Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/25—Incorporating silicon atoms into the molecule
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B11/00—Making preforms
  • B29B11/06—Making preforms by moulding the material
  • B29B11/10—Extrusion moulding
• • 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
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages
  • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
  • C07F7/1888—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of other Si-linkages, e.g. Si-N
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/20—Incorporating sulfur atoms into the molecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/22—Incorporating nitrogen atoms into the molecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
  • C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2021/00—Use of unspecified rubbers as moulding material

Definitions

• the present invention relates to novel compounds useful as modifiers in rubber compositions, processes for their preparation, and novel rubber compositions comprising these compounds.
• documents FR 2149339 and FR 2206330 describe sulfur compounds comprising two terminal organosilicon groups used as coupling agent.
• WO 2012/007684 discloses coupling agents comprising a nitrogenous associative group and a nitrogen dipole.
• US 2006/086450 discloses vulcanizable elastomeric compositions comprising silica coupling agents, in particular bis (trialkoxysilylorgano) polysulfides, mercaptosilanes and blocked mercaptosilanes.
• the compounds containing a trialkoxysilyl group and a nitrogen function without a linking group between the nitrogen function and the polysulfide function are either too stable at the level of the bond between the nitrogen function and the polysulfide function, or are not stable enough. Moreover, the proximity between the polysulfide function and the nitrogen function does not allow charge-polymer coupling by this part of the molecule.
• CN 102491344 describes the synthesis of silica nanoparticles whose surface is functionalized by a sulfhydryl disulfide benzimidazole group.
• the silica nanoparticles are first functionalized using 3-mercaptopropyltrimethoxysilane and then using S- (2-aminoethylthio) -2-thiopyridine and finally by various other steps.
• the described polysulfide compounds have an oxysilane group bonded to a silica nanoparticle.
• the invention relates firstly to a compound of formula (I)
• A represents an associative group comprising at least one nitrogen atom
• Q1 and Q2 represent independently of one another a linking group
• x is an integer ranging from 2 to 6
• each R 'independently represents an alkyl group having 1 to 4 carbon atoms.
• A is selected from imidazolidinone, azoyl, ureyl, bis-ureyl and ureido-pyrimidyl groups.
• A corresponds to one of the following formulas (II) to (VI):
• R denotes a hydrocarbon group which may optionally contain heteroatoms
• Y denotes an oxygen or sulfur atom, preferably an oxygen atom.
• A is a group of formula (VII):
• Q 1 and Q 2 are independently a linear or branched, substituted or unsubstituted, C1-C24, preferably C1-C10, divalent hydrocarbon radical, optionally interrupted and / or substituted by one or more nitrogen atoms or oxygen, and more preferably an uninterrupted and unsubstituted C1-C6 hydrocarbon radical; Q1 and Q2 are preferably identical.
• x is equal to 4.
• all the R ' are identical in the Z group, and preferably each R' is the ethyl group.
• the compound has the following formula (VIII):
• the invention also relates to a mixture of different compounds of formula (I)
• A represents an associative group comprising at least one nitrogen atom, Qi and Q2 independently of one another represent a linking group,
• x is an integer from 2 to 6
• each R 'independently represents an alkyl group having 1 to 4 carbon atoms
• the invention also relates to a composition
• a composition comprising a compound of formula (I) as defined above, as well as the following compounds of formula () and (I "):
• the invention also relates to a process for preparing a compound of formula (I) as defined above, comprising a step of reacting a sulfur compound with a compound of formula (IX)
• - Xi and X2 independently represent a Cl atom or an SH group.
• X1 and X2 each represent an atom
• A is a group of formula (VII)
• Q 1 and Q 2 independently represent a divalent C 1 -C 6 hydrocarbon radical, more preferably a divalent C 2 -C hydrocarbon radical; and or
• the sulfur compound is sulfur, X1 is an SH group and X2 is a Cl group or vice versa, and:
• A is a group of formula (VII):
• Q1 and Q2 independently represent a C1-C6 divalent hydrocarbon radical, more preferably a C2-divalent hydrocarbon radical; and or
• X1 represents SH and X2 represents Cl.
• the invention also relates to a process for preparing a compound of formula (I) as defined above, comprising a reaction step in the presence of a base of a compound of formula ( ⁇ ) with a compound of formula (I "):
• A is a group of formula (VII):
• Q1 and Q2 independently represent a C1-C6 divalent hydrocarbon radical, more preferably a C2-divalent hydrocarbon radical; and or
• the groups R 'in the group Z are ethyl groups; and or preferably the base is a sodium alkoxide, more preferably sodium methoxide or sodium ethoxide.
• the invention also relates to a rubber composition
• a rubber composition comprising at least one diene elastomer, a reinforcing filler, a chemical crosslinking agent and a modifying agent, optionally already grafted onto the elastomer, said modifying agent being a compound of formula (I ) as defined above or a mixture as defined above.
• the diene elastomer comprises a substantially unsaturated diene elastomer selected from natural rubber, synthetic polyisoprenes, polybutadienes, butadiene copolymers, isoprene copolymers, and mixtures thereof; and / or comprises a substantially saturated elastomer selected from butyl rubbers, copolymers of dienes and alpha-olefins such as EPDMs and mixtures thereof.
• the chemical crosslinking agent comprises from 0.5 to 12 phr of sulfur, preferably from 1 to 10 phr of sulfur, or from 0.01 to 10 phr of one or more peroxide compounds.
• the amount of modifying agent ranges from 0.01 to 50 mol%, preferably from 0.01 mol% to 5 mol%.
• the invention also relates to a method for preparing a rubber composition as defined above, comprising one or more thermomechanical kneading steps of the diene elastomer, the reinforcing filler, the chemical crosslinking agent and the agent. modification and an extrusion and calendering step.
• the invention also relates to an article manufactured in whole or in part with a rubber composition as defined above, preferably selected from among seals, thermal or acoustic insulators, cables, sheaths, insoles footwear, packaging, coatings (paints, films, cosmetics), patches (cosmetics or dermopharmaceuticals), other systems for trapping and release of active ingredients, dressings, elastic collars, vacuum tubes and tubes and hoses for transporting fluids.
• a rubber composition as defined above, preferably selected from among seals, thermal or acoustic insulators, cables, sheaths, insoles footwear, packaging, coatings (paints, films, cosmetics), patches (cosmetics or dermopharmaceuticals), other systems for trapping and release of active ingredients, dressings, elastic collars, vacuum tubes and tubes and hoses for transporting fluids.
• the invention also relates to a tire comprising a rubber composition as defined above.
• the invention also relates to a modified polymer obtained by grafting a compound of formula (I) as defined above or a mixture as defined above.
• the polymer is a diene elastomer, preferably an essentially unsaturated diene elastomer chosen from natural rubber, synthetic polyisoprenes, polybutadienes, butadiene copolymers, isoprene copolymers and mixtures of these elastomers. or a substantially saturated elastomer selected from butyl rubbers and copolymers of dienes and alpha-olefins such as EPDMs and mixtures thereof.
• the invention also relates to a process for the preparation of a modified polymer comprising a grafting step of a compound of formula (I) as defined above or of a mixture as defined above on a polymer comprising at least one less unsaturation.
• the present invention overcomes the disadvantages of the state of the art. It provides more particularly compounds of formula (I) for obtaining rubber compositions both having improved properties and having a reduced manufacturing cost.
• the compounds of formula (I) can be prepared in a few steps, for example from two to four stages, some of which can be carried out in the same reactor, and from inexpensive raw materials.
• the invention makes it possible to obtain rubber compositions having high mechanical properties and good wear resistance.
• the invention makes it possible to obtain low hysteretic rubber compositions having a high average rigidity at high deformations, while having a high elongation at break or a high tensile strength. These rubber compositions make it possible to obtain tires having a reduced rolling resistance.
• the compounds according to the invention comprise both a silane functional group capable of reacting, for example with a filler (for example siliceous) to form covalent bonds, and an associative group capable of forming non-covalent bonds (eg, hydrogen) with a filler such as a siliceous filler.
• a silane functional group capable of reacting, for example with a filler (for example siliceous) to form covalent bonds
• an associative group capable of forming non-covalent bonds (eg, hydrogen) with a filler such as a siliceous filler.
• the simultaneous presence of the strong and weak bonds is capable of conferring advantageous mechanical properties on the rubber composition, such as, for example, better dispersion of the filler than with the compounds of the state of the art comprising only silane functions, and less wear than with the compounds of the state of the art comprising only associative groups.
• the invention relates to a compound of formula (I):
• S is a sulfur atom
• x is an integer
• A represents an associative group comprising at least one nitrogen atom
• Q 1 and Q 2 are linking groups and Z trialkoxysilane:
• each R 'independently represents an alkyl group having 1 to 4 carbon atoms.
• sociative groups groups capable of associating with each other by hydrogen, ionic and / or hydrophobic bonds. It is, according to a preferred embodiment of the invention, groups capable of associating with hydrogen bonds.
• each associative group preferably comprises at least one donor "site” and one acceptor site with respect to the hydrogen bonding so that two identical associative groups are -complementary and can associate with each other by forming at least two hydrogen bonds.
• the associative groups according to the invention are also capable of associating by hydrogen, ionic and / or hydrophobic bonds with functions present on fillers.
• the group A is chosen from imidazolidinone, ureyl, bis-ureyl, ureido-pyrimidyl and triazolyl groups.
• the associative group A corresponds to one of the following formulas (II) to (VI):
• - R denotes a hydrocarbon group (preferably C1-C10, more preferably C1-C6) linear, branched or cyclic (preferably linear), which may optionally contain heteroatoms (and preferably not containing )
• Y denotes an oxygen or sulfur atom, preferably an oxygen atom.
• the two nitrogen atoms are connected by a divalent organic group, such as a hydrocarbylene group such as alkylene, substituted alkylene, cycloalkylene, substituted cycloalkylene, arylene or substituted arylene.
• the hydrocarbylene group contains from 1 to 10 carbon atoms.
• the hydrocarbylene group may also contain heteroatoms such as nitrogen, oxygen or sulfur. These heteroatoms can be included in the hydrocarbylene chain or in substitution for a carbon.
• the group of formula (II) has 5 or 6 atoms.
• the group A is a di or tri-nitrogen heterocycle, with 5 or 6 atoms, preferably diazotized, and comprising at least one carbonyl function.
• the group A is the imidazolidinone group of formula (VII):
• the linking groups Q 1 and Q 2 can be any divalent radical. They are preferably chosen so as not to, or very little, interfere with the associative group A and with the trialkoxysilane group Z.
• Said groups Q1 and Q2 are then considered in particular to be groups inert with respect to the associative group A.
• group inert with respect to the associative group A is meant a group which does not include associative functions such as that defined according to the invention. They are then also considered as inert groups vis-à-vis the trialkoxysilane Z group, that is to say they are not likely to form a covalent bond with such a group (located on another molecule of the compound ).
• the groups Q1 and Q2 are preferably independently a divalent, linear, branched or cyclic hydrocarbon radical. They may independently contain one or more aromatic radicals, and / or one or more heteroatoms.
• the divalent hydrocarbon radical may optionally be substituted, the substituents preferably being inert with respect to the associative group A and the trialkoxysilane group Z.
• the groups Q1 and Q2 are independently a linear or branched, substituted or unsubstituted C1-C24, preferably C1-C10, divalent hydrocarbon radical, optionally interrupted and / or substituted by one or more atoms of nitrogen or oxygen, and more preferably a divalent hydrocarbon radical C1-C6, uninterrupted and unsubstituted, and more preferably linearly.
• Q1 and Q2 may be different or the same, but preferably Q1 and Q2 are the same.
• x is an integer from 2 to 6.
• x is an integer from 2 to 5, where x is an integer from 2 to 4, where x is an integer from 3 to 5, or x is an integer of 2 or 3, where x is an integer equal to 3 or 4.
• x is 2, or 3, or 4, or
• the groups R 'in the alkoxysilane compound Z may be preferably methyl, ethyl, propyl, isopropyl or butyl groups. Ethyl groups are preferred. Preferably all the groups R 'are identical.
• the compound of the invention is chosen from the compounds of formula (VIII) below:
• the invention also relates to mixtures of different compounds of formula (I) with different values of x (the compounds being identical elsewhere).
• the invention relates to mixtures of compounds of formula (I) with x varying from 2 to 6, or from 2 to 5, or from 2 to 4, the compounds being identical elsewhere.
• Such a mixture can be considered as a compound of formula (I) with x having a certain statistical distribution and in particular an average value which is not necessarily entire, and which is between 2 and 6 (preferably between 2 and 5). , more preferably between 2 and 4).
• the invention also relates to a mixture of compound of formula (I) with the following symmetrical compounds of formula () and (I "):
• the invention also relates to mixtures of compounds of formulas (I), ( ⁇ ) and (I ") with different values of x (the compounds being identical elsewhere), in particular with x ranging from 2 to 6, or from 2 to 5, or from 2 to 4 and having an average value not necessarily whole between 2 and 6, or between 2 and 5, or between 2 and 4.
• the compounds according to the invention may be prepared according to a process generally comprising a step of reaction of a sulfur compound with a compound of formula (IX)
• A, Z, Qi and Q2 have the meanings defined above, and
• X 1 and X 2 independently represent a Cl atom or an SH group.
• At least one of X1 and X2 is a Cl atom.
• A is a group of formula (VII):
• Q 1 and Q 2 are independently a divalent linear or branched C1-C10 hydrocarbon radical, more preferably a C2 linear divalent hydrocarbon radical.
• Q1 and Cte are identical.
• the Z group is preferably the triethoxysilane group.
• Sodium tetrasulfide may be prepared for example by reacting sulfur with anhydrous sodium sulfide; this can be prepared by reacting sodium ethoxide with hydrogen sulfide.
• Sodium tetrasulfide is preferably prepared in situ by adding sulfur to an ethanolic solution of sodium sulphide.
• the substitution Final nucleophile is preferably carried out in the solvent used for the preparation of sodium tetrasulfide, that is to say ethanol.
• the temperature of this step may be between room temperature and the reflux temperature of the solvent. Preferably, this step is carried out at reflux temperature of the solvent.
• the salt formed can be removed by filtration and the final product can be isolated by evaporation of the solvent.
• the compounds according to the invention of formula (I) with x ranging from 2 to 6, preferably from 2 to 5, and more particularly from 2 to 4, are prepared by a process comprising a step Sulfur reaction with a compound of formula SH - Qi - Z and a compound of formula Cl - Q2 - A, or with a compound of formula Cl - Q1 - Z and a compound of formula SH - Q2 - A, in which A, Z, Q1 and Q2 have the meanings defined above.
• A is a group of formula (VII):
• Q 1 and Q 2 are independently a divalent linear or branched C1-C10 hydrocarbon radical, more preferably a C2 linear divalent hydrocarbon radical.
• Q1 and Q2 are identical.
• the Z group is preferably the triethoxysilane group.
• the compound of formula SH - Q1 - Z is obtained by the reaction of a compound of formula Cl - Q1 - Z with sodium hydrogen sulfide NaSH; or the compound of formula SH - Q2 - A is obtained by the reaction of a compound of formula Cl - Q2 - A with sodium hydrogen sulfide NaSH.
• This process preferably involves reacting the mercaptan compound with sodium alkoxide and sulfur in a solvent, and then adding the chlorinated compound to the reaction mixture.
• the sodium alkoxide and the solvent are preferably sodium methoxide and methanol, or sodium ethoxide and ethanol.
• the temperature of this step may be between room temperature and the reflux temperature of the solvent.
• the solvent is refluxed.
• the salt formed can be removed by filtration and the final product can be isolated by evaporation of the solvent.
• the implementation of such a method generally makes it possible to obtain a mixture of polysulfide compounds having a distribution of the number of sulfur atoms ranging from 2 to 6, more particularly from 2 to 5, and mainly from 2 to 4. .
• the compound of formula (VIII) with x ranging from 2 to 6, more particularly from 2 to 5, and mainly from 2 to 4, may be prepared according to the following synthetic scheme:
• the compound of formula (I) may be prepared by reacting in the presence of a base the symmetrical compounds of formulas ( ⁇ ) and (I ") respectively:
• Q1 and Q2 independently represent a C1-C6 divalent hydrocarbon radical, more preferably a C2 divalent hydrocarbon radical.
• the Z group is a triethoxyilsane group.
• the invention also relates to a rubber composition
• a rubber composition comprising at least one diene elastomer, a reinforcing filler, a chemical crosslinking agent and a modifying agent, optionally already grafted onto the elastomer, said modifying agent being a compound according to the invention. as described above.
• the rubber composition is a simple (non-crosslinked or vulcanized) mixture of the above components.
• the rubber composition is a crosslinked or vulcanized composition from the mixture of the above constituents.
• One of the components of the rubber composition according to the invention is a diene elastomer.
• the diene elastomers can be classified in known manner into two categories, those said to be essentially unsaturated and those said to be essentially saturated. These two categories of diene elastomers can be envisaged within the scope of the invention.
• An essentially saturated diene elastomer has a level of units or units of diene origin which is low or very low (conjugated dienes) which is always less than 15% (in moles).
• butyl rubbers or copolymers of dienes and alpha-olefins such as EPDM (ethylene-propylene-diene monomer) fall within the definition of essentially saturated diene elastomers.
• essentially unsaturated diene elastomer is understood to mean a diene elastomer derived at least in part from conjugated diene monomers having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (in moles).
• conjugated diene monomers having a level of units or units of diene origin (conjugated dienes) which is greater than 15% (in moles).
• highly unsaturated diene elastomer is understood to mean in particular a diene elastomer having a degree of units of diene origin (conjugated dienes) which is greater than 50% (in moles).
• iene elastomer may be used in the invention:
• Diene elastomers of the highly unsaturated type in particular of type (a) or (b) above, are preferred.
• conjugated dienes 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di (C 1 -C 5) alkyl-1,3-butadienes, such as, for example, 2 3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1, 3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene.
• alkyl-1,3-butadienes such as, for example, 2 3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1, 3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, 2,4
• Suitable vinylaromatic compounds are, for example, styrene, ortho-, meta-, para-methylstyrene, the "vinyl-toluene" commercial mixture, para-tertiarybutylstyrene, methoxystyrenes, chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene.
• the copolymers may contain between 99% and 20% by weight of diene units and between 1% and 80% by weight of vinylaromatic units.
• the elastomers may have any microstructure which is a function of the polymerization conditions used, in particular the presence or absence of a modifying and / or randomizing agent and the amounts of randomizing modifying agent used.
• the elastomers may be, for example, block, random, sequenced or microsequential, and may be prepared in dispersion, in emulsion or in solution; they may be coupled and / or starred or functionalized with a coupling agent and / or starring or functionalization.
• diene elastomers selected from the group consisting of polybutadienes (BR), synthetic polyisoprenes (IR), natural rubber (NR), butadiene copolymers, isoprene copolymers and mixtures of these elastomers.
• Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymers (SBR), isoprene-butadiene copolymers (BIR), isoprene-styrene copolymers (SIR), isoprene-butadiene-copolymers styrene (SBIR) and mixtures of such copolymers.
• the rubber composition according to the invention also comprises at least the modifying agent which is a compound of formula (I) or one of its preferred variants described above.
• the diene elastomer may be grafted with the modifying agent prior to its introduction into the rubber composition, or may be grafted by reaction with the modifier during the manufacture of the composition.
• the rubber composition according to the invention may therefore contain a single diene elastomer grafted with the modifying agent (either grafted prior to its introduction into the composition or grafted by reaction with the modifying agent during the manufacture of the composition) , or a mixture of several diene elastomers all grafted, or some of which are grafted and the others not.
• the other diene elastomer (s) used in grafting with the grafted elastomer according to the invention are conventional diene elastomers as described above whether they are starred, coupled, functionalized or not. These elastomers are then present in the matrix at a level of between 0 and 60 phr (the limits of this range being excluded), preferably at a level ranging from more than 0 to 50 phr, more preferably from more than 0 to 30 phr. .
• the mass fraction of elastomer graft according to the invention in the elastomeric matrix is predominant and preferably greater than or equal to 50% by weight of the total weight of the matrix.
• the majority mass fraction according to the invention is the highest mass fraction of the blend.
• the diene elastomer (s) grafted according to the invention may be used in combination with any type of synthetic elastomer other than diene, or even with polymers other than elastomers, for example thermoplastic polymers.
• the level of modifying agent ranges from 0.01 to 50 mol%, preferably from 0.01 to 5 mol%.
• "modifying agent content" present in a rubber composition expressed as a molar percentage, is understood to mean the number of modifying agent molecules present in the composition per hundred diene elastomer units of the composition, be it indifferently dienic or non-dienic units.
• the amount of modifying agent on an SBR is 0.20 mol%, it means that there is 0.20 modified modifier unit per 100 styrene and butadiene SBR units.
• the level of modifying agent represents the number of graft modification for 100 units of diene elastomers, the number of units taking into account both elastomers (grafted and ungrafted), assuming that other modifying agent molecules not already grafted were not added to the diene elastomer; composition.
• Another component of the rubber composition according to the invention is the reinforcing filler.
• reinforcing filler known for its ability to reinforce a rubber composition
• a reinforcing organic filler such as carbon black
• a reinforcing inorganic filler such as silica
• charge especially a black carbon and silica blend.
• cellulosic fillers talc, calcium carbonate, mica or wollastonite, glass or metal oxides or hydrates.
• a reinforcing inorganic filler is present.
• Suitable carbon blacks are all carbon blacks, especially blacks of the type HAF, ISAF, SAF. It is also possible to use, according to the targeted applications, blacks of higher series FF, FEF, GPF, SRF.
• the carbon blacks could for example already be incorporated into the diene elastomer in the form of a masterbatch, before or after grafting and preferably after grafting (see for example WO 97/36724 or WO 99 / 16600).
• organic fillers other than carbon blacks
• reinforcing inorganic filler is intended herein to mean, by definition, any inorganic or inorganic filler as opposed to carbon black capable of reinforcing on its own, with no other means than an intermediate coupling agent, a composition rubber (for example, in the case of a rubber composition for the manufacture of tires, a reinforcing inorganic filler is able to replace, in its reinforcing function, a conventional carbon black of pneumatic grade); such a charge is generally characterized, in known manner, by the presence of hydroxyl groups on its surface.
• reinforcing inorganic filler is present indifferent whether in the form of powder, microbeads, granules, beads or any other suitable densified form.
• reinforcing inorganic filler also refers to mixtures of various reinforcing inorganic fillers, in particular highly dispersible siliceous and / or aluminous fillers as described below.
• Suitable reinforcing inorganic fillers are, in particular, mineral fillers of the siliceous type, in particular silica (SiO 2), or of the aluminous type, in particular alumina (Al 2 O 3).
• the level of reinforcing filler in the composition is between 30 and 150 phr, more preferably between 50 and 120 phr. The optimum is different depending on the specific applications targeted.
• a siliceous mineral filler is present, preferably at a rate of 30 to 150 phr.
• the reinforcing filler mainly comprises silica, preferably the content of carbon black present in the composition being between 2 and 20 phr.
• the reinforcing filler predominantly comprises carbon black, or is exclusively composed of carbon black.
• the reinforcing inorganic filler to the diene elastomer, it is optionally possible to include in the composition an at least bifunctional coupling agent (or bonding agent) intended to ensure a sufficient chemical and / or physical connection between the filler inorganic
• diene elastomer in particular organosilanes or bifunctional polyorganosiloxanes, for example bis (3-triethoxy-silylpropyl) tetrasulfide.
• Polysulphurized silanes known as symmetrical or asymmetrical silanes according to their particular structure, can be used in a known manner, as described, for example, in documents WO 03/002648 and WO 03/002649.
• the content of coupling agent when present, is preferably between 4 and 12 phr, more preferably between 3 and 8 phr.
• the composition may be devoid of coupling agent, the coupling of the reinforcing inorganic filler to the diene elastomer being provided solely by the modifying agent described above.
• reinforcing inorganic filler As an equivalent filler of the reinforcing inorganic filler described in this paragraph, it is also possible to use a reinforcing filler of another nature, in particular organic, since this reinforcing filler is covered with an inorganic layer such as silica, or else comprises on its surface functional sites, in particular hydroxyl sites, requiring coupling to establish the bond between the filler and the elastomer.
• a reinforcing filler of another nature in particular organic
• this reinforcing filler is covered with an inorganic layer such as silica, or else comprises on its surface functional sites, in particular hydroxyl sites, requiring coupling to establish the bond between the filler and the elastomer.
• Another component of the rubber composition according to the invention is the chemical crosslinking agent.
• Chemical crosslinking allows the formation of covalent bonds between the elastomer chains.
• the chemical crosslinking can be done in particular by means of a vulcanization system or by means of peroxide compounds.
• the vulcanization system itself is based on sulfur (or a sulfur-donor agent) and a primary vulcanization accelerator.
• a primary vulcanization accelerator To this basic vulcanization system may be added various known secondary accelerators or vulcanization activators such as zinc oxide, stearic acid or equivalent compounds, guanidine derivatives (in particular diphenylguanidine).
• Sulfur is used at a preferential rate of between 0.5 and 12 phr, in particular between 1 and 10 phr.
• the primary vulcanization accelerator is used at a preferred level of between 0.5 and 10 phr, more preferably between 0.5 and 5.0 phr.
• accelerator any compound that can act as an accelerator for vulcanizing diene elastomers in the presence of sulfur, especially thiazole accelerators and their derivatives, type accelerators can be used as accelerator (primary or secondary). thiurams, zinc dithiocarbamates. Preferably, a primary accelerator of the sulfenamide type is used.
• the peroxide compound (s) represent (s) from 0.01 to 10 phr.
• acyl peroxides for example benzoyl peroxide or p-chlorobenzoyl peroxide
• peroxide ketones for example methyl ethyl ketone peroxide
• peroxyesters for example butylperoxyacetate, t-butylperoxybenzoate and t-butylperoxyphthalate
• alkylperoxides for example dicumylperoxide, di-t-butylperoxybenzoate and 1,3-bis (t-butylperoxyisopropyl) benzene
• hydroperoxides for example t-butyl hydroperoxide.
• the rubber composition according to the invention may be a monophasic or multiphase mixture.
• the rubber composition according to the invention may also comprise all or part of the usual additives usually used in rubber compositions, such as, for example, petroleum cuts, solvents, plasticizers or extension oils, which these are of a nature aromatic or non-aromatic, pigments and / or dyes, tackifying resins, processing aids, lubricants, anti-radiation (anti-UV) additives, protective agents such as anti-ozone waxes (such as C32 ST Ozone wax), chemical antiozonants, antioxidants (such as 6-paraphenylenediamine), anti-fatigue agents, reinforcing resins, acceptors (eg phenolic resin) novolac) or methylene donors (for example HMT or H3M) as described for example in WO 02/10269, as well as adhesion promoters (cobalt salts for example).
• additives usually used in rubber compositions, such as, for example, petroleum cuts, solvents, plasticizers or extension oils, which these are of a nature aromatic or non-aromatic
• additives that may be added to the material according to the invention are in particular:
• lubricants such as stearic acid and its esters, waxy esters, polyethylene waxes, paraffin wax or acrylic lubricants;
• pigments such as those described in the document "Plastics Additives and Modifiers Handbook, Section VIII, Dyes", J. Edenbaum, Ed., Van Nostrand, p.884-954.
• pigments which can be used, mention may be made of carbon black, titanium dioxide, clay, metal particles or treated mica particles of the IRIODIN® brand marketed by MERCK;
• thermal and / or UV stabilizers such as stearates of tin, lead, zinc, cadmium, barium or sodium, including the Thermolite® from ARKEMA;
• co-stabilizers such as epoxidized natural oils
• antioxidants for example phenolic, sulfur or phosphitic
• blowing agents for the manufacture of expanded parts such as azodicarbonamides, azobisobutyronitrile, diethyl azobisisobutyrate;
• flameproofing agents including antimony trioxide, zinc borate and brominated or chlorinated phosphate esters
• the rubber composition according to the invention comprises, as preferred non-aromatic or very weakly aromatic plasticizing agent, at least one compound chosen from the group consisting of naphthenic, paraffinic, MES, TDAE oils, oils and the like. esters (in particular trioleates) of glycerol, the hydrocarbon plasticizing resins having a high glass transition temperature (Tg) preferably greater than 30 ° C, and mixtures of such compounds.
• Tg glass transition temperature
• composition according to the invention may also contain, in addition to the coupling agents, activators for coupling the reinforcing inorganic filler or, more generally, processing aid agents that are capable in a known manner, thanks to an improvement in the dispersion of the inorganic filler in the rubber matrix and a lowering of the viscosity of the compositions, to improve their ability to implement in the green state.
• the invention also relates to a tire comprising a rubber composition according to the invention or made from a rubber composition according to the invention.
• the invention also relates to a method for preparing a rubber composition according to the invention comprising one or more thermomechanical kneading steps of the diene elastomer, the reinforcing filler, the chemical crosslinking agent and the modifying agent, and an extrusion and calendering or extrusion blow molding, conventional molding step, injection, rotational molding or thermoforming.
• the rubber composition according to the invention can in particular be manufactured in a suitable mixer, by using two successive preparation phases: a thermomechanical working phase or mixing (sometimes referred to as a non-productive phase) at high temperature, up to a temperature maximum between 130 ° C and 200 ° C, preferably between 145 ° C and 185 ° C, followed by a second phase (sometimes called productive phase) at a lower temperature, typically less than 120 ° C, for example between 60 ° C and 100 ° C: this is a finishing phase during which is incorporated the chemical crosslinking system.
• a thermomechanical working phase or mixing sometimes referred to as a non-productive phase
• a second phase sometimes called productive phase
• this is a finishing phase during which is incorporated the chemical crosslinking system.
• the diene elastomer is grafted with the modifying agent prior to the manufacture of the rubber composition.
• the grafted diene elastomer which is introduced during the first so-called non-productive phase.
• the grafting of the diene elastomer by the modifying agent is carried out concomitantly with the manufacture of the rubber composition.
• both the diene elastomer not yet grafted and the modifying agent are introduced during the first non-productive phase.
• the reinforcing filler can then be added subsequently during this same non-productive phase in order to prevent any parasitic reaction with the modifying agent.
• the grafting yield is preferably greater than 60%, more preferably greater than 80%, and preferably subsequently the reinforcing filler, as well as all the basic constituents of the composition, with the exception of the chemical crosslinking system, by thermomechanically kneading the whole, in one or more times, until a maximum temperature of between 130 ° C. and 200 ° C, preferably between 145 ° C and 185 ° C;
• the grafting of the modifying agent can be carried out in bulk, for example in an internal mixer or an external mixer such as a roller mixer. The grafting is then carried out either at a temperature of the external mixer or the internal mixer below 60 ° C., followed by a grafting reaction step in a press or in an oven at temperatures ranging from 80 ° C. to 200 ° C. or at a temperature of the external mixer or internal mixer greater than 60 ° C without subsequent heat treatment.
• compositions thus obtained are calendered either in the form of plates (thickness of 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 assembling to the desired dimensions, for example as finished or semi-finished products, in particular as semi-finished products for tires, in particular as treads for tires.
• the invention makes it possible in particular to obtain seals, thermal or acoustic insulators, cables, sheaths, shoe soles, packaging, coatings (paints, films, cosmetic products), patches (cosmetics or dermopharmaceutical), or other asset trapping and release systems, dressings, elastic hose clamps, vacuum tubes, fluid tubes and hoses, and, in general, parts to be elastic behavior, while having good flexibility, good resistance to fatigue, shock and tear.
• These materials can also be part of adhesive or cosmetic compositions, ink formulations, varnishes or paints.
• the invention also relates to a modified polymer obtained by grafting a compound according to the invention of formula (I) or according to one of the preferred embodiments.
• the polymer contains at least one unsaturation or double bond capable of reacting with the compound according to the invention.
• the polymers in question are diene elastomers, as defined above.
• the polymer having at least one unsaturation or double bond is modified by grafting a compound of formula (I) as defined above, also called modification agent.
• the level of modifying agent ranges from 0.01 to 50 mol%, preferably from 0.01 to 5 mol%.
• the invention also relates to a process for preparing a modified polymer comprising a grafting step of a compound according to the invention as defined above, on a polymer comprising at least one unsaturation.
• the accepted mechanism for grafting is a homolytic cleavage of the polysulfide, followed by a radical addition of the radicals S 0 to the double bonds of the polymer.
• the grafting of the modifying agent can be carried out in bulk, for example in an internal mixer or an external mixer such as a roll mill, or in solution.
• the grafting process can be carried out in solution continuously or discontinuously.
• the polymer thus modified can be separated from its solution by any type of means known to those skilled in the art and in particular by a bubbling operation with water vapor.
• the grafting step can be carried out in the molten state, for example in an extruder or an internal mixer at a temperature which can range from 50 ° C. to 300 ° C. and preferably from 200 ° to 280 ° C. .
• the modifying agent may be mixed with the polymer alone, or with the aid of an additive permitting the impregnation of the solid polymer grains with the previously molten modifying agent.
• the solid mixture before introduction into the extruder or mixer may be made more homogeneous by refrigeration to solidify the modifying agent. It is also possible to determine the latter in the extruder or the mixer after a start of melting of the polymer to be grafted.
• the time at the grafting temperature can range from 30 seconds to 5 hours.
• the modifying agent may be introduced into the extruder as a masterbatch in a polymer which, preferably, may be the polymer to be grafted.
• the masterbatch may comprise up to 30% by weight of the modifying agent; then, the masterbatch is diluted in the polymer to be grafted during the grafting operation.
• the grafting can be carried out by reaction in the solvent phase, for example in anhydrous chloroform.
• the reaction temperature can range from 5 ° C. to 75 ° C., for a period ranging from a few minutes to a day and at pre-graft polymer concentrations of between 1 and 50% by weight. relative to the total weight of the solution.
• the number of associative groups introduced on the polymer is adjusted so as to obtain materials having a good dimensional stability and good mechanical properties thanks to the permanent chemical crosslinking, while being easier to implement and having particular properties, such as for example, flexible mechanical properties, because of the introduction of a different (non-permanent) crosslinking mode and likely to evolve according to the parameters of the environment of use, as, for example, the temperature or the characteristic time of stress.
• the average number of associative groups per polymer chain may be between 1 and 200.
• the ratio between the percentage of crosslinking bridges with permanent covalent bonds and the percentage of crosslinking bridges with non-covalent bonds is advantageously between 99/1 and 1/99, and preferably between 90/10 and 20/80.
• Example 1 - Synthesis of the compound of formula (VIII) from chlorinated derivatives 1 - (2-chloroethyl) imidazolidin-2-one is prepared according to Example 1b of the document WO 2012/007684.
• the mixture is cooled to 40 ° C. and 11.1 g of H 2 S (0.33 mol) are then introduced into the reaction mixture via a diffuser over a period of approximately 1 hour.
• the reaction mixture is cooled to room temperature and filtered.
• the precipitate is washed with 100 g of ethanol.
• the filtrates are collected and evaporated under vacuum. 132 g of a polysulfide mixture (yield of 91%) are obtained.
• the final product is analyzed by NMR and HPLC. The analysis shows that it is a mixture of symmetric and asymmetric polysulfides of sulfur ranks 2 to 6.
• Example 2 Synthesis of the compound of formula (VIII) from a chlorinated derivative and a mercaptan derivative 1- (2-Chloroethyl) imidazolidin-2-one is prepared according to Example 1b of WO 2012/007684.
• anhydrous sodium ethoxide (0.4 mol) is introduced in the form of a 10% by weight ethanol (272 g of solution) then 102 g of 3-mercaptopropyltriethoxysilane (0.43 mol) and 41 g of sulfur powder (1.28 mol).
• the reaction mixture is stirred at reflux for 16 hours and then 63 g of 1- (2-chloroethyl) imidazolidin-2-one (0.43 mol) are slowly added.
• the mixture is refluxed for 6 hours.
• the reaction mixture is cooled to ambient temperature and then filtered.
• the filtrate is concentrated under reduced pressure to evaporate the solvent.
• the final product is analyzed by NMR and HPLC. The analysis shows that it is a mixture of polysulfides.
• the compound of formula (VIII), the majority, is one of these products.

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• 2016
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