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
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • 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
  • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
  • C08K13/02—Organic and inorganic ingredients
• • 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
  • C08K3/02—Elements
  • C08K3/06—Sulfur
• • 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
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
  • C08K5/40—Thiurams, i.e. compounds containing 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
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/43—Compounds containing sulfur bound to nitrogen
  • C08K5/44—Sulfenamides
• • 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
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
• • 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

Definitions

• the highly saturated diene elastomer contains units of formula (II).
• the highly saturated diene elastomer is preferably a random copolymer.
• the highly saturated diene elastomer useful for the needs of the invention in particular defined according to the first embodiment, according to the second embodiment, according to the third embodiment and according to the fourth embodiment, can be obtained according to different synthesis methods known to those skilled in the art, in particular as a function of the targeted microstructure of the highly saturated diene elastomer.
• the highly saturated diene elastomer can also be prepared by a process using a catalytic system of the preformed type such as those described in documents WO 2017093654 A1, WO 2018020122 A1 and WO 2018020123 A1.
• the level of the highly saturated diene elastomer in the rubber composition is at least 80 parts by weight per hundred parts of elastomer of the rubber composition (phr).
• the level of the highly saturated diene elastomer in the rubber composition varies in a range ranging from 80 to 100 phr. More preferably, it varies in a range from 90 to 100 phr.
• the essential characteristic of the vulcanization system useful for the needs of the invention is to include sulfur and a vulcanization accelerator.
• the sulfur content and the quantity of the vulcanization accelerator in the vulcanization system are strictly greater than 0 phr.
• the sulfur content in the rubber composition defined in any one of claims 1 to 15 is greater than 0.3 phr.
• the quantity of the vulcanization accelerator in the rubber composition defined in any one of claims 1 to 15, whether it is a primary accelerator or a mixture of a primary accelerator and a secondary accelerator is at least 0.5 pce.
• Sulfur is typically provided in the form of molecular sulfur or a sulfur donor, preferably in molecular form.
• the secondary accelerator preferably represents less than 50% by mass of the vulcanization accelerator, which amounts to saying that the mass ratio between the amount of the secondary accelerator and the amount of the vulcanization accelerator in the rubber composition is preferably less than 0.5. More preferably, the mass ratio between the quantity of the secondary accelerator and the quantity of the vulcanization accelerator in the rubber composition is preferably less than or equal to 0.3.
• the mass ratio between the quantity of the secondary accelerator and the quantity of the vulcanization accelerator in the rubber composition defined in any one of claims 1 to 15 is preferably greater than 0.05, more particularly between 0.05 and 0.7.
• Any compound capable of acting as a vulcanization accelerator for diene elastomers in the presence of sulfur in particular accelerators of the thiazole type and their derivatives, accelerators of the sulfenamide types can be used as vulcanization accelerator (primary or secondary) as regards primary accelerators, such as thiurams, dithiocarbamates, dithiophosphates, thioureas and xanthates with regard to secondary accelerators.
• the mass ratio between the quantity of the secondary accelerator and the quantity of the vulcanization accelerator is preferably less than 0.5, more preferably less or equal to 0.3.
• the mass ratio between the amount of the secondary accelerator and the amount of the vulcanization accelerator is preferably less than 0.5, more preferably less than or equal to 0.3.
• sufenamide such as N-cyclohexyl-2-benzothiazyl sulfenamide or a mixture of a sulfenamide and a thiuram disulfide, particularly a mixture of N-cyclohexyl-2-benzothiazyl sulfenamide and a thiuram disulfide, more particularly a mixture of N-cyclohexyl-2-benzothiazyl sulfenamide and tetrabenzylthiuram disulfide.
• the mass ratio between the sulfur content and the quantity of the vulcanization accelerator is less than or equal to 0.7.
• This first variant can be applied when the sulfur is molecular sulfur.
• This first variant can be applied when the vulcanization accelerator is a sulfenamide such as N-cyclohexyl-2-benzothiazyl sulfenamide or a mixture of a sulfenamide and a thiuram disulfide such as a mixture of N-cyclohexyl-2- benzothiazyl sulfenamide and a thiuram disulfide or a mixture of N-cyclohexyl-2-benzothiazyl sulfenamide and tetrabenzylthiuram disulfide.
• the mass ratio between the sulfur content and the quantity of the vulcanization accelerator is less than 0.6.
• This second variant can be applied when the sulfur is molecular sulfur.
• This second variant can apply when the vulcanization accelerator is a sulfenamide such as N-cyclohexyl-2-benzothiazyl sulfenamide or a mixture of a sulfenamide and a thiuram disulfide such as a mixture of N-cyclohexyl-2-benzothiazyl sulfenamide and d 'a thiuram disulfide or a mixture of N-cyclohexyl-2-benzothiazyle sulfenamide and tetrabenzylthiuram disulfide.
• the reinforcing filler comprises a silica.
• the silica used can be any reinforcing silica known to a person skilled in the art, in particular any precipitated or pyrogenic silica having a BET specific surface as well as a CTAB specific surface both of which are less than 450 m 2 / g, preferably included in a field ranging from 30 to 400 m 2 / g, in particular from 60 to 300 m 2 / g.
• Any type of precipitated silica can be used, in particular highly dispersible precipitated silicas (called “HDS" for "highly dispersible” or “highly dispersible silica”).
• the organosilanes are chosen from the group consisting of polysulphurized organosilanes (symmetrical or asymmetrical) such as bis (3-triethoxysilylpropyl) tetrasulphide, in short TESPT marketed under the name "Si69" by the company Evonik.
• polysulphurized organosilanes symmetrical or asymmetrical
• the vulcanization system more preferably comprises, as sulfur, molecular sulfur and, as vulcanization accelerator, a sulfenamide such as N-cyclohexyl-2-benzothiazyl sulfenamide or a mixture of a sulfenamide and a thiuram disulfide such as a mixture of N-cyclohexyl-2-benzothiazyl sulfenamide and a thiuram disulfide or a mixture of N-cyclohexyl-2-benzothiazyl sulfenamide and tetrabenzylthiuram disulfide.
• a sulfenamide such as N-cyclohexyl-2-benzothiazyl sulfenamide or a mixture of a sulfenamide and a thiuram disulfide.
• the carbon black represents more than 85% by mass of the reinforcing filler, preferably 100% by mass of the reinforcing filler.
• the reinforcing filler consists of carbon black.
• the sulfur is preferably molecular sulfur.
• the vulcanization system more preferably comprises, as sulfur, molecular sulfur and, as vulcanization accelerator, a sulfenamide such as N-cyclohexyl-2-benzothiazyl sulfenamide or a mixture of a sulfenamide and a thiuram disulfide such as a mixture of N-cyclohexyl-2-benzothiazyl sulfenamide and a thiuram disulfide or a mixture of N-cyclohexyl-2-benzothiazyl sulfenamide and tetrabenzylthiuram disulfide.
• a sulfenamide such as N-cyclohexyl-2-benzothiazyl sulfenamide or a mixture of a sulfenamide and a thiuram disulfide.
• carbon blacks all carbon blacks are suitable, in particular the blacks conventionally used in tire treads (so-called pneumatic grade blacks).
• the carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a support for some of the rubber additives used. Mention may more particularly be made of reinforcing carbon blacks of the 100 and 200, 300 series, or the blacks of the 500, 600 or 700 series (ASTM grades).
• ASTM grades ASTM grades
• the carbon black is a carbon black of the 100 or 200 series.
• the rubber composition useful for the needs of the invention may also comprise all or part of the usual additives usually used in elastomer compositions intended to constitute treads such as, for example, processing agents, plasticizers, pigments , protective agents such as anti-ozone waxes, chemical anti-ozonants, anti-oxidants.
• the rubber composition useful for the needs of the invention in particular defined in any one of claims 1 to 15, is devoid of a diacrylate derivative zinc in the form of a zinc salt of formula (III) wherein Ri, R 2 and R 3 independently of one another a hydrogen atom or a hydrocarbon group selected from-C 7 alkyl groups linear, branched or cyclic, the aralkyl groups, the alkylaryl groups and the aryl groups, and possibly interrupted by one or more heteroatoms, R 2 and R 3 being able to form together a non-aromatic ring.
• the seventh embodiment can be combined with any of the embodiments of the invention which are the first embodiment, the second embodiment, the third embodiment, the fourth embodiment, the fifth embodiment and the sixth embodiment, including their preferred variants.
• the rubber composition can be manufactured in suitable mixers, using two successive preparation phases according to a general procedure well known to those skilled in the art: a first working phase or thermo-mechanical kneading (sometimes referred to as a "non-phase”). productive ”) at high temperature, up to a maximum temperature between 110 ° C and 190 ° C, preferably between 130 ° C and 180 ° C, followed by a second phase of mechanical work (sometimes referred to as" productive phase ”) at a lower temperature, typically less than 110 ° C., for example between 40 ° C. and 100 ° C., the finishing phase during which the sulfur or the sulfur donor and the vulcanization accelerator are incorporated.
• a first working phase or thermo-mechanical kneading (sometimes referred to as a "non-phase”).
• productive at high temperature, up to a maximum temperature between 110 ° C and 190 ° C, preferably between 130 ° C and 180 ° C
• a second phase of mechanical work sometimes referred
• the first (non-productive) phase is carried out in a single thermomechanical step during which is introduced, into a suitable mixer such as a usual internal mixer, all the necessary constituents, the possible setting agents. in complementary and other miscellaneous additives, with the exception of sulfur and the vulcanization accelerator.
• the total duration of the kneading, in this non-productive phase is preferably between 1 and 15 min.
• the sulfur and the vulcanization accelerator are then incorporated at low temperature, generally in an external mixer such as a cylinder mixer; the whole is then mixed (productive phase) for a few minutes, for example between 2 and 15 min.
• the rubber composition is extruded to form all or part of a profile of a tire tread. Then during the assembly of a tire usually comprising, radially from the outside to the inside, a tread, a crown reinforcement and a carcass reinforcement, the tread is laid radially on the outside. of the crown reinforcement. Radially means in a known manner in a radial direction relative to the axis of rotation of the tire.
• the tire can be in the raw state (that is to say before the tire curing step) or in the cooked state (that is to say after the tire curing step).
• the tire is preferably a tire for a vehicle intended to carry heavy loads such as, for example, heavy goods vehicles, civil engineering vehicles.
• an HRMAS 4mm z-grad probe is used for non-soluble elastomers but having the capacity to swell in a solvent. Spectra are acquired at rotational speeds from 4000Hz to 5000Hz.
• insoluble samples are done in rotors filled with the analyzed material and a deuterated solvent allowing the swelling, in general deuterated chloroform (CDCI3).
• the solvent used must always be deuterated and its chemical nature can be adapted by a person skilled in the art.
• the quantities of material used are adjusted so as to obtain spectra with sufficient sensitivity and resolution.
• the soluble samples are dissolved in a deuterated solvent (about 25 mg of elastomer in lmL), generally deuterated chloroform (CDCI3).
• a deuterated solvent about 25 mg of elastomer in lmL
• CDCI3 generally deuterated chloroform
• the solvent or solvent mixture used must always be deuterated and its chemical nature can be adapted by a person skilled in the art.
• a 30 ° single pulse sequence is used with a proton decoupling only during acquisition to avoid the "Nuclear Overhauser” effects. (NOE) and stay quantitative.
• the spectral window is adjusted to observe all of the resonance lines belonging to the molecules analyzed.
• the number of accumulations is adjusted in order to obtain a signal to noise ratio sufficient for the quantification of each pattern.
• the recycling time between each pulse is adapted to obtain a quantitative measurement.
• the force and the tear deformation are measured on a test specimen stretched at 500 mm / min to cause rupture of the test specimen.
• the tensile test piece consists of a rubber plate of parallelepiped shape, for example of thickness between 1 and 2 mm, length between 130 and 170 mm and width between 10 and 15 mm, the two lateral edges being each covered lengthwise with a cylindrical rubber bead (diameter 5 mm) allowing anchoring in the jaws of the traction machine.
• 3 very fine cuts of length between 15 and 20 mm are made using a razor blade, half-width and aligned lengthwise of the test piece, one at each end and one in the center of the test piece, before the start of the test.
• the force (N / mm) to be exerted to obtain the rupture is determined and the elongation at break is measured.
• the test was conducted in air, at a temperature of 100 ° C. High values reflect good cohesion of the rubber composition although having crack initiators.
• the elastomer (EBR) is prepared according to the following procedure:
• metallocene [ ⁇ Me SiFlu Nd (p-BH 4 ) Li (THF) ⁇ , the symbol Flu representing the fluorenyl group of formula CI 3 H 8 ] are introduced into a first Steinie bottle in a glove box.
• the catalytic solution is then introduced into the polymerization reactor.
• the temperature in the reactor is then increased to 80 ° C.
• the reaction starts by injecting a gaseous mixture of ethylene and 1,3-butadiene (80/20 mol%) into the reactor.
• the polymerization reaction takes place at a pressure of 8 bars.
• the proportions of metallocene and co-catalyst are respectively 0.00007 mol / L and 0.0004 mol / L.
• the polymerization reaction is stopped by cooling, degassing of the reactor and addition of ethanol.
• An antioxidant is added to the polymer solution.
• the copolymer is recovered by drying in a vacuum oven.
• the compositions according to the invention Cl, C4, C5, C6, C7, C8, C9, CIO prove to be much more resistant mechanically and are more cohesive than compositions C2 and C3, whether or not in the presence of crack initiation.
• a tire has an improved lifespan if it has a tread, the portion of which intended to be in contact with the road surface consists of all or part of the compositions according to the invention Cl, C4, C5, C6 , C7, C8, C9, CIO instead of compositions C2 and C3.
• Table 1 the portion of which intended to be in contact with the road surface consists of all or part of the compositions according to the invention Cl, C4, C5, C6 , C7, C8, C9, CIO instead of compositions C2 and C3.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Tires In General (AREA)

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Cited By (4)

Citations (15)

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• 2018
  • 2018-09-11 FR FR1858135A patent/FR3085683B1/fr not_active Expired - Fee Related
• 2019
  • 2019-09-11 EP EP19786647.8A patent/EP3849822B1/fr active Active
  • 2019-09-11 US US17/271,970 patent/US20210340293A1/en not_active Abandoned
  • 2019-09-11 JP JP2021513196A patent/JP2022503669A/ja active Pending
  • 2019-09-11 WO PCT/FR2019/052097 patent/WO2020053520A1/fr not_active Ceased

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