Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
  • C08L23/083—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic polyenes, i.e. containing two or more carbon-to-carbon double bonds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
  • B60C1/0016—Compositions of the tread
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/14—Peroxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
  • C08K5/3445—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/548—Silicon-containing compounds containing sulfur

Definitions

• the field of the present invention is that of diene rubber compositions reinforced with an inorganic filler such as silica and which can be used in particular for the manufacture of tires for vehicles. It relates more particularly to the treads of pneumatic or non-pneumatic tires having an improved rolling resistance/wear compromise.
• diene rubber compositions reinforced with an inorganic filler such as silica
• Diene rubber compositions reinforced with an inorganic filler generally comprise a silane as a coupling agent, such as a polysulfide or a blocked mercaptosilane, silane bearing a protected thiol function.
• the silane makes it possible to create interactions between the diene elastomer and the inorganic filler and to promote the dispersion of the inorganic filler in the rubber composition.
• compositions filled with silica as a filler, having both excellent rolling resistance and good wear resistance.
• the subject of the invention is a rubber composition based on at least:
• an elastomer matrix comprising more than 50 phr of a copolymer containing ethylene units and 1,3-diene units, the ethylene units in the copolymer representing more than 50% by mole of the monomer units of the copolymer,
• o Q represents an arenediyl ring, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms
• o E represents a divalent hydrocarbon group optionally comprising one or several heteroatoms
• crosslinking system comprising at least one radical polymerization initiator and one co-crosslinking agent chosen from the group consisting of (meth)acrylate compounds, maleimide compounds, allyl compounds, vinyl compounds and mixtures thereof.
• a subject of the present invention is also a rubber article comprising a composition according to the invention, in particular a tread of a pneumatic or non-pneumatic tire.
• composition based on means 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 one another, less partially, during the various phases of manufacture of the composition; the composition thus possibly being in the totally or partially crosslinked state or in the non-crosslinked state.
• part by weight per hundred parts by weight of elastomer (or phr) is meant within the meaning of the present invention, the part, by mass per hundred parts by mass of elastomer.
• any interval of values denoted by the expression “between a and b” represents the domain of values going from more than a to less than b (i.e. limits a and b excluded) while any interval of values denoted 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 interval represented by the expression "between a and b" is also and preferably designated.
• a majority compound it is meant within the meaning of the present invention that this compound is in the majority among the compounds of the same type in the composition, that is to say that it is the one which represents the greatest amount by mass among compounds of the same type.
• a majority elastomer is the elastomer representing the greatest mass relative to the total mass of the elastomers in the composition.
• a so-called majority filler is the one representing the greatest mass among the fillers of the composition.
• a "minority” compound is a compound which does not represent the largest mass fraction among compounds of the same type.
• by majority is meant present at more than 50%, preferably more than 60%, 70%, 80%, 90%, and more preferably the “majority” compound represents 100%.
• the term “all of the monomer units of the copolymer” or “all of the monomer units of the copolymer” means all the constituent repeating units of the copolymer which result from the insertion of the monomers into the elastomer chain by polymerization . Unless otherwise indicated, the contents of a monomer unit or repeating unit in the copolymer containing ethylene units and 1,3-diene units are given in molar percentage calculated on the basis of all the monomer units of the copolymer.
• the compounds comprising carbon mentioned in the description can be of fossil origin or biobased. In the latter case, they can be, partially or totally, derived from biomass or obtained from renewable raw materials derived from biomass. This concerns in particular polymers, plasticizers, fillers, etc. All the glass transition temperature “Tg” values described herein are measured in a known manner by DSC (Differential Scanning Calorimetry) according to standard ASTM D3418 (1999).
• composition of the tire according to the invention has the essential characteristic of comprising an elastomer matrix comprising more than 50 phr of a copolymer containing ethylene units and 1,3-diene units, the ethylene units in the copolymer representing more than 50% in mole of the monomer units of the copolymer.
• the "copolymer containing ethylene units and 1,3-diene units, the ethylene units in the copolymer representing more than 50% by mole of the monomer units of the copolymer” may be designated by “the copolymer” or by “the copolymer containing ethylene units and 1,3-diene units” for simplicity of drafting.
• elastomer matrix all of the elastomers of the composition.
• copolymer containing ethylene units and 1,3-diene units is meant any copolymer comprising, within its structure, at least ethylene units and 1,3-diene units.
• the copolymer can thus comprise monomer units other than ethylene units and 1,3-diene units.
• the copolymer can also comprise alpha-olefin units, in particular alpha-olefin units having from 3 to 18 carbon atoms, advantageously having from 3 to 6 carbon atoms.
• the alpha-olefin units can be selected from the group consisting of propylene, butene, pentene, hexene or mixtures thereof.
• the expression “ethylene unit” refers to the —(CH2—CH2)— unit resulting from the insertion of ethylene into the elastomer chain.
• the expression “1,3-diene unit” refers to the units resulting from the insertion of 1,3-diene by a 1,4 addition, a 1,2 addition or a 3,4 addition in the case of isoprene.
• the 1,3-diene units are those, for example, of a 1,3-diene or of a mixture of 1,3-dienes, the 1,3-diene(s) having from 4 to 12 carbon atoms, such as especially 1,3-butadiene and isoprene.
• the 1,3-diene is 1,3-butadiene.
• the ethylene units in the copolymer represent between 50% and 95%, preferably between 55% and 90%, by mole of the monomer units of the copolymer.
• the copolymer containing ethylene units and 1,3-diene units is a copolymer of ethylene and 1,3-diene, that is to say that the copolymer does not contain units other than the ethylene and 1,3-diene.
• the copolymer is a copolymer of ethylene and of a 1,3-diene
• the latter advantageously contains units of formula (II) and/or (III).
• a saturated 6-membered cyclic unit, 1,2-cyclohexanediyl, of formula (II) as a monomer unit in the copolymer can result from a series of very particular insertions of ethylene and 1,3-butadiene in the polymer chain during its growth.
• the copolymer of ethylene and a 1,3-diene may be devoid of units of formula (II). In this case, it preferably contains units of formula (III).
• the copolymer of ethylene and of a 1,3-diene comprises units of formula (II) or units of formula (III) or else units of formula (II) and units of formula (III)
• the molar percentages of units of formula (II) and units of formula (III) in the copolymer, respectively o and p preferably satisfy the following equation (eq. 1), more preferably equation (eq. 2), o and p being calculated on the basis of all of the monomer units of the copolymer.
• the copolymer preferably the copolymer of ethylene and of a 1,3-diene (preferably of 1,3-butadiene), is a random copolymer.
• the number-average mass (Mn) of the copolymer preferably of the copolymer of ethylene and of a 1,3-diene (preferably of 1,3-butadiene) is within a range ranging from 100,000 to 300 000 g/mol, preferably 150,000 to 250,000 g/mol.
• the Mn of the copolymer is determined in a known manner, by steric exclusion chromatography (SEC) as described below:
• the solution is filtered through a 0.45 um porosity filter before injection.
• the equipment used is a "WATERS Acquity” or “WATERS Alliance” chromatographic chain.
• the elution solvent is tetrahydrofuran with antioxidant of BHT (butylated hydroxytoluene) type at 250 ppm, the flow rate is 1 mL.min 1 , the column temperature is 35° C. and the analysis time is 40 min.
• the columns used are a set of three Agilent columns from trade name "InfinityLab PolyPore".
• the injected volume of the sample solution is 100 uL.
• the detector is an "Acquity refractometer” or “WATERS 2410" differential refractometer and the chromatographic data processing software is the "WATERS EMPOWER”.
• the average molar masses calculated relate to a calibration curve produced from standard polystyrene.
• the copolymer can be obtained according to various synthetic methods known to those skilled in the art, in particular depending on the intended microstructure of the copolymer. Generally, it can be prepared by copolymerization of at least one 1,3-diene, preferably 1,3-butadiene, and ethylene and according to known synthetic methods, in particular in the presence of a catalytic system comprising a metallocene complex. Mention may be made in this respect of catalytic systems based on metallocene complexes, which catalytic systems are described in documents EP 1 092 731, WO 2004035639, WO 2007054223 and WO 2007054224 in the name of the Applicant.
• the copolymer, including when it is random, can also be prepared by a process using a catalytic system of the preformed type such as those described in the documents WO 2017093654 Al, WO 2018020122 Al and
• the copolymer may consist of a mixture of copolymers containing ethylene units and diene units which differ from each other by their microstructures and/or by their macrostructures.
• the content of the copolymer containing ethylene units and 1,3-diene units in the composition is within a range ranging from 60 to 100 phr, preferably from 80 to 100 phr.
• the elastomer matrix can advantageously comprise only, as elastomer, the copolymer containing ethylene units and 1,3-diene units.
• the elastomer matrix may additionally comprise a diene elastomer different from the copolymer containing ethylene units and 1,3-diene units (also referred to herein as “the other elastomer”).
• the other elastomer when it is present, is in the minority, that is to say it represents less than 50%, 40%, 30%, 20%, or even less than 10% by weight of the elastomer matrix.
• the content of the other elastomer, in the composition may be within a range ranging from 0 to 40 phr, preferably from 0 to 20 phr.
• the other elastomer of the elastomer matrix of the tire according to the invention is preferably chosen from the group of highly unsaturated diene elastomers such as polybutadienes (abbreviated as "BR"), synthetic polyisoprenes (IR), natural rubber (NR ), butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
• BR polybutadienes
• IR synthetic polyisoprenes
• NR natural rubber
• butadiene copolymers butadiene copolymers
• isoprene copolymers mixtures of these elastomers.
• highly unsaturated diene elastomer generally means a diene elastomer resulting at least in part from conjugated diene monomers, having a rate of units or units of diene origin (conjugated dienes) which is greater than 50% (% in moles ).
• the rubber composition in accordance with the invention comprises a 1,3-dipolar compound.
• 1,3-dipolar compound is understood according to the definition given by IUPAC.
• the 1,3-dipolar compound corresponds to the formula (I): o Q represents an arenediyl ring, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms, o E represents a divalent hydrocarbon group optionally comprising one or more heteroatoms.
• arenediyl ring means a monocyclic or polycyclic aromatic hydrocarbon group, derived from an arene in which two hydrogen atoms have been removed. An arenediyl ring is therefore a divalent group.
• monocyclic or polycyclic aromatic hydrocarbon group is meant, within the meaning of the present invention, one or more aromatic rings whose skeleton consists of carbon atoms. That is, there are no heteroatoms in the ring skeleton.
• the arenediyl ring can be monocyclic, that is to say made up of a single ring, or polycyclic, that is to say made up of several condensed aromatic hydrocarbon rings; such condensed rings then have at least two successive carbon atoms in common. These cycles can be ortho-condensed or ortho- and peri-condensed.
• the arenediyl ring comprises from 6 to 14 carbon atoms.
• the arenediyl ring can be unsubstituted, partially substituted or fully substituted.
• An arenediyl ring is partially substituted when one or two or more hydrogen atoms (but not all the atoms) are replaced by one or two or more hydrocarbon, aliphatic, preferably saturated, linear or branched chains, optionally substituted by one or several heteroatoms. Said chains are also called substituents. If all the hydrogen atoms are replaced by said chains, then the arenediyl ring is totally substituted.
• the substituents of the arenediyl ring may be the same or different from each other.
• the arenediyl ring is substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms, this or these chains may be inert with respect to the N-substituted imidazolidinone function and nitrile oxide.
• hydrocarbon chain inert with respect to the N-substituted imidazolidinone function and nitrile oxide means a hydrocarbon chain which does not react either with said N-substituted imidazolidinone function or with said nitrile oxide.
• said hydrocarbon chain which is inert with respect to said N-substituted imidazolidinone function and to said nitrile oxide is preferably an aliphatic hydrocarbon chain which does not have alkenyl or alkynyl functions capable of reacting with said function or said group, c that is to say is a saturated aliphatic hydrocarbon chain, linear or branched, optionally substituted or interrupted by one or more heteroatoms, and preferably comprising from 1 to 24 carbon atoms.
• the group Q is a C6-CM arenediyl ring optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms. More preferably, the group Q is a C6-Ci4 arenediyl ring, optionally substituted by one or more hydrocarbon chains, identical or different, saturated, C1-C24, linear or branched, optionally substituted or interrupted by one or more heteroatoms of nitrogen, sulfur or oxygen.
• the group Q is a C6-CH arenediyl ring, optionally substituted by one or more substituents, identical or different, chosen from the group consisting of a C1-C12 alkyl (more preferably C1-C6, more preferably still in C1-C4), an OR' group, an -NHR' group, an -SR' group where R' is an alkyl group in C1-C12, more preferentially in CI-C ⁇ , more preferentially still in C1-C4.
• the compound of formula (I) is chosen from the compounds of formula (Ia) and (Ib)
• the four groups of formula (Ia) chosen from Xi to X5 other than that designating a covalent bond allowing the attachment to the group E of the group of formula (IV ) and the six groups of formula (Ib) chosen from Xi to X7 other than that designating a covalent bond allowing attachment to the group E of the group of formula (IV), which are identical or different, are chosen from the group formed by an atom of hydrogen, a C1-C12 alkyl (more preferably C1-C6, more preferably still C1-C4), an -OR' group, an -NHR' group and an -SR' group where R' is an alkyl in C1-C12, more preferentially in CI-C ⁇ , more preferentially still in C1-C4.
• X2 represents a covalent bond allowing attachment to the group E of the group of formula (IV) defined above and Xi, X3, X4 and X5, which are identical or different, represent an atom of hydrogen or an aliphatic hydrocarbon chain, preferably saturated, linear or branched, C1-C24, optionally substituted or interrupted by one or more heteroatoms.
• X2 represents a covalent bond allowing the attachment to the group E of the group of formula (IV) defined above and Xi, X3, X4 and X5, identical or different, are chosen from the group consisting of a hydrogen atom , a C1-C12 (more preferably C1-C6, even more preferably C1-C4) alkyl, an -OR' group, an -NHR' group and a -SR' group where R' is a C1- C12, more preferably C1-C6, more preferably still C1-C4.
• X2 represents a covalent bond allowing attachment to the group E of the group of formula (IV) defined above
• X4 represents a hydrogen atom and Xi, X3 and X5 represent an aliphatic hydrocarbon chain. , preferably saturated, linear or branched, C1-C24, optionally substituted or interrupted by one or more heteroatoms.
• X2 represents a covalent bond allowing attachment to the group E of the group of formula (IV) defined above
• X4 represents a hydrogen atom
• Xi, X3 and X5, which are identical or different, are chosen from the group consisting of a C1-C12 alkyl (more preferably C1-C6, even more preferably C1-C4), an -OR' group, an -NHR' group and a -SR' group where R' is a C1 alkyl -C12, more preferably C1-C6, more preferably still C1-C4.
• Xi represents a covalent bond allowing attachment to the group E of the group of formula (IV) defined above and X2 to X7, which are identical or different, represent a hydrogen atom or a Aliphatic hydrocarbon chain, preferably saturated, linear or branched, C1-C24, optionally substituted or interrupted by one or more heteroatoms.
• Xi represents a covalent bond allowing attachment to the group E of the group of formula (IV) defined above and X2 to X7, identical or different, are chosen from the group consisting of a hydrogen atom, an alkyl in C1-C12 (more preferably C1-C6, even more preferably C1-C4), an -OR' group, an -NHR' group and an -SR' group where R' is a C1-C12 alkyl, more preferably in C1-C6, more preferably still in C1-C4. More preferably still in this embodiment, Xi represents a covalent bond allowing attachment to the group E of the group of formula (IV) defined above and X2 to X7, which are identical, represent a hydrogen atom.
• the group E is a divalent hydrocarbon group which may optionally contain one or more heteroatoms.
• divalent hydrocarbon group is meant within the meaning of the present invention, a spacer group (or a linking group) forming a bridge between the group Q and the N-substituted imidazolidinone group, this spacer group being a hydrocarbon chain, saturated or unsaturated, preferably saturated, C1-C24, linear or branched, possibly containing one or more heteroatoms such as for example N, O and S.
• Said hydrocarbon chain can optionally be substituted, provided that the substituents do not react with nitrile oxide and the N-substituted imidazolidinone group as defined above.
• the group E is a hydrocarbon chain, linear or branched, preferably saturated, C1-C24, more preferably C1-C10, even more preferably in CI-C ⁇ , optionally interrupted by one or more nitrogen, sulfur or oxygen atoms.
• the group E is chosen from the group consisting of -R-, -NH-R-, -OR- and -SR- where R is an alkylene, linear or branched, C1-C24, preferably Ci-Cio, more preferably Ci-Ce.
• the group E is chosen from the group consisting of -R- and -OR- where R is a linear or branched C1 alkylene. -C24 , preferably C1-C10, more preferably Ci-C6.
• the group E is chosen from -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2- CH2- CH2- , -O-CH2-, -O-CH2-CH2-, -O-CH2-CH2-CH2- and -O-CH2-CH2-CH2-CH2-.
• the 1,3-dipolar compound is chosen from the compounds of formulas (V) to (X) below and their mesomeric forms:
• the 1,3-dipolar compound is chosen from the compounds of formulas (V), (IX) and (X) and their mesomeric forms.
• the amount of 1,3-dipolar compound introduced into the rubber composition is expressed in molar equivalent of imidazole ring.
• the 1,3-dipolar compound contains a single imidazole ring of formula (II) as defined above, one mole of 1,3-dipolar compound corresponds to one mole of imidazole ring.
• the 1,3-dipolar compound contains two imidazole rings of formula (II) as defined above, one mole of 1,3-dipolar compound corresponds to two moles of imidazole ring. In the latter case, the use of the 1,3-dipolar compound according to a molar equivalent of the imidazole ring corresponds to half a mole of 1,3-dipolar compound.
• the quantity of the 1,3-dipolar compound in the composition can be between 0 and 50, preferably between 0.01 and 15, molar equivalents per 100 moles of monomer units constituting the copolymer.
• it may be between 4 and 15 molar equivalents, for example between 5 and 15 molar equivalents.
• the amount of 1,3-dipolar compound in the composition is preferably between 0 and 3 molar equivalents, more preferably between 0 and 2 molar equivalents, even more preferably between 0 and 1 molar equivalent, or even more preferably between 0 and 0.7 molar equivalent of imidazole ring per 100 moles of monomer units constituting the copolymer.
• the amount of 1,3-dipolar compound in the composition is preferably between 0.1 and 3 molar equivalents, more preferably between 0.1 and 2 molar equivalents, even more preferably between 0.1 and 1 molar equivalent , or even more preferably between 0.1 and 0.7 molar equivalent of imidazole ring per 100 moles of monomer units constituting the copolymer.
• polar solvent means a solvent having a dielectric constant greater than 2.2.
• nucleofuge group means a leaving group which carries its bonding doublet.
• nucleophilic group means a compound comprising at least one atom bearing a free pair or a negatively charged atom.
• the process for synthesizing the compound of formula (I) comprises in particular the successive steps (bl) and (b2).
• the two steps (bl) and (b2) can be separated by a step of isolation and purification of the compound of formula (XV).
• the two steps (bl) and (b2) can be carried out according to a one-pot synthesis, that is to say that the steps (bl) and (b2) are "one pot” (one-pot synthesis process in two steps ), or without isolation of the intermediate compound of formula (XV).
• the process comprises a step (bl) of reacting a compound of formula (XIII), as mentioned above, carrying a group Y, with a compound of formula (XIV), as mentioned above, carrying a Z group.
• the Y group is chosen from hydroxyl, thiol and primary or secondary amine functions.
• the Z group can be chosen from chlorine, bromine, iodine, the mesylate group, the tosylate group, the acetate group and the trifluoromethylsulfonate group.
• Step (bl) of the process is carried out in the presence of at least one polar solvent SI, and at least one base, at a temperature T1 ranging from 70 to 150°C.
• the polar solvent SI can be a water-miscible polar solvent, preferably a protic solvent.
• Dimethylformamide (DMF), dimethylsulfoxide (DMSO), l,3-dimethyl-2-imidazolidinone (DMI), l,3-dimethyl-3,4,5,6-tetrahydro-2(lH)-pyrimidinone (DMPU), isopropanol, acetonitrile, ethanol, n-butanol and n-propanol are examples of SI solvents which can be used in the process.
• the protic solvent is alcoholic.
• the compound of formula (XIII) represents from 5 to 40% by weight, preferably from 10 to 30% by weight, relative to the weight of the solvent.
• the base can be chosen from alkaline alcoholates, alkaline carbonates, alkaline-earth carbonates, alkaline hydroxides, alkaline-earth hydroxides and mixtures thereof.
• one or more catalysts chosen from a catalyst of the silver (I) salt type, a phase transfer catalyst of the quaternary ammonium type, and mixtures thereof;
• the base is chosen from sodium methanolate, potassium carbonate and soda, more preferably potassium carbonate.
• the molar quantity of base is from 1.5 to 8 molar equivalents, preferably from 2 to 6 molar equivalents, relative to the molar quantity of compound of formula (XIII).
• step (b1) of the process is carried out at a temperature T1 ranging from 70 to 150°C.
• the temperature T1 is a temperature ranging from 70 to 120°C, more preferably from 80 to 110°C.
• step (bl) of the process is followed by step (b2) of adding to the reaction medium containing the compound of formula (XV) an aqueous solution of hydroxylamine at a temperature T2 ranging from 30 to 70°C.
• the addition of the aqueous hydroxylamine solution is carried out when the conversion of the compound of formula (XIII) is at least 70% by weight.
• the temperature T2 varies from 40 to 60°C.
• the process also comprises a stage (c) of recovery, as mentioned above, of the oxime compound of formula (XVI).
• the oxime compound of formula (XVI) is recovered by precipitation with water, optionally followed by washing with water.
• the method also comprises a step (d) of oxidation of the oxime compound of formula (XVI) with an oxidizing agent to give the compound of formula (I), in particular the preferred compounds, in the presence of at least one organic solvent S2 ; the quantity of oxidizing agent is at least 6 molar equivalents, preferably from 6.5 to 15 molar equivalents, relative to the molar quantity of oxime compound of formula (XVI).
• This amount of oxidizing agent can be added all at once or several times during step (d), preferably added twice during step (d).
• said oxidizing agent is chosen from T sodium hypochlorite, N-bromosuccinimide in the presence of a base and N-chlorosuccinimide in the presence of a base, preferably said oxidizing agent is T sodium hypochlorite.
• the organic solvent S2 is an organic solvent chosen from chlorinated solvents of the ester, ether and alcohol type, more preferably chosen from dichloromethane, ethyl acetate, butyl acetate, diethyl ether, isopropanol and ethanol, even more preferably chosen from ethyl acetate and butyl acetate.
• the oxime compound of formula (XVI) represents from 1 to 30% by weight, preferably from 1 to 20% by weight, relative to the total weight of the assembly comprising said oxime compound of formula (XVI), said organic solvent S2 and said oxidizing agent.
• the process comprises, after step (d), a step (e) of recovering the compound of formula (I).
• the method may comprise a step (a2) of manufacturing the compound of formula (XIV), prior to step (bl), by reacting a compound of the following formula (XVII) with an agent allowing the formation of the group nucleofuge Z: in which E is as previously defined.
• said agent allowing the formation of the nucleofuge group Z is thionyl chloride.
• step (a2) is carried out in the absence or in the presence of at least one S4 solvent, preferably a chlorinated solvent, more preferably dichloromethane.
• S4 solvent preferably a chlorinated solvent, more preferably dichloromethane.
• step (a2) is immediately followed by a step (a3) for recovering the compound of formula (X), preferably by purification with toluene, more preferably by crystallization of the compound of formula (X) from toluene.
• step (a3) for recovering the compound of formula (X), preferably by purification with toluene, more preferably by crystallization of the compound of formula (X) from toluene.
• Other processes for obtaining 1,3-dipolar compounds corresponding to formula (I) are known to those skilled in the art, in particular in document WO2012/07441.
• composition according to the invention also has the essential characteristic of being based on a filler mainly comprising silica.
• the silica used in the composition according to the invention can be any silica known to a person skilled in the art, in particular any precipitated or fumed silica having a BET surface area as well as a CT AB specific surface area, both of which are less than 450 m 2 /g , preferably from 30 to 400 m 2 /g, in particular from 60 to 300 m 2 /g.
• the silica advantageously has a BET specific surface comprised in a range ranging from 125 to 200 m 2 /g and/or a CT AB specific surface comprised in a range ranging from 140 to 170 m 2 /g.
• the BET surface area of silica is determined by gas adsorption using the Brunauer-Emmett-Teller method described in "The Journal of the American Chemical Society” (Vol. 60, page 309, February 1938), and more precisely according to a method adapted from standard NF ISO 5794-1, appendix E of June 2010 [multipoint volumetric method (5 points) - gas: nitrogen - vacuum degassing: one hour at 160°C - relative pressure range p/ in: 0.05 to 0.17],
• CT AB specific surface values of silica were determined according to standard NF ISO 5794-1, appendix G of June 2010. The process is based on the adsorption of CT AB (N-hexadecyl-N,N bromide, N-trimethylammonium) on the "outer" surface of the filler.
• non-HDS silica the following commercial silicas can be used: “Ultrasil ® VN2GR” and “Ultrasil ® VN3GR” silicas from Evonik, “Zeosil® 175GR” silica from Solvay, "Hi -Sil EZ120G(-D)", “Hi-Sil EZ160G(-D)”, “Hi-Sil EZ200G(-D)”, “Hi-Sil 243LD”, “Hi-Sil 210", “Hi-Sil HDP 320G” from PPG.
• the filler comprises more than 70% by weight, preferably more than 80% by weight, of silica.
• the silica content is within a range ranging from 5 to 60 phr, preferably from 10 to 55 phr, more preferably from 15 to 50 phr.
• an at least bifunctional coupling agent intended to ensure a sufficient connection, of a chemical and/or physical nature, between the silica (surface of its particles ) and the copolymer (hereinafter simply referred to as "coupling agent").
• at least bifunctional organosilanes or polyorganosiloxanes are used.
• bifunctional is meant a compound having a first functional group capable of interacting with the inorganic filler and a second functional group capable of interacting with the copolymer.
• such a bifunctional compound may comprise a first functional group comprising a silicon atom, said first functional group being capable of interacting with the hydroxyl groups of an inorganic filler and a second functional group comprising a sulfur atom, said second functional group being capable of interacting with the copolymer.
• a coupling agent is not mandatory but is preferable. If a coupling agent is used, the content of coupling agent, in the composition according to the invention, is advantageously between 0.5% and 15% by weight relative to the weight of silica. The amount of coupling agent can easily be adjusted by those skilled in the art according to the level of reinforcing inorganic filler used in the composition of the invention.
• the coupling agent is an organosilane chosen from the group consisting of polysulphide organosilanes, polyorganosiloxanes, mercaptosilanes, acrylosilanes and methacrylosilanes.
• composition according to the invention may comprise fillers other than silica, but this is not compulsory. These may include organic fillers such as carbon black.
• the blacks that can be used in the context of the present invention can be any black conventionally used in pneumatic or non-pneumatic tires or their treads (so-called tire-grade blacks).
• tire-grade blacks any black conventionally used in pneumatic or non-pneumatic tires or their treads
• These carbon blacks can be used in the isolated state, as commercially available, or in any other form, for example as a carrier for some of the rubber additives used.
• the carbon blacks could for example already be incorporated into the copolymer, in particular isoprene in the form of a masterbatch (see for example applications WO 97/36724 or WO 99/16600). Mixtures of several carbon blacks can also be used in the prescribed rates.
• the carbon black is used at a rate less than or equal to 20 phr, more preferably less than or equal to 10 phr (for example, the rate of carbon black can be within a range ranging from 0.5 to 20 phr, in particular ranging from 1 to 10 pce). Within the ranges indicated, the coloring (black pigmentation agent) and anti-UV properties of the carbon blacks are benefited, without penalizing moreover the typical performance provided by the reinforcing inorganic filler.
• the filler comprises between 80% and 99% by weight of silica and between 1% and 20% by weight of carbon black.
• composition according to the invention also comprises a crosslinking system comprising at least one radical polymerization initiator and one co-crosslinking agent chosen from the group consisting of (meth)acrylate compounds, maleimide compounds, allylic compounds, vinyls and their mixtures.
• a crosslinking system comprising at least one radical polymerization initiator and one co-crosslinking agent chosen from the group consisting of (meth)acrylate compounds, maleimide compounds, allylic compounds, vinyls and their mixtures.
• the radical polymerization initiators are a source of free radicals necessary for the polymerization of the composition according to the invention. These compounds are well known to those skilled in the art and are described in particular in documents WO 2002/22688 A1 and FR 2 899 808 A1 for example, as well as in document Denisov et al. (“Handbook of free radical initiators”, John Wiley & Sons, 2003).
• the at least radical polymerization initiator is chosen from the group consisting of peroxides, azo compounds, redox (redox) systems and mixtures thereof, preferably from the group consisting of peroxides, azo compounds, and mixtures thereof. More preferably, the at least radical polymerization initiator is a peroxide or a mixture of several peroxides. It may be any peroxide known to those skilled in the art. Among the peroxides, well known to those skilled in the art, it is preferable to use in the context of the present invention an organic peroxide.
• organic peroxide is meant an organic compound, that is to say one containing carbon, comprising an -OO- group (two oxygen atoms linked by a bond single covalent). During the crosslinking process, the organic peroxide decomposes at its unstable 0-0 bond into free radicals. These free radicals allow the creation of cross-linking bonds.
• the organic peroxide is preferably selected from the group comprising or consisting of dialkyl peroxides, monoperoxycarbonates, diacyl peroxides, peroxyketals or peroxyesters.
• the dialkyl peroxides are selected from the group comprising or consisting of dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t -butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-amylperoxy)-hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 2,5 -dimethyl- 2,5-di(t-amylperoxy)hexyne-3, a,a'-di-[(t-butyl-peroxy)isopropyl] benzene, a,a'-di-[(t-amyl- peroxy)isopropyl] benzene, di-t-amyl peroxide, 1,3,5-tri-[(t-butylperoxy)
• Certain monoperoxycarbonates such as 00-tert-butyl-O-(2-ethylhexyl) monoperoxycarbonate, 00-tert-butyl-O-isopropyl monoperoxycarbonate and 00-tert-amyl-0-2-ethyl hexyl monoperoxycarbonate can also be used.
• the preferred peroxide is benzoyl peroxide.
• the preferred peroxides are chosen from the group comprising or consisting of 1,1-di-(t-butylperoxy)-3,3,5-trimethylcyclohexane, 4,4-di-(t-butylperoxy)valerate n-butyl, ethyl 3,3-di-(t-butylperoxy)butyrate, 2,2-di-(t-amylperoxy)-propane, 3,6,9-triethyl-3,6, 9-trimethyl-l,4,7-triperoxynonane (or cyclic trimer methyl ethyl ketone peroxide), 3,3,5,7,7-pentamethyl-l,2,4-trioxepane, 4,4-bis( n-butyl t-amylperoxy)valerate, ethyl 3,3-di(t-amylperoxy)butyrate, 1,1-di(t-butylper
• the peroxyesters are chosen from the group consisting of tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate and tert-butylperoxy-3,5,5-trimethylhexanoate.
• the organic peroxide is, in a particularly preferred manner, chosen from the group consisting of dicumyl peroxide, aryl or diaryl peroxides, diacetyl peroxide, benzoyl peroxide, dibenzoyl peroxide, tertbutylcumyl peroxide, 2,5-bis(tertbutylperoxy)-2,5-dimethylhexane, n-butyl-4,4'-di(tert-butylperoxy) valerate, 00-(t-butyl) -0-(2-ethylhexyl) monoperoxycarbonate, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxybenzoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, l,3(4)-bis(tert-butylperoxyisopropyl) benzene and their mixtures.
• the organic peroxide is chosen from the group consisting of from the group consisting of dicumyl peroxide, n-butyl-4,4'-di(tert-butylperoxy)-valerate, OO-(t-butyl) O- (2-ethylhexyl) monoperoxycarbonate, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxybenzoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, 1,3(4)-bis(tert-butylperoxyisopropyl)benzene and their mixtures.
• peroxide By way of example of a peroxide which can be used in the context of the present invention and which is commercially available, mention may be made of “Dicup” from Hercules Powder Co., “Perkadox Y12” from Noury van der Lande, “Peroximon F40” from Montecatini Edison SpA, “Trigonox” from Noury van der Lande, “Varox” from RT Vanderbilt Co., or “Luperko” from Wallace & Tieman, Inc. .
• the azo compound is selected from the group consisting of 2-2'-azobis(isobutyronitrile), 2,2'-azobis(2-butanenitrile), 4,4'-azobis(4-pentanoic acid) , 1,1'-azobis(cyclohexanecarbonitrile), 2-(t-butylazo)-2-cyanopropane, 2,2'-azobis[2-methyl-N-(1,1)-bis(hydroxymethyl)- 2-hydroxyethyl] propionamide, 2,2'-azobis(2-methyl-N-hydroxyethyl]-propionamide, 2,2'-azobis(N,N'-dimethyleneisobutyramidine) dichloride, 2,2'-dichloride -azobis (2-amidinopropane), 2,2'-azobis (N,N'-dimethyleneisobutyramide), 2,2'-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)-2- hydroxyethyl] propionamide
• azo compound which can be used in the context of the present invention and which is commercially available, mention may be made of 2-2'-azobis(isobutyronitrile) from the company Sigma-Aldrich.
• redox systems is meant a combination of compounds causing an oxidation-reduction reaction which generates radicals.
• peroxides with tertiary amines for example the couples: benzoyl peroxide plus dimethylaniline; hydroperoxides with transition metals (such as cumene hydroperoxide plus cobalt naphthenate).
• the level of radical initiator, preferably of organic peroxide, in the composition according to the invention is comprised in a range ranging from 0.1 to 10 phr, preferably from 0.1 to 3 phr, even more preferably from 0.2 to 2.5 pce.
• the level of radical polymerization initiator, in the composition is preferably within a range ranging from 1 to 10% by weight, preferably between 1.25 and 8% by weight, preferably between 2 and 5% by weight , preferably between 3 and 4% by weight, relative to the weight of co-crosslinking agent.
• the co-crosslinking agent is chosen from the group consisting of (meth)acrylate compounds, maleimide compounds, allyl compounds, vinyl compounds and mixtures thereof.
• the co-agent comprises a (meth)acrylate compound, in metal salt or ester form or in polymeric form.
• the co-crosslinking agent comprises an acrylate derivative of formula (XI):
• R 2 and R3 independently represent a hydrogen atom or a Ci-Cs hydrocarbon group selected from the group consisting of linear, branched or cyclic alkyl groups, alkylaryl groups, aryl groups and aralkyls, and optionally interrupted by one or more heteroatoms, R2 and R3 possibly forming together a non-aromatic cycle,
• - A represents an atom belonging to the group consisting of alkaline earth metals or transition metals, a carbon atom, or a C1-C30 hydrocarbon group optionally interrupted and/or substituted by one or more heteroatoms,
• the bond between X and A can be an ionic bond or a covalent bond.
• A represents an atom belonging to the group consisting of alkaline-earth metals or transition metals, in particular Zn or Mg
• the bond between X and A is an ionic bond.
• A represents a carbon atom or a C1-C30 hydrocarbon group
• the bond between X and A is a covalent bond.
• cyclic alkyl group is meant an alkyl group comprising one or more cycles.
• hydrocarbon group or chain interrupted by one or more heteroatoms is meant a group or chain comprising one or more heteroatoms, each heteroatom being between two carbon atoms of said group or of said chain, or between an atom carbon of said group or of said chain and another heteroatom of said group or of said chain or between two other heteroatoms of said group or of said chain.
• hydrocarbon group or chain substituted by one or more heteroatoms is meant a group or chain comprising one or more heteroatoms, each heteroatom being linked to the hydrocarbon group or chain by a covalent bond without interrupting the hydrocarbon group or chain.
• the heteroatom(s) of A may be chosen from the group consisting of oxygen, sulfur, nitrogen, silicon, phosphorus atoms and their combinations.
• the heteroatom(s) of A are selected from the group consisting of oxygen and sulfur atoms. More preferably, the heteroatom(s) of A are oxygen atoms.
• A advantageously represents a C4-C30 hydrocarbon group, linear, branched or cyclic, interrupted and/or substituted by one or more heteroatoms chosen from oxygen, sulfur, nitrogen, silicon , phosphorus and combinations thereof, preferably selected from the group consisting of oxygen and sulfur atoms. More preferably A represents advantageously a linear, branched or cyclic C4-C30 hydrocarbon group, preferably linear or branched, interrupted and/or substituted by one or more oxygen and/or sulfur atoms, preferably interrupted and / or substituted by one or more oxygen atoms.
• A represents a C4-C30 hydrocarbon group, linear, branched or cyclic, preferably linear or branched, interrupted by one or more oxygen and/or sulfur atoms, preferably interrupted by one or more oxygen. More preferably, A represents a C4-C30 hydrocarbon group, linear or branched, interrupted by one or more oxygen atoms.
• A represents a C4-C30 hydrocarbon-based group, it may be, for example, a C5-C20 hydrocarbon-based group, preferably C6-C10.
• A comprises a cyclic hydrocarbon group
• it may be a non-aromatic or aromatic cyclic hydrocarbon group.
• the heteroatom(s) of the radicals Ri, R2, R3 and A can be, independently of each other, oxygen, sulfur, nitrogen, phosphorus or silicon atoms, preferably oxygen or silicon atoms. 'nitrogen.
• Ri, R2 and R3 can represent independently of each other a hydrogen atom, a methyl group or an ethyl group, preferably Ri, R2 and R3 represent independently of each other an atom hydrogen or a methyl group.
• R1 can represent a methyl group and R2 and R3 can each represent a hydrogen atom.
• R1, R2 and R3 may each represent a hydrogen atom.
• valence p depends on the nature of the radical A. According to the invention, p can be worth 2, 3, 4, 5 or 6. Preferably, p is worth 2, 3 or 4, preferably 2 or 3, preferably 2.
• - A represents an atom belonging to the group consisting of alkaline-earth metals or transition metals, a carbon atom or a Ci-Ci 3 hydrocarbon group, preferably Ci-Cs,
• A represents an atom belonging to the group consisting of alkaline-earth metals or transition metals, it may be, for example, an atom chosen from the group consisting of Zn and Mg.
• A represents a Ci-Ci 3 , preferably Ci-C s , hydrocarbon-based group, it may for example be a C 1-C 7 , preferably Ci-C 6 , hydrocarbon-based group.
• A represents a Ci -Ci 3 hydrocarbon group chosen from the group consisting of the following radicals:
• the C1-C13 hydrocarbon group is a radical MCH2) n r ! i! in which m is an integer ranging from 1 to 13, preferably from 1 to 8, preferably from 1 to 6, and (*) represents the point of attachment of A to the radical of formula (IX).
• the acrylate derivative of formula (VIII) can be chosen from zinc dimethacrylate (ZDMA), magnesium dimethacrylate (MgDMA), zinc diacrylate (ZMA), magnesium diacrylate ( MgMA), trimethylopropane trimethylacrylate (TMPTMA), trimethylolproprane triacrylate (TMPTA), 1,6-hexanediol diacrylate (HDD A) and mixtures thereof.
• diacrylate derivatives such as zinc diacrylate (ZD A) “DYMALINK 633” from the company Cray Valley, zinc dimethacrylate (ZDMA) “DYMALINK 634” from the company Cray Valley, trimethylolpropane trimethacrylate (TMPTMA) “SR351” from Sartomer, or 1,6-hexanediol diacrylate (HDD A) from Sigma-Aldrich.
• ZD A zinc diacrylate
• ZDMA zinc dimethacrylate
• TMPTMA trimethylolpropane trimethacrylate
• HDD A 1,6-hexanediol diacrylate
• the level of co-crosslinking agent, and preferably the total level of co-crosslinking agent, in the composition according to the invention is within a range ranging from 1 to 20 phr, preferably from 2 to 10 phr, preferably between 2 and 5 phr.
• the amount of radical polymerization initiator in the composition is within a range ranging from 1 to 10% by weight, preferably between 1.25 and 8% by weight, preferably between 2 and 5% by weight , preferably between 3 and 4% by weight, relative to the weight of co-crosslinking agent in the composition.
• the ratio of the silica content to the content of the co-crosslinking agent is within a range ranging from 2 to 9, preferably from 3 to 7.
• composition according to the invention is advantageously free of sulfur as vulcanizing agent, or contains less than 0.5 phr thereof, preferably less than 0.3 phr, preferably less than 0.2 phr and preferably less than 0.1 phr.
• the sulfur can be molecular sulfur or come from a sulfur-donating agent, such as alkyl phenol disulfides (APDS).
• the rubber compositions may optionally also comprise all or part of the usual additives usually used in elastomer compositions for tires, such as, for example, plasticizers (such as plasticizing oils and/or plasticizing resins), pigments, protection such as anti-ozone waxes, chemical anti-ozonants, antioxidants, anti-fatigue agents, reinforcing resins (as described for example in application WO 02/10269).
• plasticizers such as plasticizing oils and/or plasticizing resins
• pigments protection such as anti-ozone waxes, chemical anti-ozonants, antioxidants, anti-fatigue agents, reinforcing resins (as described for example in application WO 02/10269).
• compositions in accordance with the invention can be manufactured in suitable mixers, using two successive preparation phases well known to those skilled in the art:
• thermomechanical mixing (so-called "non-productive" phase), which can be carried out in a single thermomechanical step during which, in a suitable mixer such as a usual internal mixer (for example of the type 'Banbury'), all the necessary constituents, in particular the matrix elastomer, the filler, the co-crosslinking agent, any other miscellaneous additives, with the exception of the radical polymerization initiator.
• a suitable mixer such as a usual internal mixer (for example of the type 'Banbury')
• all the necessary constituents in particular the matrix elastomer, the filler, the co-crosslinking agent, any other miscellaneous additives, with the exception of the radical polymerization initiator.
• the incorporation of the optional filler into the elastomer can be carried out in one or more stages by mixing thermomechanically.
• the filler is already incorporated in whole or in part into the elastomer in the form of a masterbatch (“masterbatch” in English) as described for example in applications WO 97/36724 or WO 99 /16600, it is the masterbatch which is mixed directly and, if necessary, the other elastomers or fillers present in the composition which are not in the form of the masterbatch are incorporated, as well as any other various additives other than the cross-linking system.
• the non-productive phase can be carried out at high temperature, up to a maximum temperature of between 110° C. and 200° C., preferably between 130° C. and 185° C., for a duration generally of between 2 and 10 minutes.
• a second phase of mechanical work (so-called "productive" phase), which is carried out in an external mixer such as a roller mixer, after cooling the mixture obtained during the first non-productive phase to a lower temperature, typically below 120°C, for example between 40°C and 100°C.
• the radical polymerization initiator is then incorporated, and the whole is then mixed for a few minutes, for example between 5 and 15 min.
• the final composition thus obtained is then calendered, for example in the form of a sheet or a plate, in particular for characterization in the laboratory, or else extruded (or co-extruded with another rubber composition) in the form of a semi-finished (or profiled) rubber that can be used, for example, as a tire tread.
• extruded or co-extruded with another rubber composition
• a semi-finished (or profiled) rubber that can be used, for example, as a tire tread.
• crosslinking of the composition can be carried out in a manner known to those skilled in the art, for example at a temperature of between 130° C. and 200° C., under pressure. Also described herein is a process for preparing the rubber composition in accordance with the invention, further comprising a crosslinking system comprising the following steps:
• the amount of 1,3-dipolar compound added is preferably between 0 and 3 molar equivalents, more preferably between 0 and 2 molar equivalents, even more preferably between 0 and 1 molar equivalent, or even more preferably between 0 and 0.7 equivalent molar of imidazole ring per 100 moles of monomer units constituting the copolymer.
• the lower limit is preferably at least 0.1 molar equivalent of 1,3-dipolar compound.
• the 1,3-dipolar compound is mixed with the copolymer before the introduction of the other constituents of the rubber composition, in particular before the addition of the filler.
• the contact time between the copolymer and the 1,3-dipolar compound which are intimately mixed, in particular thermomechanically kneaded, is adjusted according to the mixing conditions, in particular the thermomechanical kneading, in particular according to the temperature. The higher the temperature, the shorter this contact time. Typically it is 1 to 5 minutes for a temperature of 100 to 130°C.
• At least one antioxidant is preferably added to the copolymer before it is introduced into a mixer, in particular at the end of the synthesis of the copolymer as is done conventionally.
• the final composition thus obtained is then calendered, for example in the form of a sheet or a plate, in particular for characterization in the laboratory, or else extruded, for forming, for example, a rubber profile used as a rubber component for making the tire.
• the present invention also relates to a rubber article comprising at least one composition according to the invention.
• the rubber article is advantageously chosen from the group consisting of pneumatic tires, non-pneumatic tires, caterpillars and conveyor belts.
• the rubber article is a pneumatic or non-pneumatic tire.
• the invention also relates to a pneumatic or non-pneumatic tire provided with a tread comprising at least one composition according to the invention.
• the invention also relates to a rubber track comprising at least one rubber element comprising at least one composition according to the invention, the at least one rubber element preferably being an endless rubber belt or a plurality of pads rubber, as well as a rubber conveyor belt comprising a composition according to the invention.
• the invention relates to the rubber articles described above both in the raw state (that is to say, before curing) and in the cured state (that is to say, after crosslinking or vulcanization).
• Rubber composition based on at least:
• an elastomer matrix comprising more than 50 phr of a copolymer containing ethylene units and 1,3-diene units, the ethylene units in the copolymer representing more than 50% by mole of the monomer units of the copolymer,
• o Q represents an arenediyl ring, optionally substituted by one or more hydrocarbon chains, identical or different, aliphatic, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms
• o E represents a divalent hydrocarbon group optionally comprising one or more heteroatoms
• crosslinking system comprising at least one radical polymerization initiator and one co-crosslinking agent chosen from the group consisting of (meth)acrylate compounds, maleimide compounds, allyl compounds, vinyl compounds and mixtures thereof.
• composition according to embodiment 1 in which the ethylene units in the copolymer represent between 50% and 95%, preferably between 55% and 90%, by mole of the monomer units of the copolymer.
• composition according to any one of the preceding embodiments in which the copolymer containing ethylene units and 1,3-diene units is a copolymer of ethylene and 1,3-diene.
• composition according to any one of the preceding embodiments in which the 1,3-diene is 1,3-butadiene.
• composition according to any one of the preceding embodiments, in which the copolymer contains units of formula (II) or units of formula (III) or else units of formula (II) and of formula (III): -CH2-CH(CH CH2)- (III)
• composition according to any one of the preceding embodiments in which the molar percentages of the units of formula (II) and of the units of formula (III) in the copolymer, respectively o and p, satisfy the following equation (eq. 1), preferably to equation (eq. 2), o and p being calculated on the basis of all the monomer units of the copolymer.
• composition according to any one of the preceding embodiments in which the content of the copolymer containing ethylene units and 1,3-diene units is within a range ranging from 60 to 100 phr, preferably from 80 to 100 phr.
• composition according to any one of the preceding embodiments in which the compound of formula (I) is chosen from the compounds of formulas (Ia) and (Ib): in which :
• a group chosen from Xi to X5 of formula (Ia) and a group chosen from Xi to X7 of formula (Ib) denote a covalent bond allowing attachment to the group E of the group of formula (IV) below:
• composition according to any one of the preceding embodiments in which the 1,3-dipolar compound is chosen from the compounds of formulas (V) to (X) below and their mesomeric forms: Composition according to embodiment 11, in which the 1,3-dipolar compound is chosen from the compounds of formulas (V), (IX) and (X) and their mesomeric forms.
• Composition according to any one of the preceding embodiments in which the level of the 1,3-dipolar compound is between 0 and 50, preferably between 0.01 and 15, molar equivalents, for example between 4 and 15 molar equivalents, for 100 moles of monomer units constituting the copolymer.
• composition according to any one of embodiments 1 to 12 in which the level of the 1,3-dipolar compound is between 0.1 and 3 molar equivalents, preferentially between 0.1 and 2 molar equivalents, even more preferentially between 0, 1 and 1 molar equivalent, or even more preferably between 0.1 and 0.7 molar equivalent, of imidazole ring per 100 moles of monomer units constituting the copolymer.
• the filler comprises more than 70% by weight, preferably more than 80% by weight, of silica.
• the filler comprises between 80% and 99% by weight of silica and between 1% and 20% by weight of carbon black.
• composition according to any one of the preceding embodiments in which the silica content is within a range ranging from 5 to 60 phr, preferably from 10 to 55 phr, more preferably from 15 to 50 phr.
• Composition according to any one of the preceding embodiments further comprising an agent for coupling the silica to the copolymer, the coupling agent preferably being an organosilane chosen from the group consisting of polysulphide organosilanes, polyorganosiloxanes, mercaptosilanes, acrylosilanes and methacrylosilanes.
• composition according to any one of the preceding embodiments in which the radical polymerization initiator is chosen from the group consisting of peroxides, azo compounds, redox (redox) systems and mixtures thereof.
• the radical polymerization initiator is an organic peroxide chosen from the group consisting of dicumyl peroxide, aryl or diaryl peroxides, diacetyl peroxide, benzoyl, dibenzoyl peroxide, ditertbutyl peroxide, tertbutylcumyl peroxide, 2,5-bis (tertbutylperoxy)-2,5-dimethylhexane, n-butyl-4,4'-di(tert-butylperoxy) valerate , OO-(t-butyl)-O-(2-ethylhexyl) monoperoxycarbonate, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxyisopropylcarbonate,
• composition according to any one of the preceding embodiments in which the content of the radical polymerization initiator is within a range ranging from 0.1 to 3 phr, preferably from 0.2 to 2.5 phr.
• Composition according to any one of the preceding embodiments in which the level of radical polymerization initiator is within a range ranging from 1 to 10% by weight, preferably between 1.25 and 8% by weight, preferably between 2 and 5% by weight, preferably between 3 and 4% by weight, relative to the weight of crosslinking coagent.
• composition according to any one of the preceding embodiments, in which the co-crosslinking agent comprises an acrylate derivative of formula (XI): [X]p A (XI) in which: o [X]p corresponds to a radical of formula (XII): in which :
• R2 and R3 independently represent a hydrogen atom or a Ci-Cs hydrocarbon group chosen from the group consisting of linear, branched or cyclic alkyl groups, alkylaryl groups, aryl groups and aralkyls, and optionally interrupted by one or more heteroatoms, R2 and R3 possibly forming together a non-aromatic cycle,
• • (*) represents the point of attachment of the radical of formula (XII) to A
• o A represents an atom belonging to the group consisting of alkaline earth metals or transition metals, a carbon atom, or a hydrocarbon group C1-C30 optionally interrupted and/or substituted by one or more heteroatoms, o A comprising p free valencies, p having a value ranging from 2 to 6, o it being understood that the 2 to 6 radicals X are identical or different.
• composition according to embodiment 23 in which in the acrylate derivative of formula (XI): o A represents an atom belonging to the group consisting of alkaline earth metals or transition metals, a carbon atom or a hydrocarbon group in C1-C13, o A comprising p free valences, p having a value ranging from 2 to 4, o it being understood that the 2 to 4 radicals X are identical or different.
• composition according to any one of the preceding embodiments in which the level of co-crosslinking agent is within a range ranging from 1 to 20 phr, preferably from 2 to 10 phr, preferably between 2 and 5 phr.
• Composition according to any one of the preceding embodiments in which the ratio of the level of silica to the level of the co-crosslinking agent is included in a range ranging from 2 to 9, preferably from 3 to 7.
• Composition according to one any of the preceding embodiments wherein the composition does not contain molecular sulfur or sulfur-donating agent in as a vulcanizing agent or contains less than 0.5 phr thereof, preferably less than 0.3 phr, even more preferably less than 0.1 phr.
• Rubber article comprising a composition as defined in any one of embodiments 1 to 33.
• a rubber article according to embodiment 34 said article being selected from the group consisting of pneumatic tires, non-pneumatic tires, rubber tracks and conveyor belts.
• Pneumatic or non-pneumatic tire comprising a composition as defined in any one of embodiments 1 to 33.
• Detection was carried out using a "Waters 410" refractometer.
• the molar masses were determined by universal calibration using polystyrene standards certified by “Polymer Laboratories” and double detection with a refractometer and coupling to the viscometer.
• the SEC makes it possible to apprehend the distribution of the molecular masses of a polymer.
• Mn number-average
• Mw weight-average
• the structural analysis as well as the determination of the molar purities of the synthetic molecules are carried out by an NMR analysis.
• the spectra are acquired on an Avance 3400 MHz BRUKER spectrometer equipped with a “broadband” BBFO-zgrad 5 mm probe.
• the quantitative 'H NMR experiment uses a single 30° pulse sequence and a repetition delay of 3 seconds between each of the 64 acquisitions.
• the samples are dissolved in deuterated dimethylsulfoxide (DMSO). This solvent is also used for the lock signal.
• Calibration is performed on the proton signal of deuterated DMSO at 2.44ppm relative to a TMS reference at Oppm.
• the Mooney plasticity measurement is made according to the following principle and in accordance with the ASTM D-1646 standard.
• the generally green polymer is molded in a cylindrical chamber heated to a given temperature, usually 100°C. After one minute of preheating, an L-type rotor rotates within the specimen at 2 revolutions per minute and the useful torque to maintain this movement is measured after 4 minutes of rotation.
• the modulus used here being the nominal (or apparent) secant modulus measured in the first elongation, calculated by going back to the initial section of the specimen.
• the nominal secant moduli or apparent stresses, in MPa
• the reinforcement index which is the ratio of the MSA300 modulus to the MSA100 modulus, is expressed in base 100 compared to the control composition TL. A value greater than 100 reflects an improvement in the reinforcement of the composition considered compared to the control composition.
• the elongation at break (AR%) and stress at break (CR) tests are based on standard NF ISO 37 of December 2005 on a type H2 dumbbell specimen and are measured at a tensile speed of 500 mm/min.
• the elongation at break is expressed in % elongation.
• the breaking stress is expressed in MPa.
• base 100 relative to the control composition TL.
• a value greater than 100 reflects an improvement in the mechanical properties of the composition under consideration relative to the control composition. All these tensile measurements are carried out under normal temperature (23 ⁇ 2° C.) and hygrometry (50+5% relative humidity) conditions, according to French standard NF T 40-101 (December 1979).
• the dynamic properties G* and tan( ⁇ )max were measured on a viscoanalyzer (Metravib VA4000), according to standard ASTM D 5992-96.
• the response of a sample of reticulated composition (cylindrical test piece 4 mm thick and 400 mm 2 in cross-section) was recorded, subjected to a sinusoidal stress in simple alternating shear, at the frequency of 10 Hz, under the conditions defined temperature for example at 60° C. according to standard ASTM D 1349-99.
• a deformation amplitude sweep was performed from 0.15 to 50% (go cycle), then from 50% to 0.15% (return cycle).
• the results used are the non-linearity (NL or AG*) and the loss factor tan( ⁇ ).
• tan( ⁇ )max the maximum value of tan( ⁇ ) observed, denoted tan( ⁇ )max.
• the non-linearity (NL or AG*) is the difference in shear modulus between 0.15% and 50% strain, expressed in MPa.
• the non-linearity and tan( ⁇ )max are expressed in base 100 compared to the control composition TL A value below 100 reflects an improvement in the hysteresis and therefore in the rolling resistance of the composition considered compared to the composition witness.
• the rubber compositions were produced as described in point II.6 above.
• one proceeds for the manufacture of these compositions in the following way: one introduces in an internal mixer (final filling rate: approximately 70% in volume), whose initial temperature of tank is approximately 110°C, the elastomer, where appropriate the 1,3-dipolar compound which is mixed alone with the elastomer for approximately 2 minutes at 110° C., then the silica, the coupling agent, the co-crosslinking agent, as well as the various other ingredients except peroxide.
• Thermomechanical work is then carried out (non-productive phase) in one step, which lasts about 5 to 6 minutes, until a maximum "drop" temperature of 160° C. is reached.
• the mixture thus obtained is recovered, cooled then the peroxide is incorporated on a mixer (homo-finisher) at 23° C., while mixing the whole (productive phase) for an appropriate time (for example between 5 and 12 min).
• the compositions thus obtained are then calendered, either in the form of plates (with a thickness ranging from 2 to 3 mm) or thin sheets of rubber, for the measurement of their physical or mechanical properties, or in the form of profiles that can be used directly, after cutting and/or assembly to the desired dimensions, for example as semi-finished products for tires, in particular for treads.
• the crosslinking is carried out at 150°C.
• the crosslinking time applied, t′ c (90) is the time necessary for the torque of the composition to reach 90% of the maximum torque of the composition.
• the torques of the composition are measured at 150° C. with an oscillating chamber rheometer, according to standard DIN 53529—part 3 (June 1983).
• f c (90) is determined according to standard NF T 43-015 for each of the compositions. From one composition to another, it varies approximately from 20 to 40 minutes.
• Table 1 presents the compositions tested (in phr), as well as the results obtained.
• control compositions differ from composition C1 in accordance with the invention in that they do not comprise a 1,3-dipolar compound and/or a co-crosslinking agent in accordance with the invention.
• compositions in accordance with the invention are useful for numerous applications in the field of pneumatic or non-pneumatic tires, in particular in treads for which a good compromise between the performances of reinforcement, breaking stress and rolling resistance rolling is desired.

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