Classifications

• • 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
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
• • 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
• • 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
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/06—Copolymers with styrene

Definitions

• the present invention relates to an elastomer extended to the resin, to its production process and to rubber compositions containing it. These rubber compositions can in particular be used for the manufacture of tires.
• plasticizers especially a high level of plasticizing resins.
• HDS high dispersible silica
• compositions are prepared in the usual manner by incorporating all of their constituents into mixers.
• the technical problem to be solved by the invention is to improve the processability of rubber compositions having high levels of resins.
• This object is achieved in that the Applicant has surprisingly discovered in the course of his research that the use of a specific compound gives the compositions containing it a decrease in their tackiness. This specific compound improves the processability of such rubber compositions.
• the subject of the invention is therefore an elastomer extended to the resin, the elastomer of which is a synthetic diene elastomer having an average molecular weight greater than or equal to 200000 g / mol and whose resin is a resin. plasticizing hydrocarbon.
• the number-average molar mass of the synthetic diene elastomer is less than or equal to 500000 g / mol.
• the number-average molar mass of the synthetic diene elastomer is in a range from 250000 g / mol to 450000 g / mol.
• the synthetic diene elastomer comprises at least one conjugated diene monomer having from 4 to 12 carbon atoms.
• the conjugated diene monomer having 4 to 12 carbon atoms is selected from the group consisting of 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-butadiene and 2,3-butadiene. -di (C1-C5) alkyl-1,3-butadienes, 1,3-pentadiene, 2,4-hexadiene and mixtures of these monomers.
• the conjugated diene monomer having 4 to 12 carbon atoms is selected from the group consisting of butadiene-1,3, 2-methyl-1,3-butadiene and mixtures thereof. monomers.
• the synthetic diene elastomer further comprises at least one vinylaromatic monomer having from 8 to 20 carbon atoms.
• the vinylaromatic monomer having 8 to 20 carbon atoms is selected from the group consisting of styrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, the commercial mixture. "Vinyl-toluene", para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene and mixtures of these monomers.
• the vinylaromatic monomer having from 8 to 20 carbon atoms is styrene and the conjugated diene monomer having 4 to 12 carbon atoms is 1,3-butadiene.
• the synthetic diene elastomer is functionalized by a function selected from the group consisting of groups functional groups comprising a carbon-tin bond, amino functional groups, functional groups comprising a silanol, functional groups comprising an alkoxysilane, carboxylic groups, polyether groups, epoxide groups and mixtures thereof.
• the synthetic diene elastomer is obtained by solution polymerization, preferably by homogeneous solution polymerization.
• the plasticizing hydrocarbon resin has a number-average molar mass of between 400 and 2000 g / mol, preferably between 500 and 1500 g / mol.
• the plasticizing hydrocarbon resin is selected from the group consisting of aliphatic resins, aromatic resins and mixtures of these resins.
• the plasticizing hydrocarbon resin is chosen from the group consisting of cyclopentadiene homopolymer or copolymer resins, dicyclopentadiene homopolymer or copolymer resins, homopolymer resins or terpene copolymers. , homopolymer resins or C5 cutting copolymers, homopolymer resins or C9 cutting copolymers, homopolymer resins or C5 cutting copolymer blends and C9 cutting homopolymer or copolymer resins, resins C homopolymers or copolymers of alpha-methyl-styrene and mixtures of these resins.
• the level of plasticizing hydrocarbon resin is in a range from 5 to 100 phr, preferably from 30 to 80 phr.
• the elastomer extended to the resin is obtained by mixing the synthetic diene elastomer in solution in an organic solvent and the plasticizing hydrocarbon resin in the liquid state.
• Another object of the present invention relates to a process for obtaining an elastomer extended to the resin, the process comprising at least:
• the process for obtaining further comprising between the step of removing the organic solvent (c) and the drying step (d) at least one washing step (c '). aqueous dispersion of synthetic diene elastomer particles and plasticizing hydrocarbon resin.
• the gaseous fraction enriched in organic solvent is recycled to step (a).
• the synthetic diene elastomer of step (a) is obtained either by dissolving said elastomer in the organic solvent or by solution polymerization in the organic solvent of the corresponding monomers of said elastomer.
• the plasticizing hydrocarbon resin is in the liquid state.
• the liquid plasticizing hydrocarbon resin in the liquid state is obtained by heating said resin to a temperature greater than or equal to its softening temperature.
• the liquid plasticizing hydrocarbon resin in the liquid state is obtained by dissolving said resin in an organic solvent identical to or different from the organic solvent in which the synthetic diene elastomer is located.
• the number-average molar mass of the synthetic diene elastomer is less than or equal to 500000 g / mol, more preferably is in a range from 250000 g / mol to 450000 g / mol. .
• said synthetic diene elastomer has a glass transition temperature of less than or equal to -60 ° C., more preferably in a range from -110 ° C. to -60 ° C., more preferably ranging from from -95 ° C to -65 ° C.
• the synthetic diene elastomer comprises at least one conjugated diene monomer having from 4 to 12 carbon atoms. According to a preferred embodiment, the synthetic diene elastomer further comprises at least one vinylaromatic monomer having 8 to 20 carbon atoms.
• the synthetic diene elastomer is functionalized by a functional group selected from the group consisting of functional groups comprising a carbon-tin bond, amino functional groups, functional groups comprising a silanol, the groups functional groups comprising an alkoxysilane, carboxylic groups, polyether groups, epoxide groups and mixtures thereof.
• the plasticizing hydrocarbon resin has a number-average molar mass of between 400 and 2000 g / mol, preferably between 500 and 1500 g / mol.
• the plasticizing hydrocarbon resin has a glass transition temperature greater than or equal to 20 ° C, preferably greater than or equal to 30 ° C.
• Another object of the present invention relates to an elastomer extended to the resin obtainable by the method defined above.
• the elastomer extended to the resin has a Mooney viscosity index greater than or equal to 40 UM, preferably in a range from 50 to 75 UM.
• another subject of the present invention relates to a composition based on at least one elastomer extended to the resin as defined above or capable of being obtained according to the process described above and from less a reinforcing filler.
• the composition further comprising at least one chemical crosslinking system.
• the rubber compositions containing an elastomer extended to the resin according to the invention has the advantage, despite the presence of a high level of plasticizing resin, to have a tackiness capacity on the lower mixing tools.
• the use of this elastomer extended to the resin in rubber compositions allows a gain in productivity of the mixing chain; the stops of the chain for cleaning being more limited because of a better processability of the rubber composition containing such a compound.
• Another object of the present invention relates to a semi-finished tire product comprising at least one elastomer extended to the resin as defined above or obtainable by the method described above.
• Another object of the present invention relates to a semi-finished tire product comprising at least one composition as defined above.
• Another object of the present invention relates to a tire comprising at least one elastomer extended to the resin as defined above or obtainable by the method described above.
• Another object of the present invention relates to a tire comprising at least one composition as defined above.
• SEC Size Exclusion Chromatography
• the SEC allows to apprehend the distribution of the molar masses of an elastomer.
• the equipment used is a chromatograph "WATERS alliance".
• the elution solvent is the following mixture: tetrahydrofuran + 1% vol. of diisopropylamine + 1% vol. of triethylamine or chloroform depending on the solvent used for the dissolution of the elastomer.
• the flow rate is 0.7 ml / min, the system temperature 35 ° C and the analysis time 90 min.
• a set of four WATERS columns is used in series, from trade names "STYRAGEL HMW7", “STYRAGEL HMW6E” and two "STYRAGEL HT6E".
• the injected volume of the sample solution of the elastomer is 100 ⁇ .
• the detector is a WATERS 2410 differential refractometer with a wavelength of 810 nm.
• the operating software for the chromatographic data is the "WATERS EM POWER" system.
• the average molar masses calculated relate to a calibration curve made from commercial standard polystyrene "PSS READY CAL-KIT".
• the macrostructure (Mw, Mn and Ip) of the plasticizing resin is also determined by steric exclusion chromatography (SEC) according to the following protocol.
• plasticizing resin sample There is no particular treatment of the plasticizing resin sample before analysis. This is simply solubilized at a concentration of about 1 g / l in tetrahydrofuran. Then, the solution is filtered on 0.45 ⁇ porosity filter before injection.
• the equipment used is a chromatograph "WATERS ALLIANCE 2695".
• the elution solvent is tetrahydrofuran without antioxidant.
• the flow rate is 1 ml / min, the system temperature 35 ° C and the analysis time 45 min.
• the injected volume of the solution of the plasticizing resin sample is 100 ⁇ .
• the detector is a WATERS 2410 differential refractometer with a wavelength of 810 nm.
• the operating software for the chromatographic data is the "WATERS EM POWER" system.
• the calculated average molar masses relate to a calibration curve made from commercial standard polystyrene from the company PSS polymer with the trade name "PSS READY CAL-KIT PSS-pskitrll" and a 162 g polystyrene standard. / mol of the company PSS polymer of trade name "PSS-psl62”.
• the glass transition temperature Tg is measured by means of a differential scanning calorimeter ("differential scanning calorimeter"). The analysis is performed according to the requirements of ASTM D3418-08 (2008). 1.4 Determination of the microstructure of elastomers by 1 H NMR spectroscopy
• the determination of the levels of the different monomer units and their microstructures within the elastomer are carried out by NMR analysis.
• the spectra are acquired on a BRUKER AVANCE 500 MHz spectrometer equipped with a BBIz-grad 5 mm Broad Band probe.
• the quantitative 1H NMR experiment uses a 30 ° single pulse sequence and a 5 second repetition time between each acquisition. The samples are solubilized in chloroform CDCl 3 .
• Determining the amount of plasticizing resin in the elastomer extended to the resin is also performed by size exclusion chromatography analysis (SEC).
• the equipment used is a chromatograph "Waters Alliance 2695".
• the elution solvent is tetrahydrofuran with antioxidant BHT at 250 ppm.
• the flow rate is 1 mL / min, the system temperature 35 ° C and the analysis time 35 min.
• the injected volume of the solution of the elastomer sample extended to the resin is 100 ⁇ .
• the detector is a "WATERS 2410" differential refractometer with a wavelength of 810 nm, the software for exploiting chromatographic data is the "WATERS EMPOWER” system.
• Calibrators using an elastomer not extended to the resin of the same microstructure as the elastomer extended to the resin are used. These calibrators are prepared in tetrahydrofuran with antioxidant BHT 250 ppm (BHT butylated hydroxytoluene).
• BHT 250 ppm antioxidant butylated hydroxytoluene
• Several calibrators are made from an elastomer not extended to the resin at concentrations in g / 1 precisely known so as to obtain a standard range.
• Each calibrator is injected at 100 in the chromatographic system. Using the 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 calibrant peak as a function of concentration.
• the elastomer extended to the resin is then injected following the realization of the calibration line. Since the signals of the resin and of the elastomer are separated using the SEC columns, a quantification can be carried out.
• the peak obtained for the elastomer is then integrated using the data reprocessing software; the area of said peak is then transferred to the previously constructed calibration line. It is then possible to deduce the elastomer concentration in g / L in the extended elastomer oil (Céksto).
• the concentration of the elastomer extended to the resin and put in solution is known (Cech).
• a consistometer is used as described in ASTM D-1646.
• the Mooney viscosity measurement is carried out according to the following principle: the elastomer is molded in a cylindrical chamber heated to 100 ° C. After one minute preheating, the rotor turns within the test sample at 2 tr.min "1 and the torque used for maintaining this movement after 4 minutes of rotation is measured.
• the tackiness of the rubber compositions are measured by means of a tack measurement which is also called an adhesion test, called a "probe-tack" test.
• the probe-tack 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 the surface; the composition is not vulcanized. The variation of the applied force is recorded as a function of displacement.
• the analysis is performed according to the requirements of ASTM D2979-01 (2009). The results are expressed in base 100.
• the value in base 100 for the sample to be tested is calculated according to the operation: (value of the maximum force in newtons to separate the probe from the adhesive / sample to be tested / value of the maximum force in newtons to separate the probe from ⁇ adhesive / control) x 100). In this way, a result of less than 100 indicates a decrease in tackiness which corroborates a better processability of the composition.
• the BET specific surface area of the silica is determined by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society” (Vol 60, page 309, February 1938). ), and more precisely according to a method adapted from standard NF ISO 5794-1, annex E of June 2010 [multipoint volumetric method (5 points) - gas: nitrogen - vacuum degassing: one hour at 160 ° C - pressure range relative p / po: 0.05 to 0.2].
• CTAB CTAB specific surface area values
• 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. a and b excluded) while any range of values referred to as “a to b” means the range of values from “a” to "b” (ie including strict bounds a and b).
• the carbon products mentioned in the description may 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. These include polymers, plasticizers, fillers, etc. 2.1 - Elastomer extended to the resin
• the invention relates to an elastomer extended to the resin, the elastomer of which is a synthetic diene elastomer having an average molecular weight greater than or equal to 200000 g / mol and whose resin is a plasticizing hydrocarbon resin.
• elastomer extended to the resin is meant in the sense of the present invention a composite material, solid, formed of an elastomer and a resin intimately mixed with each other.
• a first constituent of the elastomer extended to the resin according to the invention is a synthetic diene elastomer having a number average molecular weight greater than or equal to 200000 g / mol.
• elastomer or indistinctly” rubber ", the two terms being considered synonymous
• diene type an elastomer (is meant one or more elastomers) constituted at least in part (ie, a homopolymer or a copolymer) of monomeric diene units (monomers carrying two carbon-carbon double bonds, conjugated or otherwise).
• the diene elastomers can be classified in 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 proportion of units or units of diene origin (conjugated dienes) which is greater than 15% (mol%);
• diene elastomers such as butyl rubbers or copolymers of dienes and alpha-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% (% by moles)).
• 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% (mol%).
• synthetic elastomer is intended to mean an elastomer obtained by chemical synthesis from biosourced monomers or from petroleum chemistry. A synthetic elastomer is therefore distinguished from natural rubber which is a natural diene elastomer. Given these definitions, the term “synthetic diene elastomer” may be used more particularly and may be used in the elastomer extended to the resin according to the invention:
• any homopolymer of a conjugated diene monomer in particular any homopolymer obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms;
• the synthetic diene elastomer comprises at least one conjugated diene monomer having from 4 to 12 carbon atoms.
• It may therefore be a homopolymer of conjugated diene monomers having from 4 to 12 carbon atoms or of a copolymer resulting from the polymerization of conjugated diene monomers having from 4 to 12 carbon atoms with another polymerizable monomer.
• the conjugated diene monomer having 4 to 12 carbon atoms of the synthetic diene elastomer is selected from the group consisting of 1,3-butadiene, 2-methyl-1,3-butadiene and 2-methyl-1,3-butadiene.
• 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, 1,3-pentadiene, 2,4-hexadiene and mixtures of these monomers.
• the conjugated diene monomer having 4 to 12 carbon atoms is selected from the group consisting of butadiene-1,3, 2-methyl-1,3-butadiene and mixtures of these monomers.
• the other polymerizable monomer with the conjugated diene monomers having from 4 to 12 carbon atoms may be:
• alpha-olefin monomer such as propylene, 1-butene, iso-butylene, pentene, methylpentene, 1-hexene; ethylene; and
• the other polymerizable monomer is a vinylaromatic monomer having from 8 to 20 carbon atoms.
• the synthetic diene elastomer that can be used in the elastomer extended to the resin according to the invention also comprises at least one vinylaromatic monomer having from 8 to 20 carbon atoms. In this case, it is a copolymer.
• vinylaromatic monomers having 8 to 20 carbon atoms are particularly suitable styrenic monomers, namely any monomer comprising styrene, unsubstituted as substituted.
• substituted styrenes which may be mentioned are methylstyrenes (for example ⁇ -methylstyrene, m-methylstyrene or p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha-4-dimethylstyrene or diphenylethylene), para-tert-butylstyrene, chloro styrenes (e.g., ⁇ -chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene or 2,4, 6-trichlorostyrene), bromostyrenes (e.g., bromostyrene
• the vinylaromatic monomer having from 8 to 20 atoms is selected from the group consisting of styrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, the "vinyl-toluene" commercial mixture, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene and mixtures of these monomers. More preferably still, the vinylaromatic monomer having from 8 to 20 carbon atoms is styrene.
• the synthetic diene elastomer that can be used in the context of the invention is preferably chosen from the group consisting of polybutadienes (abbreviated as "BR”), synthetic polyisoprenes (abbreviated “IR”), copolymers of butadiene, isoprene copolymers and mixtures of these elastomers.
• BR polybutadienes
• IR synthetic polyisoprenes
• copolymers of butadiene isoprene copolymers and mixtures of these elastomers.
• Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (abbreviated as "SBR”), isoprene-butadiene copolymers (abbreviated as “BIR”), and isoprene-styrene copolymers (in particular: abbreviated “SIR”), and copolymers of isoprene-butadiene-styrene (abbreviated "SBIR”).
• SBR butadiene-styrene copolymers
• BIR isoprene-butadiene copolymers
• SIR isoprene-styrene copolymers
• SBIR copolymers of isoprene-butadiene-styrene
• the synthetic diene elastomer used in the elastomer extended to the resin according to the invention is a butadiene-styrene copolymer.
• copolymers of type (b) may contain from 20 to 99% by weight of diene units and from 1 to 80% by weight of vinylaromatic units.
• the synthetic diene elastomer that can be used in the context of the present invention comprises vinylaromatic monomers having from 8 to 20 carbon atoms (in particular this monomer is styrene)
• the level of this monomer is included in a range of ranging from 3 to 20% by weight relative to the total weight of the elastomer, more preferably ranging from 5 to 16% by weight relative to the total weight of the elastomer.
• the synthetic diene elastomer that can be used in the context of the present invention comprises vinylaromatic monomers having from 8 to 20 carbon atoms (in particular this monomer is styrene) and 1,3-butadiene monomers
• the level of butadiene 1,2-vinyl units is in a range from 4 to 30% by weight relative to the total weight of the polybutadiene part, more preferably from 5 to 25% by weight relative to the total weight of the polybutadiene part.
• the synthetic diene elastomers that can be used in the context of the present invention 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 amounts of modifying agent. and / or randomizing used.
• the synthetic diene elastomers that can be used in the context of the present invention can be, for example, blocks, statistics, sequenced, microsequenced, and synthesized solution; they may be coupled and / or starred or functionalized with a coupling agent and / or starring or functionalization.
• a copolymer based on conjugated diene monomers containing from 4 to 12 carbon atoms (in particular butadiene 1,3) and vinylaromatic monomers containing from 8 to 20 carbon atoms (in particular styrene) these two monomers are statistically distributed along the polymer chain.
• the synthetic diene elastomers that can be used in the context of the present invention may be synthetic diene elastomers functionalized with a functional group selected from the group consisting of functional groups comprising a carbon-tin bond.
• a functional group selected from the group consisting of functional groups comprising a carbon-tin bond.
• a reinforcing inorganic filler such as silica
• silanol or polysiloxane functional groups having a silanol end as described, for example, in FR2740778 or US6013718, and WO2008 / 141702
• alkoxysilane groups as described for example in FR2765882 or US59772308
• carboxylic groups as described for example in WO01 / 92402 or US6815473, WO2004 / 096865 or US2006 / 0089445
• polyether groups as described for example in EPI 127909 or US6503973, WO2009 / 000750 and WO2009 / 000752).
• Functional elastomers that may be mentioned are those prepared by the use of a functional initiator, especially those bearing an amine or tin function (see, for example, WO2010 / 072761).
• a functional initiator especially those bearing an amine or tin function
• elastomers such as SBR, BR, or synthetic IR
• this function is selected from the group consisting of functional groups having a carbon-tin bond, the amino functional groups, the functional groups comprising a silanol, the functional groups comprising an alkoxysilane.
• this function is selected from the group consisting of functional groups comprising a silanol and functional groups comprising an alkoxysilane.
• the functional group carrying the function may be at the end of the chain, that is to say at one end of the linear main elastomer chain. It will then be said that the diene elastomer is functionalized “at the end of the chain” or "at the end of the chain”. It is generally an elastomer obtained by reaction of an elastomer living on a functionalising agent, that is to say any molecule at least mono functional, the function being any type of chemical group known to those skilled in the art for reacting with a piece of living chain.
• This chemical group may be in the linear main elastomeric chain. It will be said that the diene elastomer is coupled or functionalized “in the middle of the chain", as opposed to the "end of the chain” position and although the group is not precisely in the middle of the elastomeric chain. It is generally an elastomer obtained by reaction of two chains of the elastomer living on a coupling agent, that is to say any molecule at least difunctional, the function being any type of chemical group known by the man of the art to react with a piece of living chain.
• This group may be central to which n elastomer chains (n> 2) are bonded forming a star structure of the elastomer. It will then be said that the diene elastomer is starred. It is generally an elastomer obtained by reaction of n chains of the elastomer living on a staring agent, that is to say any multifunctional molecule, the function being any type of chemical group known by the man of the invention. art to react with a piece of living chain.
• a functionalization reaction with an agent comprising more than one reactive function with respect to the living elastomer results in a mixture of functionalized end-of-pipe species and chain medium, constituting the linear chains of the functionalized diene elastomer, as well as, if appropriate, of star-shaped species.
• functionalized end-of-pipe species and chain medium constituting the linear chains of the functionalized diene elastomer, as well as, if appropriate, of star-shaped species.
• some species are predominant in the mixture.
• the synthetic diene elastomers that can be used in the context of the present invention carry a functional group chain medium or end of chain, more preferably end of chain.
• the synthetic diene elastomers that can be used in the context of the present invention have a high average molecular weight Mn, that is, an Mn greater than or equal to 200000 g / mol. Those skilled in the art know how to adapt the synthesis conditions of synthetic diene elastomers to obtain such Mn. Mn is measured according to the method described in paragraph 1.1.
• the synthetic diene elastomers that can be used in the context of the present invention have an Mn less than or equal to 500,000 g / mol; more preferably in a range from 250000 g / mol to 450000 g / mol.
• the synthetic diene elastomers that can be used in the context of the present invention are elastomers of low Tg.
• low Tg is meant a Tg of less than or equal to -60 ° C.
• Tg of synthetic diene elastomer used in the formulation of the elastomer extended to the resin is measured on the diene elastomer. synthetic prior to mixing with the plasticizing hydrocarbon resin. The Tg is measured according to the method described in paragraph 1.3.
• the synthetic diene elastomers that can be used in the context of the present invention have a Tg ranging from -110 ° C to -60 ° C, more preferably from -95 ° C to -65 ° C.
• the synthetic diene elastomers that can be used in the context of the present invention are obtained by solution polymerization, preferably by homogeneous solution polymerization. Any type of solution polymerization well known to those skilled in the art can be used, such as, for example, anionic polymerization or coordination polymerization.
• Solution polymerization is well known to those skilled in the art and differs from emulsion (or dispersed) polymerization in that the monomers used and the elastomer being synthesized are soluble in the solvent of the present invention. polymerization. At the end of the polymerization reaction, the formed elastomer is also dissolved in the polymerization solvent and is recovered by evaporation of said solvent or by filtration. In this type of polymerization, the polymerization solvent is very often a hydrocarbon solvent. On the contrary, in an emulsion polymerization, the polymerization solvent is water or an aqueous solution and the polymerizable monomer is insoluble in this polymerization solvent. Micelles are formed in which the polymerization reaction is carried out.
• an elastomer in the form of a latex is obtained, that is to say a stable emulsion of elastomer particles in an aqueous solution.
• the synthetic diene elastomers that can be used in the context of the present invention synthesized in solution are therefore not in the form of latices.
• the second component of the elastomer extended to the resin according to the invention is a plasticizing hydrocarbon resin.
• the name "resin” is reserved in the present application, by definition, to a compound which is solid to room temperature (23 ° C), 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 may comprise other types of atoms, used in particular as plasticizers or tackifying agents in polymeric matrices. They are inherently miscible (i.e., compatible) with the levels used with the diene elastomer compositions to which they are intended, so as to act as true diluents. They have been described, for example, in the book "Hydrocarbon Resins” by R. Mildenberg, M. Zander and G. Collin (New York, VCH, 1997, ISBN 3-527-28617-9), chapter 5 of which is devoted their applications, in particular pneumatic rubber (5.5 Rubber Tires and Mechanical Goods).
• They can be aliphatic, cycloaliphatic, aromatic, hydrogenated aromatic, aliphatic / aromatic type that is to say based on aliphatic and / or aromatic monomers. They may be natural or synthetic, whether or not based on petroleum (if so, also known as petroleum resins). They are preferably exclusively hydrocarbon-based, that is to say they contain only carbon and hydrogen atoms. Their Tg is preferably greater than or equal to 0 ° C, preferably greater than or equal to 20 ° C (most often in a range from 30 ° C to 95 ° C). In the present application, the terms “plasticizing resins”, “hydrocarbon resins” and “plasticizing hydrocarbon resins” are interchangeable.
• these plasticizing hydrocarbon resins can also be called thermoplastic resins in that they soften by heating and can be molded. They can also be defined by a point or softening point (softening point).
• the softening temperature of a plasticizing hydrocarbon 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 hydrocarbon 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. (especially between 30 ° C and 95 ° C). It is understood that the Tg of the plasticizing hydrocarbon resin used in the formulation of the elastomer extended to the resin according to the invention is measured on the plasticizing hydrocarbon resin prior to its mixing with the synthetic diene elastomer. The Tg of the plasticizing hydrocarbon resin is measured according to the method described in paragraph 1.3.
• the plasticizing hydrocarbon 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 Bail method).
• the plasticizing hydrocarbon resin that can be used in the context of the present invention has a number-average molecular weight (Mn) of between 400 and 2000 g / mol, preferably between 500 and 1500 g / mol.
• Mn number-average molecular weight
• the plasticizing hydrocarbon 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 an Mn ranging from 400 to 2000 g / mol. preferably between 500 and 1500 g / mol.
• the plasticizing hydrocarbon resins used in the context of the present invention may have all of the above preferred characteristics.
• the plasticizing hydrocarbon 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 hydrocarbon resins used in the context of the present invention, mention may be made of those selected from the group consisting of homopolymer resins or copolymers of cyclopentadiene (abbreviated to CPD), the resins of dopolopentadiene homopolymers or copolymers (abbreviated to DCPD), terpene homopolymer or copolymer resins, C5 cut homopolymer or copolymer resins, C9 cut homopolymer or copolymer resins, resin blends, and the like; C5 cutting homopolymers or copolymers and C9 cutting homopolymer or copolymer resins, alpha-methylstyrene homopolymer or copolymer resins and mixtures of these resins.
• CPD homopolymer resins or copolymers of cyclopentadiene
• DCPD dopolopentadiene homopolymers or copolymers
• plasticizing hydrocarbon resins of the above copolymers mention may be made more particularly of those selected from the group consisting of CPD / vinylaromatic copolymer resins, DCPD / vinylaromatic copolymer resins, CPD / terpene copolymer resins, DCPD / terpene copolymer resins, terpene phenol copolymer resins, CPD / C5 cut copolymer resins, DCPD / C5 cut copolymer resins, CPD / C9 cut copolymer resins, DCPD / C9 cut copolymer resins, C5 and C9 cut resins blends, terpene / vinylaromatic copolymer resins, copolymer resins terpene / phenol, C5 / vinylaromatic cut copolymer resins, and mixtures of these resins.
• pene here combines in a known manner the alpha-pinene, beta-pinene and limonene monomers; preferably, a limonene monomer is used which is present in a known manner in the form of three possible isomers: L-limonene (laevorotatory enantiomer), D-limonene (dextrorotatory enantiomer), or the dipentene, racemic of the dextrorotatory and levorotatory enantiomers .
• vinylaromatic monomer are suitable for example styrene, alpha-methylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, vinyl-toluene, para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, hydroxystyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene, any vinylaromatic monomer resulting from a C9 cut (or more generally from a C8 to C10 cut).
• the plasticizing hydrocarbon resins used in the context of the present invention are a C5 / C9 cut copolymer resin or a mixture of these resins.
• plasticizing hydrocarbon resins are well known to those skilled in the art and commercially available, for example sold by the company DRT under the name “Dercolyte” for polylimonene resins, by the company Neville Chemical. Company under the name “Super Nevtac”, by Kolon under the name “Hikorez” or by Exxon Mobil under the name “Escorez” for C5 / styrene resins or C5 / C9 cut resins or by Struktol under the name "40 MS” or "40 NS” (mixtures of aromatic and / or aliphatic resins).
• the intimate mixture of a synthetic diene elastomer as described above (including its preferred embodiments) and a plasticizing hydrocarbon resin as described above (including its preferred embodiments) allows to obtain a new material: an elastomer extended to the resin. Since the two components of this material are intimately mixed together, a single (single) Tg value is obtained when this parameter is measured for the elastomer extended to the resin. This Tg of the elastomer extended to the resin is different from that of the synthetic diene elastomer and that of the plasticizing hydrocarbon resin measured before their mixed. Surprisingly, this elastomer extended to the resin has a good Mooney viscosity, assuming good processability.
• the elastomer extended to the resin according to the invention has the advantage of being used for the manufacture of rubber composition, in particular for the manufacture of tire. Its use in this type of compositions allows a better processability of the composition in the various mixing tools. It limits the tackiness of the rubber compositions containing it with respect to a rubber composition comprising an elastomer of the same microstructure but not extended to the resin and the same level of hydrocarbon resin. Thus, the rubber composition comprising the elastomer extended to the resin according to the invention has a better processability and does not damage or very little mixing tools.
• the level of plasticizing hydrocarbon resin in the elastomer extended to the resin is in a range from 5 to 100 phr, preferably from 30 to 80 phr.
• the elastomer extended to the resin according to the invention may be obtained by mixing the synthetic diene elastomer in solution in an organic solvent and the plasticizing hydrocarbon resin in the liquid state.
• synthetic diene elastomer in solution means a homogeneous solution of a synthetic diene elastomer, that is to say that the organic solvent and said elastomer form only one phase visible to the naked eye. There is no precipitate or suspension of particles of said elastomer in the solution.
• the organic solvent may be any solvent compatible with the monomers of the synthetic diene elastomer, with the synthetic diene elastomer and with the plasticizing hydrocarbon resin.
• the organic solvent is aliphatic or alicyclic.
• n-pentane isopentane and isoamylenes (2-methyl-2-butene, 2-methyl-1-butene and 3-methyl-1-butene), 2,2 dimethylbutane, 2,2-dimethylpropane (neopentane), n-heptane, n-octane, isooctane, cyclopentane, cyclohexane, n-hexane, methylcyclopentane and methylcyclohexane, as well as mixtures of these compounds.
• Aromatic hydrocarbons for example benzene or toluene, may also be mentioned as organic solvents.
• the term "liquid plasticizing hydrocarbon resin” is intended to mean a plasticising hydrocarbon resin which, at ambient temperature, is in the solid state and which has undergone a process for passing into the liquid state.
• the plasticizing hydrocarbon resin may be heated, according to any technique well known to those skilled in the art, at a temperature above its softening temperature.
• Another example for obtaining a liquid plasticizing hydrocarbon resin in the liquid state is to solubilize said hydrocarbon resin in an organic solvent in which it is compatible. This technique is also well known to those skilled in the art.
• This organic solvent may be identical to or different from that in which the synthetic diene elastomer in solution is found.
• the solubilizing solvent of the resin must be compatible with that in which the elastomer is located.
• compatible is meant that the mixture of these two solvents forms a single phase visible to the naked eye.
• the invention also relates to a process for obtaining an elastomer extended to the resin, the process comprising at least:
• This process for obtaining an elastomer extended to the resin may be a batch or continuous process.
• the first step of the process concerns contacting at least one synthetic diene elastomer in solution in an organic solvent with at least one plasticizing hydrocarbon resin, said synthetic diene elastomer having an average molar mass in number greater than or equal to 200000 g / mol.
• This contacting can be done in any reactor well known to those skilled in the art.
• the solvent in which the synthetic diene elastomer is found may be any inert hydrocarbon solvent, preferably aliphatic or alicyclic.
• n-pentane isopentane, isoamylenes (2-methyl-2-butene, 2-methyl-1-butene and 3-methyl-1-butene), 2,2 dimethylbutane, 2,2-dimethylpropane (neopentane), n-heptane, n-octane, isooctane, cyclopentane, cyclohexane, n-hexane, methylcyclopentane and methylcyclohexane, as well as mixtures of these compounds.
• Aromatic hydrocarbons for example benzene or toluene, may also be mentioned as organic solvents.
• the synthetic diene elastomer dissolved in the organic solvent can be obtained either by dissolving said elastomer in said organic solvent or by polymerization, in solution in said organic solvent, of the corresponding monomers of said organic solvent. elastomer.
• the dissolution of the synthetic diene elastomer is carried out by any method well known to those skilled in the art, for example by immersing the balls of said elastomer in a reactor filled with the organic solvent and stirring the reaction medium. , optionally also by heating it, in order to obtain a synthetic diene elastomer in solution in the solvent.
• the synthetic diene elastomer in solution is obtained by polymerization in solution in said organic solvent of the corresponding monomers of said elastomer.
• the process of the invention may comprise a step (a ') in which it is polymerized in solution, preferably in homogeneous solution (that is to say in the above-mentioned organic solvent). ), from the corresponding monomers, a synthetic diene elastomer. In this step (a '), at least one conjugated diene monomer having from 4 to 12 carbon atoms is polymerized.
• This conjugated diene monomer having 4 to 12 carbon atoms may be selected from the group consisting of butadiene-1,3, 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 and 2-methyl-3-ethyl-1,3-butadiene; 2-methyl-3-isopropyl-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 selected from the group consisting of 1,3-butadiene, 2-methyl-1,3-butadiene and mixtures of these monomers.
• the conjugated diene monomer having 4 to 12 carbon atoms (first monomer) may also be copolymerized with at least one other polymerizable monomer, in particular which may be:
• a conjugated diene monomer having 4 to 12 carbon atoms different from the first monomer a vinylaromatic monomer having 8 to 20 carbon atoms;
• alpha-olefin monomer such as propylene, 1-butene, iso-butylene, pentene, methylpentene, 1-hexene; ethylene.
• the other polymerizable monomer is a vinylaromatic monomer having from 8 to 20 carbon atoms.
• vinylaromatic compounds are especially suitable styrenic monomers, namely any monomer comprising styrene, unsubstituted as substituted.
• substituted styrenes which may be mentioned are methylstyrenes (for example ⁇ -methylstyrene, m-methylstyrene or p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha-4-dimethylstyrene or diphenylethylene), para-tert-butylstyrene, chloro styrenes (e.g., ⁇ -chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene or 2,4, 6-trichlorostyrene), bromostyrenes (e.g., bromostyrene, m-bromostyrene, p-bromostyrene, 2,4-dibromostyrene, 2,6-dibromostyrene or 2,4,6-tribromostyrene
• the vinylaromatic monomer having from 8 to 20 carbon atoms of the synthetic elastomer that can be used in the process according to the invention is chosen from the group consisting of styrene, ortho-methylstyrene, meta-methylstyrene and para-methylstyrene. - methylstyrene, the commercial mixture "vinyl-toluene", para-tert-butylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene and households of these monomers. More preferably still, the vinylaromatic monomer having 8 to 20 carbon atoms is styrene.
• step (a ') of the process is a step in which a diene elastomer is polymerized in solution, preferably in homogeneous solution, from at least one monomer. conjugated diene having 4 to 12 carbon atoms (preferably this monomer is butadiene-1,3 or 2-methyl-1,3-butadiene) and at least one vinylaromatic monomer having 8 to 20 carbon atoms (preferably styrene).
• the polymerization can be anionic polymerization or catalyzed chain polymerization (according to the coordination-insertion mechanism). These types of polymerizations are well known to those skilled in the art and have been extensively described in the literature.
• anionic polymerization it is initiated for example by means of a polymerization initiator which may be any known anionic, mono- or polyfunctional initiator.
• a polymerization initiator which may be any known anionic, mono- or polyfunctional initiator.
• an initiator containing a metal alkaline such as lithium or an alkaline earth such as barium is used as a preferential.
• Suitable organolithium initiators include those having one or more carbon-lithium bonds such as n-butyllithium (n-BuLi), or else lithium amides.
• a catalytic system based on rare earth metal or titanium is used.
• Such systems have been described in particular in the documents WO02 / 38636, WO03 / 097708 and WO2007 / 045417.
• step (a ) in which the synthetic diene elastomer obtained in step (a ') is modified. consists in introducing a chemical function into the chain of the polymer being synthesized or at the end of the chain Such processes have been described in particular in applications WO2009133068 and WO2011042507.
• the synthetic diene elastomer may be functionalized by a function selected from the group consisting of functional groups comprising a carbon-tin bond, the amino functional groups, the functional groups comprising a silanol, the functional groups comprising an alkoxysilane, carboxylic groups, polyether groups, epoxide groups and mixtures thereof.
• the synthetic diene elastomer may be functionalized by a functional group selected from the group consisting of functional groups comprising a carbon-tin bond, amino functional groups, and functional groups. comprising a silanol, the functional groups comprising an alkoxysilane and mixtures thereof.
• the synthetic diene elastomer dissolved in the organic solvent or obtained at the end of step (a ') and / or (a ") has an average molar mass. in a number of less than or equal to 500000 g / mol
• said synthetic diene elastomer has a number-average molar mass in a range from 250000 g / mol to 450000 g / mol, Mn is measured according to the method described in US Pat. paragraph 1.1.
• the synthetic diene elastomer dissolved in the organic solvent or obtained at the end of step (a ') and / or (a ") has a transition temperature. vitreous lower or equal to -60 ° C.
• said synthetic diene elastomer has a transition temperature in a range of -110 ° C to -60 ° C, preferably -95 ° C to -65 ° C
• the Tg is measured according to the method described in paragraph 1.3.
• the resin used in the process of the invention during step (a) is a plasticizing hydrocarbon resin. As indicated above, this plasticizing hydrocarbon resin is in the solid state at room temperature (23 ° C.).
• plasticizing hydrocarbon resins can also be described as thermoplastic resins in that they soften by heating and can thus be molded. They can also be defined by a point or softening point (softening point).
• the softening temperature of a plasticizing resin is generally about 50 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 hydrocarbon resin that can be used in the process of the 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).
• the Tg is measured according to the method described in paragraph 1.3.
• the plasticizing hydrocarbon resin that can be used in the process of the 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 Bail method).
• the plasticizing hydrocarbon resin that can be used in the process of the invention has a number-average molar mass (Mn) of between 400 and 2000 g / mol, preferably between 500 and 1500 g / mol. Mn is measured according to the method described in section 1.2
• Ip polymolecularity index
• the plasticizing hydrocarbon resin that can be used in the process of the invention may have all of the preferred characteristics above.
• the plasticizing hydrocarbon resin that can be used in the process of the invention is chosen from the group consisting of aliphatic resins, aromatic resins and mixtures of these resins.
• plasticizing hydrocarbon resins used in the context of the present invention, mention may be made of those selected from the group consisting of by resins of homopolymers or copolymers of cyclopentadiene (abbreviated to CPD), resins of homopolymers or copolymers of dicyclopentadiene (abbreviated to DCPD), resins of homopolymers or copolymers of terpene, resins of homopolymers or copolymers of cutting C5, C9 homopolymer or copolymer cut resins, C5 blend homopolymer or copolymer resin blends and C9 cut homopolymer or copolymer resins, alpha-methyl homopolymer or copolymer resins, styrene and mixtures of these resins.
• CPD resins of homopolymers or copolymers of cyclopentadiene
• DCPD dicyclopentadiene
• terpene resins of homopolymers or copolymers of terpen
• the plasticizing hydrocarbon resin is in the liquid state.
• the liquid plasticizing hydrocarbon resin in the liquid state can therefore preferably be injected, by any appropriate means known to those skilled in the art, into the solvent solution containing the synthetic diene elastomer.
• the liquid plasticizing hydrocarbon resin in the liquid state can be obtained by heating said resin to a temperature greater than or equal to its softening temperature.
• This heating step is carried out by any means well known to those skilled in the art, for example using a reactor comprising heating and stirring means.
• the person skilled in the art knows how to determine the temperature at which heating takes place and the duration of heating, depending on the plasticizing hydrocarbon resin used, in order to obtain a liquid plasticizing hydrocarbon resin in the liquid state and whose viscosity allows its pumping for use in step (a).
• the temperature at which the heating takes place is greater than or equal to the softening temperature of said resin.
• the plasticizing hydrocarbon resin may be heated at a temperature ranging from 50 ° C to 200 ° C for a period of time in a range of 10 min to 2 hours.
• the plasticizing hydrocarbon resin in the liquid state can be obtained by dissolving said resin in an organic solvent identical to or different from the organic solvent in which the elastomer is located. synthetic diene.
• this organic solvent may be any inert hydrocarbon solvent, preferably aliphatic or alicyclic.
• n-pentane isopentane and isoamylenes (2-methyl-2-butene, 2-methyl-1-butene and 3-methyl-1-butene), 2,2 dimethylbutane, 2,2-dimethylpropane (neopentane), n-heptane, n-octane, isooctane, cyclopentane, cyclohexane, n-hexane, methylcyclopentane and methylcyclohexane, as well as mixtures of these compounds.
• Aromatic hydrocarbons for example benzene or toluene, may also be mentioned as organic solvents.
• the organic solvent in which the plasticizing hydrocarbon resin is dissolved is identical to that in which is found the synthetic diene elastomer.
• the dissolution of the plasticizing hydrocarbon resin can be carried out at room temperature or by heating the plasticizing hydrocarbon resin / organic solvent mixture. It is understood that when heating this mixture, the heating temperature must not be higher than the boiling temperature of the organic solvent to prevent the latter from evaporating.
• step (b) The mixing step of the process according to the invention is carried out by any means well known to those skilled in the art, for example with stirring and optionally by heating the reaction medium.
• This step makes it possible to obtain a homogeneous solution of synthetic diene elastomer and of plasticizing hydrocarbon resin. Stirring can be done for example with stirring motives in the reactor.
• homogeneous solution of synthetic diene elastomer and plasticizing hydrocarbon resin within the meaning of the present invention, the solution of synthetic diene elastomer and the plasticizing hydrocarbon resin in the liquid state after mixing form only a single liquid phase with the naked eye. There is no precipitate or particles in suspension in the reaction medium.
• the method according to the invention then comprises a step of stripping with water vapor.
• the steam stripping step is well known to those skilled in the art and makes it possible to recover a gaseous fraction enriched with organic solvent and an aqueous dispersion of particles of synthetic diene elastomer and of plasticizing hydrocarbon resin. It is carried out in a stripping column.
• Those skilled in the art can adapt, depending on the amount of organic solvent and optionally the amount of unconverted monomers present at the inlet of the stripping column, the amount of water vapor to be supplied to recover the elastomer in the form of an aqueous dispersion of synthetic diene elastomer particles and plasticizing hydrocarbon resin.
• the synthetic diene elastomer and the plasticizing hydrocarbon resin being both hydrophobic coagulate spontaneously in the form of synthetic diene elastomer particles and of plasticizing hydrocarbon resin. This coagulation makes it possible to trap the hydrocarbon resin in the synthetic diene elastomer and to form the elastomer extended to the resin. Since the organic solvent is volatile, it is entrained with the steam and a gaseous fraction enriched with organic solvent is obtained.
• this gaseous fraction enriched in organic solvent can after treatment be recycled to step (a).
• the recycled organic solvent can thus serve as a polymerization solvent or for the solubilization of the plasticizing hydrocarbon resin or the synthetic diene elastomer.
• the step of recovering the elastomer extended to the resin from the aqueous dispersion of synthetic diene elastomer and plasticizing hydrocarbon resin particles is well known to those skilled in the art and can be carried out by any means conventional separation of a solid and a fluid, such as decantation, centrifugation (spinning), filtration, drying.
• the recovery of the elastomer extended to the resin is carried out by drying the aqueous dispersion of synthetic diene elastomer particles and plasticizing hydrocarbon resin for example by placing said dispersion in a thermostatted oven or by sending this suspension in a cylinder tool.
• the purpose of step (d) is to remove the aqueous solution in order to recover the elastomer extended to the resin according to the invention in the form of a dry solid.
• the process according to the invention may comprise at least one washing step (c ') of the aqueous dispersion of synthetic diene elastomer and hydrocarbon resin particles. plasticizing. This optional step eliminates residual impurities that would not have been eliminated for example during the steam stripping step.
• the elastomer extended to the resin can then be recovered and packaged in a known manner in the form of balls, for example.
• the elastomer extended to the resin as defined above (including its preferred embodiments) or obtainable according to the process defined above (including its preferred embodiments ), according to the invention has a satisfactory Mooney viscosity despite the high average molecular weight in number of the elastomer used as a constituent and the presence of plasticizing resin. This satisfactory Mooney viscosity is a good indicator of the low stickiness of this material.
• This elastomer extended to the resin according to the invention can be advantageously used, for pneumatic application, in a reinforced rubber composition which it improves the processability on the mixing tools. This rubber composition is also the subject of the present invention.
• composition based on is meant in the sense of the present 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 between they, at least in part, during the various phases of manufacture of the composition, in particular during its extrusion or during the mixing phase.
• the rubber compositions according to the invention may be in the crosslinked state or in the uncrosslinked state, that is to say crosslinkable.
• the elastomer extended to the resin according to the invention may be according to different variants, used alone in the compositions or in blending with at least one other conventional diene elastomer.
• this other conventional diene elastomer is chosen from the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
• Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers, isoprene-butadiene copolymers, isoprene-styrene copolymers and isoprene-butadiene-styrene copolymers.
• the rubber compositions in accordance with the invention comprise, as elastomer extended to the resin, an elastomer extended to the resin for which at least one of the following characteristics is respected:
• the number-average molar mass of the synthetic diene elastomer is less than or equal to 500,000 g / mol.
• the number-average molar mass of the synthetic diene elastomer is in a range from 250000 g / mol to 450000 g / mol.
• the synthetic diene elastomer comprises at least one conjugated diene monomer having from 4 to 12 carbon atoms.
• the conjugated diene monomer having 4 to 12 carbon atoms is selected from the group consisting of 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5) alkyl; 1,3-butadienes, 1,3-pentadiene, 2,4-hexadiene and mixtures of these monomers.
• the conjugated diene monomer having 4 to 12 carbon atoms is selected from the group consisting of butadiene-1,3, 2-methyl-1,3-butadiene and mixtures of these monomers.
• the synthetic diene elastomer furthermore comprises at least one vinylaromatic monomer having from 8 to 20 carbon atoms.
• the vinylaromatic monomer having from 8 to 20 carbon atoms is chosen from the group consisting of styrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, the commercial "vinyl-toluene" mixture, para-methylstyrene, tert-butylstyrene, methoxy styrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene and mixtures of these monomers.
• the vinylaromatic monomer having from 8 to 20 carbon atoms is styrene and the conjugated diene monomer having 4 to 12 carbon atoms is butadiene-1,3.
• the synthetic diene elastomer is functionalized by a functional group selected from the group consisting of functional groups comprising a carbon-tin bond, amino functional groups, functional groups comprising a silanol, functional groups comprising an alkoxysilane, carboxylic groups, polyether groups, epoxide groups and mixtures thereof.
• the synthetic diene elastomer is obtained by solution polymerization, preferably by homogeneous solution polymerization.
• the plasticizing hydrocarbon resin has a number-average molar mass of between 400 and 2000 g / mol, preferably between 500 and 1500 g / mol.
• the plasticizing hydrocarbon resin is chosen from the group consisting of aliphatic resins, aromatic resins and mixtures of these resins.
• the plasticizing hydrocarbon resin is chosen from the group consisting of cyclopentadiene homopolymer or copolymer resins, dicyclopentadiene homopolymer or copolymer resins, terpene homopolymer or copolymer resins, homopolymer or copolymer resins of C5 cut, homopolymer resins or C9 cut copolymers, homopolymer resin blends or C5 cut copolymers and C9 cut homopolymer or copolymer resins, alpha-methyl homopolymer or copolymer resins styrene and mixtures of these resins.
• the level of plasticizing hydrocarbon resin is in a range from 5 to 100 phr, preferably from 30 to 80 phr.
• the extended elastomer to the resin obtained by mixing the synthetic diene elastomer in solution in an organic solvent and the plasticizing hydrocarbon resin in the liquid state.
• the rubber compositions of the invention comprise at least one reinforcing filler.
• reinforcing filler Any type of reinforcing filler known for its ability to reinforce a rubber composition which can be used for the manufacture of tires, may be used.
• an organic filler for example an organic filler, a reinforcing inorganic filler or a blend of these two types of filler.
• organic filler there may be mentioned carbon blacks, organic functionalized polyvinyl fillers as described in WO2006 / 069792, WO2006 / 069793, WO 2008/003434 and WO2008 / 003435.
• carbon black are suitable for all carbon blacks, including black type HAF, ISAF, SAF conventionally used in tires (so-called pneumatic grade black).
• the reinforcing carbon blacks of the 100, 200 or 300 series for example blacks NI 15, N134, N234, N326, N330, N339, N347 or N375, or else, according to the targeted applications, the blacks of higher series (for example N660, N683, N772).
• the carbon blacks could for example already be incorporated into an elastomer, in particular isoprenic, in the form of a masterbatch (see for example applications WO 97/36724 or WO 99/16600).
• any inorganic or mineral filler (whatever its color and its natural or synthetic origin), also called “white” charge, charge " clear 'or' 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 pneumatic, in other words able to replace, in its reinforcing function, a conventional carbon black pneumatic grade; such a filler is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) on its surface.
• -OH hydroxyl groups
• the physical state under which the reinforcing inorganic filler is present is indifferent, whether in the form of powder, microbeads, granules, beads or any other suitable densified form.
• reinforcing inorganic filler also refers to mixtures of different reinforcing inorganic fillers, in particular highly dispersible siliceous and / or aluminous fillers as described below.
• reinforcing inorganic fillers are particularly suitable mineral fillers of the siliceous type, in particular of silica (SiO 2 ), or of the aluminous type, in particular of alumina (Al 2 O 3 ).
• 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 specific surface and a CTAB specific surface area both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g, the BET specific surface area and the CTAB specific surface area being measured as indicated above.
• HDS Highly dispersible silicas
• silicas such as, for example, Ultrasil 7000 silicas from Evonik, Zeosil® 1165 MP and Zeosil® 1115 MP silicas from Solvay, Zeosil® Premium 200MP silica from the company Solvay company, Hi-Sil EZ150G silica from PPG, Zeopol 8715, 8745 or 8755 silicas from Huber, silicas as described in WO03 / 016215 and WO03 / 016387.
• Ultrasil 7000 silicas from Evonik Zeosil® 1165 MP and Zeosil® 1115 MP silicas from Solvay
• Zeosil® Premium 200MP silica from the company Solvay company
• Hi-Sil EZ150G silica from PPG Zeopol 8715, 8745 or 8755 silicas from Huber
• silicas as described in WO03 / 016215 and WO03 / 01
• reinforcing inorganic filler is also understood to mean mixtures of different reinforcing fillers, in particular of dispersible high siliceous fillers as described above.
• the total reinforcing filler content (carbon black and / or other reinforcing filler such as silica) is in a range from 10 to 200 phr, more preferably from 30 to 180 phr, more preferably ranging from 50 to 160 phr, the optimum being in a known manner different according to the particular applications targeted.
• the reinforcing filler is predominantly other than carbon black, that is to say it comprises more than 50% by weight of the total weight of the reinforcing filler, one or more reinforcing fillers other than carbon black, especially a reinforcing inorganic filler such as silica, or it consists exclusively of such a filler.
• black when black is also present, it may be used at a rate of less than 20 phr, more preferably less than 10 phr.
• the carbon black content may be in a range from 0.5 to 20 phr, preferably in a range from 1 to 10 phr.
• a reinforcing filler comprising predominantly carbon black and optionally silica or other inorganic reinforcing filler is used.
• the rubber compositions according to the invention further comprise, in a conventional manner, a coupling agent capable of effectively providing this connection.
• a coupling agent capable of effectively providing this connection.
• organosilanes especially polysulfurized alkoxysilanes or mercaptosilanes, or at least bifunctional polyorganosiloxanes.
• the coupling agent of the filler with the elastomer may be bis (3-triethoxysilylpropyl) tetrasulfide (abbreviated TESPT).
• TESPT bis (3-triethoxysilylpropyl) tetrasulfide
• the level of coupling agent is advantageously less than 20 phr, it being understood that it is generally desirable to use as little as possible. Its level is preferably in a range from 0.5 to 12 phr.
• the presence of the coupling agent depends on that of the reinforcing inorganic filler.
• the level of coupling agent of the inorganic reinforcing filler with the elastomer is easily adjusted by those skilled in the art according to the rate of this filler; It is typically of the order of 0.5% to 15% by weight relative to the weight of the reinforcing inorganic filler other than carbon black.
• the rubber compositions according to the invention may further comprise at least one crosslinking system based on either sulfur, sulfur and / or peroxide donors and / or bismaleimides, vulcanization accelerators, vulcanization activators.
• the crosslinking system is preferably a vulcanization system that is to say a system based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator.
• a vulcanization system that is to say a system based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator.
• various known secondary accelerators or vulcanization activators such as zinc oxide. , stearic acid or equivalent compounds, guanidine derivatives (in particular diphenylguanidine), or known vulcanization retarders.
• the primary vulcanization accelerator may be used at a preferential level within a range from 0.5 to 10 phr, more preferably in a range from 0.5 to 5.0 phr.
• accelerator any compound capable of acting as a vulcanization accelerator for diene elastomers in the presence of sulfur, in particular thiazole accelerators and their derivatives, accelerators of the thiuram type, dithiocarbamates of zinc.
• 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-benzothiazylsulfenamide (“DCBS”), N-tert-butyl-2-benzothiazylsulfenamide (“TBBS”), N-tert-butyl-2- benzothiazyl sulfenimide (“TBSI”), zinc dibenzyldithiocarbamate (“ZBEC”) and mixtures thereof.
• MBTS 2-mercaptobenzothiazyl disulfide
• TBZTD tetrabenzylthiuram disulfide
• CBS N-cyclohexyl-2-benzothiazyl sulfenamide
• the rubber compositions according to the invention may also contain, in addition to the coupling agents of the inorganic reinforcing filler with the elastomer, coupling activators, charge-covering agents or, more generally, surfactants. aids to the implementation, in a known manner, by improving the dispersion of the filler in the composition and by lowering the viscosity of the compositions, to improve its ability to implement in the green state, these agents being for example hydrolysable silanes, such as alkylakoxysilanes, polyols, polyethers, primary, secondary or tertiary amines, hydroxylated or hydrolysable polyorganosiloxanes.
• coupling agents of the inorganic reinforcing filler with the elastomer may also contain, in addition to the coupling agents of the inorganic reinforcing filler with the elastomer, coupling activators, charge-covering agents or, more generally, surfactants. aids to the implementation, in a known
• the rubber composition according to the invention may comprise, in addition to the plasticizing hydrocarbon resin already present in the elastomer extended to the resin, another plasticizing hydrocarbon resin identical to or different from that present in the elastomer. (additional resin).
• the total amount of plasticizing resin (resin present in the elastomer extended to the resin and optionally additional resin) in the rubber composition according to the invention is in a range from 5 to 100 phr, preferably ranging from 30 to 90 phr.
• plasticizing resin present in the elastomer extended to the resin and optionally additional resin
• the rubber compositions in accordance with the invention may also comprise all or part of the usual additives usually used in elastomer compositions intended for the manufacture of tires, for example pigments, non-reinforcing fillers, protection such as antiozone waxes, chemical antiozonants, antioxidants, anti-fatigue agents, plasticizers, acceptors or methylene donors (for example HMT or H3M) as described for example in the application WO02 / 10269, a crosslinking system.
• additives usually used in elastomer compositions intended for the manufacture of tires for example pigments, non-reinforcing fillers, protection such as antiozone waxes, chemical antiozonants, antioxidants, anti-fatigue agents, plasticizers, acceptors or methylene donors (for example HMT or H3M) as described for example in the application WO02 / 10269, a crosslinking system.
• the rubber compositions according to the invention can be 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 110 ° C and 190 ° C, preferably between 130 ° C and 180 ° C, followed a second phase of mechanical work (sometimes called “productive" phase) at a lower temperature, typically less than 110 ° C, for example between 40 ° C and 100 ° C, finishing phase during which is incorporated the crosslinking system (preferably the vulcanization system).
• a first working phase or thermomechanical mixing sometimes referred to as a "non-productive" phase
• a second phase of mechanical work sometimes called “productive” phase
• finishing phase during which is incorporated the crosslinking system (preferably the vulcanization system).
• thermomechanical working time of the constituents of the composition which comprises at least one reinforcing filler and at least one elastomer extended to the resin as defined above, with the exception of a crosslinking system;
• This method may also comprise, prior to performing the steps (i) and (ii) above, the steps of the process for obtaining said elastomer extended to the resin according to the method described above.
• the first phase is preferably carried out in several thermomechanical steps.
• the elastomer (s) extended to the resin, or the reinforcing filler (s), optionally, are introduced into a suitable mixer such as a conventional internal mixer.
• plasticizers including the addition of additional plasticizing resin and optionally coupling agents and / or other ingredients with the exception of the vulcanization system, at a temperature of between 20 ° C and 100 ° C, and preferably between 25 ° C and 100 ° C.
• the other ingredients ie, those that remain if all were not put initially
• the total mixing time is preferably between 2 and 10 minutes at a temperature of less than or equal to 180 ° C, and preferably less than or equal to 170 ° C.
• the crosslinking system (preferably the vulcanization system) is then incorporated at low temperature. (typically below 100 ° C), typically in an external mixer such as a roll mill; the whole is then mixed (productive phase, step (ii)) 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 a characterization in the laboratory, or extruded, for example to form a rubber profile used for the manufacture.
• semi-finished products in order to obtain products such as a tread.
• These products can then be used for the manufacture of tires, according to the techniques known to those skilled in the art, namely by superimposing the layers of sowing-finished products on each other before baking the tire.
• the crosslinking (or baking or vulcanization) is conducted in a known manner at a temperature generally between 130 ° C and 200 ° C, under pressure, for a sufficient time which may vary for example between 5 and 90 min depending in particular, the cooking temperature, the vulcanization system adopted, the kinetics of vulcanization of the composition under consideration or the size of the tire.
• the subject of the invention is also a semi-finished product for a tire comprising at least one elastomer extended to the resin as described above, including its preferred embodiments or that can be obtained according to the method described herein. above including its preferred embodiments.
• the invention also relates to a semi-finished tire product comprising at least one rubber composition as described above including its preferred embodiments.
• the invention also relates to a tire comprising at least one elastomer extended to the resin as described above including its preferred embodiments or obtainable according to the method described above including its preferred embodiments.
• the invention also relates to a tire comprising at least one composition as described above.
• the tire of the invention may be especially intended to equip vehicles.
• These vehicles may be tourism-type motor vehicles, SUV ("Sports Utility Vehicles"), two-wheelers (including motorcycles), airplanes, such as industrial vehicles chosen from light trucks, "heavy vehicles” - this is that is, metros, buses, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering vehicles, other transport or handling vehicles.
• Two elastomers not extended to the resin and two elastomers extended to the resin are synthesized according to the protocols described below.
• the glass transition temperature of the elastomers serving as starting material, plasticizing resins as starting material and the glass transition temperature of the elastomers extended to the resin are measured according to the method described in section 1.3.
• the number-average molar masses of elastomer and of the plasticizing resin are respectively measured according to the method described in paragraph 1.1 and 1.2. Viscosities were measured according to the method described in section 1.6.
• the level of plasticizing resin in the elastomers extended to the resin was measured according to the method described in section 1.5.
• This level is determined by weighing a solids content at 140 ° C. under the reduced pressure of 200 mmHg.
• the polymer chains are then functionalized by the addition of hexamethylcyclotrisiloxane in the reactor at a level of 0.4 molar equivalents relative to the end of the lithium chain. Functionalization is carried out at 60 ° C for 30 minutes.
• the polymer chains are neutralized by the addition of 0.9 parts per hundred parts of elastomers (phr) of 4,4'-methylene-bis-2,6-tert-butylphenol and 0.2 part per hundred parts.
• a homogeneous solution of styrene-butadiene copolymer functionalized in the organic solvent is obtained.
• the functionalized elastomer is separated from its solution by a stripping operation with water vapor to recover a dispersion of elastomeric particles in an aqueous solution. This dispersion is dried on cylinder tools at 100 ° C for 15 minutes.
• This level is determined by weighing a solids content at 140 ° C., under the reduced pressure of 200 mmHg.
• the polymer chains are then functionalized by the addition of hexamethylcyclotrisiloxane to the reactor at a level of 0.degree. 4 molar equivalent compared to lithium chain end. Functionalization is carried out at 60 ° C for 30 minutes.
• the polymer chains are neutralized by the addition of 0.9 parts per hundred parts of elastomers (phr) of 4,4'-methylene-bis-2,6-tert-butylphenol and 0.2 part per hundred parts.
• elastomers (pce) of N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine.
• a homogeneous solution of styrene-butadiene copolymer functionalized in the organic solvent is obtained.
• the copolymer solution in methylcyclohexane is then transferred into a 450 liter reactor and stirred for 15 minutes.
• This homogeneous solution of functionalized styrene-butadiene copolymer and resin is then subjected to a stripping operation with water vapor in order to recover a dispersion of elastomer / resin particles in an aqueous solution.
• This dispersion is dried on cylinder tools at 100 ° C for 15 minutes.
• the extended elastomer B is recovered from the resin, the characteristics of which are shown in Table I.
• the plasticizing hydrocarbon resin is commercially available from Exxon Mobil under the reference "Escorez 2173". Its characteristics are as follows:
• the polymer chains are then functionalized by adding hexamethylcyclotrisiloxane to the reactor at a rate of 0.4 molar equivalent with respect to lithium chain end. Functionalization is carried out at 60 ° C for 30 minutes.
• the polymer chains are neutralized by the addition of 0.9 parts per hundred parts of elastomers (phr) of 4,4'-methylene-bis-2,6-tert-butylphenol and 0.2 part per hundred parts.
• a homogeneous solution of styrene-butadiene copolymer functionalized in methylcyclohexane is obtained.
• the elastomer is separated from its solution by a steam stripping operation to recover a dispersion of elastomeric particles in an aqueous solution. This dispersion is dried on cylinder tools at 100 ° C for 15 minutes.
• the polymer chains are then functionalized by adding hexamethylcyclotrisiloxane to the reactor at a level of 0.4 molar equivalents relative to the end of the lithium chain. Functionalization is carried out at 60 ° C for 30 minutes.
• the polymer chains are neutralized by the addition of 0.9 parts per hundred parts of elastomers (phr) of 4,4'-methylene-bis-2,6-tert-butylphenol and 0.2 part per hundred parts.
• a homogeneous solution of styrene-butadiene copolymer functionalized in methylcyclohexane is obtained.
• the copolymer solution in methylcyclohexane is then transferred to a 450 liter reactor and stirred for 15 minutes.
• a solution of 2.17 Kg of "Escorez 2173" resin dissolved in 4 liters of methylcyclohexane is then added to the copolymer solution.
• the copolymer and resin solution is stirred for two hours at room temperature under nitrogen pressure of 0.4 bar with a speed of stirring at 400 rpm. This gives a homogeneous solution of functionalized styrene-butadiene copolymer and resin in the solvent.
• This homogeneous solution of functionalized styrene-butadiene copolymer and resin is then subjected to a stripping operation with water vapor in order to recover a dispersion of elastomer / resin particles in an aqueous solution.
• This dispersion is dried on cylinder tools at 100 ° C for 15 minutes.
• Mooney viscosity is a well-known parameter of the man's craft. It is generally accepted that the lower the Mooney viscosity of an elastomer, the more difficult it is to use this elastomer, especially in mixtures. Moreover, a Mooney viscosity of an elastomer greater than 100 UM. is also not sought by formulators of rubber compositions. [00245] Table II
• the elastomer A (outside the invention) is representative of an elastomer conventionally used in rubber compositions, in particular for the manufacture of tires. It has a Mooney viscosity of 40 UM representative of a good aptitude of the elastomer to be processable because little tacky.
• This test aims to show the improved processability properties of a composition according to the invention (Cl) comprising an elastomer extended to the resin according to the invention with respect to a control composition (Tl) comprising an elastomer same microstructure but not extended to the resin.
• compositions T1 and C1 are presented in Table III.
• the rates of the different constituents are expressed in phr.
• the results of the tack properties measured on the green (i.e. uncured) compositions are shown in Table IV.
• composition C1 differs from the composition T1 by the nature of the elastomer: it comprises an elastomer extended to the resin.
• Compositions C1 and T1 have the same total content of plasticizing resin (76 phr).
• Coupling agent Bis [3- (triethoxysilyl) propyl] Tetrasulfide silane (TESPT) sold by Evonik under the reference "Si69";
• TDAE oil TDAE oil marketed by Klaus Dahleke under the reference 3VIVATEC500;
• Plasticizing resin resin sold by Exxon Mobil under the reference "Escorez 1102";
• Plasticizing resin resin sold by Exxon Mobil under the reference “Escorez 2173";
• compositions are prepared according to the following protocol:
• the mixture thus obtained is recovered, cooled and the vulcanization system (sulfur and accelerator) is added to an external mixer (homogenizer) at 70 ° C., mixing the whole (productive phase) for about 5 hours. at 6 min.
• compositions thus obtained are then calendered in the form of plates (thickness of 2 to 3 mm) for measuring their physical or mechanical properties before firing.
• composition C1 comprising an elastomer extended to the resin according to the present invention exhibits significantly lower adhesive properties than the composition Tl representative of a rubber composition intended for the manufacture of a tire. This result is all the more surprising since the compositions C1 and T1 have the same total content of plasticizing resin, namely 76 phr.

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