Classifications

• • 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
  • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/14—Peroxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
  • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
  • C08K5/31—Guanidine; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/548—Silicon-containing compounds containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

• a tire having a tread comprising a diene elastomer, a thermoplastic elastomer and a peroxide
• the present invention relates to tires provided with a tread.
• the tread comprises, as elastomer, diene elastomers. This type of tread is well known and described in many documents.
• treads comprising a mixture of diene elastomer and thermoplastic elastomer.
• WO 2010/105984 discloses tread compositions comprising a styrene-butadiene copolymer (SBR), a polybutadiene (BR) and an unsaturated thermoplastic styrene elastomer (TPS) and a reinforcing filler to improve the strength tire wear.
• SBR styrene-butadiene copolymer
• BR polybutadiene
• TPS unsaturated thermoplastic styrene elastomer
• This composition is quite conventionally crosslinked with sulfur.
• thermoplastic elastomer being a block copolymer comprising at least one block elastomer and at least one thermoplastic block, and the total content of thermoplastic elastomer being within a range of 65 to 100 phr (parts by weight per hundred parts of elastomer).
• a tread comprising, as thermoplastic elastomer, the styrene / isoprene / styrene triblock copolymer (SIS) or a triblock styrene / butadiene-styrene hydrogenated styrene / styrene random copolymer (SOE) as permitting a reduction of the resistance. rolling relative to treads of conventional composition.
• SIS styrene / isoprene / styrene triblock copolymer
• SOE hydrogenated styrene / styrene random copolymer
• a constant objective of tire manufacturers remains to improve a balance of performance that is difficult to reconcile, such as the rolling resistance of the tires and their grip on wet surfaces or the ease of implementation. (processability) and the temperature resistance of the compositions. Indeed, the improvement of the adhesion supposes to increase the hysteretic losses whereas the improvement of the rolling resistance supposes to lower the hysteretic losses. Also, low rigidity at high temperature is sought for the ease of implementation while it is also important to have compositions having good resistance to high temperature when using the tires.
• a tire whose tread at least comprises a composition based on a specific elastomeric matrix and a peroxide-based crosslinking system makes it possible to reconcile the essential performance is low rolling resistance, good wear resistance and good temperature resistance.
• the invention therefore relates to a tire of which at least the tread comprises a composition based on at least one diene elastomer, at a rate of between 35 and 99 phr (parts by weight per hundred parts of elastomer), a thermoplastic elastomer of elastomeric block and thermoplastic block copolymer type, at a level of between 1 and 65 phr, and an organic peroxide-based crosslinking system.
• the tire according to the invention as defined above preferably comprises a crown with a crown reinforcement, two flanks, two beads, a carcass reinforcement anchored to the two beads and extending from one side to the other.
• the invention relates more particularly to tires intended to equip non-motorized vehicles such as bicycles, or tourism-type motor vehicles, SUV ("Sport Utility Vehicles"), two wheels (including motorcycles), airplanes, as industrial vehicles chosen from vans, "heavy vehicles” - that is to say, metro, bus, road transport vehicles (trucks, tractors, trailers), off-the-road vehicles such as agricultural or civil engineering vehicles; other transport or handling vehicles.
• thermoplastic elastomers TPE are part of the elastomers.
• 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 (that is, terminals a and b excluded).
• any range of values designated by the expression “from a to b” signifies the range of values from a to b (that is to say, including the strict limits a and b).
• a majority reinforcing filler is the reinforcing filler representing the largest mass relative to the total weight of the reinforcing fillers in the composition.
• a “minor” compound is a compound that does not represent the largest mass fraction among compounds of the same type.
• the tire according to the invention has the essential characteristic of comprising at least the tread comprises a composition based on at least one diene elastomer, at a rate of between 35 and 99 phr (parts by weight per cent). elastomer parts), a thermoplastic elastomer of elastomeric block and thermoplastic block copolymer type, at a content of between 1 and 65 phr, and an organic peroxide-based crosslinking system.
• TPE Thermoplastic Elastomer
• thermoplastic elastomers (abbreviated as "TPE”) have an intermediate structure between thermoplastic polymers and elastomers. They are block copolymers, made up of rigid, thermoplastic blocks, connected by flexible blocks, elastomers.
• thermoplastic elastomer may preferably be a specific TPE, block copolymer comprising at least one elastomer block of the polyether type and at least one non-styrenic thermoplastic block (TPNS).
• TPNS non-styrenic thermoplastic block
• a polyether block when reference is made to a polyether block, it is therefore a predominantly elastomeric block (that is, that is to say more than 50% by weight, preferably greater than 80% by weight) composed of a polymer resulting from the polymerization of ether-type monomer, and, when reference is made to a non-styrenic block, it is a block composed mainly (that is to say more than 50% by weight, preferably more than 80% by weight) of a polymer resulting from the polymerization of monomer other than the styrenic compounds (i.e., styrene and substituted and / or functionalized styrenes).
• styrenic compounds i.e., styrene and substituted and / or functionalized styrenes.
• said thermoplastic elastomer may be another specific TPE, block copolymer comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block (H) SBR and at least one styrenic copolymer-type thermoplastic block (PS). ).
• H butadiene-styrene random copolymer elastomer block
• PS styrenic copolymer-type thermoplastic block
• this copolymer may or may not be hydrogenated, and when reference is made to a styrenic block, it is a compound block predominantly (ie more than 50% by weight, preferably more than 80% by weight) of a styrenic polymer such as polystyrene.
• the thermoplastic elastomer is chosen from the group consisting of block copolymers comprising at least one elastomer block of the polyether type and at least one non-styrenic type thermoplastic block, the block copolymers comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block and at least one styrenic type thermoplastic block (TPE (H) SBR -PS), and mixtures of these thermoplastic elastomers.
• block copolymers comprising at least one elastomer block of the polyether type and at least one non-styrenic type thermoplastic block
• the block copolymers comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block and at least one styrenic type thermoplastic block (TPE (H) SBR -PS), and mixtures of these thermoplastic elastomers.
• H styrenic type thermo
• thermoplastic elastomer is chosen from the group consisting of block copolymers comprising at least one elastomer block of polyether type and at least one polyamide thermoplastic block (PEBA), the block copolymers comprising at least one elastomeric block of the type polyether and at least one polyester thermoplastic block (COPE), the block copolymers comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block and at least one styrenic type thermoplastic block (TPE (H) SBR-PS), and mixtures of these thermoplastic elastomers.
• PEBA polyamide thermoplastic block
• COPE polyester thermoplastic block
• TPE (H) SBR-PS styrenic type thermoplastic block
• thermoplastic elastomer is chosen from the group consisting of block copolymers comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block and at least one styrenic type thermoplastic block (TPE (H) SBR-PS ), and mixtures of these thermoplastic elastomers.
• block copolymers comprising at least one optionally hydrogenated butadiene-styrene random copolymer elastomer block and at least one styrenic type thermoplastic block (TPE (H) SBR-PS ), and mixtures of these thermoplastic elastomers.
• TPEs and in particular preferential TPEs are described in more detail in the following.
• the number-average molecular weight (denoted by Mn) of the TPE is preferably between 30,000 and 500,000 g / mol, more preferably between 40,000 and 400,000 g / mol.
• Mn number-average molecular weight
• the number-average molecular weight (Mn) of the TPE elastomer is determined in a known manner, by steric exclusion chromatography (SEC).
• SEC steric exclusion chromatography
• the sample is solubilized beforehand in tetrahydrofuran at a concentration of approximately 1 g / l; then the solution is filtered on 0.45 ⁇ porosity filter before injection.
• the apparatus used is a "WATERS alliance" chromatographic chain.
• the elution solvent is tetrahydrofuran, the flow rate 0.7 ml / min, the system temperature 35 ° C and the analysis time 90 min.
• a set of four WATERS columns in series, of trade names "STYRAGEL"("HMW7",”HMW6E” and two “HT6E”) is used.
• the injected volume of the solution of the polymer sample is 100 ⁇ .
• the detector is a "WATERS 2410" differential refractometer and its associated software for the exploitation of chromatographic data is the “WATERS MILLENIUM” system.
• the calculated average molar masses relate to a calibration curve made with polystyrene standards. The conditions are adaptable by those skilled in the art.
• the TPEs have two glass transition temperature peaks (Tg, measured according to ASTM D3418), the lowest temperature being relative to the elastomeric portion (for example polyether or (H) SBR) of the TPE at blocks, and the highest temperature being relative to the thermoplastic part (for example non-styrenic or polystyrene) of the TPE.
• Tg glass transition temperature peaks
• the soft blocks of the TPEs are defined by a Tg lower than the ambient temperature (25 ° C), while the rigid blocks have a Tg greater than 80 ° C.
• the TPE when reference is made to the glass transition temperature of the TPE, it is the Tg relative to the elastomeric block.
• the TPE preferably has a glass transition temperature ("Tg") which is preferably less than or equal to 25 ° C, more preferably less than or equal to 10 ° C.
• Tg glass transition temperature
• a value of Tg higher than these minima can reduce the performance of the tread when used at very low temperatures; for such use, the Tg of the TPE is more preferably still less than or equal to -10 ° C.
• the Tg of the TPE is greater than -100 ° C.
• the TPE may be copolymers with a small number of blocks (less than 5, typically 2 or 3), in which case these blocks preferably have high masses, greater than 15000 g / mol.
• These TPEs can be, for example, diblock copolymers, comprising a thermoplastic block and an elastomer block. They are often also triblock elastomers with two rigid segments connected by a flexible segment. The rigid and flexible segments can be arranged linearly, star or connected.
• each of these segments or blocks often contains at least more than 5, usually more than 10 base units (e.g., styrene units and butadiene / styrene units for a styrene / (H) block copolymer SBR / styrene).
• the TPE may also comprise a large number of blocks (more than 30, typically from 50 to 500) smaller, in which case these blocks preferably have low masses, for example from 500 to 5000 g / mol, these TPEs will be called multiblock TPEs later, and are a sequence of elastomeric blocks - thermoplastic blocks.
• the TPE is in a linear form.
• TPE is a diblock copolymer: thermoplastic block / elastomeric block.
• the TPE can also be a triblock copolymer: thermoplastic block / elastomer block / thermoplastic block, that is to say a central elastomer block and two terminal thermoplastic blocks, at each of the two ends of the elastomeric block.
• the multiblock TPE may be a linear sequence of elastomeric blocks-thermoplastic blocks.
• the TPE useful for the purposes of the invention is in a star shape at least three branches.
• the TPE may then consist of a stellate elastomer block with at least three branches and a thermoplastic block, located at the end of each of the branches of the elastomeric block.
• the number of branches of the central elastomer can vary, for example from 3 to 12, and preferably from 3 to 6.
• the TPE is in a branched form or dendrimer.
• the TPE can then consist of a connected elastomeric block or dendrimer and a thermoplastic block, located at the end of the branches of the dendrimer elastomer block. 1.1.2. Nature of elastomeric blocks
• the elastomeric blocks of the TPE for the purposes of the invention may be all elastomers known to those skilled in the art.
• the fraction of elastomeric block in the TPE is in a range from 30 to 95%, preferably from 40 to 92%, more preferably from 50 to 90%.
• These elastomer blocks preferably have a Tg (glass transition temperature) measured by DSC according to the ASTM D3418 standard of 1999, less than 25 ° C, preferably less than 10 ° C, more preferably less than 0 ° C and very preferably below -10 ° C. Also preferably, the T g of the elastomeric blocks is greater than -100 ° C. In particular, blocks having a Tg of between 20 ° C. and -70 ° C. and more particularly between 0 ° C. and -50 ° C. are suitable.
• the elastomeric blocks of the TPE have in total a number-average molecular weight ("Mn") ranging from 25,000 g / mol to 350,000 g / mol, preferably from 35,000 g / mol to 250,000 g / mol. g / mol so as to give the TPE good elastomeric properties and sufficient mechanical strength and compatible with the use in tread tire.
• Mn number-average molecular weight
• the elastomer block is of random copolymer type of butadiene and styrene ((H) SBR).
• the (H) SBR block comprises a styrene content, a 1,2-butadiene content of the butadiene part, and a -1,4-linkage content of the butadiene part, the latter consisting of a content of trans-1,4 bonds and a content of cis-1,4 bonds when the butadiene part is not hydrogenated.
• the determination of the degree of hydrogenation is carried out by NMR analysis.
• the spectra are acquired on a BRUKER 500 MHz Avance spectrometer equipped with a 1H-X 5 mm Cryoprobe.
• the quantitative 1H NMR experiment uses a 30 ° single pulse sequence and a 5 second repetition time between each acquisition.
• the samples (approximately 25 mg) are solubilized in the CS 2 approximately 1 ml, ⁇ of deuterated cyclohexane are added to make the lock during the acquisition.
• the chemical shifts are calibrated against the impurity protonated CS 2? Ppm to 7.18 ppm 1H referenced on TMS (? Ppm in 1H OPPM).
• the 1H NMR spectrum makes it possible to quantify the microstructure by integrating the signal mass characteristic of the different patterns:
• Styrene from (H) SBR and polystyrene blocks It is quantifiable in the aromatics zone between 6.0ppm and 7.3ppm for 5 protons (by removing the signal integral of the CS2 impurity at 7.18ppm).
• PB 1-2 from (H) SBR. It is quantifiable in the ethylenic zone between 4, 6ppm and 5, 1 ppm for 2 protons.
• PB 1-4 from (H) SBR. It is quantifiable in the ethylenic zone between 5.1 ppm and 6.1 ppm for 2 protons and by removing 1 proton from the PB 1-2 motif.
• the hydrogenated PB 1-2 from the hydrogenation and having only aliphatic protons.
• the CH3 during hydrogenated PB 1-2 have been identified and are quantifiable in the aliphatic zone between 0.4 and 0.8 ppm for 3 protons.
• the double bond content of the butadiene part of the block (H) SBR can decrease to a content of 0 mol% for a block (H) SBR totally. hydrogen.
• the elastomer block (H) SBR is hydrogenated in such a way that a proportion ranging from 25 to 100 mol% of the double bonds in the butadiene portion are hydrogenated. More preferably from 50 to 100 mol% and very preferably from 80 to 100 mol% of the double bonds in the butadiene portion are hydrogenated.
• the styrenic part of the blocks (H) SBR may be composed of monomers chosen from styrene monomers, and in particular selected from the group consisting of unsubstituted styrene, substituted styrenes and mixtures thereof.
• substituted styrenes those selected from the group consisting of methylstyrenes (preferentially ⁇ -methylstyrene, m-methylstyrene and p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha 4-dimethylstyrene and diphenylethylene), para-tert-butylstyrene, chlorostyrenes (preferentially ⁇ -chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene and 2-chlorostyrene).
• methylstyrenes preferentially ⁇ -methylstyrene, m-methylstyrene and p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha 4-di
• bromostyrenes preferentially ⁇ -bromostyrene, m-bromostyrene, p-bromostyrene, 2,4-dibromostyrene, 2,6-dibromostyrene and 2,4,6-tribromostyrene
• fluoro styrenes preferentially ⁇ -fluorostyrene, m-fluorostyrene, p-fluorostyrene, 2,4-difluorostyrene, 2,6-difluorostyrene and 2,4,6-trifluorostyrene
• para-hydroxy-styrene and mixtures thereof.
• the elastomer blocks may be of polyether type, in particular a polyether may be composed of monomers chosen from cyclic alcohols or ethers, preferably aliphatic aliphatic alcohols or ethers, such as, for example ethanol or tetrahydrofuran.
• a polyether may be composed of monomers chosen from cyclic alcohols or ethers, preferably aliphatic aliphatic alcohols or ethers, such as, for example ethanol or tetrahydrofuran.
• the polyethers those selected from the group consisting of polytetramethylene glycol (PTMG), polyethylene glycols (PEG), polypropylene ether glycol (PPG), polyhexamethylene ether glycol, polytrimethylenether glycol (PO 3 G), poly ( 3-alkyltetrahydrofuran), and mixtures thereof.
• the polyether is selected from the group consisting of polytetramethylene glycol (PTMG), polyethylene glycols (PEG) and mixture
• the elastomeric block may also consist of several elastomeric blocks as defined above. 1.1.3. Nature of thermoplastic blocks
• the glass transition temperature characteristic (Tg) of the thermoplastic rigid block will be used. This characteristic is well known to those skilled in the art. It allows in particular to choose the temperature of industrial implementation (transformation). In the case of an amorphous polymer (or a polymer block), the implementation temperature is chosen to be substantially greater than the Tg. In the specific case of a polymer (or a polymer block) semi - Crystalline, we can observe a melting temperature then higher than the glass transition temperature. In this case, it is rather the melting temperature (Tf) which makes it possible to choose the implementation temperature of the polymer (or polymer block) considered. Thus, later, when we speak of "Tg (or Tf, if any)", we must consider that this is the temperature used to choose the temperature of implementation.
• the TPE elastomers comprise one or more thermoplastic block (s) preferably having a Tg (or Tf, where appropriate) greater than or equal to 80 ° C.
• this thermoplastic block has a Tg (or Tf, if applicable) in a range of 80 ° C to 250 ° C.
• the Tg (or Tf, if appropriate) of this thermoplastic block is preferably from 80 ° C to 200 ° C, more preferably from 80 ° C to 180 ° C.
• thermoplastic block fraction in the TPE is in a range from 5 to 70%, preferably from 8 to 60%, more preferably from 10 to 50%.
• the thermoplastic blocks of the TPE have in total a number-average molecular weight ("Mn") ranging from 5,000 g / mol to 150,000 g / mol, so as to give the TPE good elastomeric properties and a sufficient mechanical strength and compatible with the use in tire tread.
• Mn number-average molecular weight
• thermoplastic blocks of the TPE are constituted (s) from polymerized styrenic monomers (PS).
• PS polymerized styrenic monomers
• Preferred polystyrenes (PS) are obtained from styrenic monomers selected from the group consisting of unsubstituted styrene, substituted styrenes, and mixtures thereof.
• substituted styrenes those selected from the group consisting of methylstyrenes (preferentially o-methylstyrene, m-methylstyrene and p-methylstyrene, alpha-methylstyrene, alpha-2-dimethylstyrene, alpha-4-dimethylstyrene and diphenylethylene), para-tert-butylstyrene, chlorostyrenes (preferentially ⁇ -chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene and 2,4,6-trichloro styrene), bromostyrenes (preferably bromostyrene, m-bromostyrene, p-bromostyrene, 2,4-dibromostyrene, 2,6-dibromostyrene and 2,4,6-dibro
• fluoro styrenes preferentially ⁇ -fluorostyrene, m-fluorostyrene, p-fluorostyrene, 2,4-difluorostyrene, 2,6-difluorostyrene and 2,4,6-trifluorostyrene
• para-hydroxy styrene and mixtures thereof.
• the PS blocks are blocks obtained from unsubstituted polystyrene.
• the polystyrene block as defined above may be copolymerized with at least one other monomer so as to form a thermoplastic block having a Tg (or Tf, where appropriate) as defined above.
• this other monomer capable of copolymerizing with the polymerized monomer may be chosen from diene monomers, more particularly conjugated diene monomers having 4 to 14 carbon atoms, and vinylaromatic type monomers having from 8 to 20 carbon atoms.
• TPEs with an optionally hydrogenated butadiene-styrene random copolymer elastomer block and a thermoplastic block of the type styrenic (TPE (H) SBR-PS), are also sometimes noted SOE, and they are most preferred for the purposes of the invention.
• H type styrenic
• thermoplastic blocks of the TPE are constituted (s) from polymerized non-styrenic monomers (TPNS).
• TPNS polymerized non-styrenic monomers
• Non-styrenic thermoplastic blocks (TPNS) are non-styrenic blocks, that is to say preferably thermoplastics resulting from the polymerization of any suitable monomer and not comprising styrenic monomers or less than 5%.
• the TPNS blocks are blocks selected from polyamide blocks, polyesters, and mixtures thereof.
• the TPNS blocks are polyamide blocks and / or polyesters.
• the TPNS blocks are chosen from the group consisting of polyamides of PA6, PAU or PA12 type, or polyesters of PET or PBT type and mixtures thereof.
• TPEs with particular polyether blocks and TPNS in which the non-styrenic thermoplastic blocks are polyamides are usually denoted TPE-A or TPA (thermoplastic copolyamide) or PEBA (amide block copolyether), and they are particularly preferred for the needs of the invention.
• TPE-A or TPA thermoplastic copolyamide
• PEBA amide block copolyether
• TPEs with particular polyether blocks and TPNS in which the non-styrenic thermoplastic blocks are polyesters are usually denoted TPE-E or TPC (thermoplastic copolyester) or COPE (ether-ester block copolymer), and they are also particularly preferred for the purposes of the invention.
• thermoplastic block may also consist of several thermoplastic blocks as defined above.
• the TPE elastomer (that is to say the TPE elastomer or elastomers) represents between 1 and 65%, preferably from 10 to 60% by weight. more preferably from 20 to 50%, and most preferably from 30 to 45% by weight of all the elastomers present in the elastomer composition.
• the amount of TPE elastomer is in a range between 1 and 65 phr, preferably 10 to 60 phr, better 20 to 50 phr and especially 30 to 45 phr. Indeed, with an amount of TPE elastomer less than 1 phr, the effect on the reduction of the rolling resistance is noticeable whereas, beyond 65 phr of TPE elastomer, the composition takes a thermoplastic nature with consequence a very strong evolution of the properties with the temperature.
• the composition of the tread according to the invention comprises at least one (that is to say one or more) diene rubber.
• the total diene elastomer content is between 35 and 99 phr, preferably in a range ranging from 40 to 90 phr, preferably from 50 to 80 phr, more preferably from 55 to 70 phr.
• elastomer or “diene” rubber, it is to be understood in a known way (one or more elastomers) is to be understood, at least in part (ie a homopolymer or a copolymer) of diene monomers (monomers carrying two double bonds). carbon carbon, conjugated or not).
• 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% (% by weight). mole).
• the term “highly unsaturated” diene elastomer is particularly understood to mean a diene elastomer having a content of units of diene origin (conjugated dienes) which is greater than 50%.
• diene elastomers such as certain butyl rubbers or copolymers of dienes and alpha olefins EPDM type can be qualified as "substantially saturated" diene elastomers (low or very low diene origin ratio). low, always less than 15%).
• iene elastomer is understood to mean, whatever the category above, which may be used in the compositions according to the invention:
• diene elastomer Any type of diene elastomer can be used in the invention.
• elastomers are preferably used. essentially unsaturated, in particular of types (a) and (b) above, for the manufacture of the tread of the tire according to the present invention.
• conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5) alkyl-1,3-butadienes, such as for example 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl 1,3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.
• alkyl-1,3-butadienes such as for example 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl 1,3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-he
• Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the "vinyl-toluene" commercial mixture, para-tertiarybutylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene.
• the copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinylaromatic units.
• the elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of modifying and / or randomizing agent used.
• the elastomers may for example be prepared in dispersion or in solution; they may be coupled and / or starred or functionalized with a coupling agent and / or starring or functionalization.
• alkoxysilane groups such as as described for example in FR 2,765,882 or US 5,977,238), carboxylic groups (as described for example in WO 01/92402 or US 6,815,473, WO 2004/096865 or US 2006/0089445) or groups polyethers (as described for example in EP 1 127 909 or US Pat. No. 6,503,973).
• functionalized elastomers mention may also be made of elastomers (such as SBR, BR, NR or IR) of the epoxidized type.
• the diene elastomer is chosen from the group consisting of essentially unsaturated diene elastomers, and the mixtures of these elastomers. More preferably, the diene elastomer is chosen from the group consisting of homopolymers obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms, the copolymers obtained by copolymerization of one or more conjugated dienes with each other or with one or more aromatic vinyl compounds having 8 to 20 carbon atoms, and mixtures thereof.
• the diene elastomer is chosen from the group consisting of polybutadienes, synthetic polyisoprenes, natural rubber, butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
• the diene elastomer is selected from the group consisting of polybutadienes (BR), butadiene-styrene copolymers (SBR), and mixtures thereof.
• the diene elastomer is most preferably a butadiene-styrene copolymer or a mixture of butadiene-styrene copolymers.
• the characteristic composition of the tire according to the invention has the essential feature of comprising an organic peroxide-based crosslinking system, which may be any organic peroxide known to those skilled in the art.
• organic peroxides well known to those skilled in the art, it is preferable to use for the invention an organic peroxide chosen from dicumyl peroxide, aryl or diaryl peroxides, peroxide. diacetyl, benzoyl peroxide, dibenzoyl peroxide, ditertbutyl peroxide, tertbutylcumyl peroxide, 2,5-bis (tertbutylperoxy) -2,5-dimethylhexane, and mixtures thereof.
• dicumyl peroxide aryl or diaryl peroxides
• peroxide peroxide. diacetyl, benzoyl peroxide, dibenzoyl peroxide, ditertbutyl peroxide, tertbutylcumyl peroxide, 2,5-bis (tertbutylperoxy) -2,5-dimethylhexane, and mixtures thereof.
• the organic peroxides can be chosen from the group of the following peroxides: bis (2,4-di-chlorobenzoyl) peroxide or DCBP-50 ("Perkadox PD-50S-ps-a” from AKZO Nobel Chemical BV or “Luperox CST” from the company ARKEMA), benzoyl peroxide or BP-50 ("Perkadox L-50S-ps” from AKZO Nobel Chemical BV), dicumyl peroxide ("Di-Cup 40C” from Geo Specialty Chemicals, Inc. or "Varox DCP-40C” from RT Vanderbilt Company, Inc.
• the amount of organic peroxide to be used for the purposes of the invention is less than or equal to 10 phr.
• the amount of organic peroxide in the composition is in a range from 0.1 to 10 phr. Indeed, below an amount of 0.1 phr, the effect of the peroxide is not significant while beyond 10 phr, the properties of elongation rupture and therefore resistance of the composition are decreased . More preferably, the amount of peroxide in the composition is in a range from 0.2 to 6 phr, preferably from 0.5 to 5 phr.
• composition according to the invention may further comprise a reinforcing filler.
• a reinforcing filler When a reinforcing filler is used, it is possible to use any type of filler usually used for the manufacture of tires, for example an organic filler such as carbon black, an inorganic filler such as silica, or a cutting of these two types of filler, including a cut of carbon black and silica.
• an organic filler such as carbon black
• an inorganic filler such as silica
• a cutting of these two types of filler including a cut of carbon black and silica.
• the majority reinforcing filler may be silica, or alternatively carbon black.
• carbon blacks are suitable all carbon blacks conventionally used in tires (so-called pneumatic grade black).
• pneumatic grade black For example, mention will be made more particularly of reinforcing carbon blacks of the series 100, 200 or 300 (ASTM grades), such as for example the blacks NI 15, N134, N234, N326, N330, N339, N347, N375, or else according to targeted applications, blacks of higher series (for example N660, N683, N772), or even N990.
• any inorganic or mineral filler (regardless of its color and origin (natural or synthetic), 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 for manufacturing tire, in other words able to replace, in its reinforcing function, a conventional carbon black pneumatic grade, such a charge is generally characterized, in known manner, by the presence of hydroxyl groups (-OH) at its
• the physical state in which the reinforcing inorganic filler is present is indifferent, whether in the form of powder, microbeads, granules, beads or any other suitable densified form.
• the term “reinforcing inorganic filler” also refers to mixtures of different reinforcing inorganic fillers, in particular highly dispersible siliceous and / or a
• reinforcing inorganic fillers are especially 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 surface and a CTAB specific surface both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g.
• HDS highly dispersible precipitated silicas
• a coupling agent or bonding agent
• a coupling agent at least bifunctional intended to ensure a sufficient connection, of a chemical nature and / or physical, between the inorganic filler (surface of its particles) and the elastomer, in particular organosilanes or bifunctional polyorganosiloxanes.
• the reinforcing filler is carbon black and / or silica.
• the majority reinforcing filler is carbon black.
• the majority reinforcing filler is silica.
• the reinforcing charge volume ratio, optional, in the composition is in a range of 0 to 30%, which corresponds to a rate of 0 to 100.
• the composition comprises less than 20% and preferably less than 15% by weight of reinforcing filler (in particular between 5 and 15%).
• the level of charge is preferably preferably less than 100 phr, especially less than 60 phr, more preferably a level in a range from 3 to 50 phr, better 5 to 40 phr. 1.5.
• the elastomers and the peroxide-based crosslinking system described above are sufficient on their own for the tread of the tire according to the invention to be usable.
• the elastomer composition described above does not comprise a plasticizing agent such as oil or thermoplastic resin, or, if it comprises, it comprises less than 20 phr ( in particular between 0.5 and 20 phr, preferably less than 15 phr (especially between 0.5 and 15 phr), more preferably less than 10 phr (especially between 0.5 and 10 phr), better still less than 5 phr. (in particular between 0.5 and 5 phr). Also preferentially, the composition does not comprise a plasticizer.
• a plasticizing agent such as oil or thermoplastic resin
• plasticizing agent is an oil (or plasticizing oil or extender oil) or a plasticizing resin whose function is to facilitate the implementation of the rolling, particularly its integration with the tire by a lowering of the module and an increase in tackifiant power.
• the composition comprises a plasticizer
• any oil preferably of a slightly polar nature, capable of spreading, plasticizing elastomers, especially thermoplastics.
• these oils are liquids (that is to say, as a reminder, substances having the ability to eventually take the shape of their container), as opposed in particular to resins or rubbers which are inherently solid.
• Any type of plasticising resin known to those skilled in the art can also be used.
• the elastomer composition described above may comprise the various additives usually present in the rolling bands known to those skilled in the art.
• one or more additives chosen from protective agents such as antioxidants or antiozonants, anti-UV agents, the various agents of implementation or other stabilizers, or the promoters able to promote the adhesion to the rest of the structure will be chosen.
• the composition according to the invention may optionally comprise a thermoplastic resin based on optionally substituted polyphenylene ether units (abbreviated as "EPP resin”). This type of compound is described for example in the encyclopedia "Ullmann's Encyclopedia of Industrial Chemistry” published by VCH, vol A 21, pages 605-614, 5th edition, 1992.
• the optional PPE resin for the invention preferably has a glass transition temperature (Tg), measured by DSC according to the ASTM D3418 standard of 1999, in a range from 0 to 280 ° C, preferably from 5 to 250 ° C and more preferably from 5 to 220 ° C. Below 0 ° C, the EPP resin does not allow a a shift of sufficient Tg in the composition comprising it and above 280 ° C, one can meet manufacturing problems including to obtain a homogeneous mixture.
• Tg glass transition temperature
• the PPE resin is a compound comprising predominantly polyphenylene units of general formula (I):
• R1, R2, R3 and R4 represent independently of each other identical or different groups selected from hydrogen; hydroxy, alkoxy, halogen, amino, alkylamino, dialkylamino groups; hydrocarbon groups containing at least 2 carbon atoms, optionally interrupted by hetero atoms and optionally substituted; R1 and R3 on the one hand and R2 and R4 on the other hand can form together with the carbon atoms to which they are attached one or more rings contiguous to the benzene ring of the compound of formula (I)
• n is an integer comprised in a range from 3 to 300.
• R 1, R 2, R 3 and R 4 represent, independently of each other, identical or different groups chosen from:
• linear, branched or cyclic alkyl groups comprising from 1 to 25 carbon atoms (preferably from 2 to 18), optionally interrupted by heteroatoms selected from nitrogen, oxygen and sulfur, and optionally substituted with hydroxy, alkoxy, amino, alkylamino, dialkylamino, or halogen.
• aryl groups comprising from 6 to 18 carbon atoms (preferably from 6 to 12), optionally substituted by hydroxyl, alkoxy, amino, alkylamino, dialkylamino, alkyl or halogen groups.
• R1, R2, R3 and R4 represent, independently of one another, identical or different groups chosen from:
• linear, branched or cyclic alkyl groups comprising from 1 to 12 carbon atoms (preferably from 2 to 6), optionally interrupted by hetero atoms and optionally substituted by hydroxyl or alkoxy groups containing from 1 to 6 carbon atoms, amino, alkylamino having 1 to 6 carbon atoms, dialkylamino having 2 to 12 carbon atoms, or halogen,
• aryl groups comprising from 6 to 18 carbon atoms (preferably from 6 to 12), optionally substituted with hydroxyl groups, alkoxy groups having from 1 to 6 atoms, amino, alkylamino groups having from 1 to 6 atoms, dialkylamino group having from 2 to to 12 carbon atoms, alkyl having 1 to 12 carbon atoms, or halogen.
• R 1 and R 2 represent an alkyl group and in particular a methyl group; and R3 and R4 represent hydrogen atoms.
• the PPE resin is a poly (2,6-dimethyl-1,4-phenylene ether).
• n is an integer in a range from 3 to 50, more preferably from 5 to 30, preferably from 6 to 20.
• the EPP resin is a compound comprising more than 80% by weight, and more preferably more than 95% by weight, polyphenylene units of general formula (I).
• the PPE resins have variable number average molecular weights (Mn) in particular of approximately 1000 to 45000 g / mol, most often from 15000 to 45000 g / mol, the Mn being measured in a known manner.
• Mn number average molecular weights
• SEC also named GPC, as in US4588806, column 8
• the level of PPE resin in the composition is preferably in a range from 1 to 50 phr, more preferably from 2 to 40 phr, more preferably from 2 to 30 phr and very preferably from 2 to 20 pce.
• the composition of the tread preferably does not comprise any plasticizer system other than the PPE resin, or comprises thereof with a total plasticizer content of less than 20. pce, preferably less than 15 phr. 2.
• the tread compositions for the tire according to the invention are 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 (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 by a second mechanical working phase (sometimes referred to as a "productive" phase) at a lower temperature, typically less than 110 ° C, for example between 60 ° C and 100 ° C, finishing phase during which the peroxide-based crosslinking system is incorporated; such phases have been described, for example, in EP-A-0501227, EP-A-0735088, EP-A-0810258, WO00 / 05300 or WO00 / 05301, for sulfur vulcanization systems.
• a first phase of work or thermomechanical mixing sometimes referred to as a "non-productive" phase
• TPE and diene elastomers are introduced during the first step, directly in their commercial form, for example in the form of beads or granules.
• a preferred alternative may be to prepare a masterbatch comprising elastomers only and optionally other optional ingredients, with the exception of the crosslinking system, which masterbatch is then used for the preparation of the complete mixture.
• this masterbatch can be prepared in a twin-screw extruder at a temperature between 180 ° C and 280 ° C, for example at 230 ° C.
• the tread for the tire according to the invention is then extruded in a conventional manner, in order to produce the profile.
• the tread is then carved in the tire baking mold.
• This tread may be mounted on a tire in a conventional manner, said tire comprising in addition to the tread according to the invention, a top, two flanks and two beads, a carcass reinforcement anchored to the two beads. , and a crown frame.
• Tire tread compositions according to the invention were prepared as indicated above.
• the dynamic properties G * and tan ( ⁇ ) max are measured on a viscoanalyzer (Metravib V A4000), according to the ASTM D 5992 - 96 standard.
• the response of a sample of vulcanized composition (cylindrical specimen of 4) is recorded. mm thick and 400 mm2 in section), subjected to a sinusoidal stress in alternating single shear, at a frequency of 10 Hz, according to ASTM D 1349-99, at 40 ° C.
• a peak-to-peak deformation amplitude sweep of 0.1 to 100%, (forward cycle), followed by 100% to 1% (return cycle), at 10 Hz is performed.
• the results used are the complex dynamic shear modulus. (G *) and the loss factor (tan ⁇ ).
• the hysteresis is represented by the tan ( ⁇ ) max return.
• the results will be indicated according to the performance, in base 100, the value 100 being attributed to the witness.
• a result lower than 100 indicating a decrease in the rolling resistance performance (increase in the value of tan (ô) max at 40 ° C), and inversely, a result greater than 100, will indicate an increase in the performance (decrease of the value of tan ( ⁇ ) max at 40 ° C).
• the abrasion experiment may for example be conducted on a LATIOO abraser, a device known to those skilled in the art, the result of which is a loss of mass per km.
• the cylindrical test piece is in accordance with the usual practice. It is applied with a fixed load of eg 75N against a circular track. This test tube cylindrical is subjected to a drift of 16 degrees or 13 or 9, but it will prefer a drift of 5.5 degrees.
• the speed of rotation of the abrasive disc is 40, 25km / h but we prefer a value of 12km / h.
• results will be indicated according to the performance, in base 100, the value 100 being attributed to the witness.
• a result less than 100 indicating a decrease in abrasion resistance, and vice versa, a result greater than 100, will indicate an increase in the resistance to abrasion and therefore to wear.
• results will be indicated according to the performance, in base 100, the value 100 being attributed to the witness.
• a tire tread composition according to the invention (A2) was prepared as indicated above and compared to two control compositions: a common tire tread composition (AO) and a peroxide crosslinking composition. (Al).
• the compositions of these treads are presented in Table 1 below. Table 1
• DPG Diphenylguanidine ("Perkacit DPG” from Flexsys);
• compositions it is possible to note the possibility of lowering the level of reinforcing filler and of plasticizer with respect to the control composition, thanks to the use of TPE elastomers in blending with the diene elastomer in the composition. of the tread.

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