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
  • C08C19/26—Incorporating metal 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
• • 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
  • B60C1/0016—Compositions of the tread
• • 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
  • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
  • B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
• • 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
  • C08C19/24—Incorporating phosphorus 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F236/06—Butadiene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/06—Copolymers with styrene
• • 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
  • B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
  • B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
  • B60C2011/0016—Physical properties or dimensions
  • B60C2011/0025—Modulus or tan delta

Definitions

• the invention relates to a modified diene elastomer extended to the resin, to its method of manufacture and to rubber compositions containing it, these rubber compositions being intended in particular for the manufacture of semi-finished articles for tires and for the manufacture of tyres.
• a tire tread must meet a large number of often contradictory technical requirements, including good grip on dry and wet roads while offering low rolling resistance.
• Another means of achieving the compromise of grip performance on both dry and wet roads while offering low rolling resistance consists in using a high content of plasticizing resins in the low-hysteretic rubber compositions.
• this use of high content of plasticizing resins results in an increase in the tackiness of the composition. This increase in the tackiness of the composition is detrimental to the processability of the rubber composition in the various mixing tools.
• the Applicant sought to further improve the processability of resin-extended diene elastomers by further reducing the tackiness of the rubber compositions containing them without impairing the other properties of these compositions.
• the object of the present invention is therefore to provide resin-extended diene elastomers which make it possible to obtain rubber compositions exhibiting a compromise of improved rolling resistance/processability performance.
• the improvement of this compromise must also not be made to the detriment of the quality of the extradat.
• This object is achieved by specific resin-extended diene elastomers and by rubber compositions containing them. More specifically, this objective is achieved by the selection of a modified diene elastomer extended to the resin capable of being obtained by a process comprising at least:
• the modified diene elastomer extended to the resin • a stage of elimination of the organic solvent to obtain the modified diene elastomer extended to the resin; the modified diene elastomer extended to the resin having a Mn2/Mnl ratio strictly greater than 1.00 and an Mn2 greater than or equal to 200,000 g/mol.
• This modified diene elastomer extended to the resin as defined above advantageously confers on the rubber compositions containing it a tackiness significantly reduced compared to the diene elastomers extended to the resin of the prior art (therefore an improved processability) while retaining good hysteresis properties.
• the modified diene elastomer extended to the resin as defined above has the advantage of providing a rubber composition of homogeneous and uniform quality, which is reflected during its extrusion by a good finish of the extradate. , both at its surface and at its edges.
• Another object of the present invention relates to a rubber composition based on at least one resin-extended modified diene elastomer as defined above, at least one reinforcing filler and at least one crosslinking system.
• These compositions have the following advantages: they have little or no sticking to mixing tools and other tools for manufacturing compositions and semi-finished articles for tires; they have good hysteresis properties; and their extrusion is reproducible and homogeneous.
• Another object of the present invention relates to a semi-finished rubber article for a tire comprising at least one crosslinkable or crosslinked rubber composition such as defined above.
• the semi-finished article for a tire is a tread.
• Another object of the present invention is a tire comprising at least one rubber composition as defined above or a semi-finished article defined above.
• the number-average molar mass (Mn), and if applicable the weight-average molar mass (Mw) and the polydispersity index (Ip) of the elastomers are determined in a known manner, by triple detection steric exclusion chromatography "SEC -3D” (SEC: Size Exclusion Chromatography).
• Triple detection steric exclusion chromatography has the advantage of measuring average molar masses directly without calibration.
• the refractive index increment dn/dc of the sample is determined.
• the sample is dissolved beforehand in tetrahydrofuran at different precisely known concentrations (0.5 g/l; 0.7 g/l; 0.8 g/l; 1 g/l and 1.5 g/l ); then each solution is filtered through a filter with a porosity of 0.45 ⁇ m.
• Each solution is then injected directly using a syringe pump into a Wyatt differential refractometer under the trade name “OPTILAB T-REX” with a wavelength of 658 nm and thermostated at 35°C.
• the refractive index is measured by the refractometer.
• Wyatt's ASTRA software plots the detector signal as a function of sample concentration.
• the ASTRA software automatically determines the directing coefficient of the line corresponding to the refractive index increment of the sample in tetrahydrofuran at 35°C and at the wavelength of 658 nm.
• the previously prepared and filtered 1 g/l solution is used, which is injected into the chromatographic system.
• the equipment used is a “WATERS alliance” chromatographic chain.
• the elution solvent is antioxidized tetrahydrofuran, with BHT (2,6-diter-butyl 4-hydroxy toluene) of 250 ppm, the flow rate is 1 ml.min 1 , the system temperature 35°C and the 60 min analysis time.
• the columns used are a set of three AGILENT columns with the trade name “PL GEL MIXED B LS”.
• the injected volume of the sample solution is 100 ⁇ l.
• the detection system is made up of a Wyatt differential viscometer with the trade name "VISCOSTAR II”, a Wyatt differential refractometer with the trade name “OPTILAB T-REX” with a wavelength of 658 nm, a Wyatt multi-angle static light with a wavelength of 658 nm and trade name “DAWN HELEOS 8+”.
• the value of the refractive index increment dn/dc of the sample solution is integrated obtained above.
• the chromatographic data processing software is the “ASTRA from Wyatt” system.
• the SEC (Size Exclusion Chromatography) technique separates macromolecules in solution according to their size through columns filled with a porous gel. The macromolecules are separated according to their hydrodynamic volume, the largest being eluted first.
• the equipment used is a “WATERS alliance” chromatographic chain.
• the elution solvent is either antioxidant tetrahydrofuran, with BHT (butylated hydroxytoluene) of 250 ppm, or tetrahydrofuran without antioxidant, the flow rate is 1 ml.min 1 , the system temperature 35° C and the duration of 45 min analysis.
• the columns used are either a set of three AGILENT columns with the trade name “POLYPORE” or a set of four AGILENT columns, two with the trade name “PL GEL MIXED D” and two with the trade name “PL GEL MIXED E”.
• the injected volume of the plasticizing polymer sample solution is 100 ⁇ l.
• the detector is a "WATERS 2410" differential refractometer and the chromatographic data processing software is the "WATERS EMPOWER" system.
• the average molar masses calculated relate to a calibration curve produced from standard polystyrene.
• Tg glass transition temperatures
• NIR Near infrared spectroscopy
• the microstructure of elastomers is characterized by the technique of near infrared spectroscopy (NIR).
• NIR near infrared
• NIR near-infrared
• the principle of the method is based on the Beer-Lambert law generalized to a multicomponent system. The method being indirect, it calls upon a multivariate calibration [Vilmin, F.; Dussap, C.; Coste, N.
• Applied Spectroscopy 2006, 60, 619-29 carried out using standard elastomers with a composition determined by 13C NMR.
• the styrene content and the microstructure are then calculated from the NIR spectrum of an elastomer film approximately 730 ⁇ m thick.
• the acquisition of the spectrum is carried out in transmission mode between 4000 and 6200 cm' 1 with a resolution of 2 cm 1 , using a near infrared spectrometer with Fourier transform Bruker Tensor 37 equipped with an InGaAs detector cooled by Peltier effect.
• the inherent viscosity of elastomers at 25°C is determined from a solution of elastomer at 0.1 g.dl -1 in toluene, according to the following principle:
• the inherent viscosity is determined by measuring the flow time t of the polymer solution and the flow time t 0 of the toluene, in a capillary tube.
• C concentration of the polymer solution in toluene in g.dl 1
• t flow time of the polymer solution in toluene in seconds
• t 0 flow time of the toluene in seconds
• inh inherent viscosity expressed in dl.g -1 .
• the dynamic properties, and in particular tan ⁇ max, are measured on a viscoanalyzer (Metravib VA4000), according to standard ASTM D 5992-96.
• the response of a sample of vulcanized composition (cylindrical specimen 2 mm thick and 79 mm 2 in section) subjected to a sinusoidal stress in simple alternating shear, at a frequency of 10 Hz, under normal conditions is recorded. temperature (23°C) according to standard ASTM D 1349-99.
• a deformation amplitude sweep is performed from 0.1% to 50% peak-peak (outward cycle), then from 50% to 0.1% peak-peak (return cycle).
• the result more particularly exploited is the loss factor tan ô.
• tan ⁇ max the maximum value of tan ⁇ observed is indicated, denoted tan ⁇ max.
• This value is representative of the hysteresis of the material and in this case of the rolling resistance: the more the value of tan ô max is lower, the lower the rolling resistance.
• the results of the dynamic properties are given in base 100. An index less than 100 will indicate an improvement in the hysteresis properties, therefore an improvement in the rolling resistance performance of a tire.
• the stickiness of rubber compositions is measured by means of a tack measurement which is also called an adhesion test, called the "probe-tack” or “mico-tack” test. This test corresponds to a contact test between a surface (a probe) and an adhesive (the composition).
• the test is carried out at a temperature of 70° C. corresponding to the temperature of the rubber composition and of the surface; the composition not being vulcanized. The variation of the applied force as a function of the displacement is recorded.
• the test is carried out according to the requirements of the ASTM D2979-01 (2009) standard under the following conditions:
• the stickiness index is calculated in base 100 compared to the control with the peeling energy at 70°C. In this way, a result of less than 100 indicates a decrease in tackiness which corroborates better processability of the composition.
• the appearance of the extrudate is scored according to the B system, namely a surface score ranging from E to A, the letter E being the worst score, and an edge score ranging from 1 to 10 in ascending order, 1 being the lowest score.
• the determination of the amount of plasticizing resin in the resin-extended elastomer is also carried out by analysis of steric exclusion chromatography with refractive index (SEC-RI).
• the injected volume of the resin-extended elastomer sample solution is 100 ⁇ l.
• the detector is a "WATERS 2410" differential refractometer, with a wavelength of 810 nm, and the chromatographic data processing software is the “WATERS EMPOWER” system.
• Calibrators using a non-resin extended elastomer of the same microstructure as the resin extended elastomer are used. These calibrators are prepared in tetrahydrofuran with 250 ppm BHT antioxidant (butylated hydroxytoluene BHT). Several calibrators are made from an elastomer not extended with resin at precisely known concentrations in g/1 so as to obtain a standard range. Each calibrant is injected at 100 ⁇ l into the chromatographic system. Using data reprocessing software, each calibrator peak is integrated. It is then possible to know the total area of the peak of each calibrator. A calibration line is then constructed by plotting the area of the calibrator peak as a function of the concentration.
• the resin-extended elastomer is then injected after the calibration line has been produced.
• the signals of the resin and the elastomer being separated using SEC columns, it is therefore possible to perform a quantification.
• the peak obtained for the elastomer is then integrated using data reprocessing software; the area of said peak is then plotted on the previously constructed calibration line. It is then possible to deduce the elastomer concentration in g/1 in the elastomer extended to the resin (Céiasto).
• the concentration of the elastomer extended to the resin and dissolved is known (Cech).
• the quantification of the resin content is therefore carried out indirectly by the following relationship:
• any interval of values designated by the expression “between a and b” represents the range of values going from more than a to less than b (i.e. limits a and b excluded) while any interval of values denoted by the expression “from a to b” means the range of values going from a to b (that is to say including the strict limits a and b).
• the expression “part by weight per hundred parts by weight of elastomer” “or phr”, is meant within the meaning of the present invention, the part, by mass per hundred parts by mass of elastomer.
• a so-called majority species in a modified elastomer is that representing the largest weight fraction among the constituent species of the modified diene elastomer, relative to the total weight of the modified diene elastomer. In a system comprising a single compound of a certain type, this is the majority within the meaning of the present invention.
• primary or secondary amine means a primary or secondary amine both protected and unprotected by a protective group known to those skilled in the art.
• modified diene elastomer means a mixture of macromolecules resulting from the reaction of a living diene elastomer with a modifying agent comprising at least two reactive functions with respect to the reactive end of the elastomer. living dienic.
• a modification reaction with a modifying agent comprising more than one function reactive towards the living elastomer results in a mixture of macromolecules modified at the end of chains and macromolecules coupled or spangled with at least three branches and at most as many branches as there are reactive functions carried by the modifying agent; the coupled and star shapes constituting the branched chains of the modified elastomer.
• the molar ratio of the modifying agent to the living chains, and the number of its reactive functions certain species are more or less present, or even predominant, in the mixture.
• the expression "monomer unit”, whether diene or otherwise, is understood as a repeating unit of the polymer derived from the monomer in question.
• the expression "branching unit” is understood as a non-repetitive unit (there is only one in the polymer), resulting from the modifying agent on which has or have reacted live diene elastomer chains, and to which the diene elastomer chains are attached.
• the branching unit may consist, for example, of an atom to which the chains of diene elastomers are attached, this atom possibly being or not substituted by groups and/or chemical functions.
• the compounds mentioned in the description can be of fossil origin or biosourced. In the latter case, they can be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. In the same way, the mentioned compounds can also come from the recycling of already used materials, that is to say that they can be, partially or totally, resulting from a recycling process, or even obtained from raw materials themselves resulting from a recycling process. This concerns in particular polymers, plasticizers, fillers, etc.
• resin-extended elastomer is meant, within the meaning of the present invention, a material of the composite type, solid, formed of an elastomer and a resin intimately mixed with each other; the mixing of the resin with the elastomer being carried out in a liquid medium in an organic solvent, preferably in a non-polar organic solvent.
• the resin is therefore mixed in an elastomer in solution; that is to say the organic solvent and said elastomer form only a single phase visible to the naked eye. There is no precipitate or suspension of particles of said elastomer in the solution. This definition therefore excludes materials which would have been obtained by mass-mixing (or dry-mixing) an elastomer with a resin.
• Tg a single (single) value of Tg is obtained when measuring this parameter for the resin-extended elastomer.
• This Tg of the elastomer extended to the resin is different from that of the synthetic elastomer and that of the plasticizing resin measured before their mixing.
• a first object of the present invention relates to a resin-extended modified diene elastomer obtainable by a process comprising at least:
• the modified diene elastomer extended to the resin • a stage of elimination of the organic solvent to obtain the modified diene elastomer extended to the resin; the modified diene elastomer extended to the resin having a Mn2/Mnl ratio strictly greater than 1.00 and an Mn2 greater than or equal to 200,000 g/mol.
• the modified diene elastomer extended to the resin based on a plasticizer resin and a diene elastomer according to the invention comprises at least one modified diene elastomer and at least one plasticizer resin.
• This modified diene elastomer extended to the resin can also contain other extenders such as, for example, extender oils, in particular extender oils of petroleum or natural origin, such as, for example, oils comprising triglycerides.
• the modified diene elastomer extended to the resin also comprises an extender oil, the content of the latter is preferably lower than the content of the resin in the modified diene elastomer.
• the resin-extended modified diene elastomer according to the invention consists, preferably essentially, of a modified diene elastomer as defined below and at least one plasticizing resin; that is, it does not include extender oil.
• the diene elastomer extended to the resin usable in the context of the present invention has the following characteristics: it comprises within its structure a branching unit and at least two branches of diene elastomer obtained by anionic polymerization of at least one conjugated diene monomer having from 4 to 12 carbon atoms, the plasticizing resin is intimately mixed in the modified diene elastomer, it has a number-average molar mass Mnl measured before the modification step by triple detection steric exclusion chromatography, it has a number-average Mn2 molar mass measured after the modification step by triple detection steric exclusion chromatography greater than or equal to 200,000 g/mol and an Mn2/Mnl ratio strictly greater than 1.00, it has a transition temperature vitreous measured according to the ASTM D3418-08 standard and before its extension to the resin within a range ranging from -95°C to -70°C. Thanks to these characteristics, this modified diene elastomer extended to the resin makes it
• this diene elastomer is not modified within the meaning of the present invention; that is to say that it is mainly, or even preferentially, exclusively linear. It can however be functionalized at the end of the chain or at the end of the chain, but this functionalization is not a branching unit within the meaning of the present invention.
• the Mn2/Mnl ratio is greater than or equal to 1.10, more preferably is greater than or equal to 1.20; preferably is within a range from 1.30 to 4.00; more preferably in a range from 1.40 to 2.00.
• the number-average molar mass Mnl is greater than or equal to 140,000 g/mol, preferably within a range from 150,000 g/mol to 200,000 g/mol and the modified diene elastomer extended to the resin has a Mn2 ratio /Mnl strictly greater than 1.00, more preferably ranging in a range from 1.30 to 4.00, more preferably still in a range ranging from 1.40 to 2.00.
• the resin-extended modified diene elastomer according to the invention has a number-average molar mass Mn2 greater than or equal to 220,000 g/mol, more preferably greater than or equal to 230,000 g/mol, more preferably still greater than or equal to 250000 g/mol.
• the resin-extended modified diene elastomer according to the invention has a number-average molar mass Mn2 greater than or equal to 220,000 g/mol, more preferably greater than or equal to 230,000 g/mol, more preferably still greater than or equal to equal to 250,000 g/mol and an Mn2/Mnl ratio greater than or equal to 1.10, more preferably is greater than or equal to 1.20; preferably is within a range from 1.30 to 4.00; more preferably in a range from 1.40 to 2.00.
• elastomer capable of being used in the context of the present invention must be understood in known manner a synthetic elastomer consisting at least in part of conjugated diene monomer units or not.
• synthetic diene elastomer more particularly means: any homopolymer of a diene monomer, particularly a conjugated diene monomer, in particular any homopolymer obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms;
• copolymers with one or more vinylaromatic monomers may contain from 85.0 to 99.9% by weight of conjugated diene units and from 0.1 to 15.0% by weight of units derived from vinylaromatic monomers.
• the resin extended diene modified elastomer is obtained from a process, preferably a continuous process, comprising at least one anionic polymerization step in an organic solvent.
• the polymerization step is implemented in a conventional manner by anionic polymerization initiated for example by means of an organic compound of an alkali or alkaline-earth metal.
• Anionic polymerization generates elastomer chains having a reactive site at the end of the chain. We then commonly speak of living elastomer or living chain.
• the polymerization initiator can be any known anionic initiator.
• An initiator containing an alkali metal such as lithium or an alkaline-earth metal such as barium is preferably used.
• Suitable initiators containing lithium are in particular those comprising a carbon-lithium bond or a nitrogen-lithium bond.
• Representative compounds are aliphatic organolithiums such as ethyllithium, n-butyllithium (nBuLi), isobutyllithium, and lithium amides obtained from a cyclic secondary amine, such as pyrrolidone and hexamethyleneimine.
• anionic polymerization initiators are known to those skilled in the art.
• the polymerization initiator can be n-butyllithium.
• the polymerization can be carried out in a manner known per se, continuously or discontinuously, preferably continuously.
• the polymerization is generally carried out at temperatures between 0°C and 110°C and preferably from 40°C to 100°C, or even from 50°C to 90°C.
• the polymerization process is implemented in solution, in a more or less concentrated or diluted medium.
• the organic polymerization solvent is preferably an inert hydrocarbon solvent which may for example be an aliphatic or alicyclic hydrocarbon such as pentane, hexane, heptane, isooctane, cyclohexane, cyclopentane, methylcyclohexane or an aromatic hydrocarbon. such as benzene, toluene, xylene.
• the anionic polymerization step can also be carried out in the presence of at least one vinylaromatic monomer having from 8 to 20 carbon atoms.
• Suitable vinylaromatic monomers are, for example, styrene, ortho-, meta-, para-methylstyrene, the commercial "vinyl-toluene" mixture, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene and mixtures of these monomers.
• the vinylaromatic monomer is styrene.
• Suitable conjugated diene monomers having from 4 to 12 carbon atoms include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-di(C1-C5 alkyl) - 1,3-butadienes such as for example 2,3-dimethyl-l,3-butadiene, 2,3-diethyl-l,3-butadiene, 2-methyl-3-ethyl-l,3-butadiene , 2-methyl-3-isopropyl-1,3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene and mixtures of these monomers.
• the conjugated diene monomer having 4 to 12 carbon atoms is 1,3-butadiene or 2-methyl-1,3-butadiene, more preferably is 1,3-butadiene.
• the modified diene elastomer may be chosen from the group consisting of polybutadienes, synthetic polyisoprenes, butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
• the modified diene elastomer is chosen from the group consisting of polybutadienes, synthetic polyisoprenes, copolymers of butadiene and styrene (SBR), copolymers of isoprene and styrene (SIR), copolymers of isoprene and butadiene (BIR) and isoprene-butadiene-styrene (SBIR) copolymers.
• the modified diene elastomer is chosen from the group consisting of polybutadienes and copolymers of butadiene and styrene. More preferably still, the modified diene elastomer is a copolymer of styrene and butadiene.
• the diene elastomers can have any microstructure depending on the polymerization conditions used. Diene elastomers can be block, random, block, microblock. Preferably, the diene elastomer is a statistical diene elastomer.
• a polar compound preferably a compound belonging to the group consisting of diethers, diamines, tetrahydrofurans (such as THF), and tetrahydrofurfuryl ethers.
• Tetramethylethylenediamine is preferably suitable as diamine.
• diethers are 1,2-diethoxyethane, 1,2-di-methoxyethane, tetrahydrofurfuryl ethers such as tetrahydrofurfurylethyl ether and tetrahydrofurfurylpropyl ether.
• the first step of the process generates living diene elastomer chains having a reactive site at the end of the chain. These living chains, or living diene elastomers, then react with the modifying agent during the modification step.
• the modifying agent comprises at least one atom bearing at least two functions reactive with respect to the living diene elastomer, this atom being chosen from the group consisting of phosphorus, tin and of silicon.
• the number of elastomeric branches cannot be less than two and cannot be greater than the valence of the atom carrying said at least two reactive functions.
• the at least two reactive functions of the modifying agent are chosen from the group consisting of halogen atoms, C1-C10 alkoxy groups and C6-C12 aryloxy groups; preferably are chosen from the group consisting of halogen atoms, C1-C4 alkoxy groups and C6-C12 aryloxy groups.
• Ci-Cj alkyl is meant a linear, branched or cyclic hydrocarbon-based group comprising from i to j carbon atoms; i and j being integers.
• C1-Cj alkyloxy is meant an -O-alkyl group comprising from i to j carbon atoms; i and j being integers; the alkyl being as defined above.
• Ci-Cj aryl is meant within the meaning of the present invention one or more aromatic rings having i to j carbon atoms, which can be joined or fused.
• the aryl groups can be monocyclic or bicyclic groups, preferably monocyclic.
• an aryl can be phenyl.
• the aryl groups can be substituted by one or more substituents, which are identical or different.
• substituents of the aryl groups mention may be made, by way of example, of the alkyl groups (as defined above).
• C 1 -C 1 -aryloxy is meant an -O-aryl group comprising from i to j carbon atoms; i and j being integers; the aryl being as defined above.
• the atom bearing the two reactive functions can also be substituted by a function capable of interacting with a reinforcing charge.
• the modifying agent corresponds to the following general formula (I):
• Z represents an atom selected from the group consisting of Si, Sn and P;
• T represents a halogen atom or an OR4 radical with R4 a C1-C10 alkyl or a C6-C12 aryl;
• R2 represents, independently of each other, a C1-C10 alkyl, preferably a C1-C4 alkyl;
• R3 represents a saturated or unsaturated, cyclic or non-cyclic, C 1 -C 8 aliphatic divalent hydrocarbon radical, or a C 6 -C 18 aromatic divalent hydrocarbon radical, preferably a C 1 -C 10 alkanediyl;
• - Y is a hydrogen atom or a function capable of interacting with a reinforcing charge;
• p represents an integer equal to 0, 1 or 2;
• q represents an integer equal to 0 or 1;
• r represents an integer equal to 2, 3 or 4 provided that:
• Ci-Cj alkanediyl is meant, within the meaning of the present invention, a divalent group of general formula C n H 2 n derived from an alkane having between i and j carbon atoms.
• the divalent group can be linear or branched and optionally be substituted.
• halogen designates an atom chosen from the group formed by fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).
• F fluorine
• Cl chlorine
• Br bromine
• I iodine
• the halogen is chlorine.
• R4 independently of each other, represents a C1-C8 alkyl or a C6-C12 aryl, more preferably a C1-C4 alkyl or a C6 aryl. More preferably still, R4, independently of each other, represents a methyl, an ethyl or a phenyl substituted or not by one or more C1-C6 alkyls. More preferably still, R4, independently of each other, represents a methyl, an ethyl or a phenyl substituted or not by one or more t-butyl groups.
• R2 independently of each other, represents a methyl, an ethyl or a propyl.
• R3 is a C1-C10 alkanediyl, more preferably a C1-C6 alkanediyl, more preferably still propanediyl.
• the function capable of interacting with the reinforcing filler comprises at least one heteroatom chosen from nitrogen, sulfur, oxygen and phosphorus.
• the function capable of interacting with the reinforcing filler is a function chosen from the group consisting of primary, secondary or tertiary amines, isocyanates, imines, cyanos, thiols, carboxylates , epoxides and primary, secondary or tertiary phosphines.
• the function capable of interacting with a reinforcing filler is preferably a primary amine, protected or not, secondary, protected or not, or tertiary.
• the nitrogen atom can then be substituted by two groups, identical or different, which can be a trialkyl silyl radical, the alkyl group having 1 to 4 carbon atoms, or a C1-C10 alkyl radical, preferably C1 alkyl -C4, more preferably a methyl or ethyl radical, or the two nitrogen substituents together form a heterocycle containing a nitrogen atom and at least one carbon atom, preferably from 2 to 6 carbon atoms .
• the alkyl substituents present on the nitrogen atom are linear or branched and advantageously have from 1 to 10 carbon atoms, preferably 1 to 4, more preferably 1 or 2.
• suitable as alkyl substituents are methylamino groups -, dimethylamino-, ethylamino-, diethylamino, propylamino-, dipropylamino-, butylamino-, dibutylamino-, pentylamino-, dipentylamino, hexylamino, dihexylamino, hexamethyleneamino, preferably diethylamino and dimethylamino groups.
• the alkoxy substituents are linear or branched and generally have from 1 to 10 carbon atoms, or even 1 to 8, preferably from 1 to 4, more preferably 1 or 2.
• the modifying agent of formula (I) can be chosen from 3-(N,N-dialkylaminopropyl)trialkoxysilanes and 3-(N,N-dialkylaminopropyl)alkyldialkoxysilanes, the alkyl group being the methyl or ethyl group and the alkoxy group being the methoxy or ethoxy group.
• the modifying agent of formula (I) can be chosen from 3-(N,N-alkyltrimethylsilylaminopropyl)trialkoxysilanes and 3-(N,N-alkyltrimethylsilylaminopropyl)alkyldialkoxysilanes, the alkyl group being the methyl or ethyl group and the alkoxy group being the methoxy or ethoxy group.
• the modifying agent of formula (I) can be chosen from 3-(N,N-bistrimethylsilylaminopropyl)trialkoxysilanes and 3-(N,N-bistrimethylsilylaminopropyl)alkyldialkoxysilanes, the alkyl group being the methyl or ethyl group and the alkoxy group being the methoxy or ethoxy group.
• the modifying agent of formula (I) can be chosen from 3-(N,N-dimethylaminopropyl)trimethoxysilane, 3-(N,N-dimethylaminopropyl)triethoxysilane, 3-(N,N-diethylaminopropyl) trimethoxysilane, 3-(N,N-diethylaminopropyl)triethoxysilane, 3-(N,N-dipropylaminopropyl)trimethoxysilane, 3-(N,N-dipropylaminopropyl)triethoxysilane, 3-(N,N-dibutylaminopropyl)trimethoxysilane, 3-(N,N-dibutylaminopropyl)triethoxysilane, 3-(N,N-dipentylaminopropyl)trimethoxysilane, 3-(N,N-dipentylaminopropyl)triethoxys
• the modifying agent of formula (I) is 3-(N,N-dimethylaminopropyl)trimethoxysilane.
• the modifying agent of formula (I) can be chosen from 3-(N,N-methyltrimethylsilylaminopropyl)trimethoxysilane, 3-(N,N-methyltrimethylsilylaminopropyl)triethoxysilane, 3-(N,N-ethyltrimethylsilylaminopropyl) trimethoxysilane, 3-(N,N-ethyl Itrimethyl Isily laminopropyl)triethoxy silane, 3-(N,N-propy Itrimethyl Isily laminopropyl)trimethoxy silane, 3-(N,N-propyltrimethylsilylaminopropyl)triethoxysilane. More preferentially, the modifying agent of formula (I) is 3-(N,N-methyltrimethylsilylaminopropyl)trimethoxysilane.
• the function capable of interacting with a reinforcing filler is an isocyanate function.
• the modifying agent of formula (I) can be chosen from 3-(isocyanatopropyl)trialkoxysilanes and 3-(isocyanatopropyl)alkyldialkoxysilanes, the alkyl group being the methyl or ethyl group and the alkoxy group being the methoxy or ethoxy. More preferably still, the modifying agent of formula (I) is 3-(isocyanatopropyl)dimethylaminopropyl)-trimethoxysilane and 3-
• the function capable of interacting with a reinforcing filler is an imine function.
• the modifying agent of formula (I) can be chosen from N-(l,3-dimethylbutylidene)-3-(trimethoxysilyl)-l-propanamine, N-(l,3-dimethylbutylidene)-3- (triethoxysilyl)-l-propanamine, N-(l,3-methylethylidene)-3-(trimethoxysilyl)-l-propanamine, N-(l,3-methylethylidene)-3-(triethoxysilyl)-l-propanamine, N-ethylidene-3-(trimethoxysilyl)-l-propanamine, N-ethylidene-3-(triethoxysilyl)-1-propanamine, N-(1-methylpropylidene)-3-(trimethoxysilyl)-1-propanamine, N-(1
• the function capable of interacting with a reinforcing filler is a cyano function.
• the modifying agent of formula (I) can be chosen from 3-(cyanopropyl)trialkoxysilanes and 3-(cyanopropyl)alkyldialkoxysilanes, the alkyl group being the methyl or ethyl group and the alkoxy group being the methoxy or ethoxy. More preferentially, the modifying agent of formula (I) can be chosen from 3-(cyanopropyl)trimethoxy silane and 3-(cyanopropyl)triethoxy silane.
• the function capable of interacting with a reinforcing charge is a function derived from thiol -SR, protected or not, R being a protective group or H. Mention may be made by way of example of (S- trialkylsilylmercaptopropyl)trialkoxysilanes and (S-trialkylsilylmercaptopropyl)alkyldialkoxysilanes, the alkyl group on the silicon carrying alkoxysilane groups being the methyl or ethyl group and the alkoxy group being the methoxy or ethoxy group.
• the alkyl group on the silicon bonded to the sulfur atom is the methyl or tert-butyl group.
• the modifying agent of formula (I) can be chosen from (S-trimethylsilylmercaptopropyl)trimethoxysilane, (S-trimethylsilylmercaptopropyl)triethoxysilane, (S-tert-butyldimethylsilylmercaptopropyl)trimethoxysilane, (S-tert-butyldimethylsilylmercaptopropyl) triethoxysilane.
• the function capable of interacting with a reinforcing filler is a carboxylate function.
• carboxylate function mention may be made of acrylates or methacrylates.
• Such a function is preferably a methacrylate.
• the modifying agent of formula (I) can be chosen from 3-(methacryloyloxypropyl)trialkoxysilanes and 3-(methacryloyloxypropyl)alkyldialkoxysilanes, the alkyl group being the methyl or ethyl group and the alkoxy group being the methoxy or ethoxy group .
• the modifying agent of formula (I) can be chosen from 3-(methacryloyloxypropyl)trimethoxysilane and 3-(methacryloyloxypropyl)triethoxysilane.
• the function capable of interacting with a reinforcing filler is an epoxide function.
• the modifying agent of formula (I) can be chosen from 3-(glycidyloxypropyl)trialkoxysilanes and 3-(glycidyloxypropyl)alkyldialkoxysilanes, the alkyl group being the methyl or ethyl group and the alkoxy group being the methoxy or ethoxy group .
• the modifying agent of formula (I) can be chosen from 2- (glycidyloxyethyl) trimethoxysilane, 2- (glycidyloxyethyl) triethoxysilane, 3- (glycidyloxypropyl) trimethoxysilane, 3 - (glycidyloxypropyl) triethoxy silane, 2 -(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)-ethyltriethoxysilane.
• the function capable of interacting with a reinforcing filler is a primary phosphine function, protected or not, secondary, protected or not, or tertiary.
• the modifying agent of formula (I) can be chosen from 3-(P,P-bistrimethylsilylphosphinopropyl)trialkoxysilanes, 3-(P,P-bistrimethylsilylphosphinopropyl)alkyldialkoxysilanes, 3-(P,P-alkyltrimethylsilylphosphinopropyl) trialkoxysilanes, 3-(P,P-alkyltrimethylsilylphosphinopropyl)alkyldialkoxysilanes, 3-(P,P-dialkylphosphinopropyl)trialkoxysilanes and 3-(P,P-dialkylphosphinopropyl)alkyldialkoxysilanes, the alkyl group being the methyl, eth
• the modifier of formula (I) can be chosen from 3-(P,P-bistrimethylsilylphosphinopropyl)trimethoxysilane, 3-(P,P-bistrimethylsilylphosphinopropyl)triethoxysilane, 3-(methyltrimethylsilylphosphinopropyl)trimethoxysilane, 3 - (methyltrimethylsilylphosphinopropyl)triethoxysilane, 3- (ethyltrimethylsilylphosphinopropyl)trimethoxysilane, 3-
• the preferred agent of formula (I) may have the following characteristics:
• Z represents an atom selected from the group consisting of P, Sn and Si; preferably P or Si;
• T represents a halogen atom, preferably chlorine, or an OR4 radical with R4 a C1-C4 alkyl or a C6 aryl;
• R2 represents, independently of each other, a C1-C4 alkyl; more preferably methyl or ethyl;
• R3 represents a C1-C6 alkanediyl, more preferably propanediyl;
• modifying agent compounds such as tin tetrachloride, methyl tin trichloride, dimethyl tin dichloride, dibutyl tin dichloride, tetrachlorosilane, methyltrichlorosilane and dimethyldichlorosilane, tetraalkoxysilanes which are such that each alkyl group contains from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, trialkylphosphites which are such that each group alkyl contains from 1 to 10 carbon atoms or triarylphosphites which are such that each aryl group contains from 6 to 12 carbon atoms, the aryl groups possibly being substituted by one or more C 1 -C 6 alkyls; preferably substituted with one or more t-butyl groups.
• modifying agent compounds such as tin tetrachloride, methyl tin trichloride, dimethyl tin dichloride, dibuty
• the amount of modifying agent to react with the living diene elastomer essentially depends on the type of modified diene elastomer desired.
• the molar ratio of reactive groups of the agent with respect to the living elastomer, to the metal of the polymerization initiator is at least 0.05, preferably at least 0, 10, more preferably at least 0.15, and at most 0.70, preferably at most 0.60.
• the molar ratio of the modifying agent to the metal of the polymerization initiator has a value in a range ranging from 0.20 to 0.55.
• the conditions for adding and reacting the modifying agent on the living diene elastomer are standard in terms of modification in anionic polymerization and known to those skilled in the art. These conditions do not include any particular limitations.
• the organic solvent used during the step of modifying the diene elastomer by the modifying agent is the same as that used during the anionic polymerization step.
• this modification reaction on the living diene elastomer can take place at a temperature between -20°C and 100°C, by adding the modifying agent to the living elastomer chains or vice versa.
• This reaction can of course be carried out with one or more different modifying agents.
• the mixing of the living elastomer with the modifying agent can be carried out by any appropriate means, in particular using any mixer having static type stirring and/or any dynamic mixer of the perfectly stirred type known by the man of the trade.
• the latter determines the reaction time between the living diene polymer and the modifying agent, which can vary from a few minutes, for example two minutes, to several hours, for example two hours.
• Those skilled in the art will know how to adapt the anionic polymerization and modification conditions to obtain a modified diene elastomer having a Tg measured according to the ASTM D3418-08 standard measured before its extension to the resin comprised in a range from -95°C to -70°C, preferably within a range from -90°C to -80°C.
• the solution comprising the modified diene elastomer having a number-average molar mass Mn2 measured by triple detection steric exclusion chromatography, at least one resin plasticizer as defined below.
• the addition of the plasticizing resin can be carried out directly in said solution of modified diene elastomer, that is to say by adding the resin in solid form, or else the resin in solid form can be dissolved beforehand in a solvent organic, preferably in the same organic solvent as that used in the preceding step, that is to say in the modification step and/or in the polymerization step.
• the resin can be heated to a temperature above its softening point and be incorporated into the solution containing the modified diene elastomer in molten form.
• the solvent is removed by any means known to those skilled in the art, such as for example steam stripping.
• the modified diene elastomer extended to the resin is recovered in the form of “crumb” which can be washed and dried, and possibly shaped in the form of rubber balls for their storage.
• extender oils are plasticizing oils chosen from the group consisting of naphthenic oils (low or high viscosity, in particular hydrogenated or not), paraffinic oils, MES (Medium Extracted Solvated) oils, TDAE oils (Treated Distillate Aromatic Extracts), RAE oils (Residual Aromatic Extract oils), TRAE oils (Treated Residual Aromatic Extract) and SRAE oils (Safety Residual Aromatic Extract oils), mineral oils, vegetable oils, plasticizers ethers, ester plasticizers, phosphate plasticizers, sulfonate plasticizers and mixtures of these compounds.
• the amount of extension oil added will always be lower than the amount of resin added in the solution-modified diene elastomer.
• the process for manufacturing the modified diene elastomer extended to the resin does not include the addition of a plasticizing oil before the removal of the organic solvent.
• the modified diene elastomer extended to the resin according to the invention has the following characteristics: it comprises within its structure a branching unit and at least two branches of diene elastomer obtained by anionic polymerization of at least one conjugated diene monomer having from 4 to 12 carbon atoms, the resin and the elastomer being intimately mixed, it has a number-average molar mass Mnl measured before the modification step by steric exclusion chromatography triple detection, it has a number-average Mn2 molar mass measured after the modification step by triple detection steric exclusion chromatography greater than or equal to 200,000 g/mol and an Mn2/Mnl ratio strictly greater than 1.00, it has a glass transition temperature measured according to standard ASTM D3418-08 and before its extension to the resin comprised in a range ranging from -95°C to -70°C.
• the branching unit of the resin-extended diene elastomer comprises at least one atom selected from the group consisting of a phosphorus atom, a silicon atom and a tin atom.
• the modified diene elastomer extended to the resin according to the invention comprises branched chains and may correspond to the following general formula (II): in which :
• E represents a branch of the diene elastomer
• Z represents an atom selected from the group consisting of P, Si and Sn;
• Ri represents, independently of each other, a hydrogen atom, a C1-C10 alkyl or a C6-C12 aryl;
• R2 represents, independently of each other, a C1-C10, preferably C1-C4, alkyl;
• R3 represents a divalent aliphatic hydrocarbon-based radical, saturated or not, cyclic or not, C1-C18, or an aromatic divalent hydrocarbon-based C6-C18 radical, R3 is preferably a C1-C10 alkanediyl;
• - Y represents a hydrogen atom or a function likely to interact with a reinforcing charge
• m is an integer being equal to 2, 3 or 4
• n is an integer equal to 0, 1 or 2
• p is an integer being equal to 0, 1 or 2
• R independently of each other, can represent a C1-C8 alkyl or a C6-C12 aryl, more preferably a C1-C4 alkyl or an aryl in C6. More preferably still, R4, independently of each other, can represent a methyl, an ethyl or a phenyl substituted or not by one or several C1-C6 alkyls. More preferably still, R 1 , independently of each other, can represent a methyl, an ethyl or a phenyl substituted or not by one or more t-butyl groups.
• R2 independently of each other, can represent a methyl, an ethyl or a propyl.
• R3 can be a C1-CIO alkanediyl, preferably a C1-C6 alkanediyl, more preferably still propanediyl.
• the function capable of interacting with a reinforcing filler can comprise at least one heteroatom chosen from nitrogen, sulphur, oxygen and phosphorus.
• the function capable of interacting with the reinforcing filler is a primary, secondary or tertiary amine function, isocyanates, imines, cyanos, thiols, carboxylates , epoxides, primary, secondary or tertiary phosphines.
• amines substituted by C1-CIO alkyl radicals preferably C1-C4 alkyl, more preferably a methyl or ethyl radical, or cyclic amines forming a heterocycle containing a nitrogen atom and at least one carbon atom, preferably 2 to 6 carbon atoms.
• methylamino-, dimethylamino-, ethylamino-, diethylamino-, propylamino-, dipropylamino-, butylamino-, dibutylamino-, pentylamino-, dipentylamino-, hexylamino-, dihexylamino-, hexamethyleneamino- groups are suitable, preferably diethylamino groups.
• - and dimethylamino-
• ketimines By way of imine function, mention may be made of ketimines.
• carboxylate function mention may be made of acrylates or methacrylates. Such a function is preferably a methacrylate.
• epoxy By way of epoxide function, mention may be made of epoxy or glycidyloxy groups.
• phosphines substituted with C1-C10 alkyl radicals preferably C1-C4 alkyl radicals, more preferably a methyl or ethyl radical, or else diphenylphosphine.
• C1-C10 alkyl radicals preferably C1-C4 alkyl radicals, more preferably a methyl or ethyl radical, or else diphenylphosphine.
• the methylphosphino-, dimethylphosphino-, ethylphosphino-, diethylphosphino, ethylmethylphosphino- and diphenylphosphino- groups are suitable.
• the preferred modified diene elastomer extended to the resin of formula (II) may be the one in which: E represents a branch of a butadiene homopolymer or a butadiene copolymer; preferably a branch of a polybutadiene or a copolymer of styrene and butadiene;
• Z represents an atom selected from the group consisting of P, Sn and Si; preferably P or Si;
• Ri represents, independently of each other, a hydrogen atom or a C1-C4 alkyl or a C6 aryl
• R2 represents, independently of each other, a C1-C4 alkyl; more preferably methyl or ethyl;
• R3 represents a C1-C6 alkanediyl, more preferably propanediyl;
• the second constituent of the modified diene elastomer extended to the resin in accordance with the invention is a plasticizing resin.
• the term “resin” is reserved in the present application, by definition, for a compound which is solid at room temperature (23° C., 1 atm), as opposed to a liquid plasticizer at room temperature such as an oil.
• Plasticizing resins are polymers well known to those skilled in the art. These are hydrocarbon resins essentially based on carbon and hydrogen but which may contain other types of atoms, which can be used in particular as plasticizers or tackifying agents in polymer matrices. They are by nature miscible (i.e., compatible) at the rates used with the compositions of diene elastomer(s) for which they are intended, so as to act as true diluting agents. They have been described, for example, in the work entitled "Hydrocarbon Resins" by R. Mildenberg, M. Zander and G.
• plasticizing resins (most often comprised within a range ranging from 30° C. to 95° C.).
• hydrocarbon resins and plasticizing hydrocarbon resins” are interchangeable.
• Tg of the resins that can be used in the context of the present invention is measured according to standard ASTM D3418-08 (2008).
• these plasticizing resins can also be qualified as thermoplastic resins in the sense that they soften on heating and can thus be molded. They can also be defined by a softening point or temperature.
• the softening temperature of a plasticizing resin is generally about 50° C. to 60° C. higher than its Tg value.
• the softening point is measured according to the ISO 4625 standard of 2012 (“Ring and Bail” method).
• the plasticizing resin that can be used in the context of the present invention has a Tg greater than or equal to 0° C., preferably greater than or equal to 20° C., preferably greater than or equal to 30° C. (in particular between 30° C. and 95°C). It is understood that the Tg of the plasticizing resin used in the formulation of the modified diene elastomer extended to the resin in accordance with the invention is measured on the plasticizing resin prior to its mixing with the modified diene elastomer.
• the plasticizing resin that can be used in the context of the present invention has a softening point greater than or equal to 50° C. (in particular between 50° C. and 150° C.) measured according to the ISO 4625 standard of 2012 (“Ring and Lease”).
• the plasticizing resin that can be used in the context of the present invention has a number-average molar mass (Mn) of between 400 and 2000 g/mol, preferably between 500 and 1500 g/mol.
• IP polydispersity index
• the Mn, the Mw and the Ip of the plasticizing resins are measured according to the method of steric exclusion chromatography with refractive index as described above.
• the plasticizing resin that can be used in the context of the present invention may have a Tg greater than or equal to 20° C., preferably greater than or equal to 30° C. and a Mn of between 400 and 2000 g/mol, preferably between 500 and 1500 g/mol.
• the plasticizing resins which can be used in the context of the present invention may have all of the preferential characteristics above.
• the plasticizing resin that can be used in the context of the present invention is chosen from the group consisting of aliphatic resins, aromatic resins and mixtures of these resins.
• plasticizing resins which can be used in the context of the present invention, mention may be made of those chosen from the group consisting of resins of homopolymers or copolymers of cyclopentadiene (in abbreviated form CPD), resins of homopolymers or copolymers of dicyclopentadiene (in abbreviated form DCPD), resins of homopolymers or copolymers of terpene, resins of homopolymers or copolymers of C5 cut, resins of homopolymers or copolymers of C9 cut, mixtures of resins of homopolymers or copolymers of C5 cut and resins of homopolymers or copolymers of C9 cut, resins of homopolymers or copolymers of alpha-methyl-styrene and mixtures of these resins.
• CPD resins of homopolymers or copolymers of cyclopentadiene
• DCPD dicyclopentadiene
• plasticizing resins above are well known to those skilled in the art and commercially available, for example sold by the company Exxon Mobil under the name "Escorez” with regard to C5/styrene cut resins or C5 cut resins or C5 cut resins or C9 and CPD or DCPD resins.
• the content of plasticizing resin in the resin-extended elastomer is within a range ranging from 5 to 100 phr, preferably from 30 to 80 phr.
• the level of plasticizing resin in the resin-extended diene modified elastomers was measured according to the method described above.
• Rubber composition comprising the resin-extended modified diene elastomer
• the modified diene elastomer of the invention as defined above can be used in any rubber compositions, in particular those intended for the manufacture of semi-finished articles for tires and for the manufacture of tires.
• Another object of the present invention relates to a rubber composition based on at least one resin-extended modified diene elastomer as defined above, a reinforcing filler and a crosslinking system.
• reinforcing filler known for its ability to reinforce a rubber composition that can be used in particular for the manufacture of tires, for example an organic filler such as carbon black, an inorganic filler such as silica or else a mixture of these two types of fillers.
• Suitable carbon blacks are all carbon blacks, in particular the blacks conventionally used in tires or their treads. Among the latter, mention will be made more particularly of the reinforcing carbon blacks of the 100, 200, 300 series, or the blacks of the 500, 600 or 700 series (ASTM D-1765-2017 grades), such as for example the blacks NI 15, N134 , N234, N326, N330, N339, N347, N375, N550, N683, N772). These carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a carrier for some of the rubber additives used.
• the carbon blacks could for example already be incorporated into the diene elastomer, in particular isoprene in the form of a masterbatch or “masterbatch” (see for example applications WO97/36724-A2 or W099/16600-A1).
• reinforcing inorganic filler should be understood here any inorganic or mineral filler, whatever its color and its origin (natural or synthetic), also called “white” filler, “clear” filler or even “non-black” filler. as opposed to carbon black, capable of reinforcing on its own, with no other means than an intermediate coupling agent, a rubber composition intended for the manufacture of tires.
• certain reinforcing inorganic fillers can be characterized in particular by the presence of hydroxyl (—OH) groups at their surface.
• Suitable reinforcing inorganic fillers are in particular mineral fillers of the siliceous type, preferably silica (SiCh) or of the aluminous type, in particular alumina (Al2O3).
• the silica used can be any reinforcing silica known to those skilled in the art, in particular any precipitated or fumed silica having a BET specific surface area as well as a CTAB specific surface area, both of which are less than 450 m 2 /g, preferably comprised in a range ranging from 30 to 400 m 2 /g, in particular from 60 to 300 m 2 /g.
• any type of precipitated silica in particular highly dispersible precipitated silicas (called “HDS” for “highly dispersible” or “highly dispersible silica”).
• HDS highly dispersible precipitated silicas
• These precipitated silicas, highly dispersible or not, are well known to those skilled in the art. Mention may be made, for example, of the silicas described in applications W003/016215-A1 and W003/016387-Al. company Evonik, the “Zeosil® 1085GR”, “Zeosil® 1115 MP”, “Zeosil® 1165MP”, “Zeosil® Premium 200MP”, “Zeosil® HRS 1200 MP” silicas from Solvay.
• non-HDS silica the following commercial silicas can be used: “Ultrasil ® VN2GR”, “Ultrasil ® VN3GR” silicas from Evonik, “Zeosil® 175GR” silica from Solvay, “Hi-Sil EZ120G(-D)” silica, “Hi -Sil EZ160G(-D)", “Hi-Sil EZ200G(-D)", “Hi-Sil 243LD”, “Hi-Sil 210", “Hi-Sil HDP 320G” from PPG company.
• the reinforcing filler is mainly silica, that is to say that it comprises more than 50% by weight of the total weight of the reinforcing filler, of silica.
• silica as a reinforcing filler may require the use of a coupling agent to establish the bond between the filler and the elastomer. It is then possible to use as coupling agents organosilanes, in particular polysulphide alkoxysilanes or mercaptosilanes, or alternatively at least bifunctional polyorganosiloxanes.
• the rubber composition according to the invention may also contain, in addition, coupling activators, filler recovery agents or more generally implementation aid agents capable in a known manner, thanks to an improvement in the dispersion of the reinforcing filler within the modified diene elastomer extended to the resin and to a lowering of the viscosity of the composition, to improve its ability to be implemented in the uncured state, these agents being for example silanes hydrolyzable such as alkylalkoxysilanes, polyols, polyethers, primary, secondary or tertiary amines, hydroxylated or hydrolyzable polyorganosiloxanes.
• coupling activators such as alkylalkoxysilanes, polyols, polyethers, primary, secondary or tertiary amines, hydroxylated or hydrolyzable polyorganosiloxanes.
• the rubber composition according to the invention may also contain, in addition, at least one plasticizer.
• this plasticizer is preferably chosen from resins with a high glass transition temperature (Tg), low Tg resins, plasticizing oils, and mixtures thereof.
• Tg glass transition temperature
• the plasticizer is chosen from high Tg resins, plasticizing oils, and mixtures thereof.
• this resin may be identical to that used for the extension of the modified elastomer or may be of a different chemical nature.
• a high Tg resin is solid at room temperature (23°C and 1 atm)
• a plasticizing oil is liquid at room temperature
• a low Tg hydrocarbon resin is viscous at room temperature.
• the Tg is measured according to the ASTM D3418-08 (2008) standard.
• high Tg hydrocarbon resins are thermoplastic resins whose Tg is greater than 20°C.
• the preferred high Tg resins that can be used in the context of the invention are well known to those skilled in the art and commercially available.
• the plasticizer may optionally comprise a resin that is viscous at 20°C, a so-called “low Tg” resin, that is to say which by definition has a Tg comprised in a range comprised between -40°C and 20°C.
• the plasticizer may also contain a plasticizing oil (or extender oil) which is liquid at 20°C, said to be at "low Tg", that is to say which by definition has a Tg of less than 20°C, preferably less at 40°C.
• a plasticizing oil or extender oil which is liquid at 20°C, said to be at "low Tg", that is to say which by definition has a Tg of less than 20°C, preferably less at 40°C.
• any extender oil whether aromatic or non-aromatic known for its plasticizing properties with respect to elastomers, can be used.
• plasticizing oils chosen from the group consisting of naphthenic oils (low or high viscosity, in particular hydrogenated or not), paraffinic oils, MES oils (Medium Extracted Solvates), TDAE oils (Treated Distillate Aromatic Extracts), RAE oils (Residual Aromatic Extract oils), TRAE oils (Treated Residual Aromatic Extract) and SRAE oils (Safety Residual Aromatic Extract oils), mineral oils, vegetable oils, ether plasticizers, ester plasticizers, phosphate plasticizers , sulfonate plasticizers and mixtures of these compounds.
• the rubber composition in accordance with the invention may also comprise, in addition, all or part of the usual additives and processing agents, known to those skilled in the art and usually used in rubber compositions for tires, in particular rubber compositions for treads, such as, for example, non-reinforcing fillers, pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, anti-oxidants, anti-fatigue agents, reinforcing resins ( as described for example in application WO 02/10269).
• additives and processing agents known to those skilled in the art and usually used in rubber compositions for tires, in particular rubber compositions for treads, such as, for example, non-reinforcing fillers, pigments, protective agents such as anti-ozone waxes, chemical anti-ozonants, anti-oxidants, anti-fatigue agents, reinforcing resins ( as described for example in application WO 02/10269).
• the rubber composition according to the invention comprises at least one crosslinking system, for example based on sulfur and other vulcanizing agents, and/or peroxide and/or bismaleimide.
• the rubber composition in accordance with the invention is manufactured in suitable mixers, using two successive preparation phases well known to those skilled in the art: a first phase of work or thermomechanical mixing (so-called “non-productive” phase), which can be carried out in a single thermomechanical step during which all the necessary constituents, in particular the modified diene elastomer extended with the resin, are introduced into a suitable mixer such as a usual internal mixer (for example of the "Banbury” type) as defined above, the reinforcing filler(s), any other miscellaneous additives, with the exception of the crosslinking system.
• the incorporation of the reinforcing filler into the resin-extended modified diene elastomer can be carried out in one or more stages by thermomechanical mixing.
• the non-productive phase is carried out at high temperature, up to a maximum temperature of between 110° C. and 200° C., preferably between 130° C. and 185° C., for a duration generally of between 2 and 10 minutes;
• a second phase of mechanical work (so-called "productive" phase), which is carried out in an external mixer such as a roller mixer, after the mixture has cooled obtained during the first non-productive phase down to a lower temperature, typically below 120°C, for example from 30°C to 100°C.
• the crosslinking system is then incorporated, and all of these ingredients is then mixed for a few minutes, for example between 5 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 characterization in the laboratory, or even extruded in the form of a semi-finished (or profiled) rubber that can be used by example as a tire tread for a vehicle.
• the composition can be either in the raw state (before crosslinking or vulcanization), or in the cured state (after crosslinking or vulcanization), can be a semi-finished product which can be used in a tire.
• crosslinking of the composition can be carried out in a manner known to those skilled in the art, for example at a temperature of between 130° C. and 200° C., under pressure.
• composition according to the invention can constitute any semi-finished product of the tire and particularly a tread.
• Another object of the present invention relates to a semi-finished rubber article for a tire comprising at least one crosslinkable or crosslinked composition as defined previously.
• this semi-finished article is a tread.
• Another object of the present invention relates to a tire comprising at least one rubber composition defined above or a semi-finished article defined above.
• the invention therefore finally relates to a tire comprising a semi-finished article consisting in whole or in part of a composition according to the invention, in particular a tread.
• Resin-extended modified diene elastomer obtainable by a process comprising at least:
• modified diene elastomer extended to the resin • a stage of elimination of the organic solvent to obtain the modified diene elastomer extended to the resin; and the modified diene elastomer extended to the resin having an Mn2/Mnl ratio strictly greater than 1.00 and an Mn2 greater than or equal to 200,000 g/mol.
• Resin-extended modified diene elastomer according to any one of the preceding embodiments, in which the number-average molar mass Mnl is greater than or equal to 140,000 g/mol, preferably comprised within a range from 150,000 g/mol to 200000 g/mol.
• the vinylaromatic monomer having 8 to 20 carbon atoms is selected from the group consisting of styrene, ortho-methylstyrene, meta- methylstyrene, para-methylstyrene, commercial vinyl-toluene mixture, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, diviny
• plasticizing resin has a glass transition temperature greater than or equal to 0°C, preferably greater than or equal to 20°C, preferably greater than or equal to equal to 30°C, more preferably still comprised in a range between 30°C and 95°C.
• Resin-extended modified diene elastomer according to any one of the preceding embodiments, in which the level of plasticizing resin is comprised in a range extending from 5 to 100 phr, preferably from 30 to 80 phr. 19.
• a resin-extended modified diene elastomer according to any of the preceding embodiments, wherein the plasticizing resin is selected from the group consisting of resins of cyclopentadiene homopolymers or copolymers, resins of dicyclopentadiene homopolymers or copolymers, resins of homopolymers or copolymers of terpene, resins of homopolymers or copolymers of C5 cut, resins of homopolymers or copolymers of C9 cut, mixtures of resins of homopolymers or copolymers of C5 cut and of resins of homopolymers or copolymers of C9 cut, resins of homopolymers or copolymers of alpha-methyl-styrene and mixtures of these resins.
• the plasticizing resin is selected from the group consisting of resins of cyclopentadiene homopolymers or copolymers, resins of dicyclopentadiene homopolymers or copolymers, resin
• Z represents an atom selected from the group consisting of Si, Sn and P;
• T represents a halogen atom or an OR4 radical with R4 a C1-C10 alkyl or a C6-C12 aryl;
• R2 represents, independently of each other, a C1-C10, preferably C1-C4, alkyl;
• R3 represents a saturated or unsaturated, cyclic or non-cyclic, C 1 -C 8 aliphatic divalent hydrocarbon radical, or a C 6 -C 18 aromatic divalent hydrocarbon radical, preferably a C 1 -C 10 alkanediyl;
• - Y is a hydrogen atom or a function likely to interact with a reinforcing charge; p represents an integer equal to 0, 1 or 2; q represents an integer equal to 0 or 1; r represents an integer equal to 2, 3 or 4; and provided that:
• R4 independently of each other represents a C1-C8 alkyl or a C6-C12 aryl, more preferably a C1-C4 alkyl or C6 aryl. More preferably still, R4, independently of each other, represents a methyl, an ethyl or a phenyl substituted or not by one or more C1-C6 alkyls. More preferably still, R4, independently of each other, represents a methyl, an ethyl or a phenyl substituted or not by one or more t-butyl groups.
• R3 is a C1-C10 alkanediyl, more preferably a C1-C6 alkanediyl, even more preferably propanediyl.
• Resin-extended modified diene elastomer according to any one of embodiments 23 to 27, in which in formula (I), the function capable of interacting with the reinforcing filler comprises at least one heteroatom chosen from nitrogen, sulfur, oxygen and phosphorus.
• Resin-extended modified diene elastomer according to any one of embodiments 23 to 28, in which in formula (I), the function capable of interacting with the reinforcing filler is a function chosen from the group consisting of amines primary, secondary or tertiary, isocyanates, imines, cyanos, thiols, carboxylates, epoxides and primary, secondary or tertiary phosphines.
• Resin-extended modified diene elastomer according to any one of embodiments 23 to 29, in which in formula (I), the function capable of interacting with the reinforcing filler is a function chosen from the group consisting of amines primary, secondary or tertiary.
• a resin-extended diene modified elastomer according to any one of embodiments 23 to 27, wherein in formula (I), q is 0; Z represents a phosphorus atom, T represents a halogen atom or an OR4 radical with R4 a Cl-CIO alkyl or a C6 aryl; R2 represents, independently of each other, a C1-C10, preferably C1-C4, alkyl; p represents an integer equal to 0 or 1; r represents an integer equal to 2 or 3 and r + p 3 .
• a resin-extended diene modified elastomer according to any one of embodiments 23 to 30, wherein in formula (I), q is an integer equal to 1; Z represents a silicon atom; T represents a halogen atom or an OR4 radical with R4 a C1-C10 alkyl; R2 represents, independently of each other, a C1-C10, preferably C1-C4, alkyl; R3 represents a saturated or unsaturated, cyclic or non-cyclic, C 1 -C 8 aliphatic divalent hydrocarbon radical, or a C 6 -C 18 aromatic divalent hydrocarbon radical, preferably a C 1 -C 10 alkanediyl; Y is a hydrogen atom or a function likely to interact with a reinforcing charge; p represents an integer equal to 0, 1 or 2; r represents an integer equal to 2, 3 or 4; and r + p + q 4.
• a resin-extended diene modified elastomer according to any one of embodiments 23 to 30, wherein in formula (I), q is an integer equal to 1; Z represents a silicon atom; T represents a halogen atom or an OR4 radical with R4 a C1-C4 alkyl; R2 represents, independently of each other, a C1-C4 alkyl, preferably methyl or ethyl; R3 represents a C1-C6 alkanediyl, more preferably propanediyl; Y an amine function; p represents an integer equal to 0, 1 or 2; r represents an integer equal to 2, 3 or 4; and r + p + q 4.
• Rubber composition based on at least one resin-extended modified diene elastomer defined according to any one of the preceding embodiments 1 to 36, a reinforcing filler and a crosslinking system.
• Semi-finished rubber article for tires comprising at least one crosslinkable or crosslinked composition according to embodiment 37 or 38, preferably the semi-finished article being a tread.
• a tire comprising at least one rubber composition defined according to embodiment 37 or 38 or a semi-finished article defined according to embodiment 39.
• the characteristics of the elastomers, resins, oils and compositions are determined according to the methods described above.
• n-Butyllithium (n-BuLi) is introduced in sufficient quantity to neutralize the protic impurities brought by the various constituents present in the reactor inlet.
• the different flow rates are calculated so that the average residence time in the reactor is 25 min.
• the temperature is maintained at 95°C.
• the degree of conversion obtained at this stage is 97% by weight. It is determined by dry extract at 140° C. under reduced pressure of 200 mm Hg. The polymer thus treated is then separated from its solution by a steam stripping operation, then dried on a roller tool at 100° vs.
• the polymer thus obtained is subjected to an antioxidant treatment with the addition of 0.4 phr of 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol) and 0.2 phr of N-(1,3 -dimethylbutyl)-N'-phenyl- p-phenylenediamine.
• a homogeneous solution of copolymer of styrene and unmodified functionalized butadiene is obtained.
• a solution prepared from “Escorez 5600” resin from Exxon at 70% by weight in methylcyclohexane is added to the elastomeric solution in the amount of 53 parts per 100 parts by weight of elastomer.
• the mixing is carried out in a static mixer consisting of 36 Kenics KMR type mixing elements.
• the unmodified diene elastomer/resin mixture in methylcyclohexane is then separated from the methylcyclohexane by a steam stripping operation, then dried on a roller tool at 100°C.
• the characteristics of the unmodified resin-extended polymer A obtained at this stage i.e. the final inherent viscosity, the final Mn, the final Mw and the final Ip, are given in Table 2.
• n-Butyllithium (n-BuLi) is introduced in sufficient quantity in order to neutralize the protic impurities provided by the various constituents present.
• the different flow rates are calculated so that the average residence time in the reactor is 35 min.
• the temperature is maintained at 95°C.
• the degree of conversion obtained at this stage is 95% by weight. It is determined by dry extract at 140° C. under reduced pressure of 200 mm Hg. The polymer thus treated is then separated from its solution by a steam stripping operation, then dried on a roller tool at 100°C.
• the characteristics of the polymer obtained at this stage that is to say the initial inherent viscosity, the initial Mn, the initial Mw, the initial Ip and its glass transition temperature are given in Table 2.
• the polymer thus obtained is subjected to an antioxidant treatment with the addition of 0.6 phr of 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol) and 0.2 phr of N-(1,3 -dimethylbutyl)-N'-phenyl-p-phenylenediamine.
• a homogeneous solution of functionalized and modified styrene and butadiene copolymer is obtained.
• a solution prepared from Escorez 5600 resin from Exxon at 70% by weight in methylcyclohexane is added to the elastomeric solution at 51 parts per 100 parts by weight of elastomer.
• the modified diene elastomer/resin mixture in methylcyclohexane is then separated from the methylcyclohexane by a steam stripping operation, then dried on a roller tool at 100°C.
• the characteristics of the resin-extended modified polymer C obtained at this stage i.e. the final inherent viscosity, the final Mn, the final Mw and the final Ip, are given in Table 2.
• the characteristics of the resin-extended modified polymer D obtained at this stage i.e. the final inherent viscosity, the final Mn, the final Mw and the final Ip, are given in Table 2.
• Elastomers A to F have been used for the preparation of tread type rubber compositions, each comprising silica as a reinforcing filler.
• the formulations are expressed in percentage by weight per 100 parts by weight of elastomer (phr) and are presented in Table 3.
• Zerosil 1165 MP highly dispersible silica marketed by Solvay with a BET specific surface area of 160 m 2 /g and a CT AB specific surface area of 155 m 2 /g
• Tg 55°C measured according to ASTM D3418-08 and
• Mn 500 g/ml measured according to the SEC-RI method described above.
• TDAE oil TDAE oil marketed by the company Klaus Dahleke under the reference “3VIVATEC500”
• compositions are produced, initially, by thermomechanical work, then, in a second finishing step, by mechanical work.
• thermomechanical work is carried out using pallets whose average speed is 50 rpm and whose temperature is 90°C.
• thermomechanical work is still carried out for two minutes, up to a maximum drop temperature of approximately 160°C.
• the mixture thus obtained is recovered, cooled and then, in an external mixer (homo-finisher), the sulfur and the sulfenamide are added at 30° C., while still mixing the whole thing for a period of 3 to 4 minutes (second time mechanical work).
• compositions thus obtained are then calendered, either in the form of plates (with a thickness ranging from 2 to 3 mm) or thin sheets of rubber, for the measurement of their physical or mechanical properties, or in the form of profiles that 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.
• the crosslinking is carried out at 150° C. for 40 min.
• composition T2 When the number-average molar mass of an elastomer extended with the unmodified resin is increased, a reduction in the tackiness of the composition comprising such an elastomer (control composition T2) relative to the control composition T1 is observed.
• control composition T2 When one continues to increase the number average molecular weight of a resin-extended elastomer by modifying that elastomer with a modifier to obtain a modified diene elastomer extended to resin and comprising branched chains, a very significant decrease in the tackiness of the compositions containing such elastomers (composition C1 and C2 according to the invention) is observed. It is noted that this decrease in the tackiness of the compositions of the invention does not affect the quality of the extrudate which retains an excellent surface grade and a good edge grade.

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• 2021
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