Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
  • B60C1/0016—Compositions of the tread
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
  • B60C1/0041—Compositions of the carcass layers
• • 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
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
  • C08J5/041—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with metal fibres
• • 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
• • 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
  • B60C2001/0066—Compositions of the belt layers
• • 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
  • B60C2001/0083—Compositions of the cap ply layers
• • 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
  • C08J2315/00—Characterised by the use of rubber derivatives
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • 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
  • C08K5/07—Aldehydes; Ketones
• • 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
  • C08K5/13—Phenols; Phenolates
  • C08K5/134—Phenols containing ester 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
  • C08K5/17—Amines; Quaternary ammonium compounds
  • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups

Definitions

• Rubber composition based on at least one functionalized elastomer comprising polar functional groups and a specific phenolic compound
• the present invention relates to rubber compositions based on at least one elastomer comprising polar functional groups, as well as to composites, finished or semi-finished articles, and tires comprising these compositions.
• the vulcanization systems have been improved over the years, in association with the processes for preparing the rubber compositions in order to overcome the drawbacks mentioned above.
• the compositions are often complex and include, in addition to molecular sulfur, or a molecular sulfur donor, vulcanization accelerators, activators, and optionally vulcanization retarders.
• the reinforcing plies which in a known manner comprise a rubber mixture and reinforcing cables, for example metallic, generally require specific formulations for the rubber mixture, in particular the need for a rate of high sulfur and zinc oxide, a small amount of stearic acid, the presence of cobalt salt, the use of accelerator with long delay phase in order, in particular, to ensure the adhesion function.
• these vulcanization systems with a high sulfur content constitute a strong constraint during the production of semi-finished products, in particular to avoid premature crosslinking.
• compositions of the prior art could be prepared in a simplified manner compared to the compositions of the prior art, and that these compositions could have improved adhesion properties.
• - Gi represents a hydroxyl, carboxyl, alkoxyl or hydrogen atom group
• - G2 represents a hydroxyl group or the hydrogen atom
• - G3 represents the hydrogen atom or a group chosen from hydroxyl, carboxyl, hydrogenocarbonyl, alkyl, carboxylalkyl, carboxylalkenyl, carbonylalkyl, aryl, aryloxy, arylthioxy, arylcarbonyl, amino, aminoalkyl groups;
• At least one of the substituents Gi to G3 comprises an oxygen atom
• said rubber composition not simultaneously comprising an alkyHmidazole and a polycarboxylic acid of general formula (P1) : A representing a covalent bond or a hydrocarbon group comprising at least 1 carbon atom, optionally substituted and optionally interrupted by one or more heteroatoms.
• general formula (I) comprises at least one aromatic ring carrying at least two hydroxyl functions in meta position relative to each other, the two ortho positions of at least one of the hydroxyl functions being unsubstituted.
• composition according to the preceding embodiment in which at least two aromatic rings of the phenolic compound of general formula (I) carry at least two hydroxyl functions in meta position relative to each other, the two ortho d positions 'at least one of the hydroxyl functions of at least one aromatic ring being unsubstituted.
• composition according to embodiment 1 in which the phenolic compound of general formula (I) is chosen from the group consisting of resorcinol, phloroglucinol, 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide, 2,2 ', 4,4'-tetrahydroxybenzophenone and mixtures of these compounds.
• At least one of the two phenolic compounds comprises at least two hydroxyl functions.
• a composition according to any one of the preceding embodiments also comprising at least one polyaldehyde.
• the functionalized elastomer is chosen from the group consisting of functionalized diene elastomers, functionalized olefin elastomers and their mixtures.
• NR natural rubber
• IR synthetic polyisoprenes
• BR polybutadienes
• butadiene copolymers butadiene copolymers
• isoprene copolymers and mixtures of these elastomers.
• butadiene and isoprene copolymers are chosen from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR), copolymers of isoprene-butadiene-styrene (SBIR) and mixtures of such copolymers.
• SBR butadiene-styrene copolymers
• BIR isoprene-butadiene copolymers
• SIR isoprene-styrene copolymers
• SBIR copolymers of isoprene-butadiene-styrene
• composition according to the preceding embodiment in which the polar functional groups of the functionalized elastomer comprise at least one group chosen from hydroxyl, carbonyl, imine and epoxide groups, preferably chosen from primary aldimine, aldehyde and epoxide groups, preferably epoxy.
• composition according to any one of the preceding embodiments in which said composition is devoid of cobalt salts or contains less than 1 phr thereof.
• a rubber composition according to any one of the preceding embodiments said composition being devoid of zinc or zinc oxide, or else comprising only a very small amount, preferably less than 1 phr, preferably less of 0.5 phr, more preferably less than 0.2 phr.
• reinforcing element comprises a metal surface.
• metal surface of said reinforcing element comprises a metal chosen from the group consisting of iron, copper, zinc, tin, aluminum, cobalt, nickel and the alloys comprising at least one of these metals.
• a finished or semi-finished article comprising a composition according to any one of
• achievements 1 to 20 or a composite according to any one of achievements 21 to 25.
• a tire comprising a composition according to any one of embodiments 1 to
• a tire comprising an internal layer comprising a composition according to any one of embodiments 1 to 20 or a composite according to any one of the embodiments
• composition based on is meant a composition comprising the mixture and / or the in situ reaction product of the various constituents used, some of these constituents being able to react and / or being intended to react with each other, less partially, during the various stages of manufacturing the composition; the composition thus being able to be in the fully or partially crosslinked state or in the non-crosslinked state.
• part by weight per hundred parts by weight of elastomer (or phr), it is understood within the meaning of the present invention, the part, by mass per hundred parts by mass of elastomer.
• any range of values designated by the expression “between a and b” represents the range of values going from more than a to less than b (ie limits a and b excluded) while any range of values designated by the expression “from a to b” signifies the range of values going from a to b (that is to say including the strict limits a and b).
• the compounds comprising carbon mentioned in the description can be of fossil origin or bio-based. In the latter case, they can be, partially or totally, from from biomass or obtained from renewable raw materials from biomass. Are concerned in particular polymers, plasticizers, fillers, etc.
• elastomer or rubber comprising polar functional groups
• polar functional groups any type of elastomer in the sense known to those skilled in the art, whether a homopolymer or a block copolymer, random or other, having elastomeric properties, functionalized, that is to say bearing functional groups chosen from polar functional groups.
• the rubber composition in accordance with the invention may contain a single functionalized elastomer or a mixture of several functionalized elastomers (which will then be noted in the singular as being "functionalized elastomer" to represent the sum of the functionalized elastomers of the composition), the functionalized elastomer which can be used in combination with any type of non-functionalized elastomer, for example diene, or even with elastomers other than diene elastomers.
• the functionalized elastomer is predominant in the rubber composition according to the invention, that is to say it is either the only elastomer or it is the one which represents the largest mass, among all of the elastomers of the composition.
• the rubber composition comprises from more than 50 to 100 phr, preferably from 70 to 100 phr, of elastomer functionalized in blending with 0 to 50 phr and preferably 0 to 30 phr , of one or more other elastomers, minority, not functionalized.
• the composition comprises, for all of the 100 phr of elastomer, one or more functionalized elastomers comprising polar functional groups.
• the functionalized elastomer is preferably chosen from the group consisting of functionalized diene elastomers, functionalized olefin elastomers and their mixtures.
• the functionalized elastomer is chosen from functionalized olefin elastomers and mixtures of these.
• the functionalized elastomer is chosen from functionalized diene elastomers and mixtures of these.
• the glass transition temperature Tg of the elastomers described in the present text is measured in a known manner by DSC (Differential Scanning Calorimetry), for example and unless otherwise specified, according to standard ASTM D3418 of 1999.
• Size Exclusion Chromatography (SEC) is used to determine the macrostructure of polymers. The SEC allows to separate the SEC
• the macromolecules are separated according to their hydrodynamic volume, the most
• the SEC makes it possible to apprehend the molecular weight distribution of a polymer.
• Preparation of the polymer There is no particular treatment of the polymer sample before analysis. This is simply dissolved in tetrahydrofuran (THF) which contains 1% vol. diisopropylamine, 1% vol. of triethylamine and 0.1% vol. distilled water, at a concentration of about 1 g / l. Then the solution is filtered on a 0.45 gm porosity filter before injection.
• THF tetrahydrofuran
• the apparatus used is a "WATERS alliance" chromatograph.
• the eluting solvent is tetrahydrofuran which contains 1% vol. diisopropylamine, 1% vol. triethylamine.
• the flow rate is 0.7 ml / min, the system temperature 35 ° C and the analysis time 90 min.
• a set of four WATERS columns is used in series, with the trade names "STYRAGEL HMW7", “STYRAGEL HMW6E” and two “STYRAGEL HT6E".
• the volume injected with the solution of the polymer sample is 100 m ⁇ .
• the detector is a "WATERS 2410" differential refractometer and the software for processing the chromatographic data is the "WATERS EMPOWER" system.
• diene-type elastomer By functionalized diene-type elastomer, it is recalled that an elastomer which is derived at least in part (ie a homopolymer or a copolymer) from diene monomers (monomers carrying two carbon-carbon double bonds, conjugate) must be understood. or not), this polymer being functionalized, that is to say that it carries functional groups chosen from polar functional groups.
• a first characteristic of functionalized diene elastomers is therefore to be diene elastomers.
• diene elastomers can be classified into two categories: "essentially unsaturated” or "essentially saturated”. We generally mean by
• essentially unsaturated means a diene elastomer derived at least in part from conjugated diene monomers, having a rate of units or units of diene origin (conjugated dienes) which is greater than 15% (% by moles); This is how diene elastomers such as butyl rubbers or copolymers of dienes and alpha-olefins of the EPDM type do not enter into the preceding definition and can be qualified in particular as “essentially saturated” diene elastomers (content of reasons of weak or very weak diene origin, always less than 15%).
• the diene elastomers included in the composition according to the invention are preferably essentially unsaturated.
• the other monomer can be ethylene, an olefin or a diene, conjugated or not.
• conjugated dienes having from 4 to 12 carbon atoms are suitable, in particular 1,3 dienes, such as in particular 1,3 butadiene and isoprene.
• olefins suitable are vinyl aromatic compounds having 8 to 20 carbon atoms and aliphatic crmonoolefins having 3 to 12 carbon atoms.
• vinyl aromatic compounds examples include styrene, ortho-, meta-, para-methylstyrene, the commercial "vinyl-toluene” mixture, para-tert-butylstyrene.
• aliphatic chloroolefins in particular, acyclic aliphatic crmonoolefins having from 3 to 18 carbon atoms are suitable.
• the functionalized diene elastomer is preferably a diene elastomer of the highly unsaturated type, in particular a diene elastomer chosen from the group consisting of natural rubber (NR), synthetic polyisoprenes (IR), polybutadienes (BR), copolymers butadiene, isoprene copolymers and mixtures of these elastomers.
• Such copolymers are more preferably chosen from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR), isoprene copolymers- butadiene-styrene (SBIR) and mixtures of such copolymers.
• SBR butadiene-styrene copolymers
• BIR isoprene-butadiene copolymers
• SIR isoprene-styrene copolymers
• SBIR isoprene copolymers- butadiene-styrene
• the above diene elastomers can, for example, be block, statistical, sequenced, microsequenced, and be prepared in dispersion or in solution; they can be coupled and / or starred or else functionalized with a coupling and / or star-forming agent or
• polybutadienes are suitable and in particular those having a content of -1,2 units between 4% and 80% or those having a cis%, 4 content greater than 80%, polyisoprenes, butadiene-styrene copolymers and in particular those having a styrene content of between 5% and 50% by weight and more particularly between 20% and 40%, a content of -1,2 bonds of the butadiene part of between 4% and 65%, a content in trans% bonds, 4 of between 20% and 80%, butadiene-isoprene copolymers and in particular those having an isoprene content of between 5% and 90% by weight and a glass transition temperature of -40 ° C.
• isoprene-styrene copolymers and in particular those having a styrene content of between 5% and 50% by weight and a Tg of between -25 ° C and -50 ° C.
• butadiene-styrene-isoprene copolymers those which have a styrene content of between 5% and 50% by weight and more particularly between 10% and 40% and an isoprene content of between 15% and 60% are particularly suitable.
• Olefinic elastomers By elastomer of the functionalized olefin type, it is recalled that an elastomer carrying functional groups chosen from polar functional groups must be understood, and the elastomeric chain of which is a carbon chain mainly comprising olefinic monomer units denoted O.
• the monomers O can come from any olefin known to those skilled in the art, such as, for example, ethylene, propylene, butylene, isobutylene, these monomers being
• O is an ethylene unit [-CH2-CH2-], and in this preferential case,
• the functionalized olefin elastomer is a functionalized ethylenic elastomer.
• the molar level of O is greater than 50%. More specifically, the molar level of O is between 50 and 95%, preferably between 65 and 85%.
• the olefin elastomer within the meaning of the present invention is therefore a copolymer also comprising from 5 to 50 mol% of non-olefinic units, that is to say different from O.
• non-olefinic units consist in part or in whole of units carrying functional groups, denoted R, necessary for the needs of the invention.
• the level (molar%) of motif R of the functionalized olefin elastomers described above can vary widely depending on the particular embodiments of the invention, preferably in a range of 0.1% to 50%, preferably in a range from 0.3% to 50%, more preferably in a range from 0.3% to 30%, and very preferably in a range from 2.5 to 30%.
• the level of R units is less than 0.1%, the targeted technical effect is likely to be insufficient while above 50%, the elastomer would no longer be predominantly olefinic.
• non-olefinic units are not entirely R units, other units, denoted A ′ are present in the carbon chain so that the total molar ratio represented by the monomers O, R and A ′ is equal to 100%.
• the non-olefinic monomers useful for the preparation of functionalized olefinic elastomers can be chosen from non-olefinic monomers which do not lead to unsaturations and the monomers which, once polymerized, lead to unsaturations carried by the elastomeric chain (other than diene monomers ).
• the non-olefinic monomers which do not lead to unsaturations are essentially vinyl and acrylic / methacrylic monomers.
• such monomers can be chosen from styrene, vinyl acetate, vinyl alcohol, acrylonitrile, methyl acrylate, methyl methacrylate, these monomers being optionally substituted by alkyl, aryl or d groups. 'other functionalized groups.
• non-diene monomers useful for the preparation of olefinic elastomers carrying unsaturations by copolymerization are all those known to those skilled in the art for forming unsaturated elastomers, such as for example dicyclopentadienyloxyethyl methacrylate.
• Polar functional groups such as for example dicyclopentadienyloxyethyl methacrylate.
• the rubber composition is based on at least one functionalized elastomer comprising polar functional groups.
• polar functional groups in the elastomer allows its crosslinking with the phenolic compound of general formula (I) independently of the rest of the structure of the elastomer, for example diene or olefinic, the whole also having adhesion properties. improved.
• polar functional group in the sense of the present invention a functional group having a non-zero dipole moment, resulting from opposite charges (that is to say having positive partial charges and negative partial charges) arranged asymmetrically.
• the polar bonds in the polar functional group can for example be bonds between carbon atoms and other atoms having a relatively high electronegativity, such as O, N, F and Cl.
• the polar functional groups of the functionalized elastomer comprise at least one atom chosen from halogens, oxygen, and nitrogen.
• the polar functional groups of the functionalized elastomer comprise a group chosen from hydroxyl, carbonyl, imine and epoxide groups.
• hydroxyl group is meant a group of formula ⁇ H.
• carbonyl group is meant a group comprising a carbon atom linked by a double bond to an oxygen atom.
• imine group is meant a group comprising a carbon atom linked by a double bond to a nitrogen atom.
• epoxy group is meant a group comprising an oxygen atom bridged on a carbon-carbon bond.
• the functional groups present in the elastomer are obtained in a manner known to those skilled in the art by copolymerization or by post-polymerization modification, and are either carried directly by the skeleton of the chain, or carried by a lateral group according to the mode d 'obtaining.
• the functionalized elastomer of the rubber composition according to the invention comprises at least one group chosen from the primary aldimine, aldehyde and epoxide, preferably epoxide, groups.
• the functionalized elastomer comprising polar functional groups is preferably a functionalized elastomer comprising epoxy groups.
• the functionalized elastomers comprising epoxy groups indiscriminately called “epoxidized elastomers” or “epoxy functionalized elastomers”, are, in known manner, solid at room temperature (20 ° C); by solid is meant any substance which does not have the capacity to take term, at the latest after 24 hours, under the sole effect of gravity and at room temperature (20 ° C), the shape of the container which contains it .
• the epoxidation rate (molar%) of the epoxidized elastomers can vary to a large extent according to the particular embodiments of the invention, preferably in a range of 0.1% to 80%, preferably in a range of 0, 1% to 50%, more preferably in a range from 0.3% to 50%.
• the epoxidation rate is less than 0.1%, the targeted technical effect is likely to be insufficient, while above 80%, the intrinsic properties of the polymer are degraded.
• the functionalization rate in particular
• epoxidation is more preferably within a range of 0.3% to 30%, preferably within a range of 2.5% to 30%.
• the epoxidized diene elastomers can for example be obtained in a known manner by epoxidation of the equivalent non-epoxidized diene elastomer, for example by processes based on chlorohydrin or bromohydrin or processes based on hydrogen peroxides, of alkyl hydroperoxides or peracids (such as peracetic acid or performic acid), see in particular Kautsch. Kunststoff Kunststoffst. 2004, 57 (3), 82.
• the epoxy functions are then in the polymer chain.
• ENR epoxidized natural rubbers
• ENRs are for example sold under the names “ENR-25” and “ENR-50” (respective epoxidation rates of 25% and 50%) by the company Guthrie Polymer.
• Epoxidized BRs are also well known, sold for example by the company Sartomer under the name “Poly Bd” (for example “Poly Bd 605E”).
• Epoxidized SBRs can be prepared by epoxidation techniques well known to those skilled in the art.
• Diene elastomers bearing epoxy groups have been described for example in US 2003/120007 or EP 0763564, US 6903165 or EP 1403287.
• the epoxidized diene elastomer is chosen from the group consisting of epoxidized natural rubbers (NR) (abbreviated “ENR”), epoxidized synthetic polyisoprenes (IR), epoxidized polybutadienes (BR) preferably having a rate of bonds cis-1,4 greater than 90%, epoxidized butadiene-styrene copolymers (SBR) and mixtures of these elastomers.
• NR epoxidized natural rubbers
• EMR epoxidized synthetic polyisoprenes
• BR epoxidized polybutadienes
• SBR epoxidized butadiene-styrene copolymers
• the epoxidized diene elastomers can also have pendant epoxy functions. In this case, they can be obtained either by post-polymerization modification (see for example J. Appl. Polym. Sci. 1999, 73, 1733), or by radical copolymerization of the diene monomers with monomers carrying epoxy functions, in particular the esters of methacrylic acid comprising epoxy functions, such as for example glycidyl methacrylate (this radical polymerization, in particular in mass, in solution or in dispersed medium - in particular dispersion, emulsion or suspension - is well known to those skilled in the art of the synthesis of polymers, let us quote for example the following reference : Macromolecules 1998, 31, 2822) or by the use of nitrile oxides carrying epoxy functions.
• document US20110098404 describes the emulsion copolymerization of 1,3 butadiene, styrene and glycidyl methacrylate.
• Epoxidized olefinic elastomers and methods for obtaining them are well known to those skilled in the art. Olefinic elastomers bearing epoxy groups have been described for example in documents EP 0247580 or US 5576080.
• the company Arkema offers commercially, epoxidized polyethylenes under the trade names "Lotader AX8840" and "Lotader AX8900".
• the epoxide function can be carried directly by the carbon skeleton, and is then mainly obtained by epoxidation of carbon-carbon double bonds initially present after copolymerization.
• This epoxidation of unsaturated polymers is well known to those skilled in the art, and can be carried out, for example, by methods based on chlorohydrin or bromohydrin, by direct oxidation methods or by methods based on peroxides. hydrogen, alkyl hydroperoxides or peracids (such as peracetic acid or performic acid).
• the epoxide function can also be pendant and is then either already present in a monomer involved in the copolymerization with olefin (this monomer can be, for example, glycidyl methacrylate, allylglycidylether or vinyl glycidylether), or obtained by post-copolymerization modification of a pendant function.
• this monomer can be, for example, glycidyl methacrylate, allylglycidylether or vinyl glycidylether
• Epoxidized olefinic elastomers have a Tg in the vast majority of cases which is negative (that is to say less than 0 ° C).
• the epoxidized olefinic elastomers have a number average molar mass (Mn) of at least 10,000 g / mol, preferably at least 15,000 g / mol and at most 1,500,000 g / mol.
• Mn number average molar mass
• Ip polydispersity index
• the olefinic elastomer comprising epoxy functions is therefore a copolymer having at least 50% (in moles) of olefin monomer units, and with a number of different monomer units greater than or equal to 2, preferably from 2 to 5, and more preferably from 2 or 3.
• This copolymer can be obtained by copolymerization or by post-polymerization modification of an elastomer.
• the epoxy functions present in the olefinic copolymer, obtained by copolymerization or by post-polymerization modification, will either be carried directly by the skeleton of the chain, or carried by a side group depending on the method of production, for example by epoxidation or any other modification diene functions present in the elastomeric chain after
• any type of reinforcing filler known for its capacity to reinforce a rubber composition which can be used for the manufacture of tires for example an organic filler such as carbon black, an inorganic reinforcing filler such as silica, or a cutting of these two types of filler, in particular a cutting of carbon black and silica.
• carbon blacks are suitable, in particular blacks of the HAF, ISAF, SAF type conventionally used in tires (so-called pneumatic grade blacks).
• carbon blacks reinforcing series 100, 200 or 300 ASTM grades
• the carbon blacks could for example already be incorporated into an isoprene elastomer in the form of a masterbatch (see for example applications WO 97/36724 or WO 99/16600).
• the BET specific surface area of carbon blacks is measured according to standard D6556-10 [multipoint method (at least 5 points) - gas: nitrogen - relative pressure range R / R0: 0.1 to 0.3]
• any inorganic or mineral filler (whatever its color and its natural or synthetic origin), also called “white” filler, “light” filler even “non-black filler” as opposed to carbon black, capable of reinforcing on its own, without other means than an intermediate coupling agent, a rubber composition intended for the manufacture of tires, in particular other terms capable of replacing, in its reinforcing function, a conventional carbon black of pneumatic grade; such a charge is generally characterized, in a known manner, by the presence of hydroxyl groups (-OH) on its surface.
• -OH hydroxyl groups
• mineral fillers of the siliceous type in particular silica (S1O 2 ), or of the aluminous type, in particular of alumina (AI2O3) are suitable.
• the silica used can be any reinforcing silica known to those skilled in the art, in particular any precipitated or pyrogenic silica having a BET surface as well as a CTAB specific surface, both less than 450 m 2 / g, preferably from 30 to 400 m 2 / g.
• HDS highly dispersible precipitated silicas
• the physical state in which the reinforcing inorganic filler is present is immaterial, whether in the form of powder, microbeads, granules, beads or any other suitable densified form.
• the term reinforcing inorganic filler is also understood to mean mixtures of various reinforcing inorganic fillers, in particular highly dispersible siliceous and / or aluminous fillers.
• the reinforcing inorganic filler used, in particular in the case of silica preferably has a BET surface of between 45 and 400 m 2 / g, more preferably between 60 and 300 m 2 / g.
• the rate of total reinforcing filler is between 20 and 200 phr, more
• the level of reinforcement expected on a bicycle tire is of course lower than that required on a tire capable of traveling at high speed in a sustained manner, for example a motorcycle tire, a tire for a passenger vehicle or for a utility vehicle such as Heavy goods vehicle.
• a reinforcing filler comprising between 30 and 150 phr, more preferably between 50 and 120 phr of organic filler, particularly carbon black, and optionally silica; silica, when present, is preferably used at a rate of less than 20 phr, more preferably less than 10 phr (for example between 0.1 and 10 phr).
• This preferred embodiment is particularly preferred when the majority elastomer of the composition is an epoxidized isoprene rubber, more particularly epoxidized natural rubber.
• a reinforcing filler comprising between 30 and 150 phr, more preferably between 50 and 120 phr of inorganic filler, particularly silica, and optionally carbon black, is used; carbon black, when present, is preferably used at a rate of less than 20 phr, more preferably less than 10 phr (for example between 0.1 and 10 phr).
• This preferred embodiment is also particularly preferred when the majority elastomer of the composition is an epoxidized isoprene rubber, more particularly epoxidized natural rubber.
• the rubber composition according to the invention is devoid of coupling agent (or binding agent).
• composition devoid of a compound it is understood that the composition does not comprise this compound intentionally introduced into the composition and that this compound, if it is present, is in the form of traces linked for example to the process for the manufacture of the composition or the elements composing it.
• the composition devoid of this compound comprises an amount less than or equal to 0.2 phr, preferably less than or equal to 0.1 phr and preferably less than or equal to 0.05 phr of this compound.
• a reinforcing charge of another nature, in particular organic could be used, as soon as this reinforcing charge is covered with a inorganic layer such as silica, or else would have on its surface functional sites, in particular hydroxyls, making it possible to establish the bond between the filler and the elastomer in the presence or not of a covering or coupling agent.
• composition according to the invention comprises at least one phenolic compound of general formula (I)
• Gi represents a hydroxyl, carboxyl, alkoxyl or hydrogen atom group
• G2 represents a hydroxyl group or the hydrogen atom
• - G3 represents the hydrogen atom or a hydroxyl or carboxyl group
• phenolic compound designates the aromatic compound of general formula (I).
• carboxyl group or carboxylic acid function, is meant a group of formula -COOH in which the carbon atom is linked by a double bond to an oxygen atom and by a single bond to a hydroxyl group ⁇ H.
• hydrogen carbonyl group is meant a group of formula -CHO in which the carbon atom is linked by a double bond to an oxygen atom and by a single bond to a hydrogen atom.
• carboxyalkenyl group is meant a group of formula - (CnH2n-2) -COOH.
• carbonylalkyl group is meant a group of formula - (CnH2n) -CHO.
• aryloxy group means a group of general formula Aryl, in which an aryl group is linked to an oxygen atom.
• arylthioxy group is meant a group of general formula -S Aryl, in which an aryl group is linked to a sulfur atom.
• arylcarbonyl group is meant a group of general formula -CO Aryl, in which an aryl group is linked to a carbonyl group.
• amino group is meant a group of formula -NH2.
• aminoalkyl radical is meant a radical of formula -CnkhndNiED.
• n is an integer, advantageously between 1 and 15, preferably between 1 and 10, very preferably between 1 and 5, and preferably between 1 and 3.
• G3 represents the hydrogen atom or a group chosen from hydroxyl, carboxyl, carboxylalkyl, aryl, aryloxy, arylthioxy, arylcarbonyl groups.
• the phenolic compound of general formula (I) comprises at least one aromatic ring carrying at least two hydroxyl functions in meta position relative to each other, the two ortho positions of at least one of the functions hydroxyl being unsubstituted.
• the phenolic compound of general formula (I) carries at least three hydroxyl functions, preferably in the meta position relative to each other, the two ortho positions of each hydroxyl function being preferably unsubstituted.
• G3 represents a group chosen from the aryl, aryloxy, arylthioxy, arylcarbonyl groups.
• at least two aromatic rings of the phenolic compound of general formula (I) carry at least two hydroxyl functions in meta position relative to each other, the two ortho positions of at least one of the hydroxyl functions of at least one aromatic ring, and preferably of each aromatic ring, being unsubstituted.
• the phenolic compound of general formula (I) is chosen from the group consisting of resorcinol, phloroglucinol, 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide, 2,2', 4,4 '-tetrahydroxybenzophenone and mixtures of these compounds.
• the rubber composition according to the invention advantageously comprises from 0.1 to 60 phr, preferably from 0.1 to 50 phr, preferably from 0.1 to 30 phr, very preferably from 2 to 30 phr and from very preferably from 4 to 30 phr of phenolic compound. Below 0.1 phr, the phenolic compound has no significant effect on the crosslinking of the rubber composition according to the invention.
• the composition according to the invention comprises at least two phenolic compounds of general formula (I), at least one of the two phenolic compounds preferably comprising at least two hydroxyl functions.
• composition according to the invention may also comprise an aldehyde compound as defined in patent applications WO 2016/116468,
• WO 2017/103403, WO 2017/103404 and WO 2017/103406 (compounds designated respectively in these applications as aldehyde of formula (A), compound of formula W5, aldehyde of formula W and compound of formula W2).
• composition according to the invention may comprise an aldehyde chosen from the group consisting of 1,3-benzene-dicarboxaldehyde, 1,4-benzene-dicarboxaldehyde and their mixture, preferably 1,4-benzene- dicarboxaldehyde.
• this compound makes it possible to modulate the rigidity of the composition according to the invention once it has crosslinked, without penalizing the hysteretic properties.
• the rubber compositions in accordance with the invention may also comprise all or part of the usual additives, known to those skilled in the art and usually used in rubber compositions for tires, in particular of internal layers such as defined later in the present application, such as for example plasticizers (plasticizing oils and / or plasticizing resins), reinforcing or non-reinforcing fillers other than those mentioned above, pigments, protective agents such as anti-ozone waxes, chemical antr ozonants , antioxidants, anti-fatigue agents, reinforcing resins (as described for example in application WO 02/10269).
• plasticizers plasticizing oils and / or plasticizing resins
• reinforcing or non-reinforcing fillers other than those mentioned above pigments
• protective agents such as anti-ozone waxes, chemical antr ozonants , antioxidants, anti-fatigue agents, reinforcing resins (as described for example in application WO 02/10269).
• compositions can also contain agents for implementation aid
• these agents being by example of hydrolyzable silanes such as alkylalkoxysilanes (for example octyltriethoxysilane, or octane silane), polyols, polyethers, primary, secondary or tertiary amines,
• alkylalkoxysilanes for example octyltriethoxysilane, or octane silane
• polyols polyethers
• primary, secondary or tertiary amines primary, secondary or tertiary amines
• the compound of general formula (I) allows the crosslinking of the rubber composition according to the invention. That is to say, it allows, by cooking,
• the rubber composition according to the invention lacks a crosslinking system usually associated with functionalized elastomers comprising polar functional groups.
• it does not simultaneously comprise an alkyHmidazole and a polycarboxylic acid of general formula (P1) :
• a representing a covalent bond or a hydrocarbon group comprising at least 1 carbon atom and preferably from 1 to 1800 carbon atoms, optionally substituted and optionally interrupted by one or more heteroatoms.
• the rubber composition according to the invention comprises less than 20 phr, preferably less than 10 phr, very preferably less than 2 phr and very preferably does not comprise a polycarboxylic acid of general formula (Pl).
• the rubber composition according to the invention comprises less than 2 phr,
• the rubber composition according to the invention is devoid of vulcanization system, or contains less than 1 phr, preferably less than 0.5 phr and more preferably less than 0.2 phr.
• the rubber composition according to the invention is preferably devoid of molecular sulfur or contains less than 1 phr, preferably less than 0.5 phr and more preferably less than 0.2 phr.
• the composition is preferably devoid of any vulcanization accelerator or activator, as they are known to a person skilled in the art, or contains less than 1 pce, preferably less than 0.5 pce and more preferably less than 0 , 2 pce.
• the rubber composition according to the invention is preferably devoid of zinc or zinc oxide, or contains less than 1 phr, preferably less than 0.5 phr and very preferably less than 0.2 phr .
• the rubber composition according to the invention is preferably devoid of cobalt salts, as they are known to a person skilled in the art, and whose effect known to a person skilled in the art is an improvement in adhesion. , or contains less than 1 pce, preferably less than 0.5 pce, more preferably less than 0.2 pce and very preferably less than 0.1 pce.
• the rubber composition according to the invention can be manufactured in suitable mixers, using two successive preparation phases well known to those skilled in the art:
• thermomechanical working or kneading phase which can be carried out in a single thermomechanical step during which all the constituents are introduced into a suitable mixer such as a usual internal mixer (for example of the 'Banbury' type) necessary, in particular the elastomeric matrix, the fillers, any other miscellaneous additives.
• a suitable mixer such as a usual internal mixer (for example of the 'Banbury' type) necessary, in particular the elastomeric matrix, the fillers, any other miscellaneous additives.
• the incorporation of the filler into the elastomer can be carried out in one or more times by thermomechanical kneading.
• masterbatch in English
• WO 97/36724 or WO 99/16600 it is the masterbatch which is directly kneaded and, where appropriate, the other elastomers or fillers present in the composition which are not in the form of masterbatch are incorporated, as well as any other miscellaneous additives.
• the first phase is carried out at high temperature, up to a maximum temperature between 110 ° C and 190 ° C, preferably between 130 ° C and 180 ° C, for a period generally between 2 and 10 minutes.
• a second mechanical working phase which is carried out in an external mixer such as a cylinder mixer, after cooling of the mixture obtained during the first phase to a lower temperature, typically below 110 ° C., by example between 40 ° C and 100 ° C.
• the phenolic compound or compounds are then incorporated, and the whole is then mixed for a few minutes, for example between 2 and 15 min.
• the final composition thus obtained can then be calendered, for example in the form of a sheet, a plate in particular for characterization in the laboratory, or else extruded in the form of a semi-finished (or profiled) rubber used for the manufacture of a tire.
• the composition can be either in the raw state (before crosslinking), or in the cooked state (after crosslinking), can be a semi-finished product which can be used in a tire.
• the invention also relates to a composite based on at least one reinforcing element and on a rubber composition according to the invention.
• the composite expression “based at least on a reinforcing element and a composition according to the invention” it is meant a composite comprising the reinforcing element and said composition, the composition having been able to react with the surface of the reinforcing element during the various phases of manufacture of the composite, in particular during the crosslinking of the composition or during the making of the composite before crosslinking of the composition.
• Said reinforcing element is a wire element. It can be all or part metallic or textile.
• the term “wire element” means an element having a length at least 10 times greater than the largest dimension of its section, whatever the shape of the latter : circular, elliptical, oblong, polygonal, in particular rectangular or square or oval. In the case of a rectangular section, the wire element has the shape of a strip.
• said reinforcing element may be of a textile nature, that is to say made of an organic material, in particular polymeric, or inorganic, such as for example glass, quartz, basalt or carbon.
• the polymeric materials can be of the type thermoplastic, such as for example aliphatic polyamides, in particular polyamides 6 _ 6, and polyesters, in particular polyethylene terephthalate.
• the polymeric materials can be of the non-thermoplastic type, such as for example aromatic polyamides, in particular aramid, and cellulose, natural as well as artificial, in particular rayon.
• said reinforcing element comprises a metal surface.
• the metal surface of the reinforcing element constitutes at least a part
• the reinforcing element is metallic, that is to say made of a metallic material.
• composition according to the invention coats at least part of the reinforcing element, preferably all of said element.
• the metal surface of the reinforcing element is made of a material different from the rest of the reinforcing element.
• the reinforcing element is made of a material which is at least partly, preferably completely, covered by a metallic layer which constitutes the metallic surface.
• the material at least in part, preferably completely, covered by the metallic surface is of metallic or non-metallic nature, preferably metallic.
• the reinforcing element is made of the same material, in which case the reinforcing element is made of a metal which is identical to the metal of the metal surface.
• the metal surface comprises a metal chosen from the group consisting of iron, copper, zinc, tin, aluminum, cobalt, nickel and alloys comprising at least one of these metals.
• the alloys can be for example binary or ternary alloys, such as steel, bronze and brass.
• the metal surface comprises a metal chosen from the group consisting of iron, copper, tin, zinc and an alloy comprising at least one of these metals. More preferably, the metal surface comprises a metal chosen from the group consisting of steel, brass (Cu-Zn alloy), zinc and bronze (Cu-Sn alloy), and even more preferably in the group made up of brass and steel. Most preferably, the metal surface is made of brass. Some metals are subject to oxidation on contact with ambient air, the metal can be partly oxidized.
• the steel is preferably carbon steel or stainless steel.
• the steel is carbon steel, its carbon content is preferably between 0.01% and 1.2% or between 0.05% and 1.2%, or even between 0.2% and 1.2%, especially between 0.4% and 1.1%.
• the steel is stainless, it preferably contains at least 11% chromium and at least 50% iron.
• the composite is a reinforced product which comprises several reinforcing elements as defined above and a calendering gum in which the reinforcing elements are embedded, the calendering gum consisting of the rubber composition according to the invention.
• the reinforcing elements are generally arranged side by side in a main direction.
• the composite can therefore constitute a reinforcing reinforcement for the tire.
• the composite according to the invention can be in the raw state (before crosslinking of the rubber composition) or in the cooked state (after crosslinking of the rubber composition).
• the composite is cured after bringing the reinforcing element (s) into contact with the rubber composition according to the invention.
• the composite can be manufactured by a process which comprises the following stages:
• the composite can be manufactured by depositing the reinforcing element on a portion of a layer, the layer is then folded back on itself to cover the reinforcing element which is thus sandwiched over its entire length or a part of its length.
• the layers can be made by calendering. During curing of the composite, the rubber composition is crosslinked. When the composite is intended to be used as a reinforcing reinforcement in a tire, the curing of the composite generally takes place during the curing of the tire casing.
• the invention also relates to a finished or semi-finished article comprising a composition according to the invention.
• the finished or semi-finished article can be any article comprising a rubber composition. Mention may be made, for example and without limitation, of balloons, conveyor belts, shoe soles, pneumatic or non-pneumatic envelopes.
• the tire another object of the invention, has the essential characteristic of understanding the composition or the composite according to the invention.
• the tire can be in the raw state (before crosslinking of the rubber composition) or in the cooked state (after crosslinking of the rubber composition).
• the composition or composite is deposited in the raw state (that is to say before crosslinking of the rubber composition) in the structure of the tire before the curing step of the tire. pneumatic.
• the invention relates particularly to tires intended to equip motor vehicles of the tourism type, SUV ("Sport Utility Vehicles"), or two wheels (in particular motorcycles), or airplanes, or even industrial vehicles chosen from vans, "Weight- heavy ”, ie metro, bus, road transport equipment (trucks, tractors, trailers), off-road vehicles such as agricultural or civil engineering vehicles, and others.
• SUV Sport Utility Vehicles
• two wheels in particular motorcycles
• airplanes or even industrial vehicles chosen from vans, "Weight- heavy ”, ie metro, bus, road transport equipment (trucks, tractors, trailers), off-road vehicles such as agricultural or civil engineering vehicles, and others.
• An external sidewall is an elastomeric layer disposed outside the carcass reinforcement relative to the internal cavity of the tire, between the crown and the bead so as to completely or partially cover the area of the carcass reinforcement extending from the top to the bead.
• This zone generally being constituted by the layer which is impermeable to the inflation gases, sometimes called the inner waterproof layer or inner rubber.
• the internal zone of the tire that is to say that between the external and internal zones.
• This zone includes layers or plies which are called here internal layers of the tire. These are for example carcass plies, underlays of bearing, plies of tire belts or any other layer which is not in contact with the ambient air or the inflation gas of the tire.
• composition defined in this description is particularly well suited to the internal layers of tires.
• the invention also relates to a tire comprising an internal layer comprising a composition or a composite according to the present invention.
• the internal layer can be chosen from the group consisting of carcass plies, crown plies, rod stuffing, crown feet, decoupling layers, tread underlayment and combinations of these inner layers.
• the internal layer is chosen from the group consisting of carcass plies, crown plies, rod stuffing, crown feet, decoupling layers and combinations of these internal layers.
• the nominal secant modulus calculated by reducing to the initial section of the test piece was measured at second elongation (that is to say after accommodation) at 10% elongation and 100 % elongation, respectively denoted MAio and MAioo. All these measurements are carried out on cooked (or crosslinked) test pieces.
• results are expressed in base 100, the value 100 being assigned to the control.
• a result greater than 100 indicates that the composition of the example considered has greater rigidity than the control.
• compositions prepared are presented in Table 1.
• the rubber compositions thus prepared are used to make a composite in the form of a test piece according to the following protocol:
• metal reinforcements are trapped between the two plates in the raw state, at equal distance and leaving protruding on either side of these plates one end of the metal reinforcement of sufficient length for subsequent traction .
• the block comprising the metal reinforcements is then placed in a mold adapted to the targeted test conditions and left to the initiative of those skilled in the art; by way of example, in the present case, the baking of the block is carried out at 170 ° C. for a time varying from 50 min to 100 min depending on the composition under pressure of 5.5 tonnes.
• Each metal reinforcement consists of 2 steel wires of 0.7% carbon, 30 / 100th of a millimeter in diameter, twisted together, the brass coating comprises 63% of copper.
• the test tube thus constituted of the crosslinked block and of the metal reinforcements is placed in the jaws of a traction machine adapted to allow test each section in isolation, at a speed and at a temperature given according to the method described in standard ASTM D 2229-02 (for example, in this case, at 100 mm / min and room temperature).
• the adhesion levels are characterized by measuring the so-called tear-out force to tear off the sections of the test piece.
• a value greater than that of the control specimen indicates an improved result, that is to say a greater breakout force than that of the control specimen.
• the T0 test tube does not include a crosslinking system or a phenolic compound. No crosslinking is observed and therefore none of the properties on a baked test tube are measurable.
• the Tl test tube includes a conventional crosslinking system for an epoxidized natural rubber composition.
• compositions according to the invention have cooked properties of rigidity and hysteretic losses showing that they have been crosslinked.
• Compositions C2, C5 and C6 on which the adhesion tests were carried out also show good adhesion properties.
• compositions are given in pce; - : not measurable; nm: not measured

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• 2018
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