Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/549—Silicon-containing compounds containing silicon in a ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0834—Compounds having one or more O-Si linkage
  • C07F7/0838—Compounds with one or more Si-O-Si sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/548—Silicon-containing compounds containing sulfur

Definitions

• the present invention relates to crosslinking agents which can be used for crosslinking of elastomeric networks, in particular in the manufacture of tires or semi-finished products for tires.
• the principle of vulcanization lies in the creation of sulfur bridges between two macromolecules by reaction on the double bonds of these diene elastomers.
• One of the remarkable characteristics of vulcanization is the simplicity with which this reaction can be controlled by adding compounds having an accelerating or retarding effect.
• By playing on the respective sulfur and accelerator levels it is in particular possible to control the vulcanization yield, to obtain sulfur bridges of different configurations which lead, for a given rubber composition, to possible adjustments of the properties. , both raw and cooked.
• sulfur vulcanization has certain known drawbacks, among which the problem of blooming in the raw state, due to migration of sulfur to the surface of the rubber articles considered, and above all a limited resistance of the vulcanizates in the cooked state, due to thermal aging of the latter ("thermal aging").
• the vulcanizates of diene elastomers crosslinked from sulfur exhibit significant sensitivity to temperature when the latter reaches a value close to the initial curing or vulcanization temperature.
• This phenomenon known as reversion, is accompanied by a degradation of the mechanical properties of the vulcanized material.
• a first subject of the invention relates to a polysulfide siloxane compound corresponding to the general formula (I) which follows:
• the siloxane polysulphide according to the invention can be prepared by a process which constitutes another object of the invention, said process comprising the following stages (x, Z and R having the above meanings):
• product B) it is subjected either to an alcoholysis by the action of an alcohol R'-OH (R 'hydrocarbon radical), or to a hydrolysis by the action of water in an inert organic solvent, in both cases in the presence of a organic base for trapping the acid halide formed, to obtain (hereinafter product B) either a monoalkoxysilane (in this case, R 'is the hydrocarbon radical in formula (B)), or a mono-hydroxysilane (in in this case, R 'is H in formula (B)), of formula:
• product C a sulphurization step is carried out on the product B by the action of a polysulphide, in order to obtain, as intermediate product (hereinafter product C), an alkoxysilane or hydroxysilane polysulphide of formula: (VS)
• the invention also relates to the use as crosslinking agent, in a rubber composition based on diene elastomer and a reinforcing filler, of a polysulfide siloxane of formula (I) above.
• the Mooney plasticity measurement is made according to the following principle: the composition in the raw state (i.e., before baking) is molded in a cylindrical enclosure heated to 100 ° C. After one minute of preheating, the rotor turns within the test tube at 2 revolutions / minute and the torque useful for maintaining this movement is measured after 4 minutes of rotation.
• the measurements are carried out at 130 ° C, in accordance with French standard NF T 43-005 (1991).
• the evolution of the consistometric index as a function of time makes it possible to determine the toasting time of the rubber compositions, assessed in accordance with the above-mentioned standard by parameter T5 (in the case of a large rotor), expressed in minutes, and defined as the time necessary to obtain an increase in the consistometric index (expressed in MU) by 5 units above the minimum value measured for this index.
• the measurements are carried out at 150 ° C or 165 ° C, as the case may be, with an oscillating chamber rheometer, according to the DLN 53529 standard - part 3 (June 1983).
• the evolution of the rheometric torque as a function of time describes the evolution of the stiffening of the composition as a result of the vulcanization reaction (see attached FIG. 4).
• the measurements are treated in accordance with DIN 53529 - part 2 (March 1983): the minimum and maximum torques, measured in dN.m (deciNewton.meter), are respectively named C ⁇ and C max ; tj is the induction time, that is to say the time necessary for the start of the vulcanization reaction.
• the difference noted ⁇ Couple (in dN.m) between C max and C ⁇ is also measured, which makes it possible to assess the vulcanization yield.
• the mechanical or dynamic properties indicated below are those measured at the "optimum cooking", that is to say, in known manner, those obtained, for a temperature of determined cooking, after the minimum cooking time to reach the maximum rheometric torque C max .
• the dynamic properties ⁇ G * and tan max ( ⁇ ) are measured on a viscoanalyzer (Metravib VA4000), according to standard ASTM D 5992-96.
• the response of a sample of vulcanized composition (4 mm thick cylindrical test piece and 400 mm 2 section) is recorded, subjected to a sinusoidal stress in alternating single shear, at the frequency of 10 Hz, under normal conditions of temperature (23 ° C) according to standard ASTM D 1349-99.
• a deformation amplitude sweep is carried out from 0.1 to 50% (outward cycle), then from 50% to 1% (return cycle).
• the exploited results are the complex dynamic shear modulus (G *) and the loss factor tan ( ⁇ ).
• the reversion can be analyzed according to different methods, the aim being to determine, in an indirect way, the evolution of the density of the sulfur bridges, between a cooking at the optimum (C max ) and a prolonged cooking.
• the first approach consists in measuring the evolution of the rheometric torque: the parameters ⁇ R 60 and ⁇ R 120 represent the evolution in% of the torque between C max and the torque measured after 60 or 120 min of cooking, respectively, at a cooking temperature determined (e.g. 150 ° C or 165 ° C).
• the second approach consists in measuring the evolution of the MAI 00 or MA300 modules: the parameters ⁇ MA100 and ⁇ MA300 correspond to the evolution in% of the respective modules between the optimum cooking (C max ) and after a prolonged cooking of 2 hours, at a specific cooking temperature (for example 150 ° C or 165 ° C).
• the first object of the invention is therefore a siloxane polysulfide corresponding to the above formula (I): d)
• the number x, integer or fractional, is equal to or greater than 2;
• the radicals Z, which are identical or different, are divalent linking groups preferably comprising from 1 to 18 carbon atoms;
• the radicals R, which are identical or different, are hydrocarbon groups preferably comprising from 1 to 18 carbon atoms.
• This compound is characterized by the presence, in its molecule, of a polysulphide group S x (with x ⁇ 2, that is to say the disulphide group included) fixed, via two silicon atoms, on a di-siloxane cycleSi-0-Si ⁇ structure (cycle). It can therefore be described as cyclic di-siloxane polysulfide.
• the linear or branched radicals R are more preferably chosen from alkyls, cycloalkyls or aryls, in particular from -Cg alkyls, C 5 -C 8 cycloalkyls, and the phenyl radical; these alkyl, cycloalkyl or phenyl groups can also contain heteroatoms such as N, O, S.
• radicals R there may be mentioned, by way of example, those chosen from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-ethylhexyl, n-octyl, iso-octyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, phenyl, toluyl, benzyl.
• radicals R which are identical or different, are C 1 -C 3 alkyls (namely methyl, ethyl, n-propyl, isopropyl), very particularly chosen from methyl and ethyl.
• the radicals Z substituted or unsubstituted, preferably having from 1 to 18 carbon atoms, are preferably hydrocarbon radicals, saturated or unsaturated, these Z radicals being able to be interrupted within the hydrocarbon chain by at least one heteroatom such O, S or N.
• Particularly suitable are C 1 -C 18 alkylene groups or C 6 -C 12 arylene groups, more particularly C 6 -C 12 alkenes
• Particularly preferred compounds of formula (I) are those in which the radicals R, which are identical or different, are C r C 3 alkyl groups and the radicals Z, which are identical or different, are C 4 alkylene (methylene, ethylene , propylene, butylene), in particular C 2 -C 4 , with x more preferably greater than 2.
• x has an average value of between 3 and 5, more preferably close to 4 (that is to say between 3.5 and 4.5) and Z is a C 2 alkylene - C 4 .
• siloxane polysulphides of the invention can be prepared according to a new synthesis process which constitutes another object of the present invention.
• FIG. 1 The process according to the invention, for preparing a polysulphide siloxane of formula (I), is shown diagrammatically in FIG. 1 appended. It includes the following stages (x, Z and R having the previous meanings):
• a c) a sulphurization step is carried out on the product B by the action of a polysulphide, in order to obtain, as intermediate product (hereinafter product C), an alkoxysilane or hydroxysilane polysulphide of formula (C):
• the halogens (Hal) of the starting silane (product A) can be identical or different, preferably chosen from bromine and chlorine; chlorine is more preferably used.
• the starting halosilanes (products A) and their intermediate derivatives (products B or C) are liquid products; they can therefore be used as such or else in the diluted state in an appropriate solvent, during the implementation of the various steps of the process of the invention.
• the hydrolysis step of product A is carried out directly on the starting halogenated silane (product A), by the action of water in an inert organic solvent, for example an ether, and in the presence of an organic base intended to trap the acid halide formed.
• an inert organic solvent for example an ether
• the alcoholysis step of product A consists in replacing the halogen (Hal) carried by the silicon atom of product A by the alkoxyl group (OR ') of an alcohol, in the presence of a base organic agent intended to trap the acid halide released during the reaction.
• the hydrocarbon radical R 'of the alcohol (R'-OH) preferably contains 1 to 8 carbon atoms, it is more preferably chosen from C 1 - alkyls, more preferably still from C 1 alkyls, in particular methyl or ethyl.
• an organic base intended to trap the acid halide formed an amine can be used, preferably a tertiary amine such as triethylamine.
• the alcoholysis is carried out at a temperature which is preferably less than 15 ° C, more preferably less than 10 ° C.
• Sodium polysulphide Na ⁇ is preferably used, in particular this polysulfide preferably being generated by the action of sulfur (S 8 ) on NajS.
• the preparation of such a polysulphide is carried out in a solvent, organic or not, such as for example water, alcohols, ketones or ethers, solvents in which the reagents are partially or completely soluble.
• the sulfurization step in the absence of any alcohol; then preferably in the aqueous phase, more preferably in a two-phase water / organic solvent medium (for example toluene, xylene, benzene, heptane or the like), as described for example in documents EP-A-694 552 or US-A -5,405,985 relating to the synthesis of polysulphide alkoxysilanes.
• a phase transfer catalyst to which is more preferably added a salt of formula M' ⁇ al or M "SO 4 , M" being chosen from Li, Na, K and Hal being chosen from F, Cl and Br.
• the salt used is then preferably chosen from NaCl, NaBr, Na 2 SO 4 ; NaCl is even more preferably used.
• the amount of salt can vary, for example, from 10% by weight of the aqueous solution until the solution is completely saturated.
• the phase transfer catalyst is for example tetrabutyl ammonium bromide (TBAB).
• the sulfurization step is preferably carried out under an inert gas such as argon.
• the temperature of the reaction medium is not critical, it is possible, for example, to work at ambient temperature; it is however preferred to operate hot to increase the reaction rate, for example between 60 ° C and 100 ° C or even up to the boiling point of the solvent.
• the molar ratio between the hydroxysilane or the alkoxysilane (product B) and the polysulfide is preferably adjusted so as to have a slight excess of polysulfide relative to the stoichiometric amount.
• the product B is itself preferably prediluted in the inert organic solvent such as an alcohol, a ketone or an ether.
• the salt (metal halide) which has formed is removed by filtration and the filtrate is freed from the organic solvent by vacuum distillation.
• the organic phase containing the product C is isolated if necessary and the reaction solvent is successively distilled under vacuum followed by the reactant B which has not reacted.
• the cyclization step on product C is carried out differently depending on whether it is a hydroxysilane polysulfide, in this case by a condensation step preferentially catalyzed by the presence of an acid or a base, or an alkoxysilane polysulfide, in this case by an acid or basic hydrolysis step, preferably of the acid type.
• product C diluted in an organic solvent, is introduced for example into a mixture consisting of an appropriate quantity of water, for example at the rate of two molar equivalents relative to the polysulphide used. reaction, and a catalytic amount of catalyst such as an organic acid such as a carboxylic acid, more particularly trifluoroacetic acid.
• siloxane polysulfides have been found to be sufficiently effective on their own for the crosslinking of diene elastomers.
• the diene elastomer is then preferably chosen from the group of highly unsaturated diene elastomers constituted by polybutadienes (BR), natural rubber (NR), synthetic polyisoprenes (IR), butadiene copolymers (in particular butadiene-styrene (SBR), butadiene-isoprene (BIR), butadiene-acrylonitrile (NBR)), isoprene copolymers (in particular isoprene-styrene (SIR) or butadiene-styrene-isoprene (SBIR)), and mixtures of these elastomers.
• BR polybutadienes
• NR natural rubber
• IR butadiene copolymers
• SBR butadiene-styrene
• BIR butadiene-isoprene
• NBR butadiene-acrylonitrile
• any type of reinforcing filler known for its capacity to reinforce a rubber composition which can be used for the manufacture of tires for example an organic filler such as carbon black or an inorganic reinforcing filler such as silica which will be used, can be used. then associated a coupling agent.
• carbon blacks all carbon blacks are suitable, in particular blacks of the HAF, ISAF, SAF type conventionally used in tires (so-called pneumatic grade blacks), for example in the treads of these tires.
• the reinforcing carbon blacks of the 100, 200 or 300 series such as, for example, the blacks NI 15, N134, N234, N330, N339, N347, N375.
• reinforcing inorganic fillers in particular mineral fillers of the siliceous or aluminous type are suitable, in particular silica (SiO 2).
• the silica used can be any reinforcing silica known to those skilled in the art, in particular any precipitated or pyrogenic silica having a BET surface as well as a CTAB specific surface, both less than 450 m 2 / g, preferably from 30 to 400 mVg .
• Highly dispersible precipitated silicas (called "HD") are preferred, in particular when the invention is implemented for the manufacture of tires having low rolling resistance.
• any known coupling agent can be used, in particular organosilanes or polyorganosiloxanes which are at least bifunctional.
• the siloxane polysulphide previously described is preferably associated, in its function of crosslinking agent, with a primary vulcanization accelerator, at a preferential rate of between 0.1 and 5 phr, more preferably of between 0.5 and 3 phr.
• R 5 represents a hydrogen atom, a 2-mercaptobenzothiazyl group of formula (IN): or a group of formula (N)
• R 6 and R 7 independently represent a hydrogen atom, a 2-mercaptobenzothiazyl group (formula IV), a C r C 4 alkyl group or a C 5 -C 8 cycloalkyl group, preferably comprising 6 links, said cycle possibly comprising at least one heteroatom such as S, O or ⁇ .
• Thiazole accelerators and preferential derivatives are notably chosen from the group consisting of 2-mercaptobenzothiazole, 2-mercapto-benzothiazyl disulfide, ⁇ -cyclohexyl-2-benzothiazyl sulfenamide, ⁇ , ⁇ -dicyclohexyl-2-benzothiazyl sulfenamide, N - ter-butyl-2-benzothiazyle sulfenamide, N-cyclohexyl-2-benzothiazyle sulfenimide, N-ter-butyl-2-benzothiazyle sulfenimide and mixtures of these compounds.
• the compounds of the thiuram family (formula NI) and the zinc dithiocarbamate derivatives (formula VII) are also suitable:
• R 8 , R 9 , R 10 and R 11 each independently represent an alkyl group comprising from 1 to 8 carbon atoms, a benzyl group, a combination between R 8 and R 9 and a combination between R 10 and R u to form a cyclic group pentamethylene or a methyl-pentarnethylene cyclic group and in which R 8 and R 9 and R 10 and R ⁇ are linked together.
• Thiuram-type accelerators are especially chosen from the preferential group consisting of tetramethyl-thiuram monosulfide, tetramethyl-thiuram disulfide, tetraethyl-thiuram disulfide, tetrabutyl-thiuram disulfide, tetra-iso-butyl disulfide -thiuram, tefrabenzyl-thiuram disulfide and mixtures of these compounds. Among them, tefrabenzyl-thiuram disulfide is more preferably retained.
• the primary vulcanization accelerators used in the context of the present invention are even more preferably chosen from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS”), N-cyclohexyl-2-benzothiazyl sulfenamide (abbreviated “CBS”), N, N-dicyclohexyl-2-benzothiazyle sulfenamide (abbreviated “DCBS”), N-ter-butyl-2-benzothiazyle sulfenamide (abbreviated “TBBS”), N-ter-butyl-2-benzothiazyl sulfenimide (abbreviated "TBSI”) and mixtures of these compounds.
• MBTS 2-mercaptobenzothiazyl disulfide
• CBS N-cyclohexyl-2-benzothiazyl sulfenamide
• DCBS N-dicyclohexyl-2-benzothiazy
• product D The above product of formula (II-1) (hereinafter called product D) is synthesized, in the examples which follow, according to the two different processes shown diagrammatically in FIG. 1 (hydrolysis or alcoholysis).
• product B can be prepared directly by hydrolysis of the starting product A, in an inert organic solvent (ether), in the presence of water as a hydroxyl and triethylamine donor intended to trap the acid. hydrochloric acid released.
• An excess of water is preferably introduced so as to promote the desired reaction, and avoid the condensation reaction of the silanol generated on the chlorosilane added.
• the use of a slight excess of triethylamine ensures total trapping of the hydrochloric acid, the residual triethylamine being distilled once the reaction is complete.
• the sodium polysulfide generated by insertion of sulfur in sodium sulfide Na j S in aqueous medium, comes to replace the chlorine atom of two molecules of the product C in solution in toluene.
• the reaction is carried out in the presence of a phase transfer catalyst (TBAB) and sodium chloride NaCl.
• TBAB phase transfer catalyst
• reaction medium is then transferred to a separatory funnel so as to isolate the toluene phase, which is dried over magnesium sulphate after having been washed with water.
• organic solution is then filtered and taken up in ether before being distilled in a ball oven (40 ° C), in order to remove the residual chloropropyldimethylsilanol (product B).
• reaction medium is kept under stirring for 24 hours before being dried over magnesium sulphate, filtered and concentrated in vacuo.
• the disulfide S 2 level determined by NMR, is equal to approximately 18% of the polysulfide units.
• product D is carried out according to another process in accordance with the invention, in several stages, starting from chloropropyldimethylchlorosilane (product A), via chloropropyl-dimethylethoxysilane (product B ') and bis- (propyldimethylethoxysilane) polysulfide ( product C).
• the synthesis scheme applied is that shown in Figure 3 attached. a) preparation of chloropropyldimethylethoxysilane (product B ')
• the first step consists of an alcoholysis which makes it possible to replace the chlorine carried by the silicon atom of product A by an ethoxyl group of ethanol, this reaction being carried out in the presence of triethylamine intended to trap the hydrochloric acid released during the reaction.
• the ice bath is removed while the stirring is continued at room temperature overnight, under a stream of argon.
• the GC analysis gas chromatography
• the reaction medium is then filtered through an Alhin tube in order to separate the product B 'in solution in ethanol from the triethylamine hydrochloride.
• the sodium polysulfide generated by insertion of sulfur in sodium sulfide Na ⁇ in aqueous medium, comes to replace the chlorine atom of two molecules of the product (B ') in solution in toluene.
• the reaction is carried out in the presence of a phase transfer catalyst (TBAB) and sodium chloride NaCl.
• TBAB phase transfer catalyst
• reaction medium is then transferred to a separating funnel so as to isolate the toluene phase, which is dried over magnesium sulfate after having been washed with water.
• organic solution is then filtered and taken up in ether before being distilled in a ball oven (40 ° C), in order to remove the residual chloropropyldimethylethoxysilane (product B '), ie 0.52 g.
• product B ' chloropropyldimethylethoxysilane
• product B ' chloropropyldimethylethoxysilane
• reaction medium is left under stirring at room temperature for 24 h, then dried over magnesium sulfate, filtered and concentrated in vacuo. 20.5 g of a very viscous pale yellow liquid are thus isolated, corresponding predominantly according to NMR analysis to the expected product, any traces of residual solvents which can be eliminated by subjecting the product to a vacuum of 200 mm Hg, at a temperature of 40 ° C, for 48 h.
• This first test carried out using a laboratory mixer, aims to demonstrate that it is possible to crosslink, without addition of sulfur, a rubber composition using the product D previously synthesized.
• compositions tested are identical to the nature of the crosslinking agent except:
• composition Cl sulfur (1 pce); composition C-2: product D (3.7 pce); composition C-3: product D (7.5 pce).
• the composition C1 is the control of this test, the compositions C-2 and C-3 use the siloxane polysulfide in accordance with the invention, at a preferential rate of between 3 and 12 phr.
• compositions are prepared in a known manner, as follows: there is introduced into an internal mixer, filled to 70% and whose initial tank temperature is around 60 ° C., the diene elastomer (or the mixture of diene elastomers, if necessary), the reinforcing filler, then the various other ingredients with the exception of the crosslinking system comprising at least the polysulfide siloxane (product D) and an accelerator.
• Thermomechanical work non-productive phase
• total mixing time equal to approximately 7 min
• the mixture thus obtained is recovered, it is cooled and then the polysulfide siloxane (product D) and the accelerator are added on an external mixer (homo-finisher) at 40 ° C., mixing the whole (productive phase) for 3 to 4 minutes.
• the compositions thus obtained are then calendered in the form of plates (thickness of 2 to 3 mm) or of thin sheets of rubber for the measurement of their physical or mechanical properties, or extruded to form profiles which can be used directly, after cutting and / or assembly to the desired dimensions, as semi-finished products for tires, for example as treads.
• Tables 1 and 2 give the formulation of the different compositions (Table 1 - rate of the different products expressed in pce), the rheometric properties (at 165 ° C), as well as the evolution of the rheometric couple, after 2 hours at 165 ° C , representative of the thermal stability of the compositions.
• Figure 4 shows the evolution of the rheometric torque (in dN.m) as a function of time (in min), for a temperature of 165 ° C, the curves C1 to C3 corresponding respectively to compositions C1 to C-3 .
• FIG. 4 clearly confirms the ability of product D to crosslink the rubber compositions while offering them better resistance to reversion.
• the very low reversion (decrease in torque beyond C max ) for the composition C-2 illustrated both by the parameters ⁇ R ô o and ⁇ R ⁇ o in Table 2 as by the shape of the curve C2 (existence of a very long vulcanization tray) of Figure 4.
• Composition C-4 is the control composition (sulfur plus sulfenamide accelerator), compositions C-5 to C-8 use the polysulfide siloxane according to the invention, with different accelerators.
• Tables 3 and 4 give the formulation of these compositions (Table 3 - rate of the various products expressed in pce), their rheometric properties at 165 ° C and the evolution of the rheometric couple after 2 hours at 165 ° C (reversion).
• This test was carried out on a larger mixer, compared to the previous tests, to allow a characterization of the rubber compositions in the raw state as in the cooked state, at the optimum baking at 150 ° C. and after prolonged cooking (2 hours at 150 ° C).
• composition C-9 (control): sulfur (1 pce); composition C-10 (invention): product D (7.5 pce).
• Tables 5 and 6 give the formulation of the two compositions, their properties before cooking and after cooking at 150 ° C.
• the thermal stability of the compositions is characterized by the evolution of the ⁇ MA100 and ⁇ MA300 modules.
• composition according to the invention C-10 compared with composition C-9, not only does not have any penalization of the properties in the raw state, but on the contrary reveals a clearly reduced Mooney plasticity, synonymous with an ability to the implementation in the raw state which is improved.
• the roasting times T5 are identical between the two compositions.
• the composition based on the siloxane polysulfide of the invention is observed unexpectedly: values of modules under strong deformation MAI 00, MA300 and of MA300 / MA100 ratio increased, indicative of high quality reinforcement; equivalent breaking properties; improved hysteresis properties, as illustrated by significantly lower values of ⁇ G * and tan ( ⁇ ) max , favorable to rolling resistance; finally, an evolution of the parameters ⁇ MA100 and ⁇ MA300 which confirms the very good thermal stability of the compositions according to the invention, compared with that of the control composition crosslinked in a conventional manner using sulfur.
• the invention finds particularly advantageous applications in rubber compositions which can be used for the manufacture of finished articles or semi-finished products intended for any system for connecting the ground to motor vehicles, such as tires, internal safety supports for tires, wheels. , rubber springs, elastomeric joints, other suspension and anti-vibration elements.

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