# Patent

## Title
Rubber composition including a thiazole derivative

## Abstract

A rubber composition for the manufacture of tires is based on one or more diene elastomers, one or more reinforcing fillers, and a vulcanization system. The vulcanization system includes one or more thiazole compounds chosen from compounds having the following formula (I):




Certain specific thiazole derivatives are described.

## Background
FIELD OF THE INVENTION
The present invention relates to a rubber composition which can be used in particular in the manufacture of tyres or semi-finished products for tyres, such as treads, the said composition being based on a diene elastomer, on a reinforcing filler and on a vulcanization system comprising a specific thiazole compound.
RELATED ART
The vulcanization of diene elastomers by sulphur is widely used in the rubber industry, in particular the tyre industry. Use is made, to vulcanize diene elastomers, of a relatively complex vulcanization system comprising, in addition to the sulphur, a primary vulcanization accelerator, such as sulphenamides having a benzothiazole ring system, and also various secondary vulcanization accelerators or vulcanization activators, very particularly zinc derivatives, such as zinc oxide (ZnO), alone or used with fatty acids.
The sulphenamides having a benzothiazole ring system used as primary vulcanization accelerators are, for example, N-cyclohexyl-2-benzothiazolesulphenamide (abbreviated to “CBS”), N,N-dicyclohexyl-2-benzothiazolesulphenamide (abbreviated to “DCBS”), N-tert-butyl-2-benzothiazolesulphenamide (abbreviated to “TBBS”) and the mixtures of these compounds.
2-(1,3-Benzothiazol-2-yldithio)-1,3-benzothiazole (abbreviated to “MBTS”) is also known as primary vulcanization accelerator.
The rubber compositions must exhibit a sufficient crosslinking while retaining an acceptable compromise between the different rheometric properties.
BRIEF DESCRIPTION OF EMBODIMENTS OF THE INVENTION
In response to this problem, the Applicant Company has discovered a novel rubber composition comprising a thiazole compound as vulcanization accelerator. This novel rubber composition makes it possible to obtain a composition vulcanized using alternative accelerators to the known accelerators, ideally with a similar compromise in rheometric properties to that obtained with rubber compositions comprising vulcanization accelerators conventionally used.
A subject-matter of the invention is thus a rubber composition for the manufacture of tyres, based on one or more diene elastomers, on one or more reinforcing fillers and on a vulcanization system, the said vulcanization system comprising one or more thiazole compounds chosen from the compounds of following formula (I):




in which:
R1 and R2 independently represent a hydrogen atom or a C1-C25 hydrocarbon group chosen from linear, branched or cyclic alkyl groups, aralkyl groups, alkylaryl groups and aryl groups and optionally interrupted by one or more heteroatoms, it being possible for R1 and R2 to together form a non-aromatic ring but it not being possible for R1 and R2 to together form an aromatic ring,

    
    
        A is chosen from:
        
            a hydrogen atom;
            a group
        
        
    
    






in which:
R3, R4 and R5 independently represent a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms;
y is an integer greater than or equal to 1, preferably less than or equal to 10, more preferably less than or equal to 8 and very preferably less than or equal to 6;

    
    
        a group
    
    






in which:
R6 is a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms;

    
    
        a group
    
    






in which:
R7 is a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms;

    
    
        a group
    
    






in which:
Y is a C1-C18 hydrocarbon chain, optionally interrupted or substituted by one or more heteroatoms;
R8 is a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms;

    
    
        a group
    
    






in which:
X is a C1-C18 hydrocarbon chain, optionally interrupted or substituted by one or more heteroatoms;
R9 and R10 independently represent a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms, and

    
    
        a group
    
    






in which:
R11 is a hydrogen atom or a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms.
In the preceding and succeeding formulae, the arrow (→) denotes the point of attachment of the A and Aa groups to the sulphur atom respectively of the formulae (I) and (I′).
Another subject-matter of the invention is a process for preparing a rubber composition for the manufacture of tyres as defined above, comprising the following stages:

    
    
        incorporating the reinforcing filler or fillers in a diene elastomer during a first stage, everything being kneaded thermomechanically, in one or more goes, until a maximum temperature of between 110° C. and 190° C. is reached;
        subsequently incorporating, during a second stage, the crosslinking system and kneading everything up to a maximum temperature of less than 110° C.
    
    


Preferably, the invention relates to the process as defined above in which, between the thermomechanical kneading and the incorporation of the crosslinking system, the combined product is cooled to a temperature of less than or equal to 100° C. Preferably, in this case, the final stage is carried out on a second mixer.
A further subject-matter of the invention is the use of a composition according to the invention in the manufacture of a finished article or of a semi-finished product intended for a motor vehicle ground-contact system, such as a tyre, internal safety support for a tyre, wheel, rubber spring, elastomeric joint, other suspension element and vibration damper. In particular, the composition according to the invention can be used in the manufacture of semi-finished products made of rubber which are intended for tyres, such as treads, crown reinforcing plies, sidewalls, carcass reinforcing plies, beads, protectors, underlayers, rubber blocks and other internal rubbers, in particular decoupling rubbers, intended to provide the bonding or the interface between the abovementioned regions of the tyres.
A further subject-matter of the invention is a finished article or semi-finished product intended for a motor vehicle ground-contact system, in particular tyres and semi-finished products for tyres, in particular treads, comprising a composition according to the invention. The tyres in accordance with the invention are intended in particular for passenger vehicles, two-wheel vehicles as for industrial vehicles chosen from vans, heavy-duty vehicles, i.e. underground, bus, heavy road transport vehicles (lorries, tractors, trailers) or off-road vehicles, heavy agricultural vehicles or earthmoving equipment, planes, and other transportation or handling vehicles.
A further subject-matter of the invention is the use, as vulcanization accelerator in a composition based on one or more diene elastomers, on one or more reinforcing fillers and on a vulcanization system, of one or more thiazole compounds of formula (I).
A final subject-matter of the invention is a thiazole of following formula (I′):




in which:
R1a and R2a independently represent a hydrogen atom or a C1-C25 hydrocarbon group chosen from linear, branched or cyclic alkyl groups, aralkyl groups, alkylaryl groups and aryl groups and optionally interrupted by one or more heteroatoms, it being possible for R1a and R2a to together form a non-aromatic ring but it not being possible for R1a and R2a to together form an aromatic ring;

    
    
        Aa is chosen from:
        
            a group
        
        
    
    






in which:
R3a, R4a and R5a independently represent a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms,
ya is an integer greater than or equal to 1, preferably less than or equal to 10, more preferably less than or equal to 8 and very preferably less than or equal to 6,
provided that R1a and R2a do not simultaneously and respectively denote a methyl and a hydrogen atom, or an aryl and a hydrogen atom;

    
    
        a group
    
    






in which:
R6a is a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms, chosen from linear, branched or cyclic alkyl groups, aralkyl groups, optionally substituted by one or more halogens, one or more linear or branched alkyl groups, linear or branched alkoxy groups, a hydroxyl or a nitro,
and provided that R1a and R2a independently denote a hydrogen atom or an alkyl group;

    
    
        a group
    
    






in which:
R7a is a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms;
and provided that R1a and R2a respectively represent a methyl;

    
    
        a group
    
    






in which:
Xa is a C1-C18 hydrocarbon chain, optionally interrupted or substituted by one or more heteroatoms, but which cannot bear another phosphonate group,
R9a and R10a independently represent a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms,
provided that R1a and R2a independently represent a hydrogen atom or an alkyl group, and;

    
    
        a group
    
    






in which:
R11a represents a hydrogen atom or a C1-C18 hydrocarbon group,
provided that R1a and R2a independently represent a C1-C18 alkyl group.


DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION
The invention and its advantages will be easily understood in the light of the description and implementational examples which follow.
I. MEASUREMENTS AND TESTS USED
The compounds synthesized as vulcanization accelerators were characterized by mass spectrometry and NMR spectroscopy with the devices and methods indicated below.
Mass Spectrometry
The structural analysis of the expected product and also the determination of the structures of the impurities were carried out by DI/CI analysis (direct introduction in mass spectrometry with chemical ionization as ionization mode).
Operating conditions:

    
    
        Reactant gas: methane/ammonia (85/15) at 2 ml/min
        Temperature of the source: 200° C.
        Mass range swept: 50 at 1000 m/z
    
    


NMR
The structural analysis and also the determination of the molar purities of the molecules synthesized are carried out by an NMR analysis. The spectra are acquired on a Bruker Avance 500 MHz spectrometer equipped with a 5 mm BBIz-grade “broad band” probe. The quantitative 1H NMR experiment uses a simple 30° pulse sequence and a repetition time of 3 seconds between each of the 64 acquisitions. The 1H NMR spectrum coupled with the 2D 1H/13C HSQC and 1H/13C HMBC experiments make possible the structural determination of the molecules (cf. tables of assignments). The molar quantifications are carried out from the quantitative 1D 1H NMR spectrum.
The rubber compositions in which the thiazole vulcanization accelerators are tested are characterized, before and after curing, as indicated below.
Rheometry
The measurements are carried out at 150° C. with an oscillating disc rheometer, according to Standard DIN 53529—part 3 (June 1983). The change in the rheometric torque ΔTorque (in dN·m) as a function of time describes the change in the stiffening of the composition as a result of the vulcanization reaction. The measurements are processed according to Standard DIN 53529—part 2 (March 1983) (with the exception of the conversion rate constant): T0 is the induction period, that is to say the time necessary for the start of the vulcanization reaction; Tα (for example T99) is the time necessary to achieve a conversion of α%, that is to say α% (for example 99%) of the difference between the minimum and maximum torques.
The conversion rate constant, denoted K (expressed in min−1), which is first order, calculated between 30% and 80% conversion, which makes it possible to assess the vulcanization kinetics, is also measured. This constant K is determined by measuring the slope of the rise in torque on the rheogram for curing at 150° C.
II. CONDITIONS FOR THE IMPLEMENTATION OF THE INVENTION
As explained above, the composition according to the invention is based on one or more diene elastomers, on one or more reinforcing fillers and on a vulcanization system.
The expression composition “based on” should be understood as meaning a composition comprising the mixture and/or the reaction product of the various constituents used, some of these base constituents being capable of reacting or intended to react with one another, at least in part, during the various phases of manufacture of the composition, in particular during the vulcanization thereof.
In the present description, unless expressly indicated otherwise, all the percentages (%) are % by weight. Furthermore, any interval of values denoted by the expression “between a and b” represents the range of values extending from more than a to less than b (that is to say, limits a and b excluded), whereas any interval of values denoted by the expression “from a to b” means the range of values extending from a up to b (that is to say, including the strict limits a and b).
II-1. Diene Elastomer
A “diene” elastomer or rubber should be understood, in a known way, as meaning an elastomer resulting at least in part (i.e., a homopolymer or a copolymer) from diene monomers (monomers carrying two conjugated or non-conjugated carbon-carbon double bonds).
These diene elastomers can be classified into two categories: “essentially unsaturated” or “essentially saturated”. Generally, “essentially unsaturated” is understood to mean a diene elastomer resulting at least in part from conjugated diene monomers having a content of units of diene origin (conjugated dienes) which is greater than 15% (mol %); thus it is that diene elastomers, such as butyl rubbers or copolymers of dienes and α-olefins of EPDM type, do not come within the preceding definition and can in particular be described as “essentially saturated” diene elastomers (low or very low content, always less than 15%, of units of diene origin). In the category of “essentially unsaturated” diene elastomers, “highly unsaturated” diene elastomer is understood to mean in particular a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
Given these definitions, diene elastomer capable of being used in the compositions in accordance with the invention is understood more particularly to mean:
(a) any homopolymer obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms;
(b) any copolymer obtained by copolymerization of one or more conjugated dienes with one another or with one or more vinylaromatic compounds having from 8 to 20 carbon atoms;
(c) a ternary copolymer obtained by copolymerization of ethylene and of an α-olefin having from 3 to 6 carbon atoms with a non-conjugated diene monomer having from 6 to 12 carbon atoms, such as, for example, the elastomers obtained from ethylene and propylene with a non-conjugated diene monomer of the abovementioned type, such as, in particular, 1,4-hexadiene, ethylidenenorbornene or dicyclopentadiene;
(d) a copolymer of isobutene and of isoprene (butyl rubber) and also the halogenated versions, in particular chlorinated or brominated versions, of this type of copolymer.
Although it applies to any type of diene elastomer, a person skilled in the art of tyres will understand that the present invention is preferably employed with essentially unsaturated diene elastomers, in particular of the above type (a) or (b).
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, for example, 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, chlorostyrenes, vinylmesitylene, divinylbenzene or vinylnaphthalene.
The copolymers can comprise between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinylaromatic units. The elastomers can have any microstructure, which depends on the polymerization conditions used, in particular on the presence or absence of a modifying and/or randomizing agent and on the amounts of modifying and/or randomizing agent employed. The elastomers can, for example, be block, statistical, sequential or microsequential elastomers and can be prepared in dispersion, in emulsion or in solution; they can be coupled and/or star-branched or else functionalized with a coupling and/or star-branching or functionalization agent. Mention may be made, for example, for coupling to carbon black, of functional groups comprising a C—Sn bond or aminated functional groups, such as aminobenzophenone, for example; mention may be made, for example, for coupling to a reinforcing inorganic filler, such as silica, of silanol or polysiloxane functional groups having a silanol end (such as described, for example, in FR 2 740 778, U.S. Pat. No. 6,013,718 or WO 2008/141702), alkoxysilane groups (such as described, for example, in FR 2 765 882 or U.S. Pat. No. 5,977,238), carboxyl groups (such as described, for example, in WO 01/92402 or U.S. Pat. No. 6,815,473, WO 2004/096865 or US 2006/0089445) or else polyether groups (such as described, for example, in EP 1 127 909, U.S. Pat. No. 6,503,973, WO 2009/000750 or WO 2009/000752). Mention may also be made, as other examples of functionalized elastomers, of elastomers (such as SBR, BR, NR, or IR) of the epoxidized type.
The following are suitable: polybutadienes and in particular those having a content (mol %) of 1,2-units of between 4% and 80% or those having a content (mol %) of cis-1,4-units of greater than 80%, polyisoprenes, butadiene/styrene copolymers and in particular those having a Tg (glass transition temperature, 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 and especially 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 and especially those having a styrene content of between 5% and 50% by weight and a Tg of between 5° C. and −50° C. In the case of butadiene/styrene/isoprene copolymers, those having a styrene content of 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 of 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.
To summarize, the diene elastomer or elastomers of the composition according to the invention are preferably selected from the group of highly unsaturated diene elastomers consisting of polybutadienes (abbreviated to “BRs”), synthetic polyisoprenes (IRs), natural rubber (NR), butadiene copolymers, isoprene copolymers and the mixtures of these elastomers. Such copolymers are more preferably selected from the group consisting of butadiene/styrene copolymers (SBRs), isoprene/butadiene copolymers (BIRs), isoprene/styrene copolymers (SIRs) and isoprene/butadiene/styrene copolymers (SBIRs).
According to one embodiment, the diene elastomer is natural rubber.
According to another specific embodiment, the diene elastomer is predominantly (i.e., for more than 50 phr) an SBR, whether an SBR prepared in emulsion (“ESBR”) or an SBR prepared in solution (“SSBR”), or an SBR/BR, SBR/NR (or SBR/IR), BR/NR (or BR/IR) or also SBR/BR/NR (or SBR/BR/IR) blend (mixture). In the case of an SBR (ESBR or SSBR) elastomer, use is made in particular of an SBR having a moderate styrene content, for example of between 20% and 35% by weight, or a high styrene content, for example from 35% to 45%, a content of vinyl bonds of the butadiene part of between 15% and 70%, a content (mol %) of trans-1,4-bonds of between 15% and 75% and a Tg of between −10° C. and −55° C.; such an SBR can advantageously be used as a mixture with a BR preferably having more than 90% (mol %) of cis-1,4-bonds.
According to another specific embodiment, the diene elastomer is predominantly (for more than 50 phr) an isoprene elastomer. This is in particular the case when the compositions of the invention are intended to constitute, in the tyres, rubber matrices of certain treads (for example for industrial vehicles), of crown reinforcing plies (for example of working plies, protection plies or hooping plies), of carcass reinforcing plies, of sidewalls, of beads, of protectors, of underlayers, of rubber blocks and other internal rubbers providing the interface between the abovementioned regions of the tyres.
“Isoprene elastomer” is understood to mean, in a known way, an isoprene homopolymer or copolymer, in other words a diene elastomer selected from the group consisting of natural rubber (NR), synthetic polyisoprenes (IRs), various isoprene copolymers and the mixtures of these elastomers. Mention will in particular be made, among isoprene copolymers, of isobutene/isoprene (butyl rubber-IIR), isoprene/styrene (SIR), isoprene/butadiene (BIR) or isoprene/butadiene/styrene (SBIR) copolymers. This isoprene elastomer is preferably natural rubber or a synthetic cis-1,4-polyisoprene; use is preferably made, among these synthetic polyisoprenes, of polyisoprenes having a content (mol %) of cis-1,4-bonds of greater than 90%, more preferably still of greater than 98%.
According to another specific embodiment, in particular when it is intended for a tyre sidewall or for an airtight internal rubber of a tubeless tyre (or other air-impermeable component), the composition in accordance with the invention can comprise at least one essentially saturated diene elastomer, in particular at least one EPDM copolymer or one butyl rubber (optionally chlorinated or brominated), whether these copolymers are used alone or as a mixture with highly unsaturated diene elastomers as mentioned above, in particular NR or IRs, BR or SBRs.
According to another preferred embodiment of the invention, the rubber composition comprises a blend of a (one or more) “high Tg” diene elastomer exhibiting a Tg of between −70° C. and 0° C. and of a (one or more) “low Tg” diene elastomer of between −110° C. and −80° C., more particularly between −105° C. and −90° C. The high Tg elastomer is preferably selected from the group consisting of S-SBRs, E-SBRs, natural rubber, synthetic polyisoprenes (exhibiting a content (mol %) of cis-1,4-enchainments preferably of greater than 95%), BIRs, SIRs, SBIRs, and the mixtures of these elastomers. The low Tg elastomer preferably comprises butadiene units according to a content (mol %) at least equal to 70%; it preferably consists of a polybutadiene (BR) exhibiting a content (mol %) of cis-1,4-enchainments of greater than 90%.
According to another specific embodiment of the invention, the rubber composition comprises, for example, from 30 to 100 phr, in particular from 50 to 100 phr, of a high Tg elastomer as a blend with from 0 to 70 phr, in particular from 0 to 50 phr, of a low Tg elastomer; according to another example, it comprises, for the totality of the 100 phr, one or more SBRs prepared in solution.
According to another specific embodiment of the invention, the diene elastomer of the composition according to the invention comprises a blend of a BR (as low Tg elastomer) exhibiting a content (mol %) of cis-1,4-enchainments of greater than 90% with one or more S-SBRs or E-SBRs (as high Tg elastomer(s)).
The composition according to the invention can comprise just one diene elastomer or a mixture of several diene elastomers, it being possible for the diene elastomer or elastomers to be used in combination with any type of synthetic elastomer other than a diene elastomer, indeed even with polymers other than elastomers, for example thermoplastic polymers.
II-2. Reinforcing Filler
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 tyres, for example an organic filler, such as carbon black, a reinforcing inorganic filler, such as silica, or also 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 tyres (“tyre-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, or else, depending on the applications targeted, the blacks of higher series (for example N660, N683 or N772). 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 tyres, in other words capable of replacing, in its reinforcing role, a conventional tyre-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 tyre 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 total reinforcing filler (carbon black and/or reinforcing inorganic filler, such as silica) is between 20 and 200 phr, more preferably between 30 and 150 phr, the optimum being, in a known way, different depending on the specific applications targeted: the level of reinforcement expected with regard to a bicycle tyre, for example, is, of course, less than that required with regard to a tyre capable of running at high speed in a sustained manner, for example a motorcycle tyre, a tyre for a passenger vehicle or a tyre for a utility vehicle, such as a heavy-duty vehicle.
According to one embodiment of the invention, use is made of a reinforcing filler comprising between 30 and 150 phr, more preferably between 50 and 120 phr, of inorganic filler, particularly of silica and optionally of carbon black; the carbon black, when it is present, is preferably used at a content of less then 20 phr, more preferably of less than 10 phr (for example between 0.1 and 10 phr).
According to another embodiment, the reinforcing filler is 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” depending on 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 referred to as “symmetrical”, corresponding to the following general formula (III):

Z-D-Sp-D-Z,  (III)

in which:

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






in which:

    
    
        the R21 radicals, which are substituted or unsubstituted and identical to or different from one another, represent a C1-C18 alkyl, C5-C18 cycloalkyl or 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 R22, radicals, which are substituted or unsubstituted and identical to or different from one another, represent a C1-C18 alkoxyl or C5-C18 cycloalkoxyl group (preferably a group selected from C1-C8 alkoxyls and C5-C8 cycloalkoxyls, more preferably still a group selected 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 normal commercially available mixtures, the mean value of the “p” indices is a fractional number preferably of between 2 and 5, more preferably of approximately 4. However, the invention can also advantageously be carried out, for example, with alkoxysilane disulphides (p=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)alkoxyldi(C1-C4)alkylsilylpropyl)polysulphides (in particular disulphides, trisulphides or tetrasulphides), more particularly bis(monoethoxydimethylsilylpropyl)tetrasulphide, such as described in Patent Application WO 02/083782 (or US 2004/132880).
Mention will in particular be made, as coupling agents other than an alkoxysilane polysulphide, of bifunctional POSs (polyorganosiloxanes) or else of hydroxysilane polysulphides (R22=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 bearing azodicarbonyl functional groups, such as described, for example, in Patent Applications WO 2006/125532, WO 2006/125533 and WO 2006/125534.
In the rubber compositions in accordance with the invention, the content of coupling agent is preferably between 4 and 12 phr, more preferably between 3 and 8 phr.
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.
II.3 Vulcanization System
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 10 phr, more preferably of between 0.5 and 5 phr, in particular between 0.5 and 3 phr, when the composition of the invention is intended, according to a preferred form of the invention, to constitute a tyre tread.
The primary vulcanization accelerator must make possible crosslinking of the rubber compositions within industrially acceptable times, while retaining a minimum safe time (“scorch time”) during which the compositions can be shaped without risk of premature vulcanization (“scorching”).
According to the invention, the vulcanization system comprises, as primary vulcanization accelerator, one or more thiazole compounds chosen from the compounds of following formula (I):




in which:
R1 and R2 independently represent a hydrogen atom or a C1-C25 hydrocarbon group chosen from linear, branched or cyclic alkyl groups, aralkyl groups, alkylaryl groups and aryl groups and optionally interrupted by one or more heteroatoms, it being possible for R1 and R2 to together form a non-aromatic ring but it not being possible for R1 and R2 to together form an aromatic ring,

    
    
        A is chosen from:
        
            a hydrogen atom;
            a group
        
        
    
    






in which:
R3, R4 and R5 independently represent a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms;
y is an integer greater than or equal to 1, preferably less than or equal to 10, more preferably less than or equal to 8 and very preferably less than or equal to 6;

    
    
        a group
    
    






in which:
R6 is a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms;

    
    
        a group
    
    






in which:
R7 is a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms;

    
    
        a group
    
    






in which:
Y is a C1-C18 hydrocarbon chain, optionally interrupted or substituted by one or more heteroatoms;
R8 is a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms;

    
    
        a group
    
    






in which:
X is a C1-C18 hydrocarbon chain, optionally interrupted or substituted by one or more heteroatoms;
R9 and R10 independently represent a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms, and

    
    
        a group
    
    






in which:
R11 is a hydrogen atom or a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms.
The compounds of formula (I) can advantageously replace, in all or part, the accelerator compounds conventionally used.
Cyclic alkyl group is understood to mean an alkyl group composed of one or more rings.
Hydrocarbon group or chain interrupted by one or more heteroatoms is understood to mean a group or chain comprising one or more heteroatoms, each heteroatom being between two carbon atoms of the said group or the said chain or between a carbon atom of the said group or the said chain and another heteroatom of the said group or the said chain or between two other heteroatoms of the said group or the said chain.
The heteroatom or heteroatoms can be a nitrogen, sulphur or oxygen atom.
According to a first embodiment, R1 and R2 independently represent a hydrogen atom or a methyl group.
According to a second embodiment, R1 and R2 each represent a hydrogen atom.
According to a third embodiment, R1 and R2 each represent a methyl group.
The compound or compounds of formula (I) are advantageously chosen from the compounds for which the A group is chosen from

    
    
        the group
    
    






    
    
        the group
    
    






and

    
    
        the group
    
    






where y and R3 to R7 are as defined above.
The R3 to R11 groups can be independently chosen from linear, branched or cyclic alkyl groups, aryl groups, aralkyl groups and alkylaryl groups.
The X and Y groups can be independently chosen from linear, branched or cyclic alkylene groups, arylene groups and alkylarylene groups.
According to a specific embodiment, R3, R4 and R5 represent a methyl group.
According to a specific embodiment, R6 represents a C1-C4 alkyl, more preferably a C1-C3 alkyl and very preferably a methyl group or an ethyl group.
According to a specific embodiment, R7 represents a C1-C4 alkyl, more preferably a C1-C3 alkyl and very preferably a methyl group or an ethyl group, or else R7 represents an aralkyl group, such as, for example, a benzyl group.
According to a specific embodiment, Y represents a C1-C4 alkylene, more preferably a C1-C3 alkylene and very preferably a propylene group or an ethylene group and R8 represents a C1-C4 alkyl, more preferably a C1-C3 alkyl and very preferably a methyl group or an ethyl group.
According to a specific embodiment, X represents a C1-C4 alkylene, more preferably a C1-C3 alkylene and very preferably a methylene group or an ethylene group and R9 and R10 independently represent a C1-C4 alkyl, more preferably a C1-C3 alkyl and very preferably a methyl group or an ethyl group.
According to a specific embodiment, R11 represents a hydrogen atom.
Mention may be made, as specific compound of formula (I), of the following compounds:




The compound or compounds of formula (I) generally represent from 0.1 to 7 phr, preferably from 0.2 to 7 phr, more preferably from 0.5 to 7 phr and better still from 0.5 to 5 phr.
The vulcanization system of the composition according to the invention can also comprise one or more additional primary accelerators, in particular compounds of the family of the thiurams, zinc dithiocarbamate derivatives, sulphenamides, guanidines or thiophosphates.
II-4. Various Additives
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 tyres, 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 anti-ozone waxes (such as Cire Ozone C32 ST), chemical anti-ozonants or antioxidants (such as 6-PPD), anti-fatigue 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.
Preferably, the composition according to the invention comprises, as preferred non-aromatic or very weakly aromatic plasticizing agent, at least one compound selected 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.
II-5. Manufacture of the Rubber Compositions
The rubber composition according to the invention is manufactured in appropriate mixers, generally using two successive phases of preparation according to a general procedure well known to a person 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 110° C. and 190° C., preferably between 115° C. and 150° C. and more preferably still between 115° C. and 140° C., followed by a second phase of mechanical working (sometimes referred to as “productive” phase) at lower temperature, typically below 110° C., for example between 40° C. and 100° C., during which finishing phase the crosslinking or vulcanization system can be incorporated.
According to a preferred embodiment of the invention, all the base constituents of the composition of the invention, with the exception of the vulcanization system, namely the reinforcing filler or fillers and the coupling agent, if appropriate, are intimately incorporated, by kneading, in the diene elastomer or in the diene elastomers 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 110° C. and 190° C., preferably of between 115° C. and 150° C., is reached.
The two phases can be carried out consecutively on one and the same mixer or can be separated by a stage of cooling to a temperature of less than 100° C., the final stage then being carried out on a second mixer.
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 vulcanization system, 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 vulcanization system 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 tyre tread for a passenger vehicle.
II-6. Specific Thiazole Compounds
Another subject-matter of the invention is a thiazole compound of following formula (I′):




in which:
R1a and R2a independently represent a hydrogen atom or a C1-C25 hydrocarbon group chosen from linear, branched or cyclic alkyl groups, aralkyl groups, alkylaryl groups and aryl groups and optionally interrupted by one or more heteroatoms, it being possible for R1a and R2a to together form a non-aromatic ring but it not being possible for R1a and R2a to together form an aromatic ring,

    
    
        Aa is chosen from:
        
            a group
        
        
    
    






in which:
R3a, R4a and R5a independently represent a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms,
ya is an integer greater than or equal to 1, preferably less than or equal to 10, more preferably less than or equal to 8 and very preferably less than or equal to 6,
provided that R1a and R2a do not simultaneously and respectively denote a methyl and a hydrogen atom, or an aryl and a hydrogen atom;

    
    
        a group
    
    






in which:
R6a is a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms, chosen from linear, branched or cyclic alkyl groups, aralkyl groups, optionally substituted by one or more halogens, one or more linear or branched alkyl groups, linear or branched alkoxy groups, a hydroxyl or a nitro,
and provided that R1a and R2a independently denote a hydrogen atom or an alkyl group;

    
    
        a group
    
    






in which:
R7a is a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms,
and provided that R1a and R2a respectively represent a methyl;

    
    
        a group
    
    






in which:
Xa is a C1-C18 hydrocarbon chain, optionally interrupted or substituted by one or more heteroatoms, but which cannot bear another phosphonate group,
R9a and R10a independently represent a C1-C18 hydrocarbon group, optionally interrupted by one or more heteroatoms, and
provided that R1a and R2a independently represent a hydrogen atom or an alkyl group; and

    
    
        a group
    
    






in which:
R11a is a hydrogen atom or a C1-C18 hydrocarbon group, provided that R1a and R2a independently represent a C1-C18 alkyl group.
Cyclic alkyl group is understood to mean an alkyl group composed of one or more rings.
Hydrocarbon group or chain interrupted by one or more heteroatoms is understood to mean a group or chain comprising one or more heteroatoms, each heteroatom being between two carbon atoms of the said group or the said chain or between a carbon atom of the said group or the said chain and another heteroatom of the said group or the said chain or between two other heteroatoms of the said group or the said chain.
The heteroatom or heteroatoms can be a nitrogen, sulphur or oxygen atom.
According to a first embodiment, R1a and R2a independently represent a hydrogen atom or a methyl group.
According to a second embodiment, R1a and R2a each represent a hydrogen atom.
According to a third embodiment, R1a and R2a each represent a methyl group.
Advantageously, the thiazole compound of formula (I′) is such that Aa is chosen from:

    
    
        the group
    
    






    
    
        the group
    
    






    
    
        the group
    
    






ya and R3a to R7a being as defined above.
The R3a to R7a and R9a to R11a groups can be independently chosen from linear, branched or cyclic alkyl groups, aryl groups, aralkyl groups and alkylaryl groups, with the proviso of optional conditions clarified above for each of these groups.
The Xa group can be independently chosen from linear, branched or cyclic alkylene groups, arylene groups and alkylarylene groups.
According to a specific embodiment, R3a, R4a and R5a represent a methyl group.
According to a specific embodiment, R7a represents a C1-C4 alkyl, more preferably a C1-C3 alkyl and very preferably a methyl group or an ethyl group, or else R7a represents an aralkyl group, such as, for example, a benzyl group.
According to a specific embodiment, Xa represents a C1-C4 alkylene, more preferably a C1-C3 alkylene and very preferably a methylene group or an ethylene group and R9a and R10a independently represent a C1-C4 alkyl, more preferably a C1-C3 alkyl and very preferably a methyl group or an ethyl group.
II-7. Preparation of the Accelerators of General Formula (I) and (I′)
A person skilled in the art knows how to prepare the thiazole compounds of general formula (I) when the A group represents a hydrogen atom, in which case the thiazoles are substituted by a thiol. This thiol can be salified by techniques known to a person skilled in the art in order to obtain the thiolate compounds.
A person skilled in the art, starting from the thiols or thiolates described above and depending on the nature of the A or Aa group, can obtain the compounds of general formula (I) or (I′) as indicated below:

    
    
        When the A or Aa radical represents a group
    
    






as defined above, the compound can be prepared by an oxidative coupling.
An organic or inorganic oxidizing agent (for example diisopropyl azodicarboxylate or ammonium persulphate, or also iodine or a sodium hypochlorite solution) is added to a solution of the two precursor thiols. For example, this type of procedure is described in the following documents:

    
    
        with NaOCl by Mathes in U.S. Pat. No. 2,196,607 (1940),
        with (NH4)2S2O8 in Stewart, Mathes, J. Org. Chem., 1949, vol. 14, pp. 1111-1117.
    
    


For example, Birch describes the oxidative coupling of methyl mercaptan with tert-butyl mercaptan in the presence of potassium hexacyanoferrate(III) (Birch et al. Journal of the Institute of Petroleum, 1953, vol. 39, pp. 206-210).
It is also possible to follow another procedure consisting in carrying out a redistribution reaction on a symmetrical disulphide in the presence of an alkyl mercaptan, such as described, for example, by Brzezinska, Ewa and Ternay, Andrew L., Jr. in the paper Disulfides Syntheses Using 2,2′-Dithiobis(benzothiazole), Journal of Organic Chemistry (1994), 59, 8239-8244. This method consists in reacting a symmetrical disulphide and a mercaptan, such as, for example, tert-butyl mercaptan, in chloroform, which results in a redistribution.
By this reaction, the derivatives in which y or ya=1 are obtained. In order to obtain the compounds in which y or ya is greater than 1, it is possible to insert sulphur atoms into the existing sulphur-sulphur bond, for example by reaction with triphenylthiosulphenyl chloride in dichloromethane in the presence of acetic acid, as provided, for example, in Tetrahedron Letters, Volume 41, Issue 37, September 2000, pages 7169-7172.

    
    
        When the A or Aa radical represents a group
    
    






as defined above, this compound can be prepared according to a thioesterification reaction between the thiol or its corresponding thiolate with a carboxylic acid or its derivatives (acid chloride, anhydride) bearing the R6 or R6a radical.
For example, Jan Larsen and Christine Lenoir in Organic Syntheses, Coll. Vol. 9, p. 72 (1998), describe a thioesterification reaction between a thiol and an acid chloride in the presence of triethylamine to trap the hydrochloric acid formed, the reaction being carried out in dichloromethane at between 0 and 10° C.

    
    
        When the A or Aa radical represents a group
    
    






as defined above, this compound can be prepared by an addition/elimination reaction between the thiol and an alkyl chloroformate bearing the R7 or R7a radical, which can itself either be commercially available or be prepared by reaction between an alcohol and phosgene or one of its derivatives. An organic or inorganic base can be added in order to trap the hydrochloric acid formed.
This approach is described by Taylor, Roger in Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1983, pp. 291-296. The authors react ethyl mercaptan with methyl chloroformate in the presence of pyridine.
Instead of using the thiol, it is possible to use the corresponding thiolate. This approach is described by Suzuki, Shigenori, Hisamichi, Kanehiko and Endo, Katsuya in Heterocycles, 1993, vol. 35, #2, pp. 895-900. The authors react sodium methylthiolate with methyl chloroformate in order to obtain the thiocarbonate derivative.
Another synthetic route consists in reacting the thiol or its thiolate with phosgene (Chen, H. W. et al., Journal of the American Chemical Society, 1978, vol. 100, pp. 2370-2375) or one of its derivatives, such as triphosgene (WO2008/038175), optionally in the presence of an inorganic or organic base, such as a tertiary amine, for example, in order to form the chlorothioformate intermediate. This intermediate can subsequently react with an alcohol in the presence of an organic base, such as a tertiary amine, in order to form the thiocarbonate compound. This approach is, for example, described in Organic Syntheses, Coll. Vol. 5, p. 166 (1973); Vol. 44, p. 20 (1964).

    
    
        When the A radical represents a group
    
    






as defined above, this compound can be prepared by nucleophilic substitution between the thiol or its thiolate and an ester substituted by a halogen group and bearing the Y and R8 radicals, such as, for example, bromoethyl acetate or methyl 4-bromobutyrate.
For example, the reaction between 3-mercapto-5,6-diphenyl-1,2,4-triazine and ethyl 3-bromopropionate in ethyl acetate in the presence of triethylamine, in order to trap the hydrobromic acid formed, is described by Bhalla, M., Srivastava, V. K., Bhalla, T. N. and Shanker, K. in Bollettino Chimico Farmaceutico (1995), 134(1), 9-15.

    
    
        When the A or Aa radical represents a group
    
    






as defined above, this compound can be prepared by nucleophilic substitution between the thiol or its thiolate and a halogenated derivative of a phosphonate or of a phosphonic acid bearing the X, R9 and R10 or Xa, R9a and R10a radicals, and more particularly with a bromo-ou chloroalkylphosphonate.
This reaction is described, for example, for the reaction between diethyl (2-bromoethyl)phosphonate and sodium ethanethiolate in an ether (Mikolajczyk, Marian, Costisella, Burkhard and Grzejszczak, Slawomir, Tetrahedron, 1983, vol. 39, #7, pp. 1189-1193).

    
    
        When the A or Aa radical represents a group
    
    






as defined above, this compound can be prepared by nucleophilic substitution between the thiol or its thiolate and an allyl halide bearing the R11 or R11a radical, for example between the thiol and allyl bromide.
For example, the reaction between a triazinethiol and an allyl halide in the presence of potassium carbonate in alcohol is described in Patent BE 503980 of the Société Belge de l'azote et des produits chimiques du Marly (1951).
An example of a compound of formula (I) is 2-mercaptothiazole of following formula (1):




sold, for example, by ABCR.

III. EXAMPLES
A. Examples of the Synthesis of Compounds
1. Synthesis of Compound A: diethyl 2-(4,5-dimethylthiazol-2-ylthio)ethylphosphonate
Compound A is synthesized according to the following reaction scheme:




K2CO3 (2.85 g, 0.021 mol, Aldrich, >99%) is added, in one go, to a solution of 4,5-dimethylthiazole-2-thiol (3.00 g, 0.021 mol) in 30 ml of acetone. The reaction medium is stirred at a temperature of between 40 and 45° C. After stirring for 20 minutes, diethyl 2-bromoethylphosphonate (5.00 g, 0.020 mol, Aldrich, 97%) is added over a period of time of 3 minutes. The reaction medium is stirred at reflux for 1 hour and is subsequently slowly cooled (2 hours) down to ambient temperature.
The precipitate, formed of the residual salts, is filtered off and washed on the filter with 5 ml of acetone. The filtrate is concentrated under reduced pressure (5-6 mbar, 23° C.) until a constant weight is obtained.
A brown oil (5.382 g; 0.017 mol; yield 84%) is obtained.
The molar purity is greater than 93% (1H NMR).
TLC: Rf=0.5 (SiO2; EtOAc; visualization by UV and I2).
NMR Characterization of the product obtained:
The chemical shifts obtained by 1H and 13C NMR in d6-DMSO are given in the table below. The calibration is carried out with regard to DMSO (2.44 ppm in 1H, at 39.5 ppm in 13C and the 31P calibration with rs=0; rs: reference spectrum).
















No.
δ 1H (ppm)
δ 13C (ppm)

















1
2.15
14.2


2
2.23
10.7


3
/
147.8


4
/
126.5


5
/
156.9


6
3.17
26.9


7
2.15 + 2.12
25.2



(non-equivalent 1H)


8
3.95
61.1


9
1.18
16.0









The chemical shift of the 31P is 27.2 ppm.
2. Synthesis of Compound B: 4,5-dimethylthiazol-2-yl propanethioate
Compound B is synthesized according to the following reaction scheme:




A solution of propionyl chloride (9.24 g, 0.100 mol) in cyclohexane (60 ml) is added at 5° C., over a period of 15 minutes, to a solution of 4,5-dimethylthiazole-2-thiol (14.5 g, 0.100 mol) and triethylamine (11.11 g, 0.110 mol) in cyclohexane (400 ml). The temperature of the reaction medium is slowly brought back (2 hours) to 23° C. The reaction medium is subsequently stirred at this ambient temperature for 2.0-2.5 hours. Triethylamine hydrochloride Et3N.HCl is filtered off on Celite® and washed on the filter with petroleum ether (3 times with 50 ml, 40/60° C. fraction). The filtrate is washed with water (3 times with 50 ml). The organic phases are separated, combined and then concentrated under reduced pressure (3-4 mbar, 32° C.) to result in 17.93 g of crude reaction product.
The crude reaction product is dissolved in petroleum ether (500 ml) and this solution is washed with a solution of triethylamine (3.0 g, 0.030 mol) in water (150 ml). The two-phase mixture is vigourously stirred at ambient temperature for 2 hours. The organic phase is separated and washed with water (3 times with 50 ml). The separated and combined organic phases are concentrated under reduced pressure (32° C., 3-4 mbar).
A liquid (light yellow) (16.1 g, 0.080 mol, yield 80%) is obtained.
The molar purity is greater than 93% (1H NMR).
TLC: Rf=0.61 (SiO2; heptane:EtOAc=1:1; visualization by UV and I2).
NMR Characterization of the Product Obtained:
The chemical shifts obtained by 1H and 13C NMR in d1-chloroform are given in the table below. The calibration is carried out with regard to chloroform (7.2 ppm in 1H and at 77 ppm in 13C).

















δ of the 1H
δ of the 13C


No.
(ppm)
(ppm)

















1
2.29
14.5


2
2.32
11.3


3
/
149.4


4
/
131.9


5
/
148.2


6
/
193.3


7
2.65
37.0


8
1.17
9.1









3. Synthesis of Compound C: ethyl 2-(4,5-dimethylthiazol-2-ylthio)acetate
Compound C is synthesized according to the following reaction scheme:




K2CO3 (10.50 g, 0.076 mol) is added, in one go, to a solution of 4,5-dimethylthiazole-2-thiol (10.53 g, 0.073 mol) in acetone (400 ml). The reaction mixture is stirred and then ethyl chloroacetate (8.89 g, 0.073 mol) is added dropwise. The reaction medium is brought to reflux for 2.5 hours. The medium is then cooled down to 20° C. The reaction medium is filtered and the filtrate is concentrated under reduced pressure to result in an oil (15.384 g, 0.067 mol, yield 92%).
The molar purity is greater than 96% (1H NMR).
TLC: Rf=0.8 (SiO2; cyclohexane:EtOAc=1:1; visualization by UV and I2).
NMR Characterization:
The chemical shifts obtained by 1H and 13C NMR in d6-acetone are given in the table below. The calibration is carried out with regard to DMSO (1.98 ppm in 1H and at 29.8 ppm in 13C).


















δ 1H (ppm)
δ 13C (ppm)


















1
2.14
14.2


2
—
127.1


3
—
148.6


4
2.23
10.5


5
—
157.1


6
3.93
35.5


7
—
168.5


8
4.08
61.4


9
1.15
13.7









4. Synthesis of Compound D: 2-(allylthio)-4,5-dimethylthiazole
Compound D is synthesized according to the following reaction scheme:




K2CO3 (10.00 g, 0.072 mol, Aldrich, >99%) is added, in one go, to a solution of 4,5-dimethylthiazole-2-thiol (11.00 g, 0.075 mol) in 160 ml of acetone. The reaction medium is stirred at a temperature of between 40 and 45° C. for 20 minutes. Subsequently, allyl bromide (11.00 g, 0.090 mol, Acros, 99%) is added over a period of time of 2 minutes. The reaction medium is stirred at reflux for one hour and is then slowly cooled (1 hour) down to ambient temperature.
The precipitate is filtered off and washed on the filter with 10 ml of acetone. The filtrate is concentrated under reduced pressure (9-10 mbar, 24° C.) until a constant weight is obtained.
A brown oil (12.22 g; 0.066 mol; yield 87%) is obtained.
The molar purity is greater than 97% (1H NMR).
NMR Characterization:
The chemical shifts obtained by 1H and 13C NMR in d6-DMSO are given in the table below. The calibration is carried out with regard to DMSO (2.44 ppm in 1H and at 39.5 ppm in 13C).
















No.
δ 1H (ppm)
δ 13C (ppm)

















1
2.14
14.2


2
2.22
10.7


3
/
147.8


4
/
126.5


5
/
156.8


6
5.72
36.3


7
5.84
132.9


8
5.06 + 5.20
118.3









5. Synthesis of Compound E: O-benzyl S-4,5-dimethylthiazol-2-yl carbonothioate
Compound E is synthesized according to the following reaction scheme:




K2CO3 (11.480 g, 0.083 mol) is added, in one go, to a solution of 4,5-dimethylthiazole-2-thiol (10.041 g, 0.069 mol) in acetone (370 ml). The reaction mixture is stirred and benzyl chloroformate (11.810 g, 0.069 mol) is added dropwise. The reaction medium is brought to reflux for 3.5 hours. The medium is subsequently cooled down to 20° C. and then filtered. The filtrate is concentrated under reduced pressure (9-10 mbar, 30-35° C.). The solid obtained is recrystallized from 150 ml of ethanol to provide a white solid (14.695 g, 0.053 mol, yield 76%) with a melting point of 72-73° C.
The molar purity is greater than 99% (1H NMR).
NMR Characterization:
The chemical shifts obtained by 1H and 13C NMR in d6-DMSO are given in the table below. The calibration is carried out with regard to DMSO (2.44 ppm in 1H and at 39.5 ppm in 13C).

















δ of the 1H



No. of atoms
(ppm)
δ of the 13C (ppm)

















1
2.31
14.2


2
2.22
10.9


3
/
133.3


4
/
146.4


5
/
149.5


6
/
166.2


7
5.28
70.2


8
/
134.5


9/10/11
7.34
128.50 + 128.55 + 128.65









6. Synthesis of Compound F: 2-(tert-butyldisulphanyl)-4,5-dimethylthiazole
Compound F is synthesized according to the following reaction scheme:




An H2O2 solution (9.0 ml, 0.080 mol, 30% in water) is added dropwise to a solution of 2-methyl-2-propanethiol (6.31 g, 0.070 mol) and 4,5-dimethylthiazole-2-thiol (10.17 g, 0.070 mol) in ethanol (60 ml) over a period of time of 50 minutes, so that the temperature of the reaction medium is less than 31° C. The reaction medium is brought to reflux and stirred for 3.0 hours. After returning to ambient temperature, the reaction medium is diluted with heptane (200 ml) and then the solution is washed with water (4 times with 50 ml). The aqueous phase is washed with heptane (4 times with 25 ml). The combined organic phases are washed with water (twice with 50 ml), dried over sodium sulphate, filtered and concentrated under reduced pressure (Tbath 35° C., 7 mbar).
A solid (15.85 g, 0.068 mol, yield 97%) with a melting point of 31° C. is obtained.
The molar purity is greater than 99% (1H NMR).
TLC: Rf=0.78 (SiO2; heptane:EtOAc=1:1; visualization by UV and I2).
NMR Characterization:
The chemical shifts obtained by 1H and 13C NMR in d6-DMSO are given in the table below. The calibration is carried out with regard to DMSO (2.44 ppm in 1H and at 39.5 ppm in 13C).
















No.
δ 1H (ppm)
δ 13C (ppm)

















1
2.12
14.2


2
2.22
10.7


3
/
149.6


4
/
128.9


5
/
/


6
/
50.3


7/8/9
1.28
29.2









B. Examples of Compositions
Example 1
The object of this example is to compare the properties of a rubber composition comprising carbon black and silica, which can be used for the manufacture of a tyre tread, comprising MBTS as primary vulcanization accelerator (composition C1), with the properties of a rubber composition according to the invention comprising compound F (composition C2), compound B (composition C3) or compound E (composition C4) as primary vulcanization accelerator.
The formulations of the compositions are given in Table 1 below. The amounts are expressed in parts per 100 parts by weight of elastomer (phr).










TABLE 1









Tests













C1
C2
C3
C4

















BR (1)
30
30
30
30



SBR (2)
70
70
70
70



Carbon
4
4
4
4



black



(N234) (3)



Silica (4)
80
80
80
80



6-PPD (5)
2
2
2
2



Ozone wax
1.5
1.5
1.5
1.5



C32 ST (6)



Resin (7)
20
20
20
20



Silane, liq. (8)
6.5
6.5
6.5
6.5



SAD (9)
2
2
2
2



DPG (10)
1.5
1.5
1.5
1.5



ZnO
1.5
1.5
1.5
1.5



Sulphur
1.2
1.2
1.2
1.2



MBTS*
1.2
—
—
—



Compound F
—
1.7
—
—



Compound B
—
—
1.5
—



Compound E
—
—
—
2.0







(1) Polybutadiene with 0.7% of 1,2-; 1.7% of trans-1,4-; 98% of cis-1,4-(Tg = −105° C.) (mol %)



(2) Butadiene-styrene copolymer SSBR (SBR prepared in solution) with 25% of styrene, 59% of 1,2-polybutadiene units and 20% of trans-1,4-polybutadiene units (Tg = −24° C.) (mol %); content expressed as dry SBR (SBR extended with 9% by weight of MES oil, i.e. a total of SSBR + oil equal to 76 phr)



(3) Carbon black



(4) Silica “Zeosil 1165MP” from Rhodia, “HDS” type (BET and CTAB: approximately 160 m2/g);



(5) Antioxidant 6-PPD



(6) Anti-ozonant



(7) Aliphatic resin (C5 pure) “Hikorez A-1100”, sold by Kolon



(8) Coupling agent



(9) Stearin “Pristerene” from Uniqema



(10) Diphenylguanidine (Perkacit DPG from Flexsys)



*MBTS from G-Quimica, sold under the reference Rubator MBTS






The rheometric properties at 150° C. are given in Table 2 below.









TABLE 2









Tests












C1
C2
C3
C4

















k
0.59
0.28
0.44
0.44



T0
0.92
11.50
1.91
1.75



(min)










The rheometric properties obtained for the compositions according to the invention show that compounds F, B and E can be used as vulcanization accelerator in rubber compositions comprising one or more reinforcing fillers.
Example 2
The object of this example is to compare the properties of a rubber composition comprising carbon black, which can be used for the manufacture of a tyre tread, comprising MBTS as primary vulcanization accelerator (composition C1), with the properties of a rubber composition according to the invention comprising compound F (composition C2), compound B (composition C3) or compound E (composition C4) as primary vulcanization accelerator.
The formulations of the compositions are given in Table 3 below. The amounts are expressed in parts per 100 parts by weight of elastomer (phr).










TABLE 3









Tests













C1
C2
C3
C4

















NR (1)
100
100
100
100



Carbon black
47
47
47
47



(N234)



SAD (2)
2.5
2.5
2.5
2.5



ZnO
3
2.7
2.7
2.7



Sulphur
1.5
1.5
1.5
1.5



MBTS (3)
0.38
—
—
—



Compound F
—
0.53
—
—



Compound B
—
—
0.46
—



Compound E
—
—
—
0.64







(1) Natural rubber



(2) Stearin “Pristerene” from Uniqema



(3) MBTS from G-Quimica, sold under the reference Rubator MBTS






The rheometric properties at 150° C. are given in Table 4 below.










TABLE 4









Tests













C1
C2
C3
C4

















K
0.32
0.16
0.42
0.37



T0 (min)
1.25
10.66
0.88
1.57










The rheometric properties obtained for the compositions according to the invention show that compounds F, B and E can be used as vulcanization accelerator in rubber compositions comprising one or more reinforcing fillers.

## Claims

1. A rubber composition for the manufacture of tires, based on one or more diene elastomers, on one or more reinforcing fillers and on a vulcanization system, characterized in that the said vulcanization system comprises one or more thiazole compounds chosen from the compounds of following formula (I):




in which:
R1 and R2 independently represent a hydrogen atom or a C1-C25 hydrocarbon group chosen from linear, branched or cyclic alkyl groups, aralkyl groups, alkylaryl groups and aryl groups and optionally interrupted by one or more heteroatoms, it being possible for R1 and R2 to together form a non-aromatic ring but it not being possible for R1 and R2 to together form an aromatic ring,
A is chosen from:
a hydrogen atom;
a group







in which:
R3, R4 and R5 independently represent a C1-C18 hydrocarbon group;
y is an integer greater than or equal to 1;

a group







in which:
R6 is a C1-C18 hydrocarbon group;

a group







in which:
R7 is a C1-C18 hydrocarbon group;

a group







in which:
Y is a C1-C18 hydrocarbon chain,
R8 is a C1-C18 hydrocarbon group;

a group







in which:
X is a C1-C18 hydrocarbon chain;
R9 and R10 independently represent a C1-C18 hydrocarbon group, and

a group







in which:
R11 is a hydrogen atom or a C1-C18 hydrocarbon group.

2. The rubber composition according to claim 1, characterized in that R1 and R2 independently represent a hydrogen atom or a methyl group.

3. The rubber composition according to claim 2, characterized in that R1 and R2 each represent a hydrogen atom.

4. The rubber composition according to claim 2, characterized in that R1 and R2 each represent a methyl group.

5. The rubber composition according to claim 1, characterized in that A is chosen from
the group




the group





and
the group





where y and R3 to R7 are as defined in claim 1.

6. The rubber composition according to claim 1, characterized in that the R3 to R11 groups are independently chosen from linear, branched or cyclic alkyl groups, aryl groups, aralkyl groups and alkylaryl groups.

7. The rubber composition according to claim 1, characterized in that the X and Y groups are independently chosen from linear, branched or cyclic alkylene groups, arylene groups and alkylarylene groups.

8. The rubber composition according to claim 1, characterized in that the said thiazole compound or compounds represent from 0.1 to 7 phr, parts by weight per hundred of diene elastomer.

9. The rubber composition according to claim 1, characterized in that the diene elastomer or elastomers are selected from the group consisting of polybutadienes, natural rubber, synthetic polyisoprenes, butadiene copolymers, isoprene copolymers and the mixtures of these elastomers.

10. The rubber composition according to claim 1, characterized in that the reinforcing filler or fillers are chosen from silica, carbon black and their mixtures.

11. The rubber composition according to claim 1, characterized in that the reinforcing filler or fillers are present at a content of between 20 and 200 phr.

12. A process for preparing the rubber composition for the manufacture of tires as defined in claim 1, characterized in that it comprises the following stages:
incorporating the reinforcing filler or fillers in a diene elastomer during a first stage, the reinforcing filler or fillers and the diene elastomer being kneaded thermomechanically, in one or more goes, until a maximum temperature of between 110° C. and 190° C. is reached; and
subsequently incorporating, during a second stage, the vulcanization system and kneading the reinforcing filler or fillers, the diene elastomer, and the vulcanization system up to a maximum temperature of less than 110° C.

13. The process according to claim 12, in which, between the thermomechanical kneading and the incorporation of the vulcanization system, the combined product is cooled to a temperature of less than or equal to 100° C.

14. A method of manufacturing a finished article or a semi-finished product intended for a motor vehicle ground-contact system comprising the step of incorporating the rubber composition according to claim 1 in the finished article or semi-finished product.

15. A finished article or semi-finished product intended for a motor vehicle ground-contact system comprising a rubber composition as defined in claim 1.

16. A tire comprising a rubber composition as defined in claim 1.

17. A tread comprising a rubber composition as defined in claim 1.