US20110021702A1 - Functionalized vinyl polymer nanoparticles - Google Patents

Functionalized vinyl polymer nanoparticles Download PDF

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US20110021702A1
US20110021702A1 US12/309,081 US30908107A US2011021702A1 US 20110021702 A1 US20110021702 A1 US 20110021702A1 US 30908107 A US30908107 A US 30908107A US 2011021702 A1 US2011021702 A1 US 2011021702A1
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nanoparticles according
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monomer
nanoparticles
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Sylvie Gandon-Pain
Alain Hut
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Michelin Recherche et Technique SA Switzerland
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Michelin Recherche et Technique SA Switzerland
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen

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  • the present invention relates to reinforcing fillers capable of reinforcing polymeric matrices or compositions, more particularly to reinforcing fillers of organic type and to their use for reinforcing such matrices, in particular elastomeric matrices involved in the manufacture of tyres for automobiles.
  • a first subject of the invention relates to nanoparticles of functionalised, cross-linked vinyl polymer, usable in particular as reinforcing filler in a polymeric matrix, characterised in that said vinyl polymer is a copolymer of at least the following monomers, which are all copolymerisable by free-radical polymerisation:
  • the subject of the invention is also the use of nanoparticles according to the invention for reinforcing a polymeric, in particular elastomeric, matrix.
  • a particular subject of the invention is the use of nanoparticles according to the invention for reinforcing finished articles or semi-finished products made of rubber, these articles or semi-finished products being in particular intended for any ground contact system for automobiles, such as tyres, internal safety supports for tyres, wheels, rubber springs, elastomeric joints and other suspension and anti-vibration elements.
  • the subject of the invention is very particularly the use of nanoparticles according to the invention for reinforcing tyres.
  • the subject of the invention is also a masterbatch comprising nanoparticles according to the invention, embedded in a polymeric, in particular elastomeric, matrix.
  • the subject of the invention is also a polymeric composition
  • a polymeric composition comprising at least one polymer, in particular elastomer, nanoparticles according to the invention and a coupling agent providing the bond between the polymer and the surface of the nanoparticles.
  • FIG. 1 is an electron microscopy (TEM) image taken of a sample of VP nanoparticles in aqueous emulsion, in accordance with the invention.
  • the filler of vinyl polymer (abbreviated to “VP”) described below consists of “nanoparticles”, that is to say particles the principal dimension of which (diameter or length) is typically less than one micrometre, generally within a range of the order of about ten nanometres to one or several hundreds of nanometres.
  • These VP nanoparticles are in the form of elementary particles (or “primary particles”), these elementary particles or nanoparticles possibly forming aggregates (or “secondary particles”) of at least two of these nanoparticles, said nanoparticles and/or aggregates possibly in turn forming agglomerates capable of disagglomerating into these nanoparticles and/or aggregates under the effect of an external force, for example under the action of mechanical working.
  • nanoparticles are characterised using a transmission electron microscope (TEM), as indicated below.
  • TEM transmission electron microscope
  • the VP filler latex diluted beforehand with water (for example 8 g of filler per litre of water) is diluted to approximately 50 times its volume in isopropanol. 40 ml of the solution thus obtained is poured into a tall-form beaker (50 ml), then dispersed using a 600 W ultrasound probe (Vibracell probe, reference 72412, sold by Bioblock Scientific), at a power of 100%, for 8 min. in pulse mode (1 sec ON/1 sec OFF).
  • CM 200 sold by FEI, acceleration voltage 200 kV
  • camera MegaView II camera sold by Soft Imaging System
  • image analysis system AnalySIS Pro A version 3.0 from Soft Imaging System
  • the settings of the TEM are optimised in known manner, according to the sample and the state of ageing of the filament (typically, condenser diaphragm 2 (50 ⁇ m diameter)—lens 3 (40 ⁇ m diameter)).
  • the magnification of the microscope is adapted so as to have sufficient resolution on the nanoparticles. For example, a magnification of 65,000 corresponds to a resolution close to 0.96 nm/pixel, on a digital image of 1248 ⁇ 1024 pixels; such a resolution permits, for example, definition of a spherical nanoparticle of 40 nm diameter with more than 1000 pixels.
  • the camera is calibrated conventionally using standards (at low magnification, a gold grid of 2160 lines/mm; at high magnification, gold beads of a diameter of 0.235 nm).
  • the diameter of the nanoparticles is measured using the software AnalySIS Pro A version 3.0 (with “Circle” option of the “Measurement” menu). For each image and for a given nanoparticle, the operator shows on the screen (using the mouse) three points located on the periphery of the image of the nanoparticle. The software then automatically traces the circle passing through these three points and stores the values of the circular area, the circular perimeter and the circular diameter of the nanoparticle in a file (Excel). As this operation is possible only for nanoparticles having well-defined contours, nanoparticles present in agglomerates are excluded from the measurement. The test is repeated on at least 2000 nanoparticles representative of the sample (from at least 10 different images, typically 50).
  • the samples of VP filler in vulcanised rubber composition are prepared in known manner by ultracryomicrotomy (see for example L. Sawyer and D. Grubb, Polymer Microscopy , p. 92, Chapman and Hall).
  • the apparatus used here is a Leica ultracryomicrotome (“EMFCS”) equipped with a diamond knife.
  • EMFS Leica ultracryomicrotome
  • the sample is cut in the form of a truncated pyramid with rectangular base, the truncated face from which the sections will be taken having a side length of less than 600 ⁇ m. This truncated pyramid is held firmly during cutting.
  • the sample is cooled to a suitable temperature (close to the glass transition temperature of the sample) so that it is sufficiently hard to permit cutting, the temperature of the knife being typically close to that of the sample.
  • the speed and thickness of cut are preferably between 1 and 2 mm/sec and between 20 and 30 nm, respectively.
  • aqueous sucrose solution 40 g in 40 ml of water
  • the sections are recovered from the enclosure of the ultracryomicrotome, then placed on a TEM grid, at ambient temperature.
  • the sucrose is then eliminated by placing the grid on the surface of a crystalliser filled with distilled water.
  • the sections may be subjected to a step of staining with osmium tetroxide (OsO 4 ), using a process well-known to the person skilled in the art (L. C. Sawyer and David Grubb, Polymer Microscopy, Chapman and Hall, London, N.Y., 1987, pp. 97-98): the grids are placed above an open crystalliser containing a mix of 20 ml distilled water and 0.1 g of OsO 4 (Agar Scientific, reference R1015); the whole, placed in an airtight desiccator, is heated in a water bath to 50° C. for 3 to 31 ⁇ 2 hours.
  • OsO 4 osmium tetroxide
  • the sections are observed using a CM 200 microscope (voltage 200 kV). To optimise the contrast, the observations are performed by conventional energy-filtered imaging (energy window ⁇ E equal to approximately 15 eV), with a GIF (Gatan Imaging Filter) imaging system and the associated software (Filter Control and Digital Micrograph 3.4).
  • energy window ⁇ E equal to approximately 15 eV
  • GIF Global Imaging Filter
  • the nanoparticles of the invention have the essential characteristic of being formed of a functionalised, cross-linked vinyl polymer, said vinyl polymer (abbreviated to “VP”) being a copolymer of at least the following monomers, all copolymerisable by free-radical polymerisation:
  • VP vinyl polymer
  • the VP above is a copolymer the monomers of which are exclusively vinyl ones or the majority weight fraction of the monomers of which (preferably equal to or greater than 50%, more preferably equal to or greater than 70%) is constituted of vinyl monomers (the minority fraction possibly resulting from one or more monomer(s) other than vinyl ones).
  • the monomer C in order to be able to cross-link the VP, must be at least bifunctional, that is to say bear at least two functions which are polymerisable by free-radical polymerisation, unlike the monomers A and B which, from the point of view of the polymerisation, must be at least monofunctional, that is to say bear at least one function which is polymerisable by free-radical polymerisation.
  • the present invention is not limited to the cases of monomers A and B which are monofunctional from the point of view of the polymerisation, each of them possibly comprising more than one function which is polymerisable by free-radical polymerisation.
  • a bifunctional monomer A or monomer B (as is the case, for example, for the di(meth)acrylates or di(meth)acrylamides described later)
  • the latter might possibly also, according to one particular embodiment of the invention, fulfil the cross-linking function of the monomer C.
  • the Z functionalisation of the VP is provided by the monomer B.
  • the molar ratio of this monomer B is preferably greater than 5%, in particular between 5 and 30%, in particular between 5 and 20%.
  • X is a halogen, in particular chlorine, or X satisfies the formula OR in which O is oxygen and R represents hydrogen or a straight-chain or branched monovalent hydrocarbon group, comprising preferably from 1 to 15 carbon atoms.
  • Z functions selected from the so-called “hydroxysilyl” ( ⁇ Si—OH) or “alkoxysilyl” ( ⁇ Si—OR′) functions are more particularly suitable, R′ being a monovalent hydrocarbon radical preferably comprising from 1 to 15 carbon atoms, more preferably selected from among alkyls, alkoxyalkyls, cycloalkyls and aryls, in particular from among C 1 -C 8 alkyls, C 2 -C 8 alkoxyalkyls, C 5 -C 10 cycloalkyls and C 6 -C 12 aryls.
  • Z corresponds to one of the formulae below:
  • radicals R 1 are selected from among methyl and ethyl and the radicals R 2 are selected from among hydroxyl, methoxyl and ethoxyl.
  • the comonomer B is selected from the group consisting of hydroxysilyl-(C 1 -C 4 ) alkyl acrylates and methacrylates, (C 1 -C 4 ) alkoxysilyl-(C 1 -C 4 ) alkyl acrylates and methacrylates, and mixs of such monomers.
  • it is selected from the group consisting of hydroxy-, methoxy-, ethoxysilyl-(C 1 -C 4 ) alkyl acrylates and methacrylates and mixs of such monomers, in particular from among hydroxy-, methoxy-, ethoxy-silylpropyl acrylates and methacrylates, more particularly from among trimethoxysilylpropyl acrylate and methacrylate.
  • the comonomer B is selected from the group consisting of styryl-(C 1 -C 4 ) alkyl-hydroxysilanes, styryl-(C 1 -C 4 ) alkyl-(C 1 -C 4 ) alkoxysilanes and mixs of such monomers.
  • styryl-(C 1 -C 4 ) alkyl hydroxy-, methoxy-, ethoxy-silanes and mixs of such monomers in particular from among styrylethylhydroxysilanes, styrylethylmethoxysilanes and styrylethylethoxysilanes; more particularly styrylethyltrimethoxysilane (or trimethoxysilylethylstyrene) is used.
  • this comonomer B bearing the function Z is used in a weight ratio which is preferably greater than 10%, more preferably of between 10 and 30%, in particular between 15 and 30%.
  • TSPM trimethoxysilylpropyl methacrylate
  • TSPA trimethoxysilylpropyl acrylate
  • TSES trimethoxysilylethylstyrene
  • non-aromatic vinyl monomer A preferably corresponds to Formula (II):
  • R 3 hydrogen
  • butyl acrylate (R′ is tert. butyl), tert. butyl methacrylate (R′ is tert. butyl), hydroxyethyl acrylate (R′ is hydroxyethyl), hydroxyethyl methacrylate (R′ is hydroxyethyl), and mixs of these compounds.
  • methyl acrylate or methyl methacrylate is used.
  • MMA still methyl methacrylate
  • monomers A of bifunctional type there could be used monomers of Formula (II) above in which the radical Y bears a second vinyl or vinylidene group which is copolymerisable by free-radical polymerisation.
  • the Z-functionalised VP is furthermore present in a cross-linked state, that is to say in a three-dimensional form, so as maintain the morphology of the filler properly at high temperature.
  • the cross-linking is provided by at least one starting comonomer (monomer C) which is polymerisable by addition reaction and is bifunctional from the point of view of the polymerisation, that is to say bears at least one second function capable of creating a three-dimensional VP network upon polymerisation.
  • This monomer C termed “cross-linking”, may be a vinyl or non-vinyl, aromatic or aliphatic monomer.
  • More preferably suitable as comonomer C are comonomers bearing two unsaturated groups, in particular ethylene groups, polymerisable by free-radical polymerisation, in particular those selected from the group consisting of di(meth)acrylates or tri(meth)acrylates to of polyols, in particular of diols or of triols (for example of ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane), alkylene di(meth)acrylamides (for example methylene bis-acrylamide), vinyl aromatic compounds, preferably styrene ones, bearing at least two vinyl groups (for example diisopropenylbenzene (DIB), divinylbenzene (DVB), trivinylbenzene (TVB)), and mixs of such comonomers.
  • comonomers bearing two unsaturated groups, in particular ethylene groups, polymerisable by free-radi
  • the VP of the nanoparticles of the invention is a polyacrylate or polymethacrylate, or a copolymer resulting from (meth)acrylate units in a majority weight fraction (preferably at least equal to or greater than 50%, more preferably equal to or greater than 70%), for example a copolymer selected from the group consisting of the copolymers MMA-TSPM-EGDMA, MMA-TSPM-PGDMA, MMA-TSPM-HGDMA and MMA-TSPM-DVB.
  • the comonomer B bearing the aforementioned function Z or the comonomer A could be also used as cross-linking comonomer, provided of course that this comonomer B or this comonomer A is itself at least bifunctional and copolymerisable by free-radical polymerisation with the other comonomers.
  • the weight ratio of cross-linking comonomer C is preferably greater than 1%, more preferably greater than 5%, in particular between 10 and 30%.
  • Various other monomers such as for example diene monomers such as butadiene, isoprene, piperylene, may possibly be added in a minority proportion, preferably less than 20% of the total weight of monomers.
  • the monomers A, B and C are different and are all three vinyl monomers, in particular are all three non-aromatic vinyl monomers.
  • the monomers A and B bear a single function polymerisable by addition, and the cross-linking monomer C bears only two functions which are polymerisable by free-radical polymerisation.
  • the cross-linked, Z-functionalised VP may be prepared by any synthesis process suitable for functionalisation of a vinyl copolymer.
  • this synthesis is carried out by free-radical polymerisation of the different monomers.
  • the general principle of such a technique is known, and has been applied in particular to the free-radical polymerisation in emulsion of Z-functionalised polystyrene (alkoxysilane or hydroxysilane) in the presence of TSPM (see for example Macromolecules 2001, 34, 5737 and Macromolecules 2002, 35, 6185), or to the synthesis of polystyrene which is cross-linked (but not functionalised) in the presence of DVB ( Polymer 2000, 41, 481).
  • the non-aromatic vinyl monomer A is an acrylate or methacrylate monomer
  • the functionalising comonomer B (bearing the function Z) is preferably selected from the group consisting of TSPM, TSPA, TSES and mixs of these monomers
  • the cross-linking comonomer C is itself a vinyl compound, preferably selected from the group consisting of HGDMA, PGDMA, EGDMA, DVB and mixs of these monomers.
  • nanoparticles of Z-functionalised, cross-linked VP, in emulsion in water that is to say in the form of a latex (typically, for example, 100 g of polymer per litre of water).
  • a latex typically, for example, 100 g of polymer per litre of water.
  • polymer “latex” must be understood in known manner to mean a colloid system composed of a suspension or an emulsion of polymer particles in an aqueous medium.
  • these VP nanoparticles characterised by TEM in accordance with section I-1-A above are preferably present in a substantially spherical form (therefore in the form of nanobeads), either in the isolated state or in the form of aggregates which themselves may possibly be agglomerated.
  • the number of nanoparticles per aggregate is typically between 2 and 100.
  • the average diameter of these nanobeads which can be measured for example by TEM as indicated in section I-1-A, is preferably between 10 and 100 nm, more preferably between 10 and 60 nm, in particular between 10 and 40 nm.
  • VP nanoparticles according to the invention previously described are advantageously usable for reinforcing polymeric matrices, the polymer of these matrices possibly being of any nature, for example a thermoplastic material, a thermohardening material, or a diene or non-diene elastomer.
  • the amount of VP nanoparticles is preferably of between 10 and 100 parts by weight per hundred parts of polymer. Owing to the low density of these nanoparticles, this amount is advantageously between 10 and 80 parts, preferably between 20 and 50 phr and even more preferably strictly greater than 30 phr.
  • the VP filler furthermore constitutes more than 80%, more preferably more than 90% (% by volume) of the entire reinforcing filler, a minority fraction (preferably less than 20%, more preferably less than 10% by volume) of this entire filler possibly being constituted by another reinforcing filler, for example an inorganic filler or carbon black.
  • the VP nanoparticles may advantageously constitute the entire reinforcing filler in said polymeric matrices.
  • VP nanoparticles previously described are advantageously incorporated into their polymer matrix by means of a masterbatch, that is to say that these particles are mixed beforehand with at least one polymer to facilitate their later incorporation into the final polymeric matrix.
  • Masterbatch should be understood in known manner to mean the mix of at least one polymer (for example an elastomer or a mix of elastomers) and a reinforcing filler, the precursor mix of the final polymer matrix, ready for use.
  • this masterbatch may be prepared by a process comprising the following steps:
  • the polymer latex may consist of a polymer already available in emulsion or for example a polymer initially in solution which is emulsified in a mix of organic solvent and water, generally by means of a surfactant (the organic solvent being eliminated at the moment of coagulation or precipitation).
  • the operation of thoroughly mixing the two latexes is performed so as to disperse the VP nanoparticles properly in the polymer, homogenise the entire mix to form a latex mix of concentration of solid matter preferably of between 20 and 500 g/l, more preferably between 50 and 350 g/l.
  • the two starting latexes are diluted in water before mixing (for example 1 volume of water to 1 volume of latex).
  • the mix of the two latexes may be precipitated by any process known to the person skilled in the art, for example by mechanical action or preferably by action of a coagulating agent.
  • the coagulating agent is any liquid compound, water-miscible but a non-solvent (or poor solvent) of the polymer, for example an aqueous saline solution, preferably an alcohol or a mix of solvents comprising at least one alcohol (for example alcohol and water, alcohol and toluene). More preferably, the coagulating agent is a single alcohol such as methanol or isopropanol.
  • the coagulation is carried out preferably with stirring, at ambient temperature, in a large volume of coagulating agent; typically, substantially a volume of alcohol at least twice the total combined volume of the two diluted latexes is used. During this step, it is preferred to pour the mix of the two latexes on to the coagulating agent, and not vice versa.
  • the masterbatch After washing and drying, the masterbatch is obtained in the form of polymer “crumbs”, comprising at least the selected polymer and the VP nanoparticles embedded in the polymer matrix.
  • additives may possibly be incorporated in the masterbatch, whether they be intended for the masterbatch proper (for example a stabilising agent, carbon black as colouring and anti-UV agent, a plasticiser, an antioxidant, etc.) or for the final polymer matrix for which the masterbatch is intended.
  • a stabilising agent for example a stabilising agent, carbon black as colouring and anti-UV agent, a plasticiser, an antioxidant, etc.
  • a plasticiser for example a plasticiser, an antioxidant, etc.
  • the polymer of the masterbatch may be any polymer, whether identical or not to the one (or ones) of the final polymer matrix. It may be advantageous to use the same polymer and to adjust the amount of VP in the masterbatch to the intended final amount, so as not to have to add polymer later, during the manufacture of the final polymeric composition comprising the nanoparticles of the invention, as reinforcing filler, and the polymer thus reinforced.
  • the nanoparticles according to the invention previously described are preferably used for reinforcing tyres or semi-finished products for tyres, these semi-finished products being in particular selected from the group consisting of treads, underlayers intended for example to be placed beneath these treads, crown reinforcement plies, sidewalls, carcass reinforcement plies, beads, protectors, inner tubes, airtight internal rubbers for tubeless tyres, internal sidewall reinforcement rubbers and other rubbers intended for bearing the load in the event of travelling on a flat tyre.
  • rubber compositions are used which are based on at least: (i) a (that is to say at least one) diene elastomer; (ii) a (that is to say at least one) VP filler according to the invention and (iii) a (that is to say at least one) coupling agent providing the bond between this VP filler and this diene elastomer.
  • the expression “based on” is to be understood to mean a composition comprising the mix and/or the product of reaction of the different base constituents used, some of these constituents being able to react and/or being intended to react together, at least in part, during the different phases of manufacture of the composition, or during the later curing thereof.
  • Elastomer or rubber (the two terms being synonymous) of “diene” type is understood in known manner to mean an elastomer resulting at least in part (i.e. a homopolymer or a copolymer) from diene monomers (monomers bearing two double carbon-carbon bonds, whether conjugated or not).
  • the diene elastomer is preferably selected from the group of highly unsaturated diene elastomers which consists of polybutadienes (abbreviated to BR), polyisoprenes (IR), natural rubber (NR), butadiene copolymers, isoprene copolymers and mixs of these elastomers.
  • the diene elastomer is majoritarily, that is to say to more than 50 phr, a styrene/butadiene copolymer (SBR), be it an SBR prepared in emulsion (“E-SBR”) or an SBR prepared in solution (“S-SBR”), or an SBR/BR, SBR/NR (or SBR/IR), or alternatively BR/NR (or BR/IR) blend (mix).
  • SBR styrene/butadiene copolymer
  • the diene elastomer is majoritarily (to more than 50 phr) an isoprene elastomer, that is to say an isoprene homopolymer or copolymer selected from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), the various isoprene copolymers and mixs of these elastomers.
  • This isoprene elastomer is preferably natural rubber, or a synthetic cis-1,4 polyisoprene having an amount of cis-1,4 bonds greater than 90%, more preferably still greater than 98% (mole %).
  • the rubber composition may contain at least one essentially saturated diene elastomer, in particular at least one EPDM copolymer or a butyl rubber (possibly chlorine or brominated), whether these copolymers be used alone or in a mix with highly unsaturated diene elastomers such as mentioned previously, in particular NR or IR, BR or SBR.
  • the coupling agent (or bonding agent) is intended to establish a sufficient connection between the surface of the VP particles and the polymer for which these particles are intended, so that the latter may fully perform their function of reinforcing filler.
  • Coupling agents are well-known to the person skilled in the art and have been described in a very large number of documents. Any coupling agent capable of ensuring, in a diene rubber composition usable for the manufacture of tyres, the effective bonding between a reinforcing inorganic filler such as a silica and a diene elastomer, in particular polyfunctional organosilanes or polyorganosiloxanes, may be used.
  • organosilanes By way of examples of organosilanes, mention may be made of bis-((C 1 -C 4 ) alkoxysilyl-(C 1 -C 4 )) alkyl polysulphides, such as, for example bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilylpropyl) polysulphides, in particular bis(3-triethoxysilylpropyl) tetrasulphide, abbreviated to TESPT, of formula [(C 2 H 5 O) 3 Si(CH 2 ) 3 S 2 ] 2 or bis-(triethoxysilylpropyl) disulphide, abbreviated to TESPD, of formula [(C 2 H S O) 3 Si(CH 2 ) 3 S] 2 .
  • TESPT bis(3-trimethoxysilylpropyl) or bis(3-triethoxysilylpropyl) polysulphides, in particular bis(
  • the amount of coupling agent is preferably less than 10 phr, more preferably less than 7 phr, in particular less than 5 phr.
  • the above rubber compositions also comprise all or some of the conventional additives usually used in elastomer compositions intended for the manufacture of tyres, such as, for example, plasticisers or extender oils, pigments, protective agents such as anti-ozone waxes, chemical antiozonants, antioxidants, anti-fatigue agents, reinforcing or plasticising resins, methylene acceptors or donors, coupling activators, covering agents, agents facilitating processability, a cross-linking system based either on sulphur or on sulphur and/or peroxide and/or bismaleimide donors, vulcanisation accelerators or vulcanisation activators.
  • plasticisers or extender oils such as, for example, plasticisers or extender oils, pigments, protective agents such as anti-ozone waxes, chemical antiozonants, antioxidants, anti-fatigue agents, reinforcing or plasticising resins, methylene acceptors or donors, coupling activators, covering agents, agents facilitating processability, a cross-link
  • two fillers of (Z-)functionalised, cross-linked polymethacrylate are synthesised by free-radical polymerisation of three different monomers—methyl methacrylate (MMA), ethylene glycol dimethacrylate (EGDMA) and filler A: trimethoxysilylpropyl methacrylate (TSPM) or filler B: trimethoxysilylpropyl acrylate (TSPA)—then incorporated in a rubber composition for a tyre in the form of masterbatches obtained by coprecipitation of a latex of the VP filler and a latex of a diene elastomer (SBR).
  • MMA methyl methacrylate
  • EGDMA ethylene glycol dimethacrylate
  • TSPA trimethoxysilylpropyl acrylate
  • the weight ratio of comonomer B bearing the Z function (here, TSPM or TSPA) is of between 20 and 30%, and that of the cross-linking comonomer C (here, EGDMA) is of between 10% and 30%.
  • the different monomers are subjected beforehand to nitrogen bubbling, as are all the aqueous solutions used with the exception of the solution of SDS (bubbling in powder state).
  • the reaction is carried out in a 1.5 l reactor equipped with a mechanical stirring means. After introduction of 840 ml water and 30 minutes' nitrogen bubbling with stirring, there are introduced in succession 50 ml of a 0.9 mol/l aqueous solution of sodium dodecyl sulphate (SDS) as surfactant, 50 ml of a 1 mol/l equimolar buffer solution of sodium hydrogen phosphate and of ammonium dihydrogen phosphate. To this solution buffered at pH 7, stirred at 350 rpm and heated to 60° C. there is added the monomer filler in the following order:
  • Filler A 48.7 g of MMA (or a weight fraction of 47.1%), 29.1 g of EGDMA (weight fraction of 28.1%) then 25.6 g of TSPM (weight fraction of 24.8%).
  • Filler B 48.7 g of MMA (or a weight fraction of 47.8%), 29.1 g of EGDMA (weight fraction of 28.6%) then 24.1 g of TSPA (Weight fraction of 23.7%).
  • the functionalised, cross-linked polymethacrylates thus obtained are in the form of a latex comprising approximately 10% by weight of solid (VP) and water to make up (approximately 90%).
  • the filler A latex is characterised in accordance with section I-1-A.
  • the TEM image given in FIG. 1 shows that the nanoparticles (elementary particles) of the invention here are in the form of nanobeads, the majority of which have a diameter of between 20 and 60 nm.
  • the average circular diameter is equal to 34 nm (standard deviation 6 nm).
  • the polymethacrylate (filler A) is isolated and dried to evaluate the amount of (Z-)functionalisation thereof provided by the monomer TSPM, by analysis of the amount of silicon, by proceeding as follows:
  • operation is as follows: the sample is calcined at 525° C. for 2 hours. The fusion is then carried out on the ash obtained, at 1150° C. ( ⁇ 50° C.) with lithium tetraborate (for example 2 g per 1 g of calcined filler), for approximately 25 min. After cooling, the entire fused bead obtained is solubilised at 80° C. in hydrochloric acid diluted to 2% in water. The solution is then transferred and adjusted in a volumetric flask.
  • the analysis of the silicon is then carried out, on the contents of the volumetric flask, by ICP/AES: the aqueous solution is delivered into an argon plasma via an introduction system, where it undergoes the phases of desolvation, atomisation then excitation/ionisation of the atoms present.
  • the emission line of the silicon at 251.611 nm is then selected by means of a monochromator, then quantified relative to a calibration curve prepared from a certified standard solution of the corresponding element (the intensity I of the line emitted being proportional to the concentration C of the corresponding element).
  • the amount of silicon thus measured is equal to 2.6% ( ⁇ 0.2%), therefore virtually equal to the theoretical amount (namely 2.8%).
  • the density of the filler A nanoparticles is measured on the powder, using a helium pycnometer: the value obtained is equal to 1.25 g/cm 3 .
  • the polymethacrylate latices are then incorporated directly into an SBR diene elastomer to obtain a masterbatch as indicated in section II-2 above.
  • the amount of polymethacrylate filler intended in the masterbatch, as in the intended final rubber composition, is 39 phr (parts by weight per hundred parts of elastomer).
  • the SBR latex is prepared in a manner known to the person skilled in the art, under the following conditions: polymerisation temperature: 5° C.; surfactant: sodium dodecyl sulphate; initiator: iron II salt/hydroperoxide redox system. The conversion is of the order of 50 to 60%.
  • the quantity of dry matter of the SBR latex is determined by weighing, on a dry extract, before preparing the masterbatch.
  • the SBR latex is diluted to 3 times its volume in water, namely:
  • Filler A 652 ml of SBR latex at 177.1 g/l (115.4 g of SBR) and 1304 ml of dilution water.
  • Filler B 408 ml of SBR latex at 195.9 g/l (80 g of SBR) and 820 ml of dilution water.
  • the polymethacrylate filler latices are cooled to room temperature and then added to the SBR latices diluted to a proportion of 39 phr of filler, i.e.:
  • Filler A 497 ml of polymethacrylate filler latex at 90.5 g/l (45 g of filler),
  • Filler B 368 ml of polymethacrylate filler latex at 84.8 g/l (31.2 g of filler).
  • the resulting mix is homogenised gently. At a rate of 100 ml/minute, the mix is then added to filler A: 5000 ml; filler B: 3500 ml of methanol stirred at 350 rpm.
  • the precipitate thus obtained is filtered off on filter paper, rinsed with water until there is constant slight residual foaming in the washing water and the washing water tests negative with silver nitrate.
  • the precipitate thus washed is dried under reduced pressure under nitrogen at 60° C. for 3 to 4 days. 156 g (filler A) and 107.7 g (filler B) of dry masterbatch are thus recovered.
  • a control composition (HD silica filler) is prepared in conventional manner, as follows: first of all (“non-productive phase”) the SBR elastomer extended beforehand with 37.5 phr of oil and part of the filler are introduced into an internal mixer, the initial tank temperature of which is approximately 90° C. After an appropriate kneading time, of the order of 1 minute, the coupling agent and the remaining part of the filler are added. The other ingredients, with the exception of the vulcanisation system, are added after 2 minutes. The internal mixer is then filled to 75%. Thermomechanical working of a duration of about 6 minutes is then performed, with an average blade speed of 70 rpm, until a dropping temperature of about 135° C. is obtained.
  • the mix obtained is recovered and cooled, then the vulcanisation system (sulphur and sulphenamide-type primary accelerator) is added on an external mixer at 30° C., by mixing everything (“productive phase”) for an appropriate time (between 5 and 12 min).
  • vulcanisation system sulphur and sulphenamide-type primary accelerator
  • compositions thus obtained are then either calendered in the form of plates (thickness of 2 to 3 mm) of rubber in order to measure their mechanical properties, or extruded in the form of a semi-finished product for tyres, for example a tread.
  • Vulcanisation (curing) is carried out at 150° C. for 40 min, under pressure.
  • the rubber compositions are characterised, before and after curing, as indicated below.
  • the measurements are effected at 150° C. with an oscillating-chamber rheometer, in accordance with DIN Standard 53529—part 3 (June 1983).
  • the evolution of the rheometric torque as a function of time describes the evolution of the stiffening of the composition following the vulcanisation reaction.
  • the measurements are processed in accordance with DIN Standard 53529—part 2 (March 1983).
  • the conversion rate constant K (in min ⁇ 1 ) of order 1, calculated between 30% and 80% conversion, is measured, which makes it possible to assess the vulcanisation kinetics (the higher K is, the faster are the kinetics).
  • the dynamic properties ⁇ G* and tan( ⁇ ) max are measured on a viscoanalysisr (Metravib VA4000), in accordance with ASTM Standard D 5992-96.
  • the response of a sample of vulcanised composition (cylindrical test piece of a thickness of 2 mm and a section of 79 mm 2 ), subjected to an alternating single sinusoidal shearing stress, at a frequency of 10 Hz, under normal conditions of temperature (23° C.) in accordance with Standard ASTM D 1349-99, is recorded. Scanning is effected at an amplitude of peak-to-peak deformation of 0.1 to 50% (outward cycle), then of 50% to 0.1% (return cycle).
  • the aim of the test is to compare the performance OF THE nanoparticles of the invention with that of the conventional inorganic filler (HD silica).
  • the three compositions prepared in accordance with section C above the general formulation of which is conventional for high-performance tyre treads, combining low rolling resistance and high wear resistance (passenger-vehicle tyres of low energy consumption known as “Green Tyres”), are compared.
  • the HD silica selected to reinforce the control composition is a tyre-grade silica having in known manner a very high reinforcing ability (“Zeosil” type “1165 MP” from Rhodia—density approximately 2.1 g/cm 3 ).
  • the diene elastomer used is the SBR the synthesis of which is described in section III-2, extended beforehand with 37.5% of TDAE oil (namely 37.5 phr of oil per 100 phr of dry SBR).
  • the amount of reinforcing filler was adjusted to equal volume fractions of filler (same volume—namely approximately 19%—of filler in each composition).
  • volume fractions of filler equal volume fractions of filler (same volume—namely approximately 19%—of filler in each composition).
  • specific surface area of the polymer filler being lesser, the quantity of TESPT coupling agent introduced into the compositions C-2 and C-3 is therefore lower.
  • compositions C-2 and C-3 (invention), the VP nanoparticles represent approximately 97% (by volume) of the entire reinforcing filler, the latter comprising a small proportion (2 phr) of carbon black.
  • Tables 1 and 2 show in succession the formulation of the different compositions (Table 1—amount of the different products expressed in phr), and their properties before and after curing at 150° C. for 40 minutes (Table 2).
  • MMA methyl methacrylate
  • EGDMA ethylene glycol dimethacrylate
  • TSPA trimethoxysilylpropyl acrylate
  • the polymethacrylate latex is incorporated directly into natural rubber.
  • the polymethacrylate filler content targeted in the masterbatch is 39 phr (parts by weight per hundred parts of elastomer).
  • the amount of NR latex dry matter is determined by weighing, on the dry extract, before preparing the masterbatch.
  • the NR latex is diluted threefold with water, i.e. 447 ml of to NR latex at 178.8 g/l (80 g of NR) and 900 ml of dilution water.
  • the polymethacrylate filler latex (Filler B synthesised in paragraph III-1-A) is cooled to room temperature and then added to the NR latex diluted to a rate of 39 phr of filler, i.e. 368 ml of polymethacrylate filler latex at 84.8 g/l (31.2 g of filler). The resulting mix is homogenised gently. At a rate of 100 ml/minute, the mix is then added to 3500 ml of methanol stirred at 350 rpm. The precipitate thus obtained is filtered through filter paper, rinsed with water until there is constant slight residual foaming in the washing water and the washing water tests negative with silver nitrate. The precipitate thus washed is dried under reduced pressure under nitrogen at 60° C. for 3 to 4 days. 110 g of dry masterbatch are thus recovered.
  • compositions of NR rubber are then prepared as indicated previously for Test 1 (dropping temperature of about 145° C.), these two compositions differing only in the nature of their reinforcing filler, as follows:
  • such rubber compositions are typically used in the parts of road contact systems, especially of tyres, usually using NR-based rubber matrices, for instance the inner safety bearings of tyres, the sidewalls, the bead zones of tyres, the underlayers of treads and also the treads of these tyres, especially for heavy-goods vehicles.
  • NR-based rubber matrices for instance the inner safety bearings of tyres, the sidewalls, the bead zones of tyres, the underlayers of treads and also the treads of these tyres, especially for heavy-goods vehicles.
  • composition C-5 of the invention the content of reinforcing filler was adjusted to equal volume fractions of filler (same volume—i.e. about 17%—of filler in each composition). Since the specific surface area of the polymer filler is lower, the amount of TESPT coupling agent introduced into composition C-5 is thus markedly lower.
  • the VP filler represents about 97% (by volume) of the total amount of reinforcing filler, the latter comprising a small proportion (1 phr) of carbon black.
  • Tables 3 and 4 show in succession the formulation of the different compositions (Table 3—amount of the different products expressed in phr), and their properties before and after curing at 150° C. for 25 minutes (Table 4).
  • the VP nanoparticles according to the invention owing to their very greatly reduced density compared with a conventional reinforcing filler such as carbon black or HD silica, make it possible to reduce very significantly the weight of the polymeric compositions.
  • VP filler since the density of the polymeric matrix becomes substantially equal to that of the VP filler itself, it thus becomes possible to increase the amount of reinforcing filler without increasing the density of said polymeric matrix.
  • nanoparticles of the invention are advantageously usable as reinforcing filler for any type of polymeric matrix, whether the polymers be in particular thermoplastic, thermohardening, or alternatively elastomers (by way of examples polyamides, polyesters, polyolefins such as polypropylene, polyethylene, PVC, polycarbonates, polyacrylics, epoxy resins, polysiloxanes, polyurethanes or diene elastomers).

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FR2957082B1 (fr) 2010-03-05 2012-03-02 Michelin Soc Tech Pneumatique dont la bande de roulement comporte un elastomere thermoplastique.
FR2957602B1 (fr) 2010-03-19 2012-04-13 Michelin Soc Tech Composition de caoutchouc pour bande de roulement de pneumatique hiver
FR2958295B1 (fr) 2010-03-31 2012-05-04 Michelin Soc Tech Pneumatique dont la bande de roulement comporte une composition de caoutchouc comprenant une resine poly(vinylester).
FR2959744B1 (fr) 2010-05-04 2012-08-03 Michelin Soc Tech Composition de caoutchouc, utilisable pour la fabrication d'un pneumatique dont la composition comporte un amidon et un plastifiant aqueux ou hydrosoluble
FR2959745B1 (fr) 2010-05-10 2012-06-01 Michelin Soc Tech Pneumatique dont la bande de roulement comporte un elastomere thermoplastique vulcanisat (tpv).
FR2960544B1 (fr) 2010-05-27 2012-08-17 Michelin Soc Tech Bandage pneumatique dont la zone sommet est pourvue d'une couche interne reduisant les bruits de roulage
FR2960543B1 (fr) 2010-05-27 2012-06-22 Michelin Soc Tech Bandage pneumatique dont la zone sommet est pourvue d'une couche interne reduisant les bruits de roulage
FR2960567B1 (fr) 2010-05-27 2012-06-22 Michelin Soc Tech Renfort filaire composite pour pneumatique, enrobe d'un caoutchouc a propriete de barriere a l'eau amelioree
FR2961819B1 (fr) 2010-05-27 2013-04-26 Soc Tech Michelin Bandage pneumatique dont la ceinture est pourvue d'une gomme d'enrobage reduisant les bruits de roulage
FR2961516B1 (fr) 2010-06-17 2015-06-26 Michelin Soc Tech Bandage pneumatique dont la ceinture est pourvue d'une gomme d'enrobage reduisant les bruits de roulage
FR2966157B1 (fr) 2010-10-18 2012-12-14 Michelin Soc Tech Composition de caoutchouc pour bande de roulement de pneumatique
FR2970256B1 (fr) 2010-11-30 2013-01-11 Michelin Soc Tech Pneumatique comportant une sous-couche de bande de roulement a base de caoutchouc nitrile.
FR2969165B1 (fr) 2010-12-21 2014-06-06 Michelin Soc Tech Composition a base de caoutchouc naturel et de noir de carbone comprenant un hydrazide, un hydrazone ou une poly-amine
FR2969629B1 (fr) 2010-12-23 2014-10-10 Michelin Soc Tech Composition de caoutchouc pour bande de roulement de pneumatique
FR2975998B1 (fr) 2011-06-01 2013-06-14 Michelin Soc Tech Pneumatique pour vehicule dont la bande de roulement comporte une composition de caoutchouc thermo-expansible
FR2975997B1 (fr) 2011-06-01 2013-06-14 Michelin Soc Tech Pneumatique pour vehicule dont la bande de roulement comporte une composition de caoutchouc thermo-expansible
FR2979076B1 (fr) 2011-07-28 2013-08-16 Michelin Soc Tech Pneumatique pour vehicule dont la bande de roulement comporte une composition de caoutchouc thermo-expansible
JP5927862B2 (ja) * 2011-11-24 2016-06-01 日立化成株式会社 サブミクロン重合体粒子及びこれを備えた絶縁被覆導電粒子の製造方法
FR2984899B1 (fr) 2011-12-21 2014-08-15 Michelin Soc Tech Pneumatique comprenant une composition essentiellement depourvue de derive guanidique et comprenant une diamine hydroxylee
FR2984897B1 (fr) 2011-12-21 2014-08-15 Michelin Soc Tech Pneumatique comprenant une composition essentiellement depourvue de derive guanidique et comprenant une etheramine primaire
FR2984901B1 (fr) 2011-12-22 2014-01-03 Michelin Soc Tech Composition de caoutchouc comprenant un derive de cellulose
FR2984903B1 (fr) 2011-12-22 2014-05-09 Michelin Soc Tech Pneu dont la bande de roulement comporte une composition de caoutchouc thermo-expansible reduisant les bruits de roulage
FR2984904B1 (fr) 2011-12-22 2014-01-03 Michelin Soc Tech Composition de caoutchouc
FR2984692B1 (fr) 2011-12-23 2014-01-17 Michelin Soc Tech Semelle de chaussure comportant une composition de caoutchouc a base de caoutchouc nitrile-butadiene, d'une huile et d'une resine
FR2985514B1 (fr) 2012-01-10 2014-02-28 Michelin & Cie Composition de caoutchouc
FR2986531B1 (fr) 2012-02-07 2014-02-28 Michelin & Cie Composition a base de caoutchouc naturel et d'un compose poly-aldimine
FR2989090B1 (fr) 2012-04-10 2014-05-09 Michelin & Cie Composition de caoutchouc pour bande de roulement de pneumatique comportant des microparticules de sulfate de potassium
FR2990949B1 (fr) 2012-05-22 2015-08-21 Michelin & Cie Composition de caoutchouc
FR2992322B1 (fr) 2012-06-22 2015-06-19 Michelin & Cie Pneumatique pour vehicule dont la bande de roulement comporte une composition de caoutchouc thermo-expansible
FR2995609B1 (fr) 2012-07-25 2014-11-28 Michelin & Cie Pneumatique ayant une adherence sur sol mouille amelioree
FR2993895B1 (fr) 2012-07-25 2014-08-08 Michelin & Cie Composition de caoutchouc comprenant une resine a base de lignine
FR2993892B1 (fr) 2012-07-25 2014-08-08 Michelin & Cie Composition de caoutchouc comprenant une resine epoxyde et un durcisseur poly-imine
FR2993889B1 (fr) 2012-07-27 2014-08-22 Michelin & Cie Composition de caoutchouc thermo-expansible pour pneumatique
FR2996851B1 (fr) 2012-10-15 2014-11-28 Michelin & Cie Gomme interieure de pneumatique.
FR2998509A1 (fr) 2012-11-29 2014-05-30 Michelin & Cie Bandage pour vehicule dont la bande de roulement comporte une composition de caoutchouc thermo-expansible
FR2998574B1 (fr) 2012-11-29 2015-01-16 Michelin & Cie Composition de caoutchouc comprenant un elastomere dienique fortement sature
FR2998510A1 (fr) 2012-11-29 2014-05-30 Michelin & Cie Pneumatique pour vehicule dont la bande de roulement comporte une composition de caoutchouc thermo-expansible
FR2999586B1 (fr) 2012-12-17 2014-12-26 Michelin & Cie Pneumatique comportant une composition de caoutchouc comprenant un polymere epoxyde reticule par un poly-acide carboxylique
FR2999587B1 (fr) 2012-12-17 2014-12-26 Michelin & Cie Pneumatique comportant une composition de caoutchouc comprenant un elastomere epoxyde reticule par un poly-acide carboxylique
FR2999589B1 (fr) 2012-12-17 2014-12-26 Michelin & Cie Pneumatique comportant une composition de caoutchouc comprenant un elastomere epoxyde reticule par un poly-acide carboxylique
FR2999588B1 (fr) 2012-12-17 2015-02-13 Michelin & Cie Pneumatique comportant une composition de caoutchouc comprenant un elastomere epoxyde reticule par un poly-acide carboxylique
FR3005468B1 (fr) 2013-05-07 2015-05-01 Michelin & Cie Pneumatique comprenant une composition essentiellement depourvue de derive guanidique et comprenant un compose triazine et une amine primaire
FR3005470B1 (fr) 2013-05-07 2015-05-01 Michelin & Cie Pneumatique comprenant une composition essentiellement depourvue de derive guanidique et comprenant un compose triazine et un hydroxyde de metal alcalin ou alcalino-terreux
FR3009306B1 (fr) 2013-07-30 2015-07-31 Michelin & Cie Pneu dont la zone sommet est pourvue d’une couche interne reduisant les bruits de roulage
FR3009305A1 (fr) 2013-07-30 2015-02-06 Michelin & Cie Composition de caoutchouc thermo-expansible et pneumatique comportant une telle composition
FR3009557B1 (fr) 2013-08-09 2015-09-11 Michelin & Cie Elastomere dienique modifie comprenant un elastomere dienique couple par un compose aminoalcoxysilane et fonctionnalise amine en extremite de chaine et composition de caoutchouc le comprenant
FR3009558B1 (fr) 2013-08-09 2015-09-04 Michelin & Cie Elastomere dienique couple possedant une fonction silanol en milieu de chaine et fonctionnalise amine en extremite de chaine et composition de caoutchouc le comprenant
FR3010078B1 (fr) 2013-08-30 2016-10-14 Michelin & Cie Caoutchouc naturel epoxyde et modifie
FR3011241B1 (fr) 2013-09-27 2015-10-23 Michelin & Cie Elastomere dienique tribloc dont le bloc central est un bloc polyether et fonctionnalise amine en extremite de chaine
FR3011551B1 (fr) 2013-10-08 2016-10-28 Michelin & Cie Composition de caoutchouc pour bande de roulement comprenant une polynitrone
FR3012454B1 (fr) 2013-10-30 2015-12-18 Michelin & Cie Elastomere dienique modifie comprenant majoritairement un elastomere dienique couple par un compose alcoxysilane portant un groupe epoxyde et fonctionnalise amine en extremite de chaine
FR3014880B1 (fr) 2013-12-18 2015-12-25 Michelin & Cie Pneumatique pour velocipede.
FR3015502B1 (fr) 2013-12-19 2016-02-05 Michelin & Cie Pneu dont la bande de roulement comporte des elements de sculpture avec des parois laterales rigides contenant des microparticules hydrosolubles.
FR3015501B1 (fr) 2013-12-19 2017-05-26 Michelin & Cie Pneu dont la bande de roulement comporte des elements de sculpture avec des parois laterales rigides comportant un caoutchouc thermo-expansible a l'etat cru, ou caoutchouc mousse a l'etat cuit.
FR3015503B1 (fr) 2013-12-19 2016-02-05 Michelin & Cie Pneu dont la bande de roulement comporte des elements de sculpture avec des parois laterales rigides comportant des microparticules d'oxyde ou carbure metallique.
FR3015486B1 (fr) 2013-12-23 2017-02-10 Michelin & Cie Procede de depolymerisation du caoutchouc naturel en solution par metathese
FR3022247B1 (fr) 2014-06-13 2018-01-19 Compagnie Generale Des Etablissements Michelin Procede de preparation d'un caoutchouc naturel
FR3027027B1 (fr) 2014-10-13 2016-12-09 Michelin & Cie Produit renforce comprenant une composition comprenant un systeme oxyde metallique et derive d'acide stearique equilibre et pneumatique comprenant ledit produit renforce
FR3027025B1 (fr) 2014-10-13 2016-12-09 Michelin & Cie Produit renforce comprenant une composition a faible taux de soufre et pneumatique comprenant ledit produit renforce
CN107001708A (zh) 2014-11-28 2017-08-01 米其林集团总公司 橡胶组合物
FR3030543B1 (fr) 2014-12-22 2017-01-13 Michelin & Cie Pneumatique comprenant une composition comprenant un derive d'acrylate polyfonctionnel et un peroxyde
FR3030544B1 (fr) 2014-12-22 2017-01-13 Michelin & Cie Pneumatique comprenant une composition comprenant un derive d'acrylate polyfonctionnel et un peroxyde
FR3030545B1 (fr) 2014-12-22 2018-05-25 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc comprenant une resine hydrocarbonee specifique
WO2016104815A1 (en) 2014-12-26 2016-06-30 Compagnie Generale Des Etablissements Michelin A tire having a tread comprising rubber composition comprising short fibers
FR3033329A1 (fr) 2015-03-05 2016-09-09 Michelin & Cie Pneumatique comprenant une composition comprenant un derive du diacrylate de zinc et un peroxyde
FR3033569B1 (fr) 2015-03-09 2017-03-10 Michelin & Cie Objet pneumatique pourvu d'une couche elastomere a base d'un elastomere thermoplastique sous forme d'un copolymere a blocs (a-b-(a-co-b)) n-b-c
FR3033571B1 (fr) 2015-03-09 2017-03-10 Michelin & Cie Objet pneumatique pourvu d'une couche elastomere etanche aux gaz de gonflage a base d'un coupage d'elastomeres thermoplastiques sous forme de copolymeres a blocs
FR3033567B1 (fr) 2015-03-09 2017-03-10 Michelin & Cie Objet pneumatique pourvu d'une couche elastomere etanche aux gaz de gonflage a base d'un elastomere thermoplastique sous forme d'un copolymere a blocs
FR3033568B1 (fr) 2015-03-09 2017-03-10 Michelin & Cie Objet pneumatique pourvu d'une couche elastomere etanche aux gaz de gonflage a base d'un elastomere thermoplastique sous forme d'un copolymere a blocs (a-b-b) n-b-c
EP3289011B1 (en) 2015-04-30 2019-03-20 Compagnie Générale des Etablissements Michelin A heat-expandable rubber composition
WO2016194213A1 (en) 2015-05-29 2016-12-08 Compagnie Generale Des Etablissements Michelin A rubber composition
WO2016194215A1 (en) 2015-05-29 2016-12-08 Compagnie Generale Des Etablissements Michelin A rubber composition
WO2016194214A1 (en) 2015-05-29 2016-12-08 Compagnie Generale Des Etablissements Michelin A rubber composition
FR3038315B1 (fr) 2015-07-02 2017-07-21 Michelin & Cie Elastomere dienique modifie a ip reduit et composition le contenant
FR3038314B1 (fr) 2015-07-02 2017-07-21 Michelin & Cie Elastomere dienique modifie a ip reduit et composition de caoutchouc le contenant
FR3039558B1 (fr) 2015-07-31 2017-07-21 Michelin & Cie Composition de caoutchouc comprenant une resine hydrocarbonee de faible temperature de transition vitreuse
WO2017056330A1 (en) 2015-09-30 2017-04-06 Generale Des Etablissements Michelin-Michelin Compagnie A tire comprising a rubber composition
FR3042193A1 (fr) 2015-10-08 2017-04-14 Michelin & Cie Elastomere dienique possedant une fonction en milieu de chaine et composition de caoutchouc le contenant
FR3043678B1 (fr) 2015-11-17 2018-01-05 Compagnie Generale Des Etablissements Michelin Procede de preparation d'un caoutchouc naturel stabilise.
WO2017104781A1 (en) 2015-12-17 2017-06-22 Compagnie Generale Des Etablissements Michelin A tire comprising a tread
FR3046603B1 (fr) 2016-01-11 2017-12-29 Michelin & Cie Procede de modification d'un caoutchouc naturel et caoutchouc naturel modifie
FR3047735A1 (fr) 2016-02-12 2017-08-18 Michelin & Cie Composition de caoutchouc comprenant une silice essentiellement spherique et peu structuree
WO2017170654A1 (en) 2016-03-31 2017-10-05 Compagnie Generale Des Etablissements Michelin A tire having a tread comprising a rubber composition
EP3436287B1 (en) 2016-03-31 2019-12-25 Compagnie Générale des Etablissements Michelin A tire having a tread comprising a rubber composition
FR3049607B1 (fr) 2016-03-31 2018-03-16 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc comprenant une resine hydrocarbonee specifique
FR3056595A1 (fr) 2016-09-29 2018-03-30 Compagnie Generale Des Etablissements Michelin Bande de roulement pour pneumatique comportant un elastomere thermoplastique
FR3056984A1 (fr) 2016-09-30 2018-04-06 Compagnie Generale Des Etablissements Michelin Procede d'obtention d'un coagulum et d'un melange maitre d'elastomere et de charge polymerique
FR3059003A1 (fr) 2016-11-18 2018-05-25 Compagnie Generale Des Etablissements Michelin Pneumatique pourvu d'un flanc externe a base d'au moins un melange d'elastomere dienique et d'un amide
FR3059669A1 (fr) 2016-12-07 2018-06-08 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc comprenant un elastomere dienique, un derive de polyacrylate et d'un elastomere thermoplastique specifique
FR3060592A1 (fr) 2016-12-15 2018-06-22 Compagnie Generale Des Etablissements Michelin Pneumatique comportant une composition de caoutchouc comprenant un polymere porteur d'un groupement diene conjugue reticule par un dienophile
JP2020502358A (ja) 2016-12-20 2020-01-23 コンパニー ゼネラール デ エタブリッスマン ミシュラン 変性ジエンエラストマーを含むゴム組成物
FR3061186B1 (fr) 2016-12-22 2019-05-24 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc comprenant une resine hydrocarbonee specifique
FR3064640A1 (fr) 2017-04-04 2018-10-05 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc a base de resine renforcante et d'un derive d'aminobenzoate
FR3065001A1 (fr) 2017-04-11 2018-10-12 Compagnie Generale Des Etablissements Michelin Elastomere dienique modifie par un groupement comprenant un atome de silicium, procede pour sa synthese et composition de caoutchouc le contenant
WO2019002771A1 (fr) 2017-06-30 2019-01-03 Compagnie Generale Des Etablissements Michelin Compositions de caoutchouc ayant une bonne tenue au fluage
EP3697840B1 (fr) 2017-10-20 2021-12-01 Compagnie Générale des Etablissements Michelin Composition de caoutchouc comprenant une resine de polyphenylene ether comme plastifiant
FR3074183B1 (fr) 2017-11-30 2020-07-24 Michelin & Cie Composition de caoutchouc a haut module comprenant un systeme de reticulation au soufre efficace
EP3727880A1 (fr) 2017-12-19 2020-10-28 Compagnie Generale Des Etablissements Michelin Composition comprenant un compose polysulfure
WO2019122687A1 (fr) 2017-12-19 2019-06-27 Compagnie Generale Des Etablissements Michelin Composition comprenant un compose polysulfure
WO2019122686A1 (fr) 2017-12-19 2019-06-27 Compagnie Generale Des Etablissements Michelin Produit renforce comprenant une composition comprenant un compose polysulfuré et pneumatique comprenant ledit produit renforce
CA3084127A1 (fr) 2017-12-21 2019-06-27 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc reticulee par un diacide et comprenant un compose phenolique
KR102468899B1 (ko) 2017-12-22 2022-11-22 꽁빠니 제네날 드 에따블리세망 미쉘린 적어도 2개의 트리알콕시실릴 그룹을 포함하는 화합물, 디엔 엘라스토머 작용화제로서의 이의 용도, 개질된 디엔 엘라스토머 및 개질된 디엔 엘라스토머를 함유하는 조성물
CN111566147B (zh) 2017-12-28 2023-07-21 米其林集团总公司 在液相中制备橡胶配混物的方法和装置
FR3078336B1 (fr) 2018-02-27 2020-09-18 Arkema France Utilisation de l'oxyde de magnesium dans la fabrication de pneumatiques
FR3078337B1 (fr) 2018-02-27 2020-08-07 Arkema France Utilisation de l'oxyde de magnesium pour la reticulation de polymeres
FR3079838B1 (fr) 2018-04-09 2020-12-18 Michelin & Cie Composition de caoutchouc comprenant une charge renforcante a faible surface specifique
FR3079843B1 (fr) 2018-04-09 2020-10-23 Michelin & Cie Pneumatique avec bourrelets comprenant une composition de caoutchouc specifique
FR3081873B1 (fr) 2018-05-31 2020-05-22 Compagnie Generale Des Etablissements Michelin Pneumatique pourvu d'un flanc externe comportant un ou plusieurs elastomeres thermoplastiques et un ou plusieurs elastomeres dieniques synthetiques
FR3081875B1 (fr) 2018-05-31 2020-05-22 Compagnie Generale Des Etablissements Michelin Pneumatique pourvu d'un flanc externe comportant un ou plusieurs elastomeres thermoplastiques et un ou plusieurs elastomeres dieniques synthetiques
FR3081877B1 (fr) 2018-05-31 2020-05-22 Compagnie Generale Des Etablissements Michelin Pneumatique pourvu d'un flanc externe comportant un ou plusieurs elastomeres thermoplastiques et un ou plusieurs elastomeres dieniques synthetiques
FR3081874B1 (fr) 2018-05-31 2020-07-10 Compagnie Generale Des Etablissements Michelin Pneumatique pourvu d'un flanc externe comportant un ou plusieurs elastomeres thermoplastiques et un ou plusieurs elastomeres dieniques synthetiques
FR3081876B1 (fr) 2018-05-31 2020-05-22 Compagnie Generale Des Etablissements Michelin Pneumatique pourvu d'un flanc externe comportant un ou plusieurs elastomeres thermoplastiques et un ou plusieurs elastomeres dieniques synthetiques
FR3082847B1 (fr) 2018-06-21 2020-06-05 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc comprenant un elastomere fonctionnel
FR3082848B1 (fr) 2018-06-21 2020-12-11 Michelin & Cie Composition de caoutchouc comprenant une poudrette de caoutchouc specifique
FR3083242B1 (fr) 2018-07-02 2020-06-12 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc a base de resine epoxyde et d’un derive d’aminobenzoate
FR3088335A3 (fr) 2018-11-08 2020-05-15 Michelin & Cie Composition de caoutchouc a base d’un elastomere dienique modifie
FR3088333A3 (fr) 2018-11-08 2020-05-15 Michelin & Cie Composition de caoutchouc a base d'un elastomere dienique modifie
FR3088336A3 (fr) 2018-11-08 2020-05-15 Michelin & Cie Composition de caoutchouc a base d'un elastomere dienique modifie
FR3088331A3 (fr) 2018-11-08 2020-05-15 Michelin & Cie Copolymere dienique a blocs comprenant un bloc polyether et composition de caoutchouc le contenant
FR3088644A3 (fr) 2018-11-15 2020-05-22 Michelin & Cie Composition de caoutchouc de bande de roulement de pneumatique
FR3088646A3 (fr) 2018-11-15 2020-05-22 Michelin & Cie Pneumatique pourvu d'une bande de roulement
FR3089149A3 (fr) 2018-12-03 2020-06-05 Michelin & Cie Stratifié comprenant une couche de liaison comprenant un initiateur radicalaire
WO2020128257A1 (fr) 2018-12-19 2020-06-25 Compagnie Generale Des Etablissements Michelin Pneumatique comprenant une composition de caoutchouc comprenant un elastomere thermoplastique et une poudrette de caoutchouc
FR3090651A3 (fr) 2018-12-19 2020-06-26 Michelin & Cie Pneumatique comprenant une composition de caoutchouc comprenant un elastomere thermoplastique et une poudrette de caoutchouc
WO2020128256A1 (fr) 2018-12-19 2020-06-25 Compagnie Generale Des Etablissements Michelin Pneumatique comprenant une composition de caoutchouc comprenant un pro-oxydant et une poudrette de caoutchouc
FR3090644A3 (fr) 2018-12-21 2020-06-26 Michelin & Cie Produit renforce comprenant une composition comportant un compose polysulfuré
WO2020128261A1 (fr) 2018-12-21 2020-06-25 Compagnie Generale Des Etablissements Michelin Produit renforce comprenant une composition comportant un compose polysulfuré
WO2020128260A1 (fr) 2018-12-21 2020-06-25 Compagnie Generale Des Etablissements Michelin Composition de caouthcouc comprenant un compose polysulfuré
FR3090647A3 (fr) 2018-12-21 2020-06-26 Michelin & Cie Composition de caouthcouc comprenant un compose polysulfuré
FR3096052B1 (fr) 2019-05-14 2021-04-23 Michelin & Cie Pneumatique pourvu de flancs externes
FR3099168B1 (fr) 2019-07-26 2021-07-02 Michelin & Cie Pneu incorporant une composition de caoutchouc comprenant une résine hydrocarbure spécifique
FR3099166B1 (fr) 2019-07-26 2022-02-11 Michelin & Cie Pneu incorporant une composition de caoutchouc comprenant une résine hydrocarbure spécifique
FR3099767B1 (fr) 2019-08-07 2021-07-09 Michelin & Cie Composition de caoutchouc a base d’au moins un compose ayant une fonction imidazolidinone n-substituée
FR3101877B1 (fr) 2019-10-10 2022-06-17 Michelin & Cie Composition de caoutchouc comprenant un élastomère diénique comprenant des fonctions carbonates
FR3103490B1 (fr) 2019-11-21 2021-10-22 Michelin & Cie Composition de caoutchouc comprenant un polybutadiene fonctionnalise
FR3103775B1 (fr) 2019-11-28 2021-11-05 Michelin & Cie Chenille en caoutchouc comprenant des fibres d’alcool polyvinylique
FR3103819B1 (fr) 2019-11-28 2023-07-21 Michelin & Cie Bandage hors la route comprenant des fibres d’alcool polyvinylique
FR3104593B1 (fr) 2019-12-12 2021-12-03 Michelin & Cie Système de réticulation et composition de caoutchouc diénique le comprenant
FR3104590B1 (fr) 2019-12-12 2021-12-03 Michelin & Cie Composite comprenant un élément de renfort et une composition de caoutchouc
FR3104592B1 (fr) 2019-12-12 2021-12-03 Michelin & Cie Système de réticulation et composition de caoutchouc diénique le comprenant
FR3104591B1 (fr) 2019-12-16 2021-11-12 Michelin & Cie Produit renforcé à base d’au moins un élément de renfort métallique et d’une composition de caoutchouc.
FR3105239B1 (fr) 2019-12-18 2021-12-03 Michelin & Cie Procédé de préparation d’une composition de caoutchouc comprenant une poudrette de caoutchouc
FR3108910B1 (fr) 2020-04-07 2023-06-02 Michelin & Cie Composition de caoutchouc comprenant du polyethylene a basse temperature de fusion
FR3109156B1 (fr) 2020-04-09 2023-10-06 Michelin & Cie Composition de caoutchouc comprenant du polyamide a basse temperature de fusion
FR3111138B1 (fr) 2020-06-04 2022-07-08 Michelin & Cie Composition de caoutchouc.
FR3111137B1 (fr) 2020-06-04 2022-04-29 Michelin & Cie Mélange de caoutchouc
FR3111636B1 (fr) 2020-06-18 2022-08-26 Michelin & Cie Composition élastomérique comprenant un composé phénolique et un composé de la famille des oses
FR3115541B1 (fr) 2020-10-23 2023-10-20 Michelin & Cie Produit renforcé à base d’au moins un élément de renfort métallique et d’une composition de caoutchouc.
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CN101484508B (zh) 2012-11-28
CN101484508A (zh) 2009-07-15
WO2008003434A1 (fr) 2008-01-10
FR2903411B1 (fr) 2012-11-02
US8883929B2 (en) 2014-11-11
FR2903411A1 (fr) 2008-01-11
JP2009542826A (ja) 2009-12-03
EP2041207B1 (fr) 2011-11-23
JP5484901B2 (ja) 2014-05-07
ATE534690T1 (de) 2011-12-15
EP2041207A1 (fr) 2009-04-01

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