Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/20—Incorporating sulfur atoms into the molecule
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/22—Incorporating nitrogen atoms into the molecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/25—Incorporating silicon atoms into the molecule
• • 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives

Definitions

• the present invention relates to a tire comprising a rubber composition based on at least one diene elastomer, a reinforcing filler, a chemical crosslinking agent and at least one particular modifying agent.
• treads In the field of the manufacture of tires and in particular the formulation of rubber compositions in contact with the ground, called treads, it is generally sought to find the best possible compromise between antagonistic performance such as rolling resistance and the capacity tire to accept some deformations temporarily.
• the materials constituting the treads have good rigidity at low and medium deformations, in particular to ensure a low rolling resistance, while being able to accept certain deformations reversibly and without degrading under the effect of larger stresses or deformations.
• Chemical crosslinking is characterized by the establishment of covalent chemical bonds between the polymer chains.
• Another widely used method is chemical crosslinking with peroxides.
• the Applicant has discovered that the compromise between good rigidity at low and medium strain and high elongation at break can be obtained by introducing into the elastomer a specific density of non-covalent bonds between the chains.
• Physical crosslinking can be achieved by functionalizing the polymer chain by chemical molecules capable of associating with each other via non-permanent physical interactions such as ionic interactions, hydrogen bonds, ion-dipole and dipole-dipole interactions.
• modifying agent content present in a rubber composition, expressed as a percentage by weight, refers to the number of modifying agent molecules present in the composition per hundred units of diene elastomer. of the composition, whether it is indifferent dienic or non-dienic units.
• the level of modifying agent on an SBR is 0.20% molar, it means that there will be 0.20 modifier molecule per 100 styrene and butadiene SBR units.
• the level of modifying agent represents the number of molecules of grafted modification agent for 100 diene elastomer units, the number of units taking into account the two elastomers (grafted and ungrafted), assuming that other non-grafted modifying agent molecules were not added to the composition.
• the object of the invention is therefore a tire comprising at least one rubber composition based on at least one diene elastomer, a reinforcing filler, a chemical crosslinking agent and a modifying agent, optionally already grafted onto the elastomer.
• diene chosen from the compounds of formula (I) below:
• R denotes a unit containing at least one reactive group
• R 2 denotes an alkyl radical containing from 2 to 8 carbon atoms and optionally one or more heteroatoms chosen from S, N, O, Si,
• A denotes an oxygen or sulfur atom or an -NH group, preferably an oxygen atom.
• the covalently linked crosslinking bridges are formed by the presence of the chemical crosslinking system.
• the non-covalently linked crosslinking bridges are formed by the presence of the associative groups of the modifying agent once grafted along the elastomeric chain.
• the invention also relates to a method for preparing a rubber tire composition based on at least one diene elastomer, a reinforcing filler and a chemical crosslinking agent, characterized and comprising the following steps: - grafting on the diene elastomer, a modifying agent selected from the compounds of formula (I) below:
• R denotes a unit containing at least one reactive group
• Ri denotes hydrogen
• R 2 denotes an alkyl radical containing from 2 to 8 carbon atoms and optionally one or more heteroatoms chosen from S, N, O, Si,
• A denotes an oxygen or sulfur atom or a group --NH, preferably an oxygen atom
• the invention further relates to a method for preparing a rubber tire composition based on at least one diene elastomer, a reinforcing filler and a chemical crosslinking agent, characterized and comprising the following steps: - Incorporating into the diene elastomer, the reinforcing filler, a modifying agent chosen from the compounds of formula (I) below:
• R denotes a unit containing at least one reactive group
• Ri denotes hydrogen
• R 2 denotes an alkyl radical containing from 2 to 8 carbon atoms and optionally one or more heteroatoms chosen from S, N, O, Si,
• A denotes an oxygen or sulfur atom or a group --NH, preferably an oxygen atom
• the rubber composition included in the tire according to the invention may be present in at least one semi-finished rubber product of the tire, this semi-finished product being preferably chosen from the group consisting of the treads, crown reinforcement tablecloths, flanks, tablecloths carcass reinforcement, beads, protectors, rubber blocks and other internal rubbers, in particular decoupling erasers, intended to provide the connection or the interface between the aforementioned zones of the tire.
• the tires according to the invention are particularly intended for passenger vehicles such as two-wheeled vehicles (motorcycle, bicycle), industrial vehicles chosen from vans, "heavy vehicles” - i. e. metro, bus, road transport equipment (trucks, tractors, trailers), off-the-road vehicles -, agricultural or civil engineering machinery, aircraft, other transport or handling vehicles.
• passenger vehicles such as two-wheeled vehicles (motorcycle, bicycle), industrial vehicles chosen from vans, "heavy vehicles” - i. e. metro, bus, road transport equipment (trucks, tractors, trailers), off-the-road vehicles -, agricultural or civil engineering machinery, aircraft, other transport or handling vehicles.
• the elastomers and rubber compositions are characterized, before and after firing, as indicated below.
• the glass transition temperatures Tg of the polymers are measured by means of a differential scanning calorimeter. The analysis is performed according to the requirements of ASTM D341 8-08.
• NIR Near infrared spectroscopy
• NIR Near infrared spectroscopy
• SEC Size Exclusion Chromatography
• the SEC allows to apprehend the distribution of the molar masses of a polymer.
• Preparation of the polymer There is no particular treatment of the polymer sample before analysis. This is simply solubilized in (tetrahydrofuran + 1% vol diisopropylamine + 1% vol triethylamine + 1% vol distilled water) or in chloroform at a concentration of about 1 g / 1 . Then the solution is filtered on 0.45 ⁇ porosity filter before injection.
• the elution solvent is tetrahydrofuran + 1% vol. of diisopropylamine + 1% vol. triethylamine or chloroform depending on the solvent used for dissolving the polymer.
• the flow rate is 0.7 ml / min. 35 ° C and the analysis time of 90 min.
• a series of four WATERS columns in series, "STYRAGEL HMW7", “STYRAGEL HMW6E” and two “STYRAGEL HT6E" are used.
• the volume injected from the solution of the polymer sample is 100 ⁇ .
• the detector is a "WATERS 2410" differential refractometer and the software for the exploitation of chromatographic data is the “WATERS EMPOWER” system.
• the mean calculated mass masses are relative to a calibration curve made from commercial standard polystyrene "PS S READY CAL-KIT".
• Tensile tests make it possible to determine the elastic stress and the properties at break. Unless otherwise indicated, they are carried out in accordance with the French standard NF T 46-002 of September 1988. Traction data processing also makes it possible to draw the modulus curve as a function of elongation.
• the module used here is the nominal secant modulus (or apparent) measured in first elongation, calculated by reducing to the initial section of the specimen. The nominal secant moduli (or apparent stresses, in MPa) at 10%, 100% and 300% elongation respectively noted MSA 10, MSA I OO and MSA300 are measured as first elongation.
• breaking stresses (in MPa) and the elongations at break (in%) are measured at 23 ° C ⁇ 2 ° C and at 100 ° C ⁇ 2 ° C, according to standard NF T 46-002.
• the dynamic properties ⁇ * and tan ( ⁇ ) max are measured on a viscoanalyzer (Metravib VA4000), according to ASTM D 5992- 96.
• the response of a sample of vulcanized composition (cylindrical specimen 20 mm in height and 78 mm 2 in section), subjected to a sinusoidal stress relieving in alternating tension-compression, at the frequency of 10 Hz, is recorded in normal temperature conditions (23 ° C) according to ASTM D 1 349-99, or as the case may be at a different temperature (100 ° C).
• a strain amplitude sweep of 0.01% to 7% (forward cycle) is performed, followed by 7% to 0.01% (return cycle).
• the rubber composition included in the tire according to the invention is based on one or more diene elastomers, one or more reinforcing fillers, a chemical crosslinking agent and at least one agent. modification of formula (I), and optional additives conventionally used in tire rubber compositions.
• composition based on is meant a composition comprising the mixture and / or the reaction product of the various constituents used, some of these basic constituents being capable of or intended to react with one another, at least in part, during the various phases of manufacture of the composition, in particular during its chemical crosslinking.
• any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e., terminals a and b excluded) while any range of values designated by the expression “from a to b” means the domain of values ranging from a to b (that is, including the strict limits a and b).
• elastomer or “diene” rubber should be understood in known manner an elastomer derived at least in part (ie, a homopolymer or a copolymer) of monomers dienes (monomers bearing two carbon-carbon double bonds, conjugated or not).
• diene elastomers can be classified into two categories: “essentially unsaturated” or “essentially saturated”.
• the term “essentially unsaturated” is generally understood to mean a diene elastomer derived at least in part from conjugated diene monomers, having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (mol%); for example, diene elastomers such as butyl rubbers or copolymers of dienes and alpha-o-olefins of the EPDM type do not fall within the above definition and may in particular be described as "essentially saturated” diene elastomers ( low or very low diene origin, always less than 15%).
• the term “highly unsaturated” diene elastomer is particularly understood to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
• diene elastomer that can be used in the invention is more particularly understood to mean:
• diene elastomer any type of diene elastomer
• the person skilled in the tire art will understand that the present invention is preferably implemented with essentially unsaturated diene elastomers, in particular of the type (a) or (b). ) above.
• conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5) 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, 2-methyl-3-isopropyl-1 3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.
• Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the "vinyl-toluene" commercial mixture, para-tertiarybutylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene.
• the copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinylaromatic units.
• the elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of randomizing modifying agent used.
• the elastomers may be, for example, block, random, sequenced or microsequential, and may be prepared in dispersion, in emulsion or in solution; they can be coupled and / or starred or else functionalized with a coupling agent and / or starring agent or functionalization.
• aminoalkoxysilane groups as described for example in WO 2009/133068
• carboxylic groups as described, for example, in WO 01/92402, US 6,815,473, WO 2004/096865 or US 2006/0089445) or polyether groups (as described for example in EP 1 127 909, US 6,503,973, WO 2009/000750 or WO 2009 / 000752).
• functionalized elastomers mention may also be made of elastomers (such as SBR, BR, NR or IR) of the epoxidized, halogenated or anhydride or carboxylic acid type.
• Polybutadienes and in particular those having a content (% molar) in units - 1, 2 of between 4% and 80% or those having a content (% molar) of cis -1, 4 of greater than 80%, are suitable.
• Tg glass transition temperature
• styrene content of between 5% and 60% by weight and more particularly between 20% and 50%
• a (%> molar) content in 1,2-bonds of the butadiene part included between 4%> and 75%> a content (%> molar) in trans-1,4 bonds between 10%> and 80%>
• butadiene-styrene-isoprene copolymers are especially suitable those having a styrene content between 5% and 50% by weight and more particularly between 10%> and 40%>, an isoprene content of between 15% and 60% by weight and more particularly between 20% and 50%>, a content of butadiene content of between 5% and 50% by weight and more particularly between 20% and 40%, a content (% by weight) in -1,2 units of the butadiene part of between 4% and 85%; content (% molar) in trans - 1,4 units of the butadiene part between 6%> and 80%), a content (% molar) in units - 1, 2 plus -3, 4 of the isoprenic part included between 5% and 70% and a content (% molar) in trans-1,4 units of the isoprenic part of between 10% and 50%, and more generally any butadiene-styrene-isoprene copolymer having a Tg between -5
• the diene elastomer (s) used in the invention are preferably chosen from the group of highly unsaturated diene elastomers consisting of polybutadienes (abbreviated as "BR"), synthetic polyisoprenes (IR) and natural rubber (NR). , butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
• Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR) and isoprene-copolymers.
• SBIR butadiene-styrene
• the diene elastomer is predominantly (i.e., for more than 50 phr) an SBR, whether it is an SBR prepared in emulsion ("ESBR") or of a SBR prepared in solution (“S SBR”), or a blend (mixture) SBR / BR, SBR / NR (or SBR / IR), BR / NR (or BR / IR), or SBR / BR / NR (or SBR / BR / IR).
• an SBR elastomer ESBR or S SBR
• an SBR having an average styrene content for example between 20% and 35% by weight, or a high styrene content, for example 35 to 45%, a vinyl content of the butadiene part of between 15% and 70%, a content (% molar) of trans-1,4 bonds of between 15% and 75% and a Tg of between - 10 ° C and - 55 ° C;
• ESBR SBR elastomer
• an SBR having an average styrene content for example between 20% and 35% by weight, or a high styrene content, for example 35 to 45%
• a vinyl content of the butadiene part for example
• a content (% molar) of trans-1,4 bonds of between 15% and 75%
• a Tg of between - 10 ° C and - 55 ° C
• the diene elastomer is predominantly (for more than 50 phr) an isoprene elastomer.
• the compositions of the invention are intended to constitute, in tires, the rubber matrices of certain treads (for example for industrial vehicles), crown reinforcing plies (for example work webs, protective webs or hoop webs), carcass reinforcement plies, flanks, beads, protectors, underlayments, rubber blocks and other internal gums providing the interface between aforementioned areas of the tires.
• isoprene elastomer in known manner a homopolymer or copolymer of isoprene, in other words a diene elastomer chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), different isoprene copolymers and mixtures of these elastomers.
• NR natural rubber
• IR synthetic polyisoprenes
• isoprene copolymers mention will in particular be made of copolymers of isobutene-isoprene (butyl rubber - IIR), isoprene-styrene (SIR), isoprene-butadiene (BIR) or isoprene-butadiene-styrene (SBIR).
• This isoprene elastomer is preferably natural rubber or a synthetic cis-1,4 polyisoprene; of these synthetic polyisoprenes, polyisoprenes having a content (% molar) of cis-1,4 bonds greater than 90%, more preferably still greater than 98%, are preferably used.
• the composition included in the tire conforms to the
• the invention may contain at least one essentially saturated diene elastomer, in particular at least one EPDM copolymer or a butyl rubber (optionally chlorinated or brominated), whether these copolymers are used alone or as a mixture with elastomers. diene strongly unsaturated as mentioned above, including NR or IR, BR or SBR.
• the rubber composition comprises a blend of one (or more) diene elastomers called "high Tg” having a Tg between -70 ° C and 0 ° C and d one (one or more) diene elastomers known as "low Tg” of between -10 ° C and -80 ° C, more preferably between -105 ° C and -90 ° C.
• the high Tg elastomer is preferably selected from the group consisting of S-SBR, E-SBR, natural rubber, synthetic polyisoprene (having a content (% molar) of cis-1 linkages, 4 preferably greater than 95%), BIR, SIR, SBIR, and mixtures of these elastomers.
• the low Tg elastomer preferably comprises butadiene units at a rate (% molar) of at least 70%; it consists preferably of a polybutadiene (BR) having a content (% molar) of cis-1,4 chains greater than 90%>.
• the rubber composition comprises, for example, from 30 to 100 phr, in particular from 50 to 100 phr, of a high Tg elastomer in a blend with 0 to 70 phr, in particular from 0 to 50 phr, of a low Tg elastomer; according to another example, it comprises for all 100 pce one or more SBR prepared (s) in solution.
• the diene elastomer of the composition included in the tire according to the invention comprises a blend of a BR (as low elastomer Tg) having a level (mol%) more than 90% cis-1,4, with one or more S-SBR or E-SBR (as elastomer (s) high Tg).
• the rubber composition included in the tire according to the invention is based on at least one diene elastomer and at least one modifying agent.
• the diene elastomer may be grafted with the modifying agent prior to its introduction into the rubber composition, or may be grafted by reaction with the modifier during manufacture of the composition.
• the composition included in the tire according to the invention may therefore contain a single diene elastomer grafted with the modifying agent (either grafted prior to its introduction into the composition or grafted by reaction with the modifying agent during the manufacture of the composition), or a mixture of several diene elastomers, all of which are grafted, or of which some are grafted and the others not, the diene elastomer or elastomers which can be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers, for example thermoplastic polymers.
• At least one diene elastomer is grafted along its chain by a modifying agent.
• the modifying agent carries an associative group (either grafted prior to its introduction into the composition, or grafted by reaction with the modifying agent during the manufacture of the composition).
• associative groups we mean groups likely to be associated with each other by non-permanent physical interactions such as ionic interactions, hydrogen bonds, ion-dipole and dipole-dipole interactions. According to a preferred embodiment of the invention, these are groups capable of associating with hydrogen bonds, comprising a nitrogen heterocycle, preferably diazotized, generally with 5 or 6 members.
• the grafting along the elastomer chain of a modifying agent bearing an associative group makes it possible to establish crosslinking bridges with non-covalent bonds between the elastomer chains.
• the modifying agent is chosen from the compounds of formula (I) below:
• R denotes a unit containing at least one reactive group
• R 2 denotes an alkyl radical containing from 2 to 8 carbon atoms and optionally one or more heteroatoms chosen from S, N, O, Si,
• A denotes an oxygen or sulfur atom or a group
• -NH preferably an oxygen atom
• R denotes a unit -R 3 X, where R 3 denotes a C 2 -C 5 alkyl radical which may contain one or more atoms of nitrogen, oxygen, sulfur and silicon, and X is a reactive group.
• the reactive group is the functional group which makes it possible to establish the grafting with the elastomer.
• the reactive group or groups of the R unit may be chosen from amine, thiol, epoxy, isocyanate, anhydride, alcohol and carboxylic acid groups, preferably amine and thiol groups.
• the modifying agent may be chosen from 2-aminoethylimidazolidone (UDETA), 11-mercapto-N- (2- (2-oxoimidazolidin-1-yl) ethyl) undecanamide. [(2-aminoethyl) amino] ethyl) imidazolidone (UTETA) and 1- (2- ⁇ 2 - [(2-aminoethylamino] ethyl ⁇ amino) ethyl] imidazolidone (UTEPA).
• the amount of modifying agent ranges from 0.05 to 10 mol%, preferably from 0.1 to 2 mol%, better still from 0.2 to 1 mol%. II - 3. Grafting the modifying agent on the elastomer
• the grafting of the elastomer is done by reacting said elastomer with the reactive group or groups carried by the modifying agent. During this reaction, this or these reactive groups form covalent bonds with the chain of the elastomer.
• the grafting of the modifying agent can be carried out in bulk, for example in an internal mixer or an external mixer such as a roll mill, or in solution. a) Radical grafting
• the grafting of the modifying agent is carried out by radical grafting, that is to say by radical reaction between the reactive group (s) of the modifying agent and one or more double bonds of the elastomer chain.
• the preparation of the diene elastomer grafted along the chain can be obtained by a radical grafting reaction carried out in solution or in bulk using a mercaptan type reagent and intended to graft said reactive groups of the agent. of modification on the chain of the diene elastomer of departure.
• Said grafting reaction is optionally carried out in the presence of a radical initiator, such as a peroxide.
• the grafting process can be carried out continuously or discontinuously.
• the polymer thus modified can be separated from its solution by any type of means known to those skilled in the art and in particular by a stripping operation with steam. b) Grafting on a previously modified elastomer
• the grafting of the modifying agent can also be done via functional groups present on the ungrafted elastomer.
• the grafting of the modifying agent is carried out by reaction of the reactive group or groups of the agent of modification on functional groups present on the ungrafted elastomer.
• Such functional groups may be chosen from anhydride groups, halogenated epoxides and carboxylic acids.
• the modifying agent may carry amino, thiol or alcohol groups.
• the modifying agent may carry amino, thiol or alcohol groups.
• the modifying agent may carry epoxy, isocyanate, anhydride or carboxylic acid groups.
• the modifying agent may carry amino, thiol, epoxy or alcohol groups.
• the modifying agent may carry amino, thiol or alcohol groups.
• the grafting reaction is an opening of the epoxide by the amine and this reaction can be implemented in solution or mass. Said grafting reaction is optionally carried out in the presence of a base for the deprotonation of the amine.
• the grafting process can be carried out continuously or discontinuously.
• the polymer thus modified can be separated from its solution by any type of means known to those skilled in the art and in particular by a stripping operation with steam.
• reinforcing filler Any type of reinforcing filler known for its capacity to reinforce a rubber composition that can be used for manufacturing tires, for example a reinforcing organic filler such as carbon black, a reinforcing inorganic filler such as silica, may be used. or a blend of these two types of filler, in particular a black carbon and silica blend.
• Carbon blacks are suitable for all carbon blacks, in particular blacks of the HAF, ISAF, SAF type conventionally used in tires (so-called pneumatic grade blacks).
• the reinforcing carbon blacks of the 100, 200 or 300 series for example the blacks N 15, N 134, N 234, N 326, N330, N 339, N 347 and N375, will be mentioned more particularly.
• blacks of higher series FF, FEF, GPF, SRF for example blacks N660, N683, N772.
• the carbon blacks could for example already be incorporated into the isoprene elastomer in the form of a masterbatch (see for example applications WO 97/36724 or WO 99/16600).
• organic fillers other than carbon blacks there may be mentioned organic functionalized polyvinylaromatic fillers as described in applications WO-A-2006/069792 and WO-A-2006/069793.
• any inorganic or mineral filler (regardless of its color and origin (natural or synthetic), also called “white” filler, “clear” filler or “non-black filler” as opposed to carbon black, capable of reinforcing on its own, without any other means than an intermediate coupling agent, a rubber composition intended for the manufacture of tires, in other words, able to replace, in its reinforcing function, a conventional carbon black of pneumatic grade, such a charge is generally characterized, in a known manner, by the presence of hydroxyl groups (-OH) on its surface.
• -OH hydroxyl groups
• the physical state in which the reinforcing inorganic filler is present is indifferent whether in the form of powder, microbeads, granules, beads or any other suitable densified form.
• the term "reinforcing inorganic filler” also refers to mixtures of different inorganic fillers. reinforcing agents, in particular highly dispersible siliceous and / or aluminous fillers as described below.
• Suitable reinforcing inorganic fillers are, in particular, mineral fillers of the siliceous type, in particular of silica (SiO 2), or of the aluminous type, in particular alumina.
• the silica used may be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g.
• HD S highly dispersible precipitated silicas
• the reinforcing inorganic filler used in particular if it is silica, preferably has a BET surface area of between 45 and 400. m 2 / g, more preferably between 60 and 300 m 2 / g.
• the level of reinforcing filler in the composition is between 30 and 150 phr, more preferably between 50 and 120 phr.
• the optimum is different according to the particular applications concerned: the level of reinforcement expected on a bicycle tire, for example, is of course less than that required on a tire capable of driving at high speed in a sustained manner, for example a motorcycle tire, a passenger car or commercial vehicle tire such as a heavy truck.
• the reinforcing filler mainly comprises silica, preferably the content of carbon black present in the composition being between 2 and 20 phr.
• the reinforcing filler mainly comprises carbon black.
• an at least bifunctional coupling agent or bonding agent is used in known manner to ensure a sufficient chemical and / or physical connection between the inorganic filler ( surface of its particles) and the diene elastomer, in particular organosilanes or bifunctional polyorganosiloxanes.
• polysulfide silanes called “symmetrical” or “asymmetrical” silanes according to their particular structure, are used, as described for example in the applications WO03 / 002648 (or US 2005/016651) and WO03 / 002649 (or US 2005/016650).
• polysulphide silanes known as "symmetrical" silanes having the following general formula (III) are suitable in the following non-limiting definition:
• x is an integer of 2 to 8 (preferably 2 to 5);
• A is a divalent hydrocarbon radical (preferably C 1 -C 18 alkylene groups or C 6 -C 12 arylene groups, more particularly C 1 -C 10 alkylenes, especially C 1 -C 4 alkylenes, in particular propylene);
• R.1 radicals substituted or unsubstituted, identical or different, represent an alkyl group Ci-Cis cycloalkyl, C5-C18 aryl or C 6 -Ci8 (preferably groups C 1 -C 6 alkyl, cyclohexyl or phenyl, especially C 1 -C 4 alkyl groups, more particularly methyl and / or ethyl).
• polysulphurized silanes By way of examples of polysulphurized silanes, mention may be made more particularly of bis (C 1 -C 4 alkoxy-C 1 -C 4 alkylsilyl-C 1 -C 4 alkyl) polysulfides (especially disulfides, trisulphides or tetrasulfides), as for example polysulfides of bis (3-trimethoxysilylpropyl) or bis (3-triethoxysilylpropyl).
• TESPT bis (3-triethoxysilylpropyl) tetrasulfide
• TESPD bis (3-triethoxysilylpropyl) tetrasulfide
• TESPD bis (3-triethoxysilylpropyl) tetrasulfide
• polysulfides in particular disulphides, trisulphides or tetrasulphides
• bis- (monoalkoxyl (Ci-C 4 ) -dialkyl (Ci-C 4 ) silylpropyl) more particularly bis-monoethoxydimethylsilylpropyl tetrasulfide.
• POS polyorganosiloxanes
• the content of coupling agent is preferably between 0.5 and 12 phr, more preferably between 3 and 8 phr.
• Chemical crosslinking agent allows the formation of covalent bonds between the elastomer chains.
• the chemical crosslinking can be done by means of a vulcanization system or by means of peroxide compounds.
• the vulcanization system itself is based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator.
• sulfur or a sulfur-donor agent
• a primary vulcanization accelerator To this basic vulcanization system are added, incorporated during the first non-productive phase and / or during the productive phase as described later, various known secondary accelerators or vulcanization activators such as zinc oxide.
• Sulfur is used at a preferential rate of between 0.5 and 12 phr, in particular between 1 and 10 phr.
• the primary accelerator of vulcanization is used at a preferential rate of between 0.5 and 10 phr, more preferably between 0.5 and 5.0 phr.
• accelerator any compound capable of acting as a vulcanization accelerator for diene elastomers in the presence of sulfur, especially thiazo-type accelerators and their derivatives, thiuram type accelerators, zinc dithio carbamates. .
• accelerators are for example selected from the group consisting of 2-mercaptobenzothiazyl disulfide (abbreviated "MBTS”), tetrabenzylthiuram disulfide (“TBZTD”), N-cyclohexyl-2-benzothiazyl sulfenamide (“CBS”), N, N dicyclohexyl-2-benzothiazyl sulfenamide (“DCBS”), N-tert-butyl-2-benzothiazyl sulfenamide (“TBB S”), N-tert-butyl-2-benzothiazyl sulfenimide (“TBSI”), zinc dibenzyldithio carbamate (“ZBEC”) and mixtures of these compounds.
• MBTS 2-mercaptobenzothiazyl disulfide
• TBZTD tetrabenzylthiuram disulfide
• CBS N-cyclohexyl-2-benzothiazyl s
• a primary accelerator of the sulfenamide type is used.
• the peroxide compound (s) represent (s) from 0.01 to 10 phr.
• acyl peroxides for example benzoyl peroxide or p-chlorobenzoyl peroxide
• peroxide ketones for example methyl ethyl ketone peroxide
• peroxyesters for example butylperoxyacetate, t-butylperoxybenzoate and t-butylperoxyphthalate
• alkyl peroxides for example dicumyl peroxide, di-t-butyl peroxybenzoate and 1,3-bis (t-butyl peroxyisopropyl) benzene
• hydroperoxides for example t-butyl hydroperoxide. II-4.
• Various additives for example benzoyl peroxide or p-chlorobenzoyl peroxide
• peroxide ketones for example methyl ethyl ketone peroxide
• peroxyesters for example butylperoxyacetate, t-butylperoxybenzoate and t-butylperoxy
• the rubber composition included in the tire according to the invention may also comprise all or part of the usual additives normally used in elastomer compositions for the manufacture of tires, in particular treads, such as, for example, plasticizers or extension oils, whether the latter are of aromatic or non-aromatic nature, pigments, protective agents such as anti-corrosion waxes, ozone (such as C32 ST Ozone Wax), chemical antiozonants, antioxidants (such as 6-paraphenylenediamine), anti-fatigue agents, reinforcing resins, acceptors (eg phenolic novolak resin) or donors methylene (for example HMT or H3M) as described for example in the application WO 02/10269, adhesion promoters (cobalt salts for example).
• plasticizers or extension oils whether the latter are of aromatic or non-aromatic nature
• protective agents such as anti-corrosion waxes, ozone (such as C32 ST Ozone Wax), chemical antiozonants, antioxidants (such as 6-parapheny
• the composition included in the tire 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, paraffinic, MES, TDAE oils oils. , the esters (in particular trio leates) of glycerol, the plasticizing hydrocarbon resins having a high Tg preferably greater than 30 ° C, and mixtures of such compounds.
• composition included in the tire according to the invention may also contain, in addition to the coupling agents, activators for coupling the reinforcing inorganic filler or, more generally, processing assistants that are capable in known manner, thanks to an improvement of the dispersion of the inorganic filler in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to implement in the green state, these agents being, for example, hydrolysable silanes such as alkylalkoxysilanes (especially alkyltriethoxysilanes), polyols, polyethers (for example po lyethyleneglyco ls), primary, secondary or tertiary amines (for example trialkanolamines), hydroxylated or hydrolyzable POSs, for example ⁇ , ⁇ -dihydroxy-polyorganosiloxanes (in particular ⁇ , ⁇ -dihydroxy-polydimethylsiloxanes), fatty acids such as, for example, stearic acid
• the rubber composition included in the tire according to the invention is manufactured in appropriate mixers, using two successive preparation phases according to a general procedure well known to those skilled in the art: a first working phase or thermomechanical mixing (sometimes referred to as a "non-productive" phase) at a high temperature, up to a maximum temperature of between 130 ° C and 200 ° C, preferably between 145 ° C and 1 85 ° C, followed by a second phase of work mechanical (sometimes called a "productive" phase) at a lower temperature, typically less than 120 ° C, for example between 60 ° C and 100 ° C, finishing phase during which is incorporated the chemical crosslinking system.
• a first working phase or thermomechanical mixing sometimes referred to as a "non-productive" phase
• a second phase of work mechanical sometimes called a "productive” phase
• all the basic constituents of the composition included in the tire of the invention with the exception of the chemical crosslinking system, namely the reinforcing filler or fillers, the agent coupling, if appropriate, are intimately incorporated, by kneading, with the diene elastomer or the diene elastomers during the first so-called non-productive phase, that is to say that is introduced into the mixer and thermomechanically kneading, in one or more steps, at least these different basic constituents until reaching the maximum temperature between 130 ° C and 200 ° C, preferably between 145 ° C and 1 85 ° C .
• the diene elastomer has been grafted with the modifying agent prior to the manufacture of the rubber composition.
• the grafted diene elastomer which is introduced during the so-called non-productive first phase.
• the grafting of the diene elastomer by the modifying agent is carried out concomitantly with the manufacture of the rubber composition.
• both the diene elastomer not yet grafted and the agent modification are introduced during the so-called non-productive first phase.
• the first (non-productive) phase is carried out in a single thermomechanical step during which all the necessary constituents, the possible agents of the invention, are introduced into a suitable mixer such as a conventional internal mixer.
• a suitable mixer such as a conventional internal mixer.
• the total mixing time, in this non-productive phase is preferably between 1 and 15 min.
• the low temperature chemical crosslinking system is then incorporated, generally in an external mixer such as a roll mill; the whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.
• the final composition thus obtained is then calendered, for example in the form of a sheet or a plate, in particular for a characterization in the laboratory, or else extruded in the form of a rubber profile that can be used, for example, as a tread. tire for passenger vehicle.
• SBR styrene-butadiene copolymer
• 300 g of antioxidized SBR are dissolved in 2.7 L of cyclohexane (2.7 L) in a 10L jacketed reactor.
• the modifying agent 11-mercapto-N- (2- (2-oxoimidazolidin-1-yl) ethyl) undecanamide has the following formula:
• the mixture is then stirred for 4 hours at 80 ° C. and then 31 ml of a solution of 6-PPD (N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine) in methylcyclohexane at 50 g / ml. 1 are added.
• the reaction mixture is stirred at 80 ° C for 15 minutes.
• the polymer is separated from its solvent by a stripping operation (steam stripping).) In the presence of TAMOL® and calcium.
• the stripped polymer is spun on rolls and finally dried in an oven at 60 ° C under reduced pressure and under a stream of nitrogen.
• the grafting rate then reaches 0.16 mol% (estimated by NMR P, for example, NMR analysis confirms the absence of free mercaptan in the polymer.)
• the grafted elastomer (SBR-B) thus produced has a level of 11-mercapto-N- (2- (2-oxoimidazolidin-1-yl) ethyl) undecanamide of 0.16 mol%.
• the quantitative 1H NMR experiment uses a 30 ° single pulse sequence and a 3 second repetition time between each acquisition.
• the samples are solubilized in carbon disulfide (CS 2 ).
• 100% of deuterated cyclohexane (C 6 Di 2 ) are added for the lock signal.
• the diene elastomer or elastomers (grafted or ungrafted) are introduced into an internal mixer, filled to 70% and whose initial tank temperature is approximately 90.degree. grafted), the optional reinforcing agent (s), the optional coupling agent and, after one to two minutes of mixing, the various other ingredients with the exception of the vulcanization system.
• Thermomechanical work (non-productive phase) is then carried out in one step (total mixing time equal to about 5 minutes), until a maximum temperature of "fall” of between 10 ° C. and 190 ° C. is reached. preferably between 130 ° C and 180 ° C.
• the mixture thus obtained is recovered, cooled and the vulcanization system (sulfur) is added to an external mixer (homo-finisher) at a temperature below 120 ° C., for example between 60 and 100 ° C., while mixing all (productive phase) for about 5 to 6 min.
• vulcanization system sulfur
• an external mixer homo-finisher
• compositions thus obtained are then calendered either in the form of plates (thickness of 2 to 3 mm) or thin sheets of rubber for the measurement of their physical or mechanical properties, or in the form of profiles which can be used directly, after cutting and or assembly to the desired dimensions, for example as semi-finished products for tires, in particular as treads of tires.
• the object of this example is to compare the properties of a rubber composition according to the invention comprising a grafted SBR-B elastomer (composition 3) with two comparative compositions comprising a non-grafted SBR-A elastomer (compositions 1 and 2). ).
• the rubber compositions are given in Table 1. The amounts are expressed in parts per 100 parts by weight of elastomer (phr). Table 1
• SBR-A SBR copolymer as defined in paragraph III-1.
• SBR-B graft copolymer from SBR-A according to paragraph III-1 .2
• control compositions 1 and 2 differ from each other by different rates of sulfur (the level of CBS also different being adjusted to the sulfur content).
• Composition 3 according to the invention has a sulfur content (as well as the level of CB S adjusted to this level of sulfur) lower than compositions 1 and 2.
• compositions 1 and 2 It is expected between compositions 1 and 2, an increase of MSA modules for composition 2 which comprises a higher sulfur content inducing greater crosslinking at 23 ° C as 100 ° C. At 23 ° C. and at 100 ° C., a lower elongation at break at break is also observed (value of the elongation at break lower) for composition 2 than for composition 1; results also expected by those skilled in the art in view of the levels of crosslinking agent of these two compositions.
• the hysteretic properties (translated by the measurement at 100 ° C. of max tan ⁇ ) are improved in the composition 2 with respect to the composition 1. This is known to those skilled in the art and explained by an increase in the level of sulfur in the composition 2 inducing a higher crosslinking density.
• composition 3 according to the invention including a graft polymer and a lower level of crosslinking agent than compositions 1 and 2
• MSA which are between those of the compositions 1 and 2 but with a very clear improvement of the properties of elongation and breaking stress vis-à-vis the two control compositions 1 and 2.
• composition 3 vis-à-vis composition 1 the person skilled in the art expects to see a degradation of the elongation and the stress at break as we have seen for the composition 2 vis-à-vis the composition 1.

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