having from 1 to 12 carbon atoms, preferably a butyl, and X0 is a halogen atom, preferably chlorine. Mention may be made, as preferred functionalization agent, of tributyltin monochloride or dibutyltin dichloride. In the same way, the functionalization can be obtained with a tin-derived functionalization agent which can correspond to the general formula (X1yR13-ySn)—O—(SnR13-zX1z) or (X1yR13-ySn)—O—(CH2)e—O—(SnR13-zX1z), where y and z represent integers between 0 and 2 and y+z is equal to 1 or 2, R1 represents an alkyl, cycloalkyl, aryl, alkaryl or vinyl radical having from 1 to 12 carbon atoms, preferably a butyl, X1 is a halogen atom, preferably chlorine, and e represents an integer from 1 to 20, preferably 4.
According to the invention, the block copolymer b) is star-branched. Preferably, the diene elastomer b) is star-branched by a tin functional group. The star-branching can be obtained with a tri- or tetrahalotin star-branching agent which can correspond to the formula R2qSnX24-q, where q represents an integer having the value 0 or 1, R2 represents an alkyl, cycloalkyl, aryl, alkaryl or vinyl radical having from 1 to 12 carbon atoms, preferably a butyl, and X2 is a halogen atom, preferably chlorine. Mention may be made, as preferred star-branching agent, of butyltin trichloride or tin tetrachloride. In the same way, the star-branching can be obtained with a tin-derived functionalization agent which can correspond to the general formula (X3kR33-kSn)—O—(SnR33-1X31) or (X3kR33-kSn)—O—(CH2)f—O—(SnR33-lX3l), where k and 1 represent integers between 0 and 3 and k+1 integers between 3 and 6, R3 represents an alkyl, cycloalkyl, aryl, alkaryl or vinyl radical having from 1 to 12 carbon atoms, preferably a butyl, X3 is a halogen atom, preferably chlorine, and f represents an integer having a value from 1 to 20, preferably 4.
According to a preferred embodiment, the block copolymer a) is a copolymer functionalized by a tin functional group in the middle of the chain.
According to another preferred embodiment, the block copolymer b) is a copolymer star-branched by tin having 4 branches.
According to another preferred embodiment, the block copolymer a) is a copolymer functionalized by a tin functional group in the middle of the chain and the block copolymer b) is a copolymer star-branched by tin having 4 branches.
Preferably, the ratio of the number-average molecular weight Mn1 of each end polybutadiene or polyisoprene block A to the number-average molecular weight Mn2 of each of the B blocks varies from 5 to 20%.
As explained above, preferably, the block copolymer star-branched by tin represents from 5 to 45% by weight, preferably from 10 to 30% by weight, of the total weight of the functionalized diene elastomer.
Essentially unsaturated diene elastomer (i.e., the molar content of units resulting from conjugated dienes of which is greater than 15%) capable of being employed in order to obtain the said B block other than the polybutadiene or polyisoprene block or blocks, themselves corresponding to this definition, is understood to mean any homopolymer obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms, or any block, random, sequential or microsequential 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.
The following are suitable in particular as conjugated dienes: 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di(C1-C5 alkyl)-1,3-butadienes, such as 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene or 2-methyl-3-isopropyl-1,3-butadiene, an aryl-1,3-butadiene, 1,3-pentadiene or 2,4-hexadiene. The following, for example, are suitable as vinylaromatic compounds: styrene, ortho-, meta- or para-methylstyrene, the “vinyltoluene” commercial mixture, para-(tert-butyl)styrene, methoxystyrenes, chloro styrenes, vinylmesitylene, divinylbenzene or vinylnaphthalene.
Preferably, the B block or blocks are chosen from copolymers of styrene and butadiene, copolymers of styrene and isoprene, copolymers of butadiene and isoprene, styrene/butadiene/isoprene terpolymers, polyisoprene when the neighbouring A block is a polybutadiene and polybutadiene when the neighbouring A block is a polyisoprene.
The following are suitable: polybutadienes, in particular those having a content (mol %) of 1,2- units of between 4% and 80%, polyisoprenes, butadiene/styrene copolymers and in particular those having a Tg (glass transition temperature Tg, measured according to ASTM D3418) of between 0° C. and −70° C. and more particularly between −10° C. and −60° C., a styrene content of between 5% and 60% by weight and more particularly between 20% and 50%, a content (mol %) of 1,2- bonds of the butadiene part of between 4% and 75% and a content (mol %) of trans-1,4- bonds of between 10% and 80%, butadiene/isoprene copolymers, in particular those having an isoprene content of between 5% and 90% by weight and a Tg of −40° C. to −80° C., or isoprene/styrene copolymers, in particular those having a styrene content of between 5% and 50% by weight and a Tg of between 5° C. and −55° C.
In the case of butadiene/styrene/isoprene copolymers, those having a styrene content between 5% and 50% by weight and more particularly, of between 10% and 40%, an isoprene content of between 15% and 60% by weight and more particularly between 20% and 50%, a butadiene content of between 5% and 50% by weight and more particularly of between 20% and 40%, a content (mol %) of 1,2- units of the butadiene part of between 4% and 85%, a content (mol %) of trans-1,4- units of the butadiene part of between 6% and 80%, a content (mol %) of 1,2- plus 3,4- units of the isoprene part of between 5% and 70% and a content (mol %) of trans-1,4- units of the isoprene part of between 10% and 50%, and more generally any butadiene/styrene/isoprene copolymer having a Tg of between −5° C. and −70° C., are suitable in particular.
Preferably, the B block or blocks are chosen from copolymers of styrene and butadiene, copolymers of styrene and isoprene, polyisoprene when the neighbouring A block is a polybutadiene and polybutadiene when the neighbouring A block is a polyisoprene. More preferably, the B block or blocks are chosen from copolymers of styrene and butadiene.
According to a particularly preferred embodiment, A is polyisoprene and B is a copolymer of styrene and butadiene, the block copolymer a) being functionalized by the functionalization agent Bu2SnCl2 and the block copolymer b) being star-branched by the star-branching agent 5 nCl4.
According to another particularly preferred embodiment, A is polybutadiene and B is a copolymer of styrene and butadiene, the block copolymer a) being functionalized by the functionalization agent dibutyltin dichloride (Bu2SnCl2) and the block copolymer b) being star-branched by the star-branching agent tin tetrachloride (SnCl4).
The polymerization of diene monomers is initiated by an initiator. Use may be made, as polymerization initiator, of any known monofunctional anionic initiator. However, an initiator comprising an alkali metal, such as lithium, is preferably used.
Those comprising a carbon-lithium bond are suitable in particular as organolithium initiators. Use will preferably be made of a hydrocarbon organolithium initiator not comprising a heteroatom. Representative compounds are aliphatic organolithium compounds, such as ethyllithium, n-butyllithium (n-BuLi) and isobutyllithium.
The polymerization is, as known per se, 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 or cyclohexane, or an aromatic hydrocarbon, such as benzene, toluene or xylene.
The polymerization can be carried out continuously or batchwise, preferably batchwise. The polymerization is generally carried out at a temperature of between 20° C. and 120° C. and preferably in the vicinity of 30° C. to 90° C. It is, of course, also possible to add, at the end of polymerization, a transmetallation agent for modifying the reactivity of the living chain end.
The living diene elastomer resulting from the polymerization is subsequently functionalized in order to prepare the functionalized diene elastomer according to the invention.
According to one method of preparation of the functionalized diene elastomer according to the invention, the block copolymer at the living chain end can be prepared in different stages:

    
    
        the preparation of the living polyisoprene or polybutadiene block, and
        the preparation of the essentially unsaturated diene elastomer carried out in order to obtain the said block other than the polybutadiene or polyisoprene block.
    
    


According to this method of preparation, the polymerization of isoprene or butadiene diene monomers is initiated by the said organolithium initiators in order to obtain a living polyisoprene or polybutadiene diene homopolymer. The living diene homopolymer thus obtained is subsequently used as initiator in the preparation of the diene elastomer in order to obtain a living block copolymer.
The well-informed reader would understand that, during the preparation stages, appropriate processing conditions have to be deployed in order to limit the formation of dead or deactivated polyisoprene or polybutadiene diene homopolymer which thus generates chains having low molecular weights. An amount of greater than 1% by weight of these polyisoprene or polybutadiene chains would be damaging to the properties of the functionalized diene elastomer according to the invention.
The living block copolymer resulting from this method of preparation is subsequently functionalized in order to prepare the functionalized diene elastomer according to the invention.
According to a first alternative form of the preparation of the functionalized diene elastomer according to the invention, the block copolymer functionalized at the end of or in the middle of the chain by a tin functional group a) and the star-branched block copolymer b) are mixed in the appropriate proportions.
The block copolymer a) functionalized at the end of or in the middle of the said chain by a tin functional group can be obtained, in a way known per se, by reaction of a tin derivative with the living diene elastomer resulting from the polymerization.
The star-branched block copolymer b) can be obtained, in a way known per se, by reaction of a tin-comprising star-branching agent with the living diene elastomer resulting from the polymerization.
The mixing of the two elastomers can be carried out in an inert solvent, for example an aliphatic or alicyclic hydrocarbon, such as pentane, hexane, heptane, isooctane or cyclohexane, or an aromatic hydrocarbon, such as benzene, toluene or xylene, which can be the same as the polymerization solvent. The mixing is then carried out at a temperature preferably of between 20° C. and 120° C., preferably in the vicinity of 30° C. to 90° C.
According to a second alternative form of the preparation of the functionalized diene elastomer according to the invention, the living diene elastomer resulting from the polymerization stage is subjected to the reaction of a functionalization agent and to the reaction of a star-branching agent.
Thus, for example, the functionalization of the living diene elastomer resulting from the polymerization stage can be carried out at a temperature varying from 30° C. to 120° C., in the presence, to begin with, of an appropriate amount of a star-branching agent in order to star-branch preferably from 5% to 45% by weight of the living elastomer. Then, subsequently, the remaining living chains of the diene elastomer obtained after the first stage are functionalized by addition of a tin functionalization agent capable of introducing a tin functional group at the end of the chain or in the middle of the chain. The functionalization reaction of the diene elastomer is subsequently stopped by the deactivation of the remaining living chains.
The well-informed reader would understand that, during the stages of preparation of the functionalized block copolymers a) and b), appropriate processing conditions have to be deployed in order to limit the formation of the non-tin-functionalized copolymer c).
A further subject-matter of the invention is a reinforced rubber composition based on at least one reinforcing filler and on an elastomer matrix comprising at least one functionalized diene elastomer according to the invention.
The composition can comprise from 1 to 100 phr of functionalized diene elastomer according to invention.
The composition according to the invention can also comprise at least one diene elastomer other than the said functionalized diene elastomer according to the invention This or these diene elastomers other than the functionalized diene elastomer according to the invention can be chosen from the diene elastomers conventionally used in tires, such as natural rubber or a synthetic elastomer, or also another functionalized or star-branched elastomer.
Use may be made of any type of reinforcing filler known for its abilities to reinforce a rubber composition which can be used for the manufacture of tires, for example a reinforcing organic filler, such as carbon black, a reinforcing inorganic filler, such as silica, or a blend of these two types of filler, in particular a blend of carbon black and silica.
All carbon blacks, in particular blacks of the HAF, ISAF or SAF type, conventionally used in tires (“tire-grade” blacks) are suitable as carbon blacks. Mention will more particularly be made, among the latter, of the reinforcing carbon blacks of the 100, 200 or 300 series (ASTM grades), such as, for example, the N115, N134, N234, N326, N330, N339, N347 or N375 blacks.
Use may also be made, according to the applications targeted, of blacks of higher series FF, FEF, GPF or SRF, for example the N660, N683 or N772 blacks. The carbon blacks might, for example, be already incorporated in the isoprene elastomer in the form of a masterbatch (see, for example, Applications WO 97/36724 or WO 99/16600).
Mention may be made, as examples of organic fillers other than carbon blacks, of functionalized polyvinylaromatic organic fillers, such as described in Applications WO-A-2006/069792 and WO-A-2006/069793.
The term “reinforcing inorganic filler” should be understood, in the present patent application, by definition, as meaning any inorganic or mineral filler, whatever its colour and its origin (natural or synthetic), also known as “white filler”, “clear filler” or indeed even “non-black filler”, in contrast to carbon black, capable of reinforcing by itself alone, without means other than an intermediate coupling agent, a rubber composition intended for the manufacture of tires, in other words capable of replacing, in its reinforcing role, a conventional tire-grade carbon black; such a filler is generally characterized, in a known way, by the presence of hydroxyl (—OH) groups at its surface.
The physical state under which the reinforcing inorganic filler is provided is not important, whether it is in the form of a powder, of microbeads, of granules, of beads or any other appropriate densified form. Of course, the term “reinforcing inorganic filler” is also understood to mean mixtures of different reinforcing inorganic fillers, in particular of highly dispersible siliceous and/or aluminous fillers as described below.
Mineral fillers of the siliceous type, in particular silica (SiO2), or of the aluminous type, in particular alumina (Al2O3), are suitable in particular as reinforcing inorganic fillers. The silica used can be any reinforcing silica known to a person skilled in the art, in particular any precipitated or fumed silica exhibiting a BET specific surface and a CTAB specific surface both of less than 450 m2/g, preferably from 30 to 400 m2/g. Mention will be made, as highly dispersible precipitated silicas (“HDSs”), for example, of the Ultrasil 7000 and Ultrasil 7005 silicas from Degussa, the Zeosil 1165 MP, 1135 MP and 1115 MP silicas from Rhodia, the Hi-Sil EZ150G silica from PPG, the Zeopol 8715, 8745 and 8755 silicas from Huber or the silicas with a high specific surface as described in Application WO 03/16837.
When the composition according to the invention is intended for tire treads having a low rolling resistance, the reinforcing inorganic filler used, in particular if it is silica, preferably has a BET specific surface of between 45 and 400 m2/g, more preferably of between 60 and 300 m2/g.
Preferably, the content of reinforcing filler in the composition is between 30 and 150 phr, more preferably between 50 and 120 phr. The optimum is different according to the specific applications targeted: the expected level of reinforcement with regard to a bicycle tire, for example, is, of course, lower than that required with regard to a tire capable of running at high speed in a sustained manner, for example a motorcycle tire, a tire for a passenger vehicle or a tire for a utility vehicle, such as a heavy-duty vehicle.
According to one embodiment, the reinforcing filler predominantly comprises silica, the content of carbon black present in the composition preferably being between 2 and 20 phr.
According to another embodiment of the invention, the reinforcing filler predominantly comprises carbon black.
Use is made, in a known way, in order to couple the reinforcing inorganic filler to the diene elastomer, of an at least bifunctional coupling agent (or bonding agent) intended to provide a satisfactory connection, of chemical and/or physical nature, between the inorganic filler (surface of its particles) and the diene elastomer, in particular bifunctional organosilanes or polyorganosiloxanes.
Use is made in particular of silane polysulphides, referred to as “symmetrical” or “unsymmetrical” according to their specific structure, such as described, for example, in Applications WO 03/002648 (or US 2005/016651) and WO 03/002649 (or US 2005/016650).
Suitable in particular, without the definition below being limiting, are silane polysulphides known as “symetrical”, corresponding to the following general formula (III):

Z-A-Sx-A-Z,  (III)

in which:

    
    
        x is an integer from 2 to 8 (preferably from 2 to 5);
        A is a divalent hydrocarbon radical (preferably, C1-C18 alkylene groups or C6-C12 arylene groups, more particularly C1-C10, in particular C1-C4, alkylenes, especially propylene);
        Z corresponds to one of the formulae below:
    
    






in which:

    
    
        the R1 radicals, which are substituted or unsubstituted and identical to or different from one another, represent a C1-C18 alkyl group, a C5-C18 cycloalkyl group or a C6-C18 aryl group (preferably C1-C6 alkyl, cyclohexyl or phenyl groups, in particular C1-C4 alkyl groups, more particularly methyl and/or ethyl);
        the R2 radicals, which are substituted or unsubstituted and identical to or different from one another, represent a C1-C18 alkoxy group or a C5-C18 cycloalkoxyl group (preferably a group chosen from C1-C8 alkoxyls and C5-C8 cycloalkoxyls, more preferably still a group chosen from C1-C4 alkoxyls, in particular methoxyl and ethoxyl).
    
    


In the case of a mixture of alkoxysilane polysulphides corresponding to the above formula (III), in particular the standard commercially available mixtures, the mean value of the “x” symbols is a fractional number preferably between 2 and 5, more preferably close to 4. However, the invention can also advantageously be carried out, for example, with alkoxysilane disulphides (x=2).
Mention will more particularly be made, as examples of silane polysulphides, of bis((C1-C4)alkoxyl(C1-C4)alkylsilyl(C1-C4)alkyl) polysulphides (in particular disulphides, trisulphides or tetrasulphides), such as, for example, bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilylpropyl)polysulphides. Use is in particular made, among these compounds, of bis(3-triethoxysilylpropyl)tetrasulphide, abbreviated to TESPT, of formula [(C2H5O)3Si(CH2)3S2]2, or bis(triethoxysilylpropyl)disulphide, abbreviated to TESPD, of formula [(C2H5O)3Si(CH2)3S]2. Mention will also be made, as preferred examples, of bis(mono(C1-C4)alkoxydi(C1-C4)alkylsilylpropyl) polysulphides (in particular disulphides, trisulphides or tetrasulphides), more particularly bis(monoethoxydimethylsilylpropyl) tetrasulphide, such as described in the Patent Application WO 02/083782 (or US 2004/132880).
Mention will in particular be made, as coupling agent other than an alkoxysilane polysulphide, of bifunctional POSs (polyorganosiloxanes) or else of hydroxysilane polysulphides (R2=OH in the above formula III), such as described in Patent Applications WO 02/30939 (or U.S. Pat. No. 6,774,255) and WO 02/31041 (or US 2004/051210), or else of silanes or POSs carrying azodicarbonyl functional groups, such as described, for example, in Patent Applications WO 2006/125532, WO 2006/125533, WO 2006/125534 and WO 2009/062733.
In the rubber composition, the content of coupling agent is preferably between 0.5 and 12 phr, more preferably between 3 and 8 phr.
Typically, the content of coupling agent represents from 0.5% to 15% by weight, with respect to the amount of inorganic filler.
A person skilled in the art will understand that a reinforcing filler of another nature, in particular organic nature, might be used as filler equivalent to the reinforcing inorganic filler described in the present section, provided that this reinforcing filler is covered with an inorganic layer, such as silica, or else comprises, at its surface, functional sites, in particular hydroxyls, requiring the use of a coupling agent in order to form the connection between the filler and the elastomer.
The composition according to the invention can also comprise a chemical crosslinking agent.
The chemical crosslinking makes possible the formation of covalent bonds between the elastomer chains. The chemical crosslinking can be carried out using a vulcanization system or else using peroxide compounds.
The vulcanization system proper is based on sulphur (or on a sulphur-donating agent) and on a primary vulcanization accelerator. Additional to this base vulcanization system are various known secondary vulcanization accelerators or vulcanization activators, such as zinc oxide, stearic acid or equivalent compounds, or guanidine derivatives (in particular diphenylguanidine), incorporated during the first non-productive phase and/or during the productive phase, as described subsequently.
The sulphur is used at a preferred content of between 0.5 and 12 phr, in particular between 1 and 10 phr. The primary vulcanization accelerator is used at a preferred content of between 0.5 and 10 phr, more preferably of between 0.5 and 5.0 phr.
Use may be made, as (primary or secondary) accelerator, of any compound capable of acting as accelerator for the vulcanization of diene elastomers in the presence of sulphur, in particular accelerators of the thiazole type, and also their derivatives, and accelerators of thiuram and zinc dithiocarbamate types. These accelerators are, for example, chosen from the group consisting of 2-mercaptobenzothiazyl disulphide (abbreviated to “MBTS”), tetrabenzylthiuram disulphide (“TBZTD”), N-cyclohexyl-2-benzothiazolesulphenamide (“CBS”), N,N-dicyclohexyl-2-benzothiazolesulphenamide (“DCBS”), N-(tert-butyl)-2-benzothiazolesulphenamide (“TBBS”), N-(tert-butyl)-2-benzothiazolesulphenimide (“TBSI”), zinc dibenzyldithiocarbamate (“ZBEC”) and the mixtures of these compounds.
Preferably, use is made of a primary accelerator of the sulphenamide type.
When the chemical crosslinking is carried out using one or more peroxide compounds, the said peroxide compound or compounds represent from 0.01 to 10 phr.
Mention may be made, as peroxide compounds which can be used as chemical crosslinking system, of acyl peroxides, for example benzoyl peroxide or p-chlorobenzoyl peroxide, ketone peroxides, for example methyl ethyl ketone peroxide, peroxyesters, for example t-butyl peroxyacetate, t-butyl peroxybenzoate and t-butyl peroxyphthalate, alkyl peroxides, for example dicumyl peroxide, di(t-butyl)peroxybenzoate and 1,3-bis(t-butylperoxyisopropyl)benzene, or hydroperoxides, for example t-butyl hydroperoxide.
The rubber composition according to the invention can also comprise all or a portion of the usual additives generally used in elastomer compositions intended for the manufacture of tires, in particular of treads, such as, for example, plasticizers or extending oils, whether the latter are of aromatic or non-aromatic nature, pigments, protection agents, such as antiozone waxes (such as Cire Ozone C32 ST), chemical antiozonants or antioxidants (such as 6-PPD), antifatigue agents, reinforcing resins, methylene acceptors (for example, phenolic novolak resin) or methylene donors (for example, HMT or H3M), as described, for example, in Application WO 02/10269, or adhesion promoters (cobalt salts, for example).
Preferably, the composition according to the invention comprises, as preferred non-aromatic or very weakly aromatic plasticizing agent, at least one compound chosen from the group consisting of naphthenic oils, paraffinic oils, MES oils, TDAE oils, glycerol esters (in particular trioleates), plasticizing hydrocarbon resins exhibiting a high Tg preferably of greater than 30° C., and mixtures of such compounds.
The composition according to the invention can also comprise, in addition to the coupling agents, activators of the coupling of the reinforcing inorganic filler or more generally processing aids capable, in a known way, by virtue of an improvement in the dispersion of the inorganic filler in the rubber matrix and of a lowering in the viscosity of the compositions, of improving their ease of processing in the raw state, these processing aids being, for example, hydrolysable silanes, such as alkylalkoxysilanes (in particular alkyltriethoxysilanes), polyols, polyethers (for example, polyethylene glycols), primary, secondary or tertiary amines (for example, trialkanolamines), hydroxylated or hydrolysable POSs, for example α,ω-dihydroxypolyorganosiloxanes (in particular α,ω-dihydroxypolydimethylsiloxanes), or fatty acids, such as, for example, stearic acid.
The rubber composition according to the invention is manufactured in appropriate mixers, using two successive phases of preparation according to a general procedure well known to those skilled in the art: a first phase of thermomechanical working or kneading (sometimes referred to as “non-productive” phase) at high temperature, up to a maximum temperature of between 130° C. and 200° C., preferably between 145° C. and 185° C., followed by a second phase of mechanical working (sometimes referred to as “productive” phase) at lower temperature, typically below 120° C., for example between 60° C. and 100° C., during which finishing phase the chemical crosslinking agent is incorporated.
According to a preferred embodiment of the invention, all the base constituents of the composition included in the tire of the invention, with the exception of the chemical crosslinking agent, namely in particular the reinforcing filler or fillers and the coupling agent, if appropriate, are intimately incorporated, by kneading, in the functionalized diene elastomer and in the other diene elastomers, if appropriate, during the first “non-productive” phase, that is to say that at least these various base constituents are introduced into the mixer and are thermomechanically kneaded, in one or more stages, until the maximum temperature of between 130° C. and 200° C., preferably of between 145° C. and 185° C., is reached.
By way of example, the first (non-productive) phase is carried out in a single thermomechanical stage during which all the necessary constituents, the optional supplementary processing aids and various other additives, with the exception of the chemical crosslinking agent, are introduced into an appropriate mixer, such as an ordinary internal mixer. The total duration of the kneading, in this non-productive phase, is preferably between 1 and 15 min. After cooling the mixture thus obtained during the first non-productive phase, the chemical crosslinking agent is then incorporated at low temperature, generally in an external mixer, such as an open mill; everything is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.
The final composition thus obtained is subsequently calendered, for example in the form of a sheet or plaque, in particular for laboratory characterization, or else extruded in the form of a rubber profiled element which can be used, for example, as a tire tread for a passenger vehicle.
A further subject-matter of the invention is a semi-finished article made of rubber for a tire, comprising the crosslinked or crosslinkable rubber composition according to the invention. Preferably, the said article is a tread.
A final subject-matter of the invention is a tire comprising a semi-finished article according to the invention.
The invention is illustrated by the following examples.
EXAMPLE
1—Preparation of an Elastomer Matrix According to the Invention
1.1—Measurements and Tests Used—Experimental Techniques Used for the Pre-Curing Characterization of the Polymers Obtained
(a) Determination of the Molar Mass Distribution by the Size Exclusion Chromatography (Conventional SEC) Technique
Size exclusion chromatography or SEC makes it possible to separate macromolecules in solution according to their size through columns filled with a porous gel. The macromolecules are separated according to their hydrodynamic volume, the bulkiest being eluted first.
Without being an absolute method, SEC makes it possible to comprehend the distribution of the molar masses of a polymer. The various number-average molar masses (Mn) and weight-average molar masses (Mw) and the weight at the peak (Wp) can be determined from commercial standards and the polydispersity index (PI=Mw/Mn) can be calculated via a “Moore” calibration.
(1) Preparation of the Polymer:
There is no specific treatment of the polymer sample before analysis. The latter is simply dissolved in tetrahydrofuran at a concentration of approximately 1 g/l. The solution is then filtered through a filter with a porosity of 0.45 μm before injection.
(2) SEC Analysis:
The apparatus used is a “Waters Alliance” chromatograph. The elution solvent is tetrahydrofuran, the flow rate is 0.7 ml/min, the temperature of the system is 35° C. and the analytical time is 90 min. A set of four Waters columns in series, with commercial names “Styragel HMW7”, “Styragel HMW6E” and two “Styragel HT6E”, is used.
The volume of the solution of the polymer sample injected is 100 μl The detector is a “Waters 2410” differential refractometer and the software for making use of the chromatographic data is the “Waters Empower” system.
The calculated average molar masses relate to a calibration curve produced with polystyrene standards having known molar masses.
(b) Determination of the Percentage by Weight of a Population of Polymer Chains by the High Resolution Size Exclusion Chromatography Technique (HR SEC Analysis)
(1) Preparation of the Polymer:
There is no specific treatment of the polymer sample before analysis. The latter is simply dissolved in tetrahydrofuran at a concentration of approximately 1 g/l. The solution is then filtered through a filter with a porosity of 0.45 μm before injection.
(2) HR SEC Analysis:
The apparatus used is a “Waters Alliance” chromatographic line. The elution solvent is tetrahydrofuran, the flow rate is 0.2 ml/min, the temperature of the system is 35° C. and the analytical time is 205 min. A set of 3 Shodex columns in series, with the commercial name “KF805”, is used.
The volume of the solution of the polymer sample injected is 50 μl. The detector is a “Waters 2410” differential refractometer and the software for making use of the chromatographic data is the “Waters Empower” system.
The chromatogram obtained is composed of several distinct peaks. A population of polymer chains corresponds to each peak.
The value of the refractometric signal at the baseline is zero.
The percentages by weight of each population are determined by the ratio of the value of the refractometric signal at the peak top for the population concerned to the sum of the values of the refractometric signal at the peak top for all the populations.
(c) For the Polymers and Rubber Compositions, the Mooney Viscosities ML (1+4) at 100° C. Are Measured According to Standard ASTM D-1646.
Use is made of an oscillating consistometer as described in Standard ASTM D-1646. The Mooney plasticity measurement is carried out according to the following principle: the composition in the raw state (i.e., before curing) is moulded in a cylindrical chamber heated to 100° C. After preheating for one minute, the rotor rotates within the test specimen at 2 revolutions/minute and the working torque for maintaining this movement is measured after rotating for 4 minutes. The Mooney plasticity (ML 1+4) is expressed in “Mooney unit” (MU, with 1 MU=0.83 N.m).
(d) The glass transition temperatures Tg of the polymers are measured according to Standard ASTM D3418-03 using a differential scanning calorimeter.
(e) Near-infrared spectroscopy (NIR) is used to quantitatively determine the content by weight of styrene in the elastomer and its microstructure (relative distribution of the 1,2-vinyl, trans-1,4 and cis-1,4 butadiene units). The principle of the method is based on the Beer-Lambert law generalized for a multicomponent system. As the method is indirect, it involves a multivariate calibration [Vilmin, F., Dussap, C. and Coste, N., Applied Spectroscopy, 2006, 60, 619-29] carried out using standard elastomers having a composition determined by 13C NMR. The styrene content and the microstructure are then calculated from the NIR spectrum of an elastomer film having a thickness of approximately 730 μm. The spectrum is acquired in transmission mode between 4000 and 6200 cm−1 with a resolution of 2 cm−1 using a Bruker Tensor 37 Fourier-transform near-infrared spectrometer equipped with an InGaAs detector cooled by the Peltier effect.
(f) For the polymers, the intrinsic viscosity at 25° C. of a 0.1 g/dl solution of polymer in toluene is measured starting from a solution of dry polymer:
The intrinsic viscosity is determined by the measurement of the flow time t of the polymer solution and of the flow time to of the toluene in a capillary tube.
The flow time of the toluene and the flow time of the 0.1 g/dl polymer solution are measured in a Ubbelohde tube (diameter of the capillary 0.46 mm, capacity from 18 to 22 ml) placed in a bath thermostatically controlled at 25±0.1° C.
The intrinsic viscosity is obtained by the following relationship:




  
    η
    inh
  
  =
  
    
      1
      C
    
    ⁢
    
      ln
      ⁡
      
        [
        
          
            (
            t
            )
          
          
            (
            
              t
              O
            
            )
          
        
        ]
      
    
  




with:
C: concentration of the toluene solution of polymer in g/dl;
t: flow time of the toluene solution of polymer in seconds;
to: flow time of the toluene in seconds;
ηinh: intrinsic viscosity, expressed in dl/g.
(g) For the polymers, the cold flow: CF100(1+6), results from the following measurement method:
It is a matter of measuring the weight of rubber extruded through a calibrated die over 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 apparatus is a cylindrical cup pierced at the base. Approximately 40 g±4 g of rubber, preprepared in the form of a pellet (thickness of 2 cm and diameter of 52 mm), are placed in this device. A calibrated piston weighing 1 kg (±5 g) is positioned on the rubber pellet. The assembly is subsequently placed in an oven thermally stabilized at 100° C.±0.5° C.
During the first hour in the oven, the measurement conditions are not stabilized. After one hour, the product which has extruded is thus cut off and discarded.
The measurement subsequently lasts 6 hours±5 min, during which the product is left in the oven. At the end of the 6 hours, the extruded product sample has to be recovered by cutting it flush with the surface of the base. The result of the test is the weight of rubber weighed.
1.2—Preparation of the Functionalized Elastomers According to the Invention and Control for the Elastomers
(a) Preparation of a Living Polyisoprene
The living polyisoprene is prepared batchwise in a reactor with a reaction volume of 75 l, under nitrogen pressure, which reactor is equipped with a stirrer of turbine type. On the one hand, methylcyclohexane and isoprene according to the respective ratios by weight of 100/25 and, on the other hand, an amount of 10 000 μmol of active sec-butyllithium (s-BuLi) per 100 g of isoprene are introduced into this reactor.
The temperature of the reactor is maintained at 45° C. and, after a polymerization time of 30 min, the conversion of monomers is 100%.
The concentration of active polyisoprenyllithium (PILi) is determined on a withdrawn sample by successive titrations with perchloric acid, where the activity of this living polyisoprene is calculated by difference between the total basicity and the residual basicity:

    
    
        Assaying of the total basicity: approximately 1000 μmol of PILi (solution to be assayed) are introduced and 25 ml of acetic acid are introduced into 50 ml of toluene. A few drops of an acetic solution of crystal violet are introduced. Assaying is carried out with perchloric acid (0.1M in acetic acid); the solution changes from purple to emerald green at the equivalence point and then to yellow when the equivalence point has been exceeded.
        Assaying of the residual basicity: approximately 1000 μmol of trans-1,4-dibromo-2-butene are introduced. Approximately 1000 μmol of PILi (solution to be assayed) are introduced into 50 ml of toluene. After 10 minutes, 25 ml of acetic acid are added and a few drops of an acetic solution of crystal violet are introduced. Assaying is carried out with perchloric acid (0.1M in acetic acid); the solution changes from purple to emerald green at the equivalence point and then to yellow when the equivalence point has been exceeded.
        Results: the concentration of the active polyisoprenyllithium is calculated according to:
    
    






  
    t
    PILi
  
  =
  
    
      
        (
        
          
            V
            T
          
          -
          
            V
            R
          
        
        )
      
      
        V
        PILi
      
    
    ×
    
      t
      
        HClO
        ⁢
        
          
        
        ⁢
        4
      
    
  




where:
VT=volume of HClO4 necessary for the assaying of the total basicity (in ml)
VR=volume of HClO4 necessary for the assaying of the residual basicity (in ml)
tHClO4=concentration of the perchloric acid solution (in mol/l)
VPILi=volume of the PILi solution used for the sampling (in ml)
tPILi=concentration of the PILi solution analysed (in mol/l)
The concentration of the living polyisoprene is thus estimated at 0.0157 mol/l. This lithiated polyisoprene is stored under nitrogen at a temperature of 10° C. No change in the content is observed during storage for several weeks under nitrogen pressure at this temperature.
The number-average molecular weight and the polydispersity index of the living polyisoprene thus obtained, which are determined by conventional SEC on a withdrawn sample stopped by one lithium equivalent of methanol, are 9307 g/mol and 1.07 respectively. The content of 3,4 linkages of this polyisoprene is 23.7%.
(b) Preparation of a Control Elastomer a (Denoted SBR A): Copolymerization of Butadiene and Styrene Initiated by a Living Polyisoprene
The block copolymer other than the said living polyisoprene is prepared batchwise in a reactor with a reaction volume of 75 l, under nitrogen pressure, which reactor is equipped with a stirrer of turbine type. Methylcyclohexane, butadiene and styrene are introduced into this reactor according to respective proportions by weight of 100/10/6.6. 600 parts per million (by weight) of tetrahydrofuran (THF), as agent promoting vinyl bonds, are also added to this reactor.
An amount of 57 μmol of active n-butyllithium (n-BuLi) per 100 g of solution is introduced into the reactor in order to neutralize the protic impurities which are contributed by the various constituents present in the reactor with the aim of limiting the formation of dead or deactivated polyisoprene during the introduction of the living polyisoprene solution into the reactor.
545 μmol per 100 g of monomers of the living polyisoprene described in section 1-2) (a), representing the amount of active initiator for initiating the polymerization, are introduced.
The temperature of the reactor is maintained at 50° C. and, after a polymerization time of 35 min, the conversion of monomers is 70%.
The intrinsic viscosity of the copolymer before functionalization, measured on a withdrawn sample stopped by one lithium equivalent of methanol, is 1.2 dl/g and the number-average molecular weight and the polydispersity index of the same withdrawn sample, which are determined by conventional SEC, are 106 424 g/mol and 1.07 respectively.
262 μmol/100 g of monomers of a coupling agent consisting of dibutyldichlorotin are subsequently added to the same reactor. The functionalization reaction is carried out at 50° C. After 20 min of this coupling reaction, the block copolymer thus functionalized is subjected to an anti-oxidizing treatment using 0.8 phr of 2,2′-methylenebis(4-methyl-6-(tert-butyl)phenol) and 0.2 phr of N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine. Any reaction is stopped by the addition of 2 lithium equivalents of methanol.
The copolymer thus treated is separated from its solution by a steam stripping operation and is then dried on a screw machine at 150° C. for 15 sec, in order to obtain the functionalized copolymer A comprising control blocks.
The intrinsic viscosity of this copolymer A is 1.96 dl/g and its ML viscosity is 84.
The cold flow of this copolymer A is 3.3.
The SBR block of this copolymer A comprises 28.8% of styrene (by weight) and, for its butadiene part, 25.2% of vinyl units.
The glass transition temperature of this copolymer A is −50° C.
The number-average molecular weight and the polydispersity index of this copolymer A, which are determined by conventional SEC, are 166 200 g/mol and 1.12 respectively.
The percentages by weight of each population present in the copolymer A are determined by HR SEC. 2 predominant populations are distinguished: a population corresponding to 1 branch, with a weight at the peak of approximately 110 000 g/mol and a percentage by weight of approximately 4%, and a population corresponding to 2 branches or to a coupled copolymer, with a weight at the peak of approximately 210 000 g/mol and a percentage by weight of approximately 96%.
(c) Preparation of an Elastomer C According to the Invention (Denoted SBR C): Copolymerization of Butadiene and Styrene Initiated by a Living Polyisoprene
The block copolymer other than the said living polyisoprene is prepared batchwise in a reactor with a reaction volume of 75 l, under nitrogen pressure, which reactor is equipped with a stirrer of turbine type. Methylcyclohexane, butadiene and styrene are introduced into this reactor according to respective proportions by weight of 100/10/6.6. 600 parts per million (by weight) of tetrahydrofuran (THF), as agent promoting vinyl bonds, are also added to this reactor.
An amount of 45 μmol of active n-butyllithium (n-BuLi) per 100 g of solution is introduced into the reactor in order to neutralize the protic impurities which are contributed by the various constituents present in the reactor with the aim of limiting the formation of dead or deactivated polyisoprene during the introduction of the living polyisoprene solution into the reactor.
550 μmol per 100 g of monomers of the solution of the living polyisoprene described in section 1-2) (a), representing the amount of active initiator for initiating the polymerization, are introduced.
The temperature of the reactor is maintained at 50° C. and, after a polymerization time of 35 min, the conversion of monomers is 70%.
The intrinsic viscosity of the copolymer before functionalization, measured on a withdrawn sample stopped by one lithium equivalent of methanol, is 1.22 dl/g and the number-average molecular weight and the polydispersity index of the same withdrawn sample, which are determined by conventional SEC, are 105 000 g/mol and 1.07 respectively.
Subsequently, 105.6 μmol/100 g of monomers of a coupling agent consisting of dibutyldichlorotin and 82.5 μmol/100 g of monomers of a star-branching agent consisting of tetrachlorotin are added to the same reactor. The functionalization reactions are carried out at 50° C. After 20 min of reaction, the block copolymer thus functionalized is subjected to an anti-oxidizing treatment using 0.8 phr of 2,2′-methylenebis(4-methyl-6-(tert-butyl)phenol) and 0.2 phr of N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine. Any reaction is stopped by the addition of 2 lithium equivalents of methanol.
The copolymer thus treated is separated from its solution by a steam stripping operation and is then dried on a screw machine at 150° C. for 15 sec, in order to obtain the functionalized elastomer C according to the invention.
The intrinsic viscosity of this copolymer C is 2.32 dl/g and its ML viscosity is 105.
The cold flow of this copolymer C is 0.2.
The SBR block of this copolymer C comprises 28.9% of styrene (by weight) and, for its butadiene part, 25.1% of vinyl units.
The glass transition temperature of this copolymer C is −48° C.
The number-average molecular weight and the polydispersity index of this copolymer C, which are determined by conventional SEC, are 227 000 g/mol and 1.30 respectively.
The percentages by weight of each population present in the copolymer C according to the invention are determined by HR SEC. 3 predominant populations are distinguished: a population corresponding to 2 branches, block copolymer a) according to the invention, with a weight at the peak of approximately 220 000 g/mol and a percentage by weight of approximately 55%, a population corresponding to a star-branched copolymer having 4 branches, block copolymer b) according to the invention, with a weight at the peak of approximately 400 000 g/mol and a percentage by weight of approximately 35%, and a population corresponding to 1 branch, with a weight at the peak of approximately 115 000 g/mol and a percentage by weight of approximately 10%. The latter population can be regarded as the non-functional block copolymer c) according to the invention, taking into account the content of the coupling and star-branching agents used for the functionalization.
(d) Preparation of an Elastomer B According to the Invention (Denoted SBR B): Mixture of the Copolymers A and C
The elastomer B according to the invention is prepared by mixing the elastomers A and C in the proportions 1⁄3 and 2⁄3 respectively. A solution with methylcyclohexane and the elastomers A and C in the proportions 100/3.7/7.3 respectively is prepared.
Once all the elastomer has dissolved and the solution is homogeneous, the elastomer thus obtained is separated from its solution by drying in an oven at 60° C., under vacuum at 200 mmHg and under a nitrogen atmosphere. After 24 hours, the elastomer B according to the invention is obtained.
The intrinsic viscosity of this copolymer B is 2.08 dl/g and its ML viscosity is 95.
The cold flow of this copolymer B is 0.7.
The SBR block of this copolymer B comprises 28.8% of styrene (by weight) and, for its butadiene part, 25.0% of vinyl units.
The glass transition temperature of this copolymer B is −47.8° C.
The number-average molecular weight and the polydispersity index of this copolymer B, which are determined by conventional SEC, are 213 400 g/mol and 1.26 respectively.
The percentages by weight of each population present in the copolymer B according to the invention are determined by HR SEC. 3 predominant populations are distinguished: a population corresponding to 2 branches, block copolymer a) according to the invention, with a weight at the peak of approximately 225 000 g/mol and a percentage by weight of approximately 64%, a population corresponding to a star-branched copolymer having 4 branches, block copolymer b) according to the invention, with a weight at the peak of approximately 410 000 g/mol and a percentage by weight of approximately 24%, and a population corresponding to 1 branch, with a weight at the peak of approximately 115 000 g/mol and a percentage by weight of approximately 12%. The latter population can be regarded as the non-functional block copolymer c) according to the invention, taking into account the content of the coupling and star-branching agents used for the functionalization.
Comparative Examples of Rubber Compositions
A) Measurements and Tests Used
a) the Mooney viscosity ML (large rotor) or MS (small rotor) (1+4) at 100° C.: measured according to Standard ASTM: D-1646, entitled “Mooney”,
(b) the Shore A hardness: measurements carried out according to Standard DIN 53505,
(c) the tensile tests make it possible to determine the elasticity stresses and the properties at break. Unless otherwise indicated, they are carried out in accordance with French Standard NF T 46-002 of September 1988. Processing the tensile recordings also makes it possible to plot the curve of modulus as a function of the elongation, the modulus used here being the nominal (or apparent) secant modulus measured in first elongation, calculated by reducing to the initial cross-section of the test specimen. The nominal secant moduli (or apparent stresses, in MPa) are measured in first elongation, at 60° C.±2° C., at 10%, 100% and 300% elongation, respectively denoted MSA10, MSA100 and MSA300. The breaking stresses (BS) in MPa and the elongations at break (EB) in % are measured at 60° C.±2° C. according to Standard NF T 46-002.
(d) the dynamic properties ΔG* and tan(δ)max are measured on a viscosity analyser (Metravib VA4000) according to Standard ASTM D 5992-96. The response of a sample of vulcanized composition (cylindrical test specimen with a thickness of 2 mm and a cross-section of 79 mm2), subjected to a simple alternating sinusoidal shear stress, at a frequency of 10 Hz, under standard temperature conditions (23° C.) according to Standard ASTM D 1349-99 or, as the case may be, at a different temperature (60° C.), is recorded. A peak-to-peak strain amplitude sweep is carried out from 0.1% to 50% (outward cycle) and then from 50% to 0.1% (return cycle). The results made use of are the complex dynamic shear modulus (G*) and the loss factor tan(δ). The maximum value of tan(δ) observed (tan(δ)max) and the difference in complex modulus (ΔG*) between the values at 0.1% and 50% strain (Payne effect) are shown for the return cycle.
(e) for the polymers, the cold flow CF100(1+6) results from the following measurement method: it is a matter of measuring the weight of gum extruded through a calibrated die over 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 apparatus is a cylindrical cup pierced at the base. Approximately 40 g±4 g of rubber, preprepared in the form of a pellet (thickness of 2 cm and diameter of 52 mm), are placed in this device. A calibrated piston weighing 1 kg (±5 g) is positioned on the rubber pellet. The assembly is subsequently placed in an oven thermally stabilized at 100° C.±0.5° C.
During the first hour in the oven, the measurement conditions are not stabilized. After one hour, the product which has extruded is thus cut off and discarded. The measurement subsequently lasts 6 hours±5 min, during which the product is left in the oven. At the end of the 6 hours, the extruded product sample has to be recovered by cutting it flush with the surface of the base. The result of the test is the weight of rubber weighed.
B) Example
In this example, the three elastomers SBR A, SBR B and SBR C were used for the preparation of rubber compositions A, B and C, each comprising carbon black as reinforcing filler.
Each of these compositions A, B and C exhibits the following formulation (expressed in phr: parts per hundred parts of elastomer):
















Elastomer
100



N234
54



Paraffin
1



Antioxidant (1)
4



Stearic acid
1.5



ZnO
3



Sulphur
1.3



Accelerator (2)
1.3







(1) N-(1,3-dimethylbutyl)-N-phenyl-para-phenylenediamine (6-PPD)



(2) N-cyclohexyl-2-benzothiazolesulphenamide (CBS)






Each of the following compositions is produced, in a first step, by thermomechanical working and then, in a second finishing step, by mechanical working.
The elastomer, the black, the paraffin, the antioxidant, the stearic acid and the zinc monoxide are successively introduced into a laboratory internal mixer of “Banbury” type which has a capacity of 400 cm3, which is 75% filled and which has an initial temperature of approximately 70° C. The stage of thermomechanical working is carried out for from 5 to 6 minutes, up to a maximum dropping temperature of approximately 160° C. The abovementioned first step of thermomechanical working is thus carried out, it being specified that the mean speed of the blades during this first step is 70 revolutions/min.
The mixture thus obtained is recovered and cooled and then, in an external mixer (homofinisher), the sulphur and the accelerator are added at 30° C., the combined mixture being further mixed for a time of 3 to 4 minutes (abovementioned second step of mechanical working).
The compositions thus obtained are subsequently calendered, either in the form of plaques (with a thickness ranging from 2 to 3 mm) or of thin sheets of rubber, for the measurement of their physical or mechanical properties. The vulcanization is carried out at 150° C. for 15 minutes.
The properties of these three compositions are compared with one another, both in the non-vulcanized state and in the vulcanized state. The results are given in the following table:













Composition
A
B
C







Elastomer
SBR A
SBR B
SBR C


Wp Weight at the peak of
110 000
115 000
115 000


the elastomer branch 





[AB]





ML(1 + 4) 100° C.
84
95
105


(elastomer)





CF100(1 + 6) (elastomer)
3.3
0.7
0.2







Properties in the non-vulcanized state:










MS(1 + 4) 100° C.
58
61
64


(mixture)










Properties in the vulcanized state:










Shore A
67
67
68


MSA10
5.85
5.83
5.93


MSA100
2.70
2.66
2.69


MSA300
5.35
5.18
5.27


MSA300/MSA100
1.98
1.95
1.96


Losses 60° C. (%)
23
23
23







Tension:










BS (MPa)
21
19
21


EB (%)
356
338
364







Dynamic properties as a function of the strain:










ΔG* (MPa) at 60° C. 
1.37
1.51
1.42


Tanδmax at 60° C.
0.146
0.153
0.146









It should be noted that the functionalized diene elastomers B and C according to the invention exhibit lower cold flow values than that of the control functionalized diene elastomer A. The functionalized diene elastomers B and C according to the invention thus exhibit an improved cold flow with respect to the control functionalized diene elastomer A.
Furthermore, the compositions B and C according to the invention, based on the said functionalized diene elastomers B and C, exhibit a “mixture” Mooney value similar to that of the control composition A based on the functionalized diene elastomer A, taking into account the difference in branch length observed. The compositions B and C according to the invention and the control composition A thus exhibit an equivalent processability in the non-vulcanized state.
As regards the properties in the vulcanized state, the compositions B and C according to the invention and the control composition A exhibit equivalent properties and in particular similar hysteresis properties.
In other words, the compositions B and C according to the invention, based on the said functionalized diene elastomers B and C, exhibit rubber properties in the non-crosslinked state and in the crosslinked state which are equivalent, with respect to those of the composition A based on the control functionalized diene elastomer A, the cold flow furthermore being improved for the functionalized diene elastomers B and C according to the invention, with respect to the control functionalized diene elastomer A.

## Claims

1. Functionalized diene elastomer composed:
a) of a block copolymer functionalized, at the chain end or in the middle of the chain, by a tin functional group and corresponding to the following formula:


[A-BnXB-A]m 



where n and m are integers of greater than or equal to 0 and such that n+m=1 or 2,
b) of a block copolymer star-branched by tin and corresponding to the following formula:


[A-BoYB-A]p 



where o and p are integers of greater than or equal to 0 and such that o+p≧3 and o+p≦6,
c) of a content of less than 15% by weight, with respect to the total weight of the functionalized diene elastomer, of a non-tin-functional block copolymer corresponding to the following formula:


[A-B]



where:
all the A blocks are composed of a polyisoprene or all the A blocks are composed of a polybutadiene,
the B blocks are composed of a diene elastomer, the molar content of units resulting from conjugated dienes of which is greater than 15%, the B blocks being identical to one another,
X and Y independently represent a tin-comprising group,
the number-average molecular weight Mn1 of each A block varies from 2 500 to 20 000 g/mol,
the number-average molecular weight Mn2 of each B block varies from 80 000 to 350 000 g/mol,
the content of 1,2 linkages in each A block is between 1 and 20% in the case where A is a polybutadiene block,
the content of 3,4 linkages in each A block is between 1 and 25% in the case where A is a polyisoprene block,
the A-B copolymer exhibits a monomodal distribution of molecular weights before optional functionalization or optional star-branching and a polydispersity index before optional functionalization or optional star-branching of less than or equal to 1.3.

2. Elastomer according to claim 1, wherein it comprises from 5% to 45% by weight, with respect to the total weight of the functionalized diene elastomer, of the said block copolymer star-branched by tin b).

3. Elastomer according to claim 1, wherein it comprises a content strictly of greater than 0% by weight and of less than 10% by weight, with respect to the total weight of the functionalized diene elastomer, of the said non-tin-functional block copolymer c).

4. Elastomer according to claim 1, wherein the ratio of the number-average molecular weight Mn1 of each end polybutadiene or polyisoprene block A to the number-average molecular weight Mn2 of each of the B blocks varies from 5 to 20%.

5. Elastomer according to claim 1, wherein the functionalization of the copolymer a) is obtained with a monohalotin functionalization agent or a dihalotin coupling agent.

6. Elastomer according to claim 1, wherein the star-branching is obtained with a tri- or tetrahalotin star-branching agent.

7. Elastomer according to claim 1, wherein the B block or blocks are chosen from copolymers of styrene and butadiene, copolymers of styrene and isoprene, copolymers of butadiene and isoprene, styrene/butadiene/isoprene terpolymers, polyisoprene when the neighbouring A block is a polybutadiene and polybutadiene when the neighbouring A block is a polyisoprene.

8. Elastomer according to claim 1, wherein the block copolymer a) is a copolymer functionalized by a tin functional group in the middle of the chain and the block copolymer b) is a copolymer star-branched by tin having 4 branches.

9. Elastomer according to claim 1, wherein A is polyisoprene and B is a copolymer of styrene and butadiene, the block copolymer a) being functionalized by the functionalization agent Bu2SnCl2 and the block copolymer b) being star-branched by the star-branching agent SnCl4.

10. Elastomer according to claim 1, wherein A is polybutadiene and B is a copolymer of styrene and butadiene, the block copolymer a) being functionalized by the functionalization agent Bu2SnCl2 and the block copolymer b) being star-branched by the star-branching agent SnCl4.

11. Reinforced rubber composition based on at least one reinforcing filler and on an elastomer matrix, wherein the elastomer matrix comprises at least one functionalized diene elastomer as defined in claim 1.

12. Composition according to claim 11, wherein the elastomer matrix also comprises at least one diene elastomer other than the said functionalized diene elastomer.

13. Composition according to claim 11, wherein the composition further comprises a chemical crosslinking agent.

14. Semi-finished article made of rubber for a tire, wherein it comprises a crosslinkable or crosslinked rubber composition as defined in claim 11.

15. Semi-finished article according to claim 14, wherein the said article is a tread.

16. Tire, wherein it comprises a semi-finished article as defined in claim 14.

17. Elastomer according to claim 2, wherein it comprises from 10% to 30% by weight of said block copolymer star-branched by tin b).

18. Elastomer according to claim 3, wherein it comprises a content of less than 5% by weight of the said non-tin-functional block copolymer c).